Cumene sulfonate

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contaminated with aromatic compounds, on a large scale contributed to the poor economics of the process, which has now been replaced by the much more atom economic cumene route (see Chapter 2, Schemes 2.2 and 2.3). 

The authors used for the first time aromatic hydrotope solution system such as 50% sodium p-toluene sulfonate aqueous solution (NaPTSA), 40% sodium cumene sulfonate aqueous solution (NaCuS), and 20% sodium p-xy-lene sulfonate (NaXS) aqueous solution to perform Hantzsch ester synthesis. 

Similar surfactant-stabilized colloidal systems have been reported by Albach and Jautelat, who prepared aqueous suspensions of Ru, Rh, Pd, Ni nanoparticles and bimetallic mixtures stabilized by dodecyldimethylammonium propane-sulfonate [103]. Benzene, cumene and isopropylbenzene were reduced in biphasic conditions under various conditions at 100-150 °C and 60 bar H2, and TTO up to 250 were obtained. 

Hydrotropes (LD, DW, HC) Maintain product homogeneity Ability to increase surfactant solubility Color and odor Cumene sulfonate Ethyl alcohol Toluene sulfonates 0-10% 0-10%... 

Choose colorless and odorless hydrotropes like sodium xylene sulfonate, sodium cumene sulfonate, or ethanol with products for which color and odor are undesirable. 

From the recent advances the heteroatom-carbon bond formation should be mentioned. As for the other reactions in Chapter 13 the amount of literature produced in less than a decade is overwhelming. Widespread attention has been paid to the formation of carbon-to-nitrogen bonds, carbon-to-oxygen bonds, and carbon-to-sulfur bonds [29], The thermodynamic driving force is smaller in this instance, but excellent conversions have been achieved. Classically, the introduction of amines in aromatics involves nitration, reduction, and alkylation. Nitration can be dangerous and is not environmentally friendly. Phenols are produced via sulfonation and reaction of the sulfonates with alkali hydroxide, or via oxidation of cumene, with acetone as the byproduct. 

Kennerly and Patterson (13) studied the effect of several organic sulfur compounds, including thiols, sulfides, a disulfide, sulfonic acids, and a zinc dialkyl dithiophosphate, on the decomposition rate of cumene hydroperoxide in white mineral oil at 150 °C. In each case they found phenol as the major product. They suggested that the most attractive mechanism by which to explain these results involves ionic rearrangement catalyzed by acids or other electrophilic reagents (10) as... 

Batch Stirred Tank H2S04/Oleum Aromatic Sulfonation Processes. Low molecular weight aromatic hydrocarbons, such as benzene, toluene, xylene, and cumene, are sulfonated using molar quantities of 98—100% H2S04 in stirred glass-lined reactors. A condenser and Dean-Stark-type separator trap are installed on the reactor to provide for the azeotropic distillation and condensation of aromatic and water from the reaction, for removal of water and for recycling aromatic. Sulfone by-product is removed from the neutralized sulfonate by extraction/washing with aromatic which is recycled. 

In the first step a rubbery polymer latex is prepared by emulsion polymerization of styrene and butadiene, the styrene being in an amount of 25%. Divinylbenzene is added as crosslinking agent in an amount of 1%. Diphenyl oxide sulfonate is used as emulsifier in aqueous solution and sodium formaldehyde sulfoxylate acts as a buffer in order to reach a pH of 4. As radical initiator, cumene hydroperoxide is used and the polymerization is conducted 70°C for 9 h. The end of the reaction period is detected as no further pressure drop is observed due to the consumption of butadiene. 

Alkylation. Friedel-Crafts alkylation (qv) of benzene with ethylene or propylene to produce ethylbenzene [100-41 -4], CgH10, or isopropylbenzene [98-82-8], C9H12 (cumene) is readily accomplished in the liquid or vapor phase with various catalysts such as BF3 (22), aluminum chloride, or supported polyphosphoric acid. The oldest method of alkylation employs the liquid-phase reaction of benzene with anhydrous aluminum chloride and ethylene (23). Ethylbenzene is produced commercially almost entirely for styrene manufacture. Cumene [98-82-8] is catalytically oxidized to cumene hydroperoxide, which is used to manufacture phenol and acetone. Benzene is also alkylated with C1Q—C20 linear alkenes to produce linear alkyl aromatics. Sulfonation of these compounds produces linear alkane sulfonates (LAS) which are used as biodegradable deteigents. 

Charge water to mixing vessel and start agitation. Add Sodium Hydroxide, and cool to less than 90F. Add the Avanel S-74 and Sodium Cumene Sulfonate. Mix until clear and add the Sodium Hypochlori te. 

Charge the water to a mixing vessel and start agitation. Charge the Hostapur, followed by the Potassium Hydroxide and the Tetrapotassiurn Pyrophosphate. Apply cooling and then add the Mazon 9B and the Sodium Cumene Sulfonate. When product is less than B5 degrees F, add the Sodium Hypochlorite and the balance of the water. 

Sodium Cumene Sulfonate (40%) Sodium Hypochlorite (12.5%) Deionized Water... 

Inoredi ent Wt % Deionized Water 7B.DD Sodium Hydroxide (50%) 2.00 Tetrapotassiurn Pyrophosphate 12.00 Sodium Metasilicate Pentahydrate 1.00 Avanel S-150 6.00 Sodium Cumene Sulfonate (40%) 3.00... 

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. 

Sulfonated toluene, xylene, and cumene, neutralized to the corresponding ammonium or sodium salts, are important industrially as hydrotropes or coupling agents in die manufacture of liquid cleaners and other surfactant compositions. 

Pentadecylbenzene, made by the alkylation of benzene with pentamer, is coming into demand because of the higher detergency of the sulfonate, as compared with dodecylbenzene sulfonate. c. Cumene. Cumene was formerly used as an additive in aviation gasoline... 

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. 

The more efficient route via cumene has superceded the fusion of benzene sulfonic acid with caustic soda for the manufacture of phenol, and the hydrolysis of chlorobenzene to phenol requires far more drastic conditions and is no longer competitive. Ethylene chlorohydrin can be hydrolyzed to glycol with aqueous sodium carbonate. 

Before 1970, there were five different processes used to make phenol in the United States the sulfonation route, chlorobenzene hydrolysis, the Raschig process, cumene oxidation, and the benzoic acid route. By 1978, the first three processes had essentially disappeared, and 98 percent of the remaining plant capacity was based on cumene oxidation. The oxidation process is shown in Fig. 10.33. 

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. 

The analysis of surface-active anions comprises the determination of simple aromatic sulfonic acids, hydrotropes (toluene, cumene, and xylene sulfonates), alkane- and alkene sulfonates, fatty alcohol ether sulfates, alkylbenzene sulfonates, and a-sulfofatty acid methyl esters. Many of these compounds are relevant predominantly in the detergent and cleansing industry. 

The surface-active anions investigated so far include the class of aryl sulfonates. Fig. 5-37 shows a respective chromatogram with the separation of benzene, toluene, xylene, and cumene sulfonates. They are eluted in this order according to the number of carbon atoms of their substitutents. Tetrabutylammonium hydroxide was used as the ion-pair... 

Fig. 5-37. Separation of various aryl sulfonates. — Separator column IonPac NS1 (10 pm) eluent 0.002 mol/L TBAOH / acetonitrile (70 30 v/v) flow rate 1 mL/min detection UV (254 nm) injection volume 50 pL solute concentration 50 ppm benzene sulfonate, 50 ppm toluene sulfonate, 100 ppm xylene sulfonate, and 100 ppm cumene sulfonate.

Finishing liquid detergents and cleansers typically employ short-chain alkylbenzene sulfonates such as toluene sulfonate or cumene sulfonate, which, because of their hydrotropic properties, ensure the solubility of other detergent components in the aqueous environment. Analysis of hydrotropic compounds is performed with ion-pair chromatography. The compounds are eluted in order of increasing alkyl substitution. As revealed by Fig. 8-56, these compounds can be determined directly in the finished product... 

---