Oleum neutrale

Toray. The photonitrosation of cyclohexane or PNC process results in the direct conversion of cyclohexane to cyclohexanone oxime hydrochloride by reaction with nitrosyl chloride in the presence of uv light (15) (see Photochemical technology). Beckmann rearrangement of the cyclohexanone oxime hydrochloride in oleum results in the evolution of HCl, which is recycled to form NOCl by reaction with nitrosylsulfuric acid. The latter is produced by conventional absorption of NO from ammonia oxidation in oleum. Neutralization of the rearrangement mass with ammonia yields 1.7 kg ammonium sulfate per kilogram of caprolactam. Purification is by vacuum distillation. The novel chemistry is as follows ... 

Anthraquinone can be brominated, chlorinated directly to the tetrachloro (I, 4, 5, 8-) stage, nitrated easily in the 1-position, but gives the 1,5-and 1,8-dinitro-derivalives on prolonged nitration the nitro groups in these compounds are easily displaced by neutral solutions of alkali sulphites yielding the corresponding sulphonic acids. Sulphonation with 20-30 % oleum gives the 2- 2,6- and 2,7-derivatives in the presence of Hg the 1- 1,5- and 1,8- derivatives are formed. 

Peroxomonosulfa.tes, When oleum is mixed with hydrogen peroxide and the mixture is partially neutralized by potassium hydroxide, a triple salt [37222-66-5] crystallizes out. In the old nomenclature, the formula for the triple salt was written as if it comprised three salts 2... 

Cyclohexanone oxime is converted quantitatively to caprolactam by Beckmann rearrangement in the presence of oleum, which is of sufficient strength to consume the several percent water in the molten oxime. The reaction mass is neutralized with aqueous ammonia to a cmde caprolactam layer and a saturated solution of ammonium sulfate. Approximately 1.5 kg of the total 4.4 kg ammonium sulfate per kilogram of caprolactam is produced in this step. Purification is by multistage vacuum crystallization from aqueous solution in neatly quantitative yield. 

Snia Viscosa. Catalytic air oxidation of toluene gives benzoic acid (qv) in ca 90% yield. The benzoic acid is hydrogenated over a palladium catalyst to cyclohexanecarboxyhc acid [98-89-5]. This is converted directiy to cmde caprolactam by nitrosation with nitrosylsulfuric acid, which is produced by conventional absorption of NO in oleum. Normally, the reaction mass is neutralized with ammonia to form 4 kg ammonium sulfate per kilogram of caprolactam (16). In a no-sulfate version of the process, the reaction mass is diluted with water and is extracted with an alkylphenol solvent. The aqueous phase is decomposed by thermal means for recovery of sulfur dioxide, which is recycled (17). The basic process chemistry is as follows ... 

Materials that are corrosion resistant to the expected cathodic polarization qualify as impressed current cathodes. Austenitic CrNi steels are used with strong acids. The oleum (i.e., fuming sulfuric acid) and concentrated sulfuric acid tanks used in sulfonating alkanes and in the neutralization of sulfonic acids are anodi-cally protected using platinized brass as cathodes [15]. Lead cathodes are used to protect titanium heat exchangers in rayon spinning baths [16]. 

Preparation of 2-nitro-2-methyl-1 -propanol-nitrate. 50g of the 2-nitro-2-methyl-1-propanol purified as above were sifted into a mixt of 58.5g of 90.5% nitric acid.and 241,5g of 103.1% sulfuric acid (oleum) while the well-agitated mixt was maintained close to 15°. Stirring was continued for 1 hour and the mixt allowed to stand for hour. No separation of the nitration product occurred and the mixt was poured over cracked ice. An oily layer separated. The mixt was transferred to a separatory funnel, washed with water, Na bicarbonate, and twice with water to neutrality. The separated diluted spent acid together with the washings were thoroughly extracted with ether, the ether extract washed to neutrality and added to the main product. 

Dilution, separation, and neutralization can take place in the same reactor or several batch units may be used for the consecutive steps (see also Sec. XX.X). Sulfuric acid sulfonation in a continuous loop reactor system is feasible when an H2S04/AB ratio of at least 1.80 is applied. In this case, as well as when 20% oleum is used, reasonably short reaction times are sufficient to complete the reaction. With increasing H2S04/AB ratio, the amount of dark 80% sulfuric acid (spent acid) will increase proportionally. 

The material is produced from naphthalene by oleum or sulfur trioxide sulfonation under conditions conducive to the formation of the h sulfonate. Subsequent reaction with formaldehyde leads to polymerization and the sulfonic acid is neutralized with sodium hydroxide [17] or lime. The process is illustrated in Fig. 2.2. The value of n is typically low but conditions are chosen to get a proportion of higher-molecular-weight product as it is believed to be more effective [18]. The quantity of sodium sulfate by-product formed by the neutralization of excess sulfonating reagent will vary depending on the process used, but can be reduced by a subsequent precipitation process using lime [19]. 

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. 

The cyclohexanone in Eq. (21.17) exists in the form of oil droplets and forms a heavier lower phase in cyclohexane. This lower phase undergoes a Beckmann rearrangement with excess sulfuric acid or oleum to give caprolactam. Hydrogen chloride is displaced by the stronger acid and recycled to nitrosyl chloride production [see Eq. (21.16)]. The rearrangement reaction mixture is neutralized with ammonia water to give crude lactam and ammonium... 

In a glass flask equipped with a stirrer is placed 150 grams of 100 per cent sulfuric acid and to this is added carefully, over a period of 15 minutes, 150 grams of ethylbenzylaniline, maintaining the temperature of the mixture below 50° by means of external cooling. Then 150 grams of oleum (60 per cent SO3) is added slowly, and the mixture is held at 60° until a small test sample shows no turbidity when diluted with water and neutralized with dilute soda solution. This usually requires about 3 hours. The reaction mixture is then poured into 1 liter of water, and after 12 hours the free sulfonic acid which has separated is filtered off... 

Benzene itself is not attacked by concentrated sulfuric acid, but is readily converted to benzenesulfonic acid by fuming sulfuric acid. This is a solution of sulfur trioxide in concentrated sulfuric acid, and is known as oleum. Note here that the attacking electrophile is a neutral species and that the electron-deficient sulfur atom of SO3 is the electrophilic centre (Scheme 2.7). 

---