Production phenol hydrogenation

The recovery area of the plant employs fractionation to recover and purify the phenol and acetone products. Also in this section the alpha-methylstyrene is recovered and may be hydrogenated back to cumene or recovered as AMS product. The hydrogenated AMS is recycled as feedstock to the reaction area. The overall yield for the cumene process is 96 mol %. Figure 1 is a simplified process diagram. 

The neutralized cleavage product, consisting of acetone, phenol, water, hydrocarbons, and trace organic impurities, is separated in a series of distillation columns. Also in this section alpha-methylstyrene is either recovered as a product or hydrogenated to cumene. 

Caprolactam [105-60-2] (2-oxohexamethyleiiiiriiQe, liexaliydro-2J -a2epin-2-one) is one of the most widely used chemical intermediates. However, almost all of the aimual production of 3.0 x 10 t is consumed as the monomer for nylon-6 fibers and plastics (see Fibers survey Polyamides, plastics). Cyclohexanone, which is the most common organic precursor of caprolactam, is made from benzene by either phenol hydrogenation or cyclohexane oxidation (see Cyclohexanoland cyclohexanone). Reaction with ammonia-derived hydroxjlamine forms cyclohexanone oxime, which undergoes molecular rearrangement to the seven-membered ring S-caprolactam. 

By-product processing CO, H2S, methane, ammonia, H2, phenols, hydrogen cyanide, N2, benzene, xylene, etc. Electrostatic precipitator, scrubber, flaring... 

Cleavage of alkyl aryl ethers by hydrogen halides always proceeds so that the alkyl-oxygen bond is broken and yields an alkyl halide and a phenol as the final products. Either hydrogen bromide or hydrogen iodide is nonnally used. 

When an aqueous solution containing chlorobenzene (190 pM) and a nonionic surfactant micelle (Brij 58, a polyoxyethylene cetyl ether) was illuminated by a photoreactor equipped with 253.7-nm monochromatic UV lamps, phenol, hydrogen, and chloride ions formed as major products. It was reported that aromatic aldehydes, organic acids, and carbon dioxide would form from the photoreaction of chlorobenzene in water under similar conditions. A duplicate experiment was conducted using an ionic micelle (triethylamine, 5 mM), which serves as a hydrogen source. Products identified were phenol and benzene (Chu and Jafvert, 1994). 

When coniferyl alcohol is dehydrogenated, it loses its phenolic hydrogen atom to form first an aroxyl radical Ra (XI), which is in eflFect also present as the mesomeric radicals Rb (XII), Rc (XIII), and Rd (XIV). Of these limiting structures, Rb is the most favored. The existence of the radicals in these forms is recognized by their reaction products. In very dilute dioxane-water solution (1 1 vol.), the half-life of the radicals is about 45 seconds 13). 

To be effective as autoxidation inhibitors radical scavengers must react quickly with peroxyl or alkyl radicals and lead thereby to the formation of unreactive products. Phenols substituted with electron-donating substituents have relatively low O-H bond dissociation enthalpies (Table 3.1 even lower than arene-bound isopropyl groups [68]), and yield, on hydrogen abstraction, stable phenoxyl radicals which no longer sustain the radical chain reaction. The phenols should not be too electron-rich, however, because this could lead to excessive air-sensitivity of the phenol, i.e. to rapid oxidation of the phenol via SET to oxygen (see next section). Scheme 3.17 shows a selection of radical scavengers which have proved suitable for inhibition of autoxidation processes (and radical-mediated polymerization). 

With the establishment of the primary phototriplet reduction mechanism we now turn to the explanation for the effect of flow rates and the formation of polarized phenoxy radicals. Since reaction [2] is a relatively fast secondary process it is readily understood that the observation of the primary ketyl radicals will be dependent upon flow rate. The triplet polarization (E) of the secondary phenacyl radical should not have been affected but the increased contribution of the E/A Radical-Pair polarization altered the overall appearance of the polarization pattern. The diffusion model of the Radical-Pair theory relates the E/A polarization magnitude to the radical concentration within the reaction zone. Since the phenacyl radical is considered to be very chemically reactive, and the product phenol "accumulated" within the reaction zone is also a much better hydrogen donor, the following reactions will proceed within the reaction zone ... 

Figure 5.1 illustrates the key reactions implied in the manufacturing of cyclohexanone by phenol hydrogenation. The reactions are of consecutive type, in which the desired product is an intermediate. Small amounts of cyclohexene might appear at higher temperature by cyclohexanol dehydration. Additional reactions can lead to heavies by polymerization or benzene and cyclohexane by disproportionation. 

In the above equations the symbols A, B, C, D designate phenol, hydrogen, cyclohexanone and cyclohexanol. Table 5.7 presents the model parameters at 423 K and 1 atm. The model takes into account the effect of the products on the reaction rate in the region of higher conversion. This feature is particularly useful for describing the product distribution in consecutive catalytic-type reactions. Note that the adsorption coefficients are different in the two reactions. Following the authors, this assumption, physically unlikely, was considered only to increase the accuracy of modeling. 

Coproduction (biorefinery) of, for example, phenolic adhesives, polymers, waxes, and other products with hydrogen production from biomass is being discussed in the context of biomass gasification plant designs to improve the overall economics of biomass-to-hydrogen conversion.11 The technical and economic viability of such coproduction plants is unproven and was not considered in this analysis. 

TABLE 11.8 The Amounts (and Cis/Trans Isomer Ratios) of Hydrogenolysis Product in Hydrogenation of Phenol and Methyl-Substituted Phenols over Iridium Catalyst3 ... 

Analytical methods used for determining DNOC in environmental samples are given in Table 6-2. Most of the methods for products, waters, soils, and sludges rely on extraction of DNOC from an acidified matrix acidification minimizes dissociation of the phenolic hydrogen and thus facilitates extraction into an organic solvent or adsorption onto a solid phase extraction medium. The influence of pH on the adsorption of DNOC to humic materials in coal waste waters has been studied (Porschmann and Stottmeister 1993) and significant adsorption was found to occur at pH 7 but not... 

Estimate the fixed capital cost, the working capital, the cash cost of production, and total cost of production for a new 400,000 metric ton per year (400 kMTA) adipic acid plant located in Northeast Asia. The prices of adipic acid, phenol, hydrogen, and nitric acid have been forecasted for Northeast Asia as 1400/MT, 1000/MT, 1100/MT, and 380/MT, respectively. Assume a 15% cost of capital and a 10-year project life. 

Because they lack the phenolic hydrogen, esters are more stable than free vitamers, but they are not antioxidants in vitro. Tocopheryl esters hydrolyze slowly under, eg., acidic aqueous systems, thus providing antioxidant activity for emulsions, soft drinks and some dairy products (Schuler, 1990). 

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