Nitrobenzene, manufacture

Aniline is an important derivative of benzene that can be made in two steps by nitration to nitrobenzene and either catalytic hydrogenation or acidic metal reduction to aniline. Both steps occur in excellent yield. Almost all nitrobenzene manufactured (97%) is directly converted into aniline. The nitration of benzene with mixed acids is an example of an electrophilic aromatic substitution involving the nitronium ion as the attacking species. The hydrogenation of nitrobenzene has replaced the iron-... 

Patil SA, Shinde VM. 1988. Simultaneous gas chromatographic determination of nitrobenzene and 2,4-dinitrophenol in nitrobenzene manufacturing plant wastewater. Analytical Lett 21 1397-1408. 

The third principal source of nitrobenzene is the atmospheric photo-chemical reaction of nitrogen oxides with benzene, which presumably is derived from automobile fuels and, to a lesser extent, solvent uses of benzene (Dorigan and Hushon 1976). As benzene releases decline, this source (not quantified) should diminish as well. The contribution of this source is difficult to estimate since most measurements of ambient atmospheric nitrobenzene have been made in urban areas near sites of nitrobenzene manufacture, use, and disposal (see Section 5.4.1). Seasonal variations and those associated with air pollution episodes suggest that this source, although limited, may form a significant proportion of nonoccupational human exposure. 

The effluent discharge produced during nitrobenzene manufacture is the principal source of nitrobenzene release to water. Losses to wastewater have been observed to be 0.09% of production in one plant and 2.0% in another (Dorigan and Hushon 1976). 

In the following paragraphs, a study will be made of some of the more important details of nitrobenzene manufacture in order that the observations may be of value in the preparation of the other nitro compounds that win later be described. 

It is manufactured by reacting benzene with a mixture of nitric and sulphuric acids. Most of the nitrobenzene produced is used to manufacture aniline, which is obtained by reduction. A considerable proportion is used as a raw material in the dyestufTs industry, either as nitrobenzene as such, or as aniline. 

Occurs in the high-boiling fraction of coal tar. Most conveniently prepared by Skraup s reaction by healing a mixture of aniline, glycerol, sulphuric acid and nitrobenzene. Used in the manufacture of dyestuffs, and pharmaceutical products. 

Organic Reactions. Nitric acid is used extensively ia iadustry to nitrate aHphatic and aromatic compounds (21). In many iastances nitration requires the use of sulfuric acid as a dehydrating agent or catalyst the extent of nitration achieved depends on the concentration of nitric and sulfuric acids used. This is of iadustrial importance ia the manufacture of nitrobenzene and dinitrotoluene, which are iatermediates ia the manufacture of polyurethanes. Trinitrotoluene (TNT) is an explosive. Various isomers of mononitrotoluene are used to make optical brighteners, herbicides (qv), and iasecticides. Such nitrations are generally attributed to the presence of the nitronium ion, NO2, the concentration of which iacreases with acid strength (see Nitration). 

Uses. (9-Nitrochlorobenzene is used in the synthesis of azo dye intermediates such as o-chloroaniline (Fast YeUow G Base), i9-nitroani1ine (Fast Orange GR Base), o-anisidine (Fast Red BB Base), o-phenetidine, and (9-aminophenol (see Azo dyes). It also is used in corrosion inhibitors, pigments, and agriculture chemicals. -Nitrochlorobenzene is used principally in the production of intermediates for azo and sulfur dyes. Other uses include pharmaceuticals (qv), photochemicals, mbber chemicals (qv), and insecticides (see Insectcontroltechnology). Typical intermediates manufactured from the para isomer are -lutioaruline (Fast Red GC Base), anisidine, -aminophenol, -nitrophenol, -phenylenediamine, 2-chloro-/)-anisidine (Fast Red R Base), 2,4-dinitrochlorobenzene, and l,2-dichloro-4-nitrobenzene. 

Dinitrochlorobenzene is used primarily in the manufacture of azo dyes other areas include the manufacture of fungicides, mbber chemicals, and explosives. It is produced by Eastman Kodak Company and Sandoz Chemical Corporation and its bulk fob price is 2.73/kg. 2,4-Dinitrochlorobenzene is more toxic than nitrobenzene. It is an extremely powerful skin irritant and must be handled with great cate. 

Manufacture and Processing. Mononitrotoluenes are produced by the nitration of toluene in a manner similar to that described for nitrobenzene. The presence of the methyl group on the aromatic ring faciUtates the nitration of toluene, as compared to that of benzene, and increases the ease of oxidation which results in undesirable by-products. Thus the nitration of toluene generally is carried out at lower temperatures than the nitration of benzene to minimize oxidative side reactions. Because toluene nitrates at a faster rate than benzene, the milder conditions also reduce the formation of dinitrotoluenes. Toluene is less soluble than benzene in the acid phase, thus vigorous agitation of the reaction mixture is necessary to maximize the interfacial area of the two phases and the mass transfer of the reactants. The rate of a typical industrial nitration can be modeled in terms of a fast reaction taking place in a zone in the aqueous phase adjacent to the interface where the reaction is diffusion controlled. 

Aromatic amines can be produced by reduction of the corresponding nitro compound, the ammonolysis of an aromatic haUde or phenol, and by direct amination of the aromatic ring. At present, the catalytic reduction of nitrobenzene is the predominant process for manufacture of aniline. To a smaller extent aniline is also produced by ammonolysis of phenol. 

Oxidation. Aromatic amines can undergo a variety of oxidation reactions, depending on the oxidizing agent and the reaction conditions. For example, oxidation of aniline can lead to formation of phenyUiydroxylamine, nitrosobenzene, nitrobenzene, azobenzene, azoxybenzene or -benzoquinone. Oxidation was of great importance in the early stages of the development of aniline and the manufacture of synthetic dyes, such as aniline black and Perkin s mauve. 

Catalytic hydtogenation is the most efficient method for the large scale manufacture of many aromatic and ahphatic amines. Some of the commercially important amines produced by catalytic hydrogenation include aniline (from nitrobenzene), 1,6-hexanediamine (from adiponitrile), isophoronediamine (from 3-nitro-l,5,5-trimethylcyclohexanecarbonitrile), phenylenediamine (from dinitrobenzene), toluenediamine (from dinitrotoluene), toluidine (from nitrotoluene), and xyhdine (from nitroxylene). As these examples suggest, aromatic amines ate usually made by hydrogenating the... 

The major aromatics (organics having at least one ring structure with six carbon atoms) manufactured include benzene, toluene, xylene, and naphthalene. Other aromatics manufactured include phenol, chlorobenzene, styrene, phthalic and maleic anhydride, nitrobenzene, and aniline. Benzene is generally recovered from cracker streams at petrochemical plants and is used for the manufacture of phenol, styrene, aniline, nitrobenzene, sulfonated detergents, pesticides such as hexachlorobenzene, cyclohexane (an important intermediate in synthetic fiber manufacture), and caprolactam, used in the manufacture of nylon. Benzene is also used as a general purpose solvent. 

The largest user of phenol in the form of thermosetting resins is the plastics industry. Phenol is also used as a solvent and in the manufacture of intermediates for pesticides, pharmaceuticals, and dyestuffs. Styrene is used in the manufacture of synthetic rubber and polystyrene resins. Phthalic anhydride is used in the manufacture of DMT, alkyd resins, and plasticizers such as phthalates. Maleic anhydride is used in the manufacture of polyesters and, to some extent, for alkyd resins. Minor uses include the manufacture of malathion and soil conditioners. Nitrobenzene is used in the manufacture of aniline, benzidine, and dyestuffs and as a solvent in polishes. Aniline is used in the manufacture of dyes, including azo dyes, and rubber chemicals such as vulcanization accelerators and antioxidants. 

Nitrobenzene, CgH5N02, also known as oil of mirbane, is an artificially prepared benzene derivative, having a coarse, but powerful odour resembling that of oil of almonds. Its coarse odour renders it quite unsuitable for fine perfumery, but it finds considerable employment in the manufacture of cheap soaps, polishes, and other articles where more or less rancid fats are used, as it covers the bad odour of the fat and gives the product a coarse almond perfume. 

Nitric acid, manufacture, 45, 232 Nitric oxide as catalyst, 227 reaction with oxygen, 26 solubility, 20 Nitrobenzene, 344 Nitrogen... 

Ti/TiOa electrodes manufactured by impregnating a Ti surface with a soluble Tp compound and subsequent baking in air can be used for reduction processes with Ti " or Ti" species as proposed catalytic intermediates. The usefulness of such electrodes was demonstrated by the reduction of nitrobenzene in 1 M HjSO /CHjOH (1 1)... 

In the manufacture of aniline by the hydrogenation of nitrobenzene, the offgases from the reactor are cooled and the products and unreacted nitrobenzene condensed. The hydrogen and inerts, containing only traces of the condensed materials, are recycled. 

In the manufacture of aniline from nitrobenzene the reactor products are condensed and separated into an aqueous and organic phases in a decanter. The organic phase is fed to a striping column to recover the aniline. Aniline and water form an azeotrope, composition 0.96 mol fraction aniline. For the feed composition given below, make a mass balance round the column and determine the stream compositions and flow-rates. Take as the basis for the balance 100 kg/h feed and a 99.9 percentage recovery of the aniline in the overhead product. Assume that the nitrobenzene leaves with the water stream from the base of the column. 

In the manufacture of aniline, liquid nitrobenzene at 20 °C is fed to a vaporiser where it is vaporised in a stream of hydrogen. The hydrogen stream is at 30 °C, and the vaporiser operates at 20 bar. For feed-rates of 2500 kg/h nitrobenzene and 366 kg/h hydrogen, estimate the heat input required. The nitrobenzene vapour is not superheated. 

The process used in the manufacture of aniline from nitrobenzene is described in Appendix G, design problem G.8. The process involves six significant stages Vaporisation of the nitrobenzene... 

Aniline is manufactured by the hydrogenation of nitrobenzene in a fluidised bed reactor. The reactor operates at 250 °C and 20 bar. The reactor vessel is approximately 3 m diameter and 9 m high. Suggest suitable materials of construction for this reactor. 

In the manufacture of aniline by the hydrogenation of nitrobenzene, the off-gases from the reactor are cooled and the products and unreacted nitrobenzene condensed in a shell and tube exchanger. A typical composition of the condensate is, kmol/h aniline 950, cyclo-hexylamine 10, water 1920, nitrobenzene 40. The gases enter the condenser at 230 °C and leave at 50 °C. The cooling water enters the tubes at 20 °C and leaves at 50 °C. Suggest suitable materials of construction for the shell and the tubes. 

Silverstein, J. L. et al., Loss Prev., 1981,14, 78 Nitrobenzene was washed with dilute (5%) sulfuric acid to remove amines, and became contaminated with some tarry emulsion that had formed. After distillation, the hot tarry acidic residue attacked the iron vessel with hydrogen evolution, and an explosion eventually occurred. It was later found that addition of the nitrobenzene to the diluted acid did not give emulsions, while the reversed addition did. A final wash with sodium carbonate solution was added to the process [1]. During hazard evaluation of a continuous adiabatic process for manufacture of nitrobenzene, it was found that the latter with 85% sulfuric acid gave a violent exotherm above 200° C, and with 69% acid a mild exotherm at 150- 170°C [2],... 

Nitroaromatics TNT, nitrobenzene, nitrophenols, atrazine Manufacture of aniline, dyes, drugs (P,D) Explosive industry, military facilities (P, D) Manufacture of pesticides and herbicides (D) C [46]... 

Aniline is an aromatic amine used in the manufacture of dyes, dye intermediates, rubber accelerators, and antioxidants. It has also been used as a solvent, in printing inks, and as an intermediate in the manufacture of pharmaceuticals, photographic developers, plastics, isocyanates, hydroquinones, herbicides, fungicides, and ion-exchange resins. It is produced commercially by catalytic vapor phase hydrogenation of nitrobenzene (Benya and Cornish 1994 HSDB 1996). Production of aniline oil was listed at approximately 1 billion pounds in 1993 (U.S. ITC 1994). Chemical and physical properties are listed in Table 1-2. 

Nixan [Nitrocyclohexane] A process for making cyclohexane oxime (an intermediate in the manufacture of nylon) from benzene by liquid phase nitration, followed by hydrogenation of the nitrobenzene. Invented by Du Pont and operated from 1963 to 1967. 

This example involves a continuous adiabatic nitration process for the manufacture of mono-nitrobenzene (MNB) [215] by the reaction of benzene with nitric acid in a CSTR system. The process is designed to be inherently safe. No external cooling is used, but the reaction mass is heated by the reaction itself to a temperature level controlled by the amount of sulfuric add-water mixture circulating through the system. This acid actually acts as both a heat sink and as a nitration enhancer. If the sulfuric add pumps fail, the nitric add and benzene pumps are automatically shut off. 

Batch microwave reactors, reactions in, 16 554-555 Batch mixers, 16 721 Batch mononitrotoluene process, 17 265 Batch multipurpose plants, for fine chemical manufacture, 11 427 Batch nitrobenzene process, 17 252 Batch-operated settling tanks, 22 59 Batch pilot plants, 19 458 Batch plants, certified, 20 703 Batch polymerization, of vinyl acetate, 25 608... 

In the sulphonation of aniline small amounts of the o-compound are produced along with sulphanilic acid. Aniline o-sulphonic acid, however, is of no further interest. Metanilic acid, on the other hand, is also manufactured as an intermediate in the azo-dye industry. It is obtained from nitrobenzene-m-sulphonic acid by reduction. The amino-(iand hydroxy-) sulphonic adds of the naphthalene series are of the greatest technical importance. They are either diazotised themselves or serve for coupling with other diazo-compounds. In this way the most important azo-dyes are produced. 

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. 

Production volume figures for 1,3-DNB are not easily available because it is produced as a mixture with other nitrobenzene isomers during the manufacturing process. In the United States, DuPont alone reportedly generated 70,000-72,000 pounds of 1,3-DNB annually from production of dinitrobenzene and nitrobenzene (EPA 1991b). The production volumes for 1,3-DNB by other manufacturers are not known. Production data for 1,3,5-TNB by producers in the United States are unknown. 

There are nine chemicals in the top 50 that are manufactured from benzene. These are listed in Table 11.1. Two of these, ethylbenzene and styrene, have already been discussed in Chapter 9, Sections 5 and 6, since they are also derivatives of ethylene. Three others—cumene, acetone, and bisphenol A— were covered in Chapter 10, Sections 3-5, when propylene derivatives were studied. Although the three carbons of acetone do not formally come from benzene, its primary manufacturing method is from cumene, which is made by reaction of benzene and propylene. These compounds need not be discussed further at this point. That leaves phenol, cyclohexane, adipic acid, and nitrobenzene. Figure 11.1 summarizes the synthesis of important chemicals made from benzene. Caprolactam is the monomer for nylon 6 and is included because of it importance. 

The uses of aniline obtained from nitrobenzene are given in Table 11.5. Aniline s use in the rubber industry is in the manufacture of various vulcanization accelerators and age resistors. By far the most important and growing use for aniline is in the manufacture of jP,jP-methylene diphenyl diisocyanate (MDI), which is polymerized with a diol to give a polyurethane. 

Hydrolysis of the ester forms adipic acid, used to manufacture nylon—6. Carbonylations of nitroaromatics are used to synthesize an array of products including amines, carbamates, isocyanates, ureas and azo compounds. These reactions are catalyzed by iron, ruthenium, rhodium and palladium complexes. For example, carhonylation of nitrobenzene in the presence of methanol produces a carbamate ... 

Diazotization routes are mainly suited to the production of fluoroaromatics with only one or two fluorine atoms in the same ring. Two Or more fluorine atoms are often introduced via the nucleophilic displacement of chlorine atoms in an activated , i.e. electron-deficient, ring by fluoride ions. For example, the reaction of 2,4-dichloro-l-nitrobenzene with potassium fluoride has been used in the manufacture of 2,4-difluoro-l-nitrobenzene, an intermediate for the antiinflammatory aspirin derivative diflunisal (7). 

Nitrobenzene and nitrotoluenes that are manufactured are converted to aniline, isocyanates, and other products used in the production of dyes and pharmaceuticals. 

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