Phenol benzene sulfonation process

Benzene SuIfona.tion. In the benzene sulfonation process, benzene reacts with concentrated sulfuric acid to form benzenesulfonic acid at about 150°C. The benzenesulfonic acid is neutralized with sodium sulfate to produce sodium benzenesulfonate, which is then fused with caustic soda to yield sodium phenate. The sodium phenate is acidified with sulfur dioxide and a small amount of sulfuric acid to release the phenol from the sodium salt. The phenol yield by this process can be as high as 88 mol % to that of the theoretical value based on benzene. Plants employing this technology have been shut down for environmental and economic reasons. 

Benzene oxychlorination process, of phenol manufacture, 18 751 Benzeneperoxyseleninic acid, 13 466 Benzene rings, in liquid crystalline materials, 15 103-104 Benzene sulfonation process, of phenol manufacture, 18 751 Benzenesulfonic acid, 3 602 Benzene-toluene fraction, in styrene manufacture, 23 341-342 Benzene-toluene-xylene (BTX), 10 782 ... 

The cumene oxidation route is the lea ding commercial process of synthetic phenol production, accounting for more than 95% of phenol produced in the world. The remainder of synthetic phenol is produced by the toluene oxidation route via benzoic acid. Other processes including benzene via cyclohexane, benzene sulfonation, benzene chlorination, and benzene oxychl orin ation have also been used in the manufacture of phenol. A Hst of U.S. phenol production plants and their estimated capacities in 1994 are shown in Table 2, and worldwide plants and capacities are shown in Table 3. 

For many years phenol was made on a large industrial scale from the substitution reaction of benzene sulfonic acid with sodium hydroxide. This produced sodium sulfite as a by-product. Production and disposal of this material, contaminated with aromatic compounds, on a large scale contributed to the poor economics of the process, which has now been replaced by the much more atom economic cumene route (see Chapter 2, Schemes 2.2 and 2.3). 

Tyrer A process for making phenol by first sulfonating benzene. Benzene vapor was passed through hot sulfuric acid the excess of benzene served to remove the water formed in the reaction. The benzene sulfonic acid was then hydrolyzed by fusion with sodium hydroxide. Invented by D. Tyrer in 1916. See also Dennis-Bull. 

Uses Manufacture of ethylbenzene (preparation of styrene monomer), dodecylbenzene (for detergents), cyclohexane (for nylon), nitrobenzene, aniline, maleic anhydride, biphenyl, benzene hexachloride, benzene sulfonic acid, phenol, dichlorobenzenes, insecticides, pesticides, fumigants, explosives, aviation fuel, flavors, perfume, medicine, dyes, and many other organic chemicals paints, coatings, plastics and resins food processing photographic chemicals nylon intermediates paint removers rubber cement antiknock gasoline solvent for fats, waxes, resins, inks, oils, paints, plastics, and rubber. 

Phenol was prepared before World War I through the distillation of coal tar. The first synthetic process involved the sulfonation of benzene followed by desulfonation with a base. In this process, benzene sulfonic acid is prepared from the reaction of benzene and sulfuric acid ... 

The catalytic process for the production of picric acid directly from benzene in one step by the action of nitric acid in the presence of mercuric nitrate has much theoretical interest and has been applied, though not extensively, in plant-scale manufacture. It yields about as much picric acid as is procurable from the same weight of benzene by the roundabout method of sulfonating the benzene, converting the benzene sulfonic acid into phenol, and nitrating the phenol to picric acid—and the benzene which is not converted to picric acid is for the most part recovered as such or as nitrobenzene. The first mention of the process appears to be in the patent of Wolffenstein and Boeters.55... 

The most interesting feature of this method, reviewed by Stepanov,62 is the ease with which the halogen atom is replaced by a hydroxyl group during the metallization process. This was first observed as long ago as 1931 when Delfs63 obtained the copper complex of 2-(2-hydroxy-naphthyl-l-azo)phenol-4-sulfonic acid (47) by heating an aqueous solution of l-chloro-2-(2-hydroxynaphthyl-l-azo)benzene-4-sulfonic acid (48), copper sulfate, sodium hydroxide and ammonia at 80 °C for 1 hour. 

You can prepare phenols in large quantities by the pyrolysis of the sodium salt of benzene sulfonic acid, by the Dow process, and by the air oxidation of cumene. Each of these processes is described below. You can also prepare small amounts of phenol by the peroxide oxidation of phenylboronic acid and the hydrolysis of diazonium salts. 

In this process, benzene sulfonic acid is reacted with aqueous sodium hydroxide. The resulting salt is mixed with solid sodium hydroxide and fused at a high temperature. The product of this reaction is sodium phenoxide, which is acidified with aqueous acid to yield phenol. 

The ARALEX process can also be used to extract detergents from aqueous solutions containing actinides for example, contaminated laundry solutions. Detergents from all three classes (anionics such as alkyl sulfates and alkyl benzene sulfonates cationics such as N-benzyl-N-alkyl dimethyl ammonium chloride and nonionics such as polyoxyethylenated alkyl phenols) are... 

For most resorcinol plants, sulfonation/caustic fusion is the common route, however, in Japan Sumitomo Chemicals are operating the world s largest resorcinol plant based on alkylation of benzene with propylene using anhydrous AICI3 as the catalyst. Some companies even today use solid phosphoric acid (SPA) as the catalyst for alkylation. Other downstream processes, i.e., oxidation of diisopropy benzene and its clevage to resorcinol are more or less similar to phenol and cresols processes. 

Historically, several processes have been developed to an industrial scale to produce phenol, including (i) sulfonation of benzene and alkali fusion of the benzene sulfonate (ii) chlorination of benzene and hydrolysis of chlorobenzene (iii) the cumene process (Section 13.2) (iv) toluene oxidation to benzoic add and subsequent oxidative decarboxylation of the latter to phenol and (v) dehydrogenation of cyclohexanol-cyclohexanone mixtures. Today, however, only the cumene process and the toluene oxidation are still run on an industrial scale, all the other processes having been given up due to economic reasons or environmental problems. 

Phenol. The manufacture of phenol by the oxidation of benzene is described by Denton (21) and by Simons and McArthur (107). The literature on phenol by the oxidation of cumene is partly covered in the reports of Frank (33), Hawkins (43), and Kharasch (57), mentioned earlier. A brief description and flow sheet of the process is given in Chemical Engineering (16). The patents in this field are mainly held by The Distillers Co., Ltd., Hercules Powder Co., and Allied Chemical and Dye Corp. In this phenol process large amounts of acetone are obtained as a coproduct. It should also be noted that the process may be directed to the production of cumene hydroperoxide and a,a dimethylbenzyl alcohol. Krieble (61) and Kenyon and Boehmer (55) describe the preparation of phenol by the chlorination and sulfonation processes. 

Although the price of phenol has fallen considerably since the war, a fact indicating largely the efficiency of the newer process of chlorbenzene hydrolysis, and also due to improvements in the sulfonation of benzeue and the fusion of sodium benzene sulfonate, it is possible that the ideal process of direct oxidation may yet be developed to give a still lower price. A price lower than the present should stimulate further the already large demand for phenol and for its reaction products such as resins, and even open up new fields for use, a possibility of great promise in the case of synthetic resins. 

Another still more recent process which starts with cumene (isopropyl benzene) has attained considerable prominence. It does not involve hydrolysis, but consists of the oxidation of cumene to the hydroperoxide and the subsequent decomposition of the latter by sulfuric acid to phenol and acetone. Like the sulfonation process, it depends for its commercial success upon the sale of its by-products, chiefly acetone. 

Dennis-Bull A process for making phenol by first sulfonating benzene, the benzenesul-fonic acid being extracted into water. Invented in 1917 by H. Bull and L. M. Dennis. See also Tyrer. 

Sulfonation of Benzene and Alkylbenzenes. Since the main utilization of ben-zenesulfonic acid was its transformation to phenol, the importance of the sulfonation of benzene has diminished. The process, however, is still occasionally utilized since it is a simple and economical procedure even on a small scale. Excess sulfuric acid or oleum is used at 110-150°C to produce benzenesulfonic acid.97,102 Sulfonation of toluene under similar conditions yields a mixture of isomeric toluenesul-fonic acids rich in the para isomer. This mixture is transformed directly to cresols by alkali fusion. 

Most of the phenol used in the United States is made by the oxidation of cumene, yielding acetone as a byproduct. The first stqn in the reaction yields cumene hydroperoxide, which decomposes with dilute sulfuric acid to the primary products, plus acetophenone and phenyl dimethyl carbinol. Other processes include sulfonation, chlorination of benzene, and oxidation of benzene. The compound is purified by rectification. 

Phenol has been made, over the years, by a variety of processes. Historically, an important method was the sulfonation of benzene followed by desulfonation with caustic soda ... 

Friedel-Crafts technology and zeolite- or other solid catalyst-based processes are currently used for other aromatic alkylations, in particular for the manufacture of linear alkylbenzenes (LABs) made from C10-C14 olefins (Equation 8), or from the corresponding chloroparaffins and benzene, and also to make m- and p-cymene (isopropyltoluene Equation 9). LABs are used for the production of sulfonate detergents, while cymenes lead to m- and p-cresols through a procedure analogous to that used for the cumene-to-phenol process. 

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