Acid-forming oxidation processe

When fats or oils are exposed to air, they react with the oxygen or water vapor to form short-chain carboxylic acids. The short-chain acids are volatile and have unpleasant smells and tastes. For example, the strong smell and sour taste of vinegar are due to acetic acid, a two-carbon carboxylic acid. The oxidation process is called rancidification and can make foods unpalatable. The characteristic smell of rancid butter is due to the presence of butyric acid (a four-carbon acid). (Rancidity can also be the result of the hydrolysis of fats or oils.)... 

There are currentiy two principal processes used for the manufacture of monomeric acryhc esters the semicatalytic Reppe process and the propylene oxidation process. The newer propylene oxidation process is preferred because of economy and safety. In this process acroleia [107-02-8] is first formed by the catalytic oxidation of propylene vapor at high temperature ia the preseace of steam. The acroleia is thea oxidi2ed to acryhc acid [79-10-7]. 

Dead Seas Periclase Ltd., on the Dead Sea in Israel, uses yet another process to produce magnesium oxide. A concentrated magnesium chloride brine processed from the Dead Sea is sprayed into a reactor at about 1700°C (127,128). The brine is thermally decomposed into magnesium oxide and hydrochloric acid. To further process the magnesia, the product is slaked to form magnesium hydroxide which is then washed, filtered, and calcined under controlled conditions to produce a variety of MgO reactivity grades. A summary of MgO purities, for the various processes is given in Table 20. 

Modifications of Processes Based on Air Oxidation ofp-Xylene. Since the mid-1970s, starting in Japan, several companies have developed oxidation processes to yield relatively pure forms of terephthaUc acid without a separate purification. These products, normally called medium purity terephthahc acids, contain 200—300 ppm 4-formylbenzoic acid and trace amounts of acetic acid and thus do not meet normal specifications for the highest purity grades available (80,81). 

Mitsubishi Gas Chemical Co. in Japan produces pyromellitic dianhydtide in the same unit used for trimellitic anhydtide production (105). This process starts with pseudocumene, which is first carbonylated with carbon monoxide in the presence of boron trifluotide and hydrogen fluotide to form 2,4,5-trimethylbenzaldehyde. The Hquid-phase oxidation of the trimethylbenzaldehyde to pyromellitic acid and subsequent processing steps ate much the same as described for the Mitsubishi Gas Chemical process in the trimellitic acid section. The production of pyromellitic anhydtide is in conjunction with a joint venture agreement with Du Pont. 

Gumylphenol. -Cumylphenol (PGP) or 4-(1-methyl-l-phenylethyl)phenol is produced by the alkylation of phenol with a-methylstyrene under acid catalysis. a-Methylstyrene is a by-product from the production of phenol via the cumene oxidation process. The principal by-products from the production of 4-cumylphenol result from the dimerization and intramolecular alkylation of a-methylstyrene to yield substituted indanes. 4-Cumylphenol [599-64-4] is purified by either fractional distillation or crystallization from a suitable solvent. Purification by crystallization results in the easy separation of the substituted indanes from the product and yields a soHd material which is packaged in plastic or paper bags (20 kg net weight). Purification of 4-cumylphenol by fractional distillation yields a product which is almost totally free of any dicumylphenol. The molten product resulting from purification by distillation can be flaked to yield a soHd form however, the soHd form of 4-cumylphenol sinters severely over time. PGP is best stored and transported as a molten material. 

Chelants at concentrations of 0.1 to 0.2% improve the oxidative stabiUty through the complexation of the trace metal ions, eg, iron, which cataly2e the oxidative processes. Examples of the chelants commonly used are pentasodium diethylenetriarninepentaacetic acid (DTPA), tetrasodium ethylenediarninetetraacetic acid (EDTA), sodium etidronate (EHDP), and citric acid. Magnesium siUcate, formed in wet soap through the reaction of magnesium and siUcate ions, is another chelant commonly used in simple soap bars. 

The hydroxyl group of the resulting phenol is situated immediately adjacent to where the carboxyl group was previously located. This same Hquid-phase copper oxidation process chemistry has been suggested for the production of cresols by the oxidation of toluic acids. y -Cresol would be formed by the oxidation of either ortho or para toluic acids a mixture of 0- and -cresols would be produced from y -toluic acid (6). A process involving the vapor-phase catalytic oxidation of benzoic acid to phenol has been proposed, but no plants have ever been built utilizing this technology (27). 

Ethers. In the presence of anhydrous agents such as ferric chloride (88), hydrogen bromide, and acid chlorides, ethers react to form esters (see Ethers). Esters can also be prepared from ethers by an oxidative process (89). With mixed sulfonic—carboxyhc anhydrides, ethers are converted to a mixture of the corresponding carboxylate and sulfonate esters (90) ... 

Ammonium nitrate is manufactured by reacting ammonia with nitric acid. Consider the process shown by Fig. 9.19. First, namral gas is reformed and converted into hydrogen, nitrogen and carbon dioxide. Hydrogen and nitrogen are separated an fed to the ammonia synthesis plant. A fraction of the produced ammonia is employed in nitric acid formation. Ammonia is first oxidized with compressed air then absorbed in water to form nitric acid. Finally nitric acid is reacted with anunonia to oduce ammonium nitrate. 

Another approach is to use an easily oxidized substance such as acetaldehyde or methylethyl ketone, which, under the reaction conditions, forms a hydroperoxide. These will accelerate the oxidation of the second methyl group. The DMT process encompasses four major processing steps oxidation, esterification, distillation, and crystallization. Figure 10-16 shows a typical p-xylene oxidation process to produce terephthalic acid or dimethyl terephthalate. The main use of TPA and DMT is to produce polyesters for synthetic fiber and film. 

Direct Production of Concentrated Nitric Acid. The concept of direct production of nitric acid covers many processes. In one, aq nitric acid is agitated with an excess of liq nitrogen dh oxide (N2 04) until two layers are formed. 

---