The Dye Industry

Approximately 10,000 different dyes and pigments are manufactured worldwide, with a total annual market of more than 7x10 tons/year. There are several structural varieties of dyes, such as 

Several chemical and physical methods are available for the removal of color from the textile dye effluent. But the disposal of the sludge or precipitate is another problem that has not been solved. Addition of adsorbent provides several advantages, including adsorption of toxic compounds—and hence reduction of toxic effects on the microorganisms—and better sludge-settling characteristics. 

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Chromates and dichromates are used in industry as oxidising agents, for example in the coal tar industry, in the leather industry (chrome taiming), and in the dye industry as mordants. Some chromates are used as pigments, for example those of zinc and lead. Chromates and dichromates are poisonous. 

There are variations in representation of rings in different disciplines. The dye industry does not designate aromaticity or double bonds in rings. AH double bonds and aromaticity are shown in the Encyclopedia as a matter of course. For example, tetralin has an aromatic ring and a saturated ring and its stmcture appears in the Encyclopedia with its common name. Registry Number enclosed in brackets, and parenthetical CA index name, ie, tetralin [119-64-2] (1,2,3,4-tetrahydronaphthalene). With names and stmctural formulas, and especiaHy with CAS Registry Numbers, the aim is to help the reader have a concise means of substance identification. 

Aromatic amines form addition compounds and complexes with many inorganic substances, such as ziac chloride, copper chloride, uranium tetrachloride, or boron trifluoride. Various metals react with the amino group to form metal anilides and hydrochloric, sulfuric, or phosphoric acid salts of aniline are important intermediates in the dye industry. 

Compounds of type (42) are widely used in the dye industry (see Azo dyes). The Mannich reaction also takes place at C, as does halogenation and nitration. The important analgesic aminoantipyrine [83-07-8] (43) on photolysis in methanol undergoes ring fission to yield (44) (27). 

Nearly all uses and appHcations of benzyl chloride are related to reactions of the active haUde substituent. More than two-thirds of benzyl chloride produced is used in the manufacture of benzyl butyl-phthalate, a plasticizer used extensively in vinyl flooring and other flexible poly(vinyl chloride) uses such as food packaging. Other significant uses are the manufacture of benzyl alcohol [100-51-6] and of benzyl chloride-derived quaternary ammonium compounds, each of which consumes more than 10% of the benzyl chloride produced. Smaller volume uses include the manufacture of benzyl cyanide [140-29-4], benzyl esters such as benzyl acetate [140-11-4], butyrate, cinnamate, and saUcylate, benzylamine [100-46-9], and benzyl dimethyl amine [103-83-8], and -benzylphenol [101-53-1]. In the dye industry benzyl chloride is used as an intermediate in the manufacture of triphenylmethane dyes (qv). First generation derivatives of benzyl chloride are processed further to pharmaceutical, perfume, and flavor products. 

Organic colors caused by this mechanism are present in most biological colorations and in the triumphs of the dye industry (see Azinedyes Azo dyes Eluorescent whitening agents Cyanine dyes Dye carriers Dyes and dye intert diates Dyes, anthraquinone Dyes, application and evaluation Dyes, natural Dyes, reactive Polymethine dyes Stilbene dyes and Xanthenedyes). Both fluorescence and phosphorescence occur widely and many organic compounds are used in tunable dye lasers such as thodamine B [81-88-9], which operates from 580 to 655 nm. 

Sources of Raw Materials. Coal tar results from the pyrolysis of coal (qv) and is obtained chiefly as a by-product in the manufacture of coke for the steel industry (see Coal, carbonization). Products recovered from the fractional distillation of coal tar have been the traditional organic raw material for the dye industry. Among the most important are ben2ene (qv), toluene (qv), xylene naphthalene (qv), anthracene, acenaphthene, pyrene, pyridine (qv), carba2ole, phenol (qv), and cresol (see also Alkylphenols Anthraquinone Xylenes and ethylbenzenes). 

Inorga.nicNIa.teria.ls. These include acids (sulfuric, nitric, hydrochloric, and phosphoric), bases (caustic soda, caustic potash, soda ash, sodium carbonate, ammonia, and lime), salts (sodium chloride, sodium nitrite, and sodium sulfide) and other substances such as chlorine, bromine, phosphoms chlorides, and sulfur chlorides. The important point is that there is a significant usage of at least one inorganic material in all processes, and the overall toimage used by, and therefore the cost to, the dye industry is high. 

Primary intermediates were originally manufactured within the dyes industry. All the significant primaries, about 30 different products, are derived from ben2ene, toluene, or naphthalene. Actual production figures for primaries are not readily available, and in any event the amounts used within the dyes industry are variable. The primaries are Hsted here with a reference to the Eniyclopedia article that covers them in detail including production and consumption figures. 

Dye Intermedia.tes, Dye intermediates are defined as those precursors to colorants that are manufactured within the dyes industry, and they are neady always colodess. Colored precursors are conveniendy termed color bases. As distinct from primaries they are only rarely manufactured in single-product units because of the comparatively low tonnages requited. Fluorescent brightening agents (FBAs) are neither intermediates nor tme colorants. Basic manufacturing processes for FBAs are described in Reference 18 (see Fluorescent whitening agents). 

SuIfona.tlon, The sulfonic acid group is used extensively in the dyes industry for its water-solubilizing properties, and for its ability to act as a good leaving group in nucleophilic substitutions. It is used almost exclusively for these purposes since it has only a minor effect on the color of a dye. 

It is possible to introduce sulfonic acid groups by alternative methods, but these ate Htde used in the dyes industry. However, one worth mentioning is sulfitation, because it provides an example of the introduction of a sulfonic acid group by nucleophilic substitution. The process involves treating an active halogen compound with sodium sulfite. This reaction is used in the purification of m-dinitrohen7ene. 

Sulphonie aeids are water soluble, viseous liquids. Their aeidity is akin to that of sulphurie aeid they form salts with bases but fail to undergo esterifieation with aleohols. Their properties vary aeeording to the nature of R some are prone to thermal deeomposition. They are used as surfaetants and in the dye industry some have biologieal uses. 2-Amino-ethanesulphonie aeid is the only naturally oeeuning sulphonie aeid. 

Probably the most common compound of +3 chromium is potassium chrome alum, KCr(SOi)r 12H20. We know that the twelve water molecules are distributed equally, six around Cr+a and six around K+. Potassium chrome alum is just one example of the general class of solids called alums which have a 4-1 ion, a +3 ion, two sulfates, and twelve molecules of water. In the dyeing industry chrome alum is used for fixing dyes to fabrics. 

Nitrated Hydroformed Naphthas. The nitration of hydroformed naphthas with mixed nitric-sulfuric acid contg a small amt of w (Ref 2) produced materials which may be used either in expls or as intermediates in the dye industry. 

Biaryl derivatives bearing reactive groups have become increasingly important in industry. Uses for this class of compounds are constantly being developed in the production of high performance polymers. Materials such as 3,3, 4,4 -biphenyl-tetracarboxylic dianhydride 1 and 4,4 -biphenol 2 are monomers employed in the manufacture of high performance polyimides or polyesters. Applications for this family of molecules have also been found both in the dye industry and in the pharmaceutical industry. 

Shifting rapidly, the dye industry moved from Britain to France and then, after a few years, on to Germany. Fashion sped from purples through... 

Historically, bladder tumors have been associated with exposures in the aniline dye industry. However, conclusive evidence for any one particular exposure could not be obtained in these studies since the workers were exposed to many chemicals within the same work area. For example, Case et al. (1954) investigated the incidence of bladder tumors among British workers in the chemical dye industry. In addition to aniline, the workers were exposed to other aromatic amines, including a- and P-naphthylamine, benzidine, and auramine. Although exposures could not be quantified, there was insufficient evidence to suggest that aniline was a cause of bladder cancers. More recent studies indicate that P-naphthylamine, 4-aminodiphenyl, 4-nitrodiphenyl, 4,4-diaminodiphenyl, or o-toluidine may be involved in increased cancers in the dye industry (Ward et al. 1991 Benya and Cornish 1994). 

The environmental tasks of the dye industry have been defined by the ETAD (Ecological and Toxicological Association of the Dye Manufacturing Industry) as... 

Salicylic acid is manufactured on a large scale. In the dye industry it serves for the production of valuable azo-dyes which exhibit great fastness. To some extent these dyes are applied to mordanted fibres. In addition, the acid and its derivatives are widely used in pharmacy. Being a phenolcarboxylic acid it has a powerful disinfecting action (preservative). It has further proved itself an important antirheumatic and an analgetic. The derivative in which the phenolic hydroxyl group is acetylated (aspirin) has become especially popular. The first medicament of the series was the phenyl ester of salicylic acid, salol, which is produced as a by-product in the technical process. The preparation of salicylaldehyde has been described above (p. 235). 

Because a higher incidence of cancer has been found among workers in the dye industry, at one time exposure to aniline was thought to be a cause of cancer. There has, however, been no evidence to substantiate this assumption. It is now believed that any increase in the incidence of cancer among aniline workers is associated with the presence of other chemicals rather than with aniline. 

The dye industry of Europe provided another source of drugs... 

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