Industrial Aromatic Chemistry

1 History.- 2 The nature of the aromatic character.- 2.1 Molecular considerations.- 2.2 Mechanistic considerations.- 2.2.1 Electrophilic aromatic substitution.- 2.2.1.1 Orientation rules.- 2.2.2 Nucleophilic aromatic substitution.- 2.2.3 Radical reactions.- 2.2.3.1 Pyrolysis processes.- 2.2.3.2 Oxidation reactions.- 2.2.4 Rearrangement reactions.- 2.3 Nomenclature.- 3 Base materials for aromatic chemicals.- 3.1 Origin of fossil raw materials and their composition.- 3.2 Coal.- 3.2.1 Deposits, composition and uses of coal.- 3.2.2 Thermal coal conversion — tar and benzole recovery.- 3.2.3 Tar refining.- 3.2.4 Aromatics stemming from coal gasification.- 3.2.5 Production of aromatics by coal liquefaction.- 3.2.5.1 Historic development.- 3.2.5.2 Mechanisms of coal liquefaction.- 3.2.5.3 Further developments in coal hydrogenation since 1970.- 3.2.5.4 Hydropyrolysis.- 3.3 Crude oil.- 3.3.1 Reserves and characteristics of crude oil.- 3.3.2 Crude oil refining.- 3.3.2.1 Distillation.- 3.3.2.2 Catalytic cracking.- 3.3.2.3 Catalytic reforming.- 3.3.2.4 Hydrocracking.- 3.3.2.5 Thermal cracking of hydrocarbons.- 3.3.2.5.1 Steam cracking to produce olefins.- 3.3.2.5.2 Production of olefins from crude oil.- 3.3.2.5.3 Other thermal-cracking processes.- 3.4 Production of aromatic hydrocarbons with zeolites.- 3.4.1 Aromatics from alcohols.- 3.4.2 Aromatics from short-chain alkanes.- 3.5 Renewable raw materials.- 3.5.1 Furfural.- 3.5.2 Lignin.- 3.5.3 Vanillin.- 3.6 Summary review of processes for the production of aromatics.- 4 Production of benzene, toluene and xylenes.- 4.1 History.- 4.2 Pre-treatment of mixtures containing crude aromatics.- 4.2.1 Recovery of aromatics.- 4.2.1.1 Liquid-liquid extraction.- 4.2.1.2 Extractive and azeotropic distillation.- 4.3 Separation of mixed aromatics into individual constituents.- 4.4 Dealkylation, isomerization and disproportionation reactions of BTX aromatics.- 4.4.1 Dealkylation of toluene and xylenes to benzene.- 4.4.2 Isomerization of xylenes.- 4.4.3 Disproportionation.- 4.5 Quality standards.- 4.6 Economic data.- 4.7 Process review.- 5 Production and uses of benzene derivatives.- 5.1 Ethylbenzene.- 5.1.1 Recovery of ethylbenzene from aromatic mixtures.- 5.1.2 Synthesis of ethylbenzene.- 5.1.3 Production of styrene.- 5.1.4 Substituted styrenes.- 5.2 Cumene.- 5.3 Phenol.- 5.3.1 Phenol from cumene.- 5.3.2 Alternative methods for the synthesis of phenol.- 5.3.3 Recovery of phenol from the products of coal pyrolysis.- 5.3.4 Phenol derivatives.- 5.3.4.1 Bisphenol A.- 5.3.4.2 Cyclohexanol and cyclohexanone.- 5.3.4.3 Alkylphenols.- 5.3.4.3.1 Cresols.- 5.3.4.3.2 Xylenols.- 5.3.4.3.3 Higher alkyl phenols.- 5.3.4.4 Salicylic acid.- 5.3.4.5 Chlorinated phenols.- 5.3.4.6 Nitrophenols.- 5.3.4.7 Other phenol derivatives.- 5.3.4.8 Polyhydric phenols.- 5.4 Benzene hydrogenation — cyclohexane.- 5.5 Nitrobenzene and aniline.- 5.5.1 Nitrobenzene.- 5.5.2 Aniline.- 5.5.3 Aniline derivatives.- 5.5.3.1 4,4’,-Diphenylmethane diisocyanate (MDI).- 5.5.3.2 Cyclohexylamine and benzothiazole derivatives.- 5.5.3.3 Secondary and tertiary aniline bases.- 5.5.3.4 Other aniline derivatives.- 5.6 Alkylbenzenes and alkylbenzene sulfonates.- 5.7 Maleic anhydride.- 5.8 Chlorobenzenes.- 5.8.1 Chlorobenzene.- 5.8.1.1 Nitrochlorobenzenes.- 5.8.2 Dichlorobenzenes.- 5.8.3 Hexachlorocyclohexane.- 5.9 Process review.- 6 Production and uses of toluene derivatives.- 6.1 Nitro-derivatives of toluene.- 6.1.1 Mononitrotoluene and its products.- 6.1.2 Dinitrotoluenes and their derivatives.- 6.1.3 Trinitrotoluene compounds.- 6.2 Benzoic acid.- 6.3 Chlorine derivatives of toluene.- 6.3.1 Side-chain chlorination of toluene.- 6.3.1.1 Benzyl chloride.- 6.3.1.2 Benzal chloride.- 6.3.1.3 Benzotrichloride.- 6.3.2 Nuclear chlorination of toluene.- 6.4 Sulfonic acid derivatives of toluene.- 6.5 Toluenesulfonyl chloride.- 6.6 Other toluene derivatives.- 7 Production and uses of xylene derivatives.- 7.1 o-Xylene and its derivatives.- 7.1.1 Oxidation of o-xylene to phthalic anhydride.- 7.1.2 Production of phthalic esters.- 7.1.3 Other products from phthalic anhydride.- 7.1.4 Nitration of o-xylene.- 7.2 m-Xylene and its derivatives.- 7.2.1 Production of isophthalic acid.- 7.2.2 Other products from m-xylene.- 7.3 p-Xylene and its derivatives.- 7.3.1 Terephthalic acid.- 7.3.2 Other p-xylene derivatives.- 8 Polyalkylated benzenes — production and uses.- 8.1 Pseudocumene.- 8.2 Mesitylene.- 8.3 Durene.- 8.4 Other eumene derivatives.- 8.4.1 Nitrocumene and isoproturon.- 8.4.2 Cumenesulfonic acid.- 8.5 Indan and indene.- 9 Naphthalene — production and uses.- 9.1 History.- 9.2 Naphthalene recovery.- 9.2.1 Naphthalene from coal tar.- 9.2.2 Naphthalene from petroleum-derived raw materials.- 9.3 Naphthalene derivatives.- 9.3.1 Production of phthalic anhydride (PA) from naphthalene.- 9.3.2 Production and uses of naphthoquinone.- 9.3.3 Production and uses of naphthols.- 9.3.3.1 1-Naphthol and its derivatives.- 9.3.3.2 2-Naphthol and its derivatives.- 9.3.4 Sulfonic acid derivatives of naphthalene.- 9.3.5 Nitro- and aminonaphthalenes.- 9.3.6 Production of tetralin and tetralone.- 9.3.7 Production of isopropylnaphthalene derivatives.- 9.3.8 Other alkylnaphthalenes from naphthalene.- 9.4 Process review.- 10 Alkylnaphthalenes and other bicyclic aromatics-production and uses.- 10.1 Biphenyl.- 10.2 Methylnaphthalenes.- 10.3 Acenaphthene/acenaphthylene.- 11 Anthracene — production and uses.- 11.1 Production of anthracene.- 11.2 Production of anthraquinone.- 11.2.1 Oxidation of anthracene to anthraquinone.- 11.2.2 Synthetic production of anthraquinone.- 11.3 Anthraquinone derivatives.- 11.3.1 Production of anthraquinone derivatives from anthraquinone.- 11.3.2 Synthetic production of anthraquinone derivatives.- 11.4 Higher condensed dyes from anthraquinone.- 11.5 Anthraquinone as a catalyst in the production of hydrogen peroxide.- 11.6 Wood pulping with anthraquinone.- 12 Additional polynuclear aromatics — production and uses.- 12.1 Phenanthrene.- 12.2 Fluorene.- 12.3 Fluoranthene.- 12.4 Pyrene.- 13 Production and uses of carbon products from mixtures of condensed aromatics.- 13.1 Pyrolysis of aromatic hydrocarbon mixtures in the liquid phase.- 13.1.1 Formation of mesophase.- 13.1.2 Production and uses of coke from aromatic residues by the delayed coking process.- 13.1.3 Pitch coking in horizontal chamber ovens.- 13.1.4 Production of carbon fibers.- 13.2 Pyrolysis of mixtures of aromatics in the gas phase — Carbon black production.- 14 Aromatic heterocyclics — production and uses.- 14.1 Five-membered ring heterocyclics.- 14.1.1 Furan.- 14.1.2 Thiophene.- 14.1.3 Pyrrole.- 14.1.4 Five-membered ring heterocyclics with two or more hetero-atoms.- 14.2 Six-membered ring heterocyclics.- 14.2.1 Pyridine.- 14.2.2 Pyridine derivatives.- 14.2.3 Alkylated pyridines.- 14.3 Pyrimidine.- 14.4 Triazines.- 14.5 Condensed heterocyclics.- 14.5.1 Thianaphthene (2,3-Benzothiophene).- 14.5.2 Indole.- 14.5.3 Benzothiazole.- 14.5.4 Benzotriazole.- 14.5.5 Quinoline and isoquinoline.- 14.5.6 Carbazole.- 14.5.7 Dibenzofuran (Diphenylene oxide).- 15 Toxicology/Environmental aspects.- 15.1 Basic toxicological considerations.- 15.2 Aspects of occupational medicine and legislation.- 15.3 Environmental aspects and biological degradation of aromatics.- 16 The future of aromatic chemistry.