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Ecological alternatives to the reduction and

oxidation processes in dyeing with vat and
sulphur dyes

Article in Dyes and Pigments · December 2008

DOI: 10.1016/j.dyepig.2006.05.041

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1 58
2 59
3 60
Dyes and Pigments xx (2007) 1e9
4 www.elsevier.com/locate/dyepig
61
5 62
6 Review 63
7 64
8 Ecological alternatives to the reduction and oxidation processes 65
9 66
10 in dyeing with vat and sulphur dyes 67
11 68

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12 Mojca Bozic, Vanja Kokol* 69
13 70

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14 Textile Department, Faculty of Mechanical Engineering, University of Maribor, P.O. Box 224, Smetanova ul. 17, SI-2000 Maribor, Slovenia 71
15 Received 21 March 2006; accepted 8 May 2006 72
16 73
17 74
18 75

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19 Abstract 76
20 77
21 This article gives a summary of the most commonly used ecologically unfriendly processes for the reduction and oxidation of vat and sulphur 78
22 dyes. It also describes the new alternatives that are in the development stage and could be important in the near future. Sodium dithionite as the 79
23 dominant reducing agent produces large amounts of sodium sulphate, and also toxic sulphite and thiosulphate as by-products. Consequently, 80
24 high amounts of hydrogen peroxide and alkali are required for the treatment of effluents, which add to the cost of the process. Attempts 81
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25 have been made to use organic biodegradable reducing agents, enzymes, catalytic hydrogenation, and also indirect or direct, electrochemical 82
26 reductive methods that employ a redox mediator (electron-carrier). The reduction has also been carried out via the dye radical molecule or, 83
27 in the case of indigo, by direct electrochemical reduction using graphite as the electrode material. Physical techniques, for example using ul- 84
trasound, magnetic fields or UV have been shown to be effective only when used to accelerate methods using classical reduction and oxidation
28 85
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processes. However, although these methods offer some environmental benefits, there is still no satisfactory alternative reducing and/or oxidising
29 agent available today.
86
30 Ó 2006 Elsevier Ltd. All rights reserved. 87
31 88
32 Keywords: Vat and sulphur dyes; Dyeing; Reduction; Oxidation; Ecology; Catalysis; Organic agents; Electrochemistry; Ultrasound; Magnetic field; UV applica- 89
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33 tion; Biotechnology 90
34 91
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35 92
36 93
37 1. Introduction because they are practically insoluble in water and have no af- 94
38 finity for cellulose fibres in such a state. Thus, these dyes have 95
39 According to data from 2005 [1], cotton and other cellulose to be reduced (vatted) before dyeing to be converted into the 96
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40 fibres are still very important textile fibres. They are used water-soluble form (leuco enolate dye form) (Scheme 1) 97
41 worldwide (Table 1) and their consumption is increasing. which have substantivity towards fibres and which, after ab- 98
42 In the colouration of cellulose fibres, vat (including indigo) sorption into the fibres to be dyed, should be re-oxidised to 99
43 and sulphur dyes still represent a relatively large part of the the original water-insoluble dye pigment form in situ in the fi- 100
44 dyestuff market (about 31%, Fig. 1); among them about bres [4,5]. The leuco-vat anion may be compared with water- 101
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45 120 000 tons of vat dyes are being used annually [2]. It seems soluble direct dye anions, for it is the anion which is respon- 102
46 that the situation will remain constant also in the near future sible for vat dyeing. Incidentally, the word leuco comes from 103
47 mainly because vat dyes yield coloured fibres of excellent the Greek word leucos, meaning white, which is the colour 104
48 all-round fastness, particularly to light, washing and chlorine of the vat-acid of indigo. In conventional vat-dyeing processes, 105
49 bleaching. the dye is reduced in a high alkaline medium (pH 11e14) us- 106
50 However, vat and sulphur dyes require a complicated appli- ing powerful reducing agents among which sodium dithionite 107
51 cation procedure (reduction and oxidation mechanisms) (Na2S2O4) is of major importance. Because of the individual 108
52 molecular structures of different dyes, concentrations of 109
53 reducing agents and alkali, temperature and timing, each dye 110
* Corresponding author. Tel.: þ386 2 220 7896; fax: þ386 2 220 7990.
54 E-mail address: vanja.kokol@uni-mb.si (V. Kokol). requires an individual procedure. The reducing agent either 111
55 112
56 0143-7208/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved. 113
57 doi:10.1016/j.dyepig.2006.05.041 114
Please cite this article in press as: Bozic M, Kokol V, Ecological alternatives to the reduction and oxidation processes in dyeing with vat and sulphur dyes, Dyes
and Pigments (2007), doi:10.1016/j.dyepig.2006.05.041
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115 Table 1
O O Na+ 172
116 Cotton consumption [1] 173
117 Cotton consumption (million 480-pound bales)
reduction 174
118 World United Other China India Pakistan Turkey Others 175
119 total States Americas oxidation 176
120 1985 76.3 6.4 6.1 18.8 7.1 2.4 2.1 33.4 insoluble form soluble form 177
121 1990 85.4 8.7 6.6 19.4 9.0 6.2 2.6 32.9 178
1995 85.5 10.6 7.0 19.8 11.4 7.2 4.1 25.4 Scheme 1.
122 179
2000 90.5 8.9 8.5 24.7 13.3 7.9 5.1 22.1
123 2004 100.6 6.2 8.0 34.9 13.7 10.0 6.1 21.7
180
124 a negatively charged dye anion with associated positively 181
Source: Fibre Economics Bureau and authors’ estimates.
125 charged sodium cations. High pH also ionises the hydroxyl 182

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126 groups on cotton, thus giving it a negative charge. Mutual re- 183
127 pulsion of the negatively charged dye and cotton results in de- 184

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128 donates hydrogen to subtract oxygen from or add electrons to 185
other chemicals; the affected chemicals/dyes are said to be re- creased substantivity and aggravated penetration of the fibre
129 by the dye, with associated lower colour yield. On the other 186
130 duced. During the reduction process, the reducing agent itself 187
is oxidised, often irreversibly. To be practically useful, solu- hand, moderate dyebath pH values (of the order of 11) produce
131 a lower degree of ionization of the dye and the fibre, resulting 188
132 tions of a vat dye reducing agent must have a level of 189
in increased colour yield [8]. The control of the reduction pro-

PR
133 reducing power (reduction potential) sufficient to reduce all 190
commercial vat dyes to their water-soluble forms, economi- cess is carried out by measuring the redox potential [9], while
134 the kinetics and thermodynamics of the reductioneoxidation 191
135 cally and quickly [6]. The quantity of reducing agent is deter- 192
mined by the chemical structure and nature of the particular of vat dyes on cellulose material can be controlled by cyclic
136 voltammetry [10e13]. After dyeing, follows removal of the 193
137 dye (number of reducible groups, relative molecular mass, 194
content of the pure dye), the specific surface area of the dye excess of reducing agents and sodium salts, and conversion
138 195
ED
liquor, the temperature of the dye liquor, the agitation of the of the dyes back to the insoluble pigment by an oxidation re-
139 action. Commonly used oxidising agents are hydrogen perox- 196
140 liquor, and the amount of air present in the dyeing process. 197
The conversion of the vat dye into the leuco form is a hetero- ide or atmospheric oxygen under harsh conditions (high pH or
141 temperature) and/or expensive and hazardous catalysts (meta- 198
142 geneous reaction that comprises the following stages: diffusion 199
vanadate). Oxidising agents either add oxygen to, subtract hy-
CT

143 of molecules of the reducing agent to the surface of dye par- 200
ticles, sorption of the reducing agent, chemical reaction be- drogen from, or take electrons away from other chemical/dye
144 compounds; the dye structure loses at least 2 electrons from 201
145 tween the dye and reducing agent on the surface with the 202
formation of a leuco compound [7]. The aqueous alkaline so- the anion and reverts to the original pigmentary form with
146 the double bonded oxygen. The pigment or molecular aggre- 203
lutions in which the dyeings are carried out are generally set
E

147 gate thus produced becomes trapped mechanically within the 204
148 by sodium hydroxide, aqueous alkali metal salt, or potassium 205
hydroxide solutions. Depending on dyebath pH, the reduced fibre and its insolubility gives rise to excellent wash and light
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149 fastness properties of the so-dyed textile material. After oxida- 206
150 form of the dye molecule exists in unionized, mono-/di-ion- 207
ized, multi-ionized form, or as mixtures of the forms. High tion, all vat dyeings are subjected to heat treatment in the pres-
151 ence of water, generally in a weakly alkaline detergent liquor 208
152 dyebath pH values (such as 12e13 or more), result in a high 209
level of ionization of both, the vat dyes and the cotton. The at boiling temperature in order to obtain the final shade and
153 improve the fastness ratings (e.g., light- and chlorine-fastness). 210
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154 soluble form of the dye (Scheme 1) is fully ionized to give 211
The processes occurring during soaping are unknown. Crystal-
155 lization of amorphous dye particles or coarsening primary par- 212
156 ticles by aggregation is assumed to occur. If soaping takes too 213
157 long, migration of the aggregates to the surface of the textile 214
158 can cause deterioration of the rub-fastness. [6]. 215
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159 216
160 217
161 1.1. Basic characteristics of vat and sulphur dyestuffs 218
162 and their reductioneoxidation mechanism 219
163 220
164 With very few exceptions, vat dyes fall into two clearly 221
165 defined groups, anthraquinonoid including heterocyclic qui- 222
166 nones and indigoid, containing two or more keto (]O) groups 223
167 separated by a conjugated system of double bonds. The most 224
168 important vat dyes are based upon acylamino-anthraquinone 225
169 1, indanthrone 2, flavanthrone 3, pyranthrone 4, dibenzan- 226
170 throne 5, isodibenzanthrone 6, carbazole 7, benzanthrone acri- 227
171 Fig. 1. Worldwide consumption of dyes for dyeing of cellulose fibres [3]. done 8, anthraquinone oxazole 9, indigoid 10 and thioindigoid 228
Please cite this article in press as: Bozic M, Kokol V, Ecological alternatives to the reduction and oxidation processes in dyeing with vat and sulphur dyes, Dyes
and Pigments (2007), doi:10.1016/j.dyepig.2006.05.041
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229 11 structures, and so may be of any colour [4,14e16]. The vat dye was developed by Croissant and Bretonniere in 1873 286
230 dyes may be homogeneous dyes or mixtures. Since the leuco [4]. Sulphur dyes are particularly important for the production 287
231 reduction potential (enolate dye form potential) of vat dyes of inexpensive products having average fastness requirements. 288
232 lies between 650 mV and 1000 mV, it is important that The colour fastness depends greatly on the reduction condi- 289
233 the reducing agent has a reduction potential in the same range tions since over-reduction of the dye may result in low colour 290
234 or even more negative, and so harsh reducing agents are ap- yields and/or off-shades. The dyes are very fast to light and 291
235 plied. However, the chemical constitution of a vat dye (espe- washing, but not to chlorine. Since the reduction potential of 292
236 cially the number of keto groups) influences the properties sulphur dyes lies between 400 mV and 500 mV, milder 293
237 of the leuco enolate form in the dyeing process, e.g., thermal reducing agents than those used in vat dyeing may be used. 294
238 stability, substantivity, rate of absorption, diffusion into the fi- However, they are used mainly to dye cotton and other plant 295
239 bre and levelling, colour and fastness properties. The dyes are fibres in a sodium sulphide bath. A subsequent treatment 296

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240 commercially available in the form of liquids, granules, or with metal salts can improve the quality of dyeing. The sul- 297
241 powders as well as pastes. phur dyes are macromolecular compounds which in their final 298

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242 Anthraquinone dyes are based on 9,10-anthraquinone, form are characterised by di- and polysulphide bonds (eSne) 299
243 which is produced by oxidation of anthracene. As 9,10-anthra- between aromatic residues (Scheme 4). They are prepared by 300
244 quinone is essentially colourless, in order to produce commer- treating aromatic amines, phenols and aminophenoles with 301
245 cially useful dyes, strongly electron donating groups such as sulphur or sodium polysulphide or both. The starting materials 302
246 amino or hydroxyls are introduced into one or more of the are sulphuretted with sulphur or sodium polysulphide either by 303

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247 four positions. Appropriate selection of donor groups (OH, heating at 180e350  C, by boiling under reflux in a solvent, or 304
248 NH2, NHR, HNAr) and substitution pattern positions, pro- under pressure at temperatures up to about 130  C. The com- 305
249 duces a wide variety of colours, although the range is lesser mercially available sulphur dyes can be divided into three 306
250 than with azo dye structures. The reductioneoxidation mech- groups [4,14]: (1) dyes which are polymeric and water insol- 307
251 anism steps (i.e. changing the dye between insoluble and sol- uble, so their di- and polysulphide bonds have to be reduced 308
252 309
ED
uble forms and vice versa) of an anthraquinone dye are by normally using sodium dithionite and alkaline medium
253 presented in Scheme 2. (pH > 10); (2) pre-reduced, ready-to-use, but highly concen- 310
254 Another important group inside the class of vat dyes is in- trated solutions of leuco sulphur dyes containing additional re- 311
255 digo. The indigo was discovered years ago during treatment of ducing agents for stabilization. They are prepared by reduction 312
256 the plant Indigofera tinctoria, which was used both for paint- of base dyes with caustic and glucose; (3) water-soluble dyes 313
CT

257 ing and dyeing textiles such as wool and linen [14]. The in- containing thiosulphate groups and being applied with sodium 314
258 digo, also known as indigotin (CI Vat Blue 1) (10), exists as dithionite. 315
259 blue-violet needles or prisms with a pronounced coppery lus- There is another class of dyes that seems to have features in 316
260 tre. Intra- and inter-molecular hydrogen bonding are responsi- common with both, vat and sulphur dyes, i.e. polysulphide 317
E

261 ble for indigo’s extremely low solubility in water, dilute acids melt dyes or sulphurised vat dyes [4]. Sulphurised vat dyes 318
262 and dilute alkalis, as well as its high melting point. Indigo is are produced from dye intermediates by a thionation process 319
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263 readily reduced by various reagents, such as sodium dithionite, similar to that used in the preparation of sulphur dyes. They 320
264 hydroxyacetone and hydrogen, or by electrochemical methods. are similar to vat dyes by virtue of the quinoneimine structure. 321
265 In an alkaline medium the yellow-brown sodium salt of leuco Reducing agents also convert them to leuco form with a change 322
266 indigo is produced, which can be converted by acids to the so- of hue. The agent not only reduces the quinoneimine group but 323
267 called white indigo. The requisite reduction potential (approx. also transforms the disulphide groups of the dye molecule to 324
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268 600 mV) of indigo lies between that of vat dyes and sulphur sodium thiolate groups. The reduction and the associated 325
269 dyes. The mechanism of reductioneoxidation in this dyeing is cleavage of the disulphide groups render the molecule consid- 326
270 presented in Scheme 3. erably smaller. Sulphurised vat dyes are applied chiefly with 327
271 Another class of dyes that require reductioneoxidation dithionite and show a higher degree of fastness. CI Vat Blue 328
272 steps for their application is sulphur dyes. The first sulphur 43 (12) is an example of a sulphurised vat dye [17]. 329
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273 330
274 331
275 332
276 O NHCOC6H5 OH NHCOC6H5 ONa NHCOC6H5 333
277 334
278 alkali
335
reduction
279 336
280 oxidation
hydrolysis 337
281 338
282 OH ONa 339
O
283 340
anthraquinone dye insoluble form soluble form
284 341
285 Scheme 2. 342
Please cite this article in press as: Bozic M, Kokol V, Ecological alternatives to the reduction and oxidation processes in dyeing with vat and sulphur dyes, Dyes
and Pigments (2007), doi:10.1016/j.dyepig.2006.05.041
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343 O H OH H ONa H 400

344 401
345 N reduction N alkali N 402
346 403
oxidation hydrolysis
347 N N N 404
348 405
349 H O H OH H ONa 406
350 indigo insoluble form soluble form 407
351 Scheme 3.
408
352 409
353 410

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354 1.2. Reducing agents used in classical dyeing processes addition, the wastewater may contain considerable excess of 411
355 and ecological problems the reducing agent (Na2S2O4), which classified it in some 412
356 countries among the most hazardous class of waters [18]. Be- 413
357 Sodium dithionite [5,18] is normally used as the reducing sides, sodium dithionite affects the aerobic processes in water 414
358 415

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agent in the dyeing of textile material with vat dyes. For sul- treatment, so addition of an oxidation agent is required for wa-
359 phur dyes sodium dithionite is used in combination with glu- ter stabilization. Wastewaters having a high sulphate/sulphite 416
360 cose, although in some cases sulphur dyes are still being content are highly corrosive and can, for example, destroy 417
361 reduced using sulphides (Na2S, NaHS) and polysulphides waste lines (concrete pipes), so they present real technological 418
362 (Na2S8). The advantage of sodium dithionite is that it effects problems. In addition, the formed sulphate deposits can form 419
363
364
extremely rapid reduction of the vat dye, particularly at high
temperature, and therefore, in some dyeing methods it makes
DP toxic hydrogen sulphide ions (HS) by anaerobic degradation.
However, although vat dyes in the base non-soluble form do
420
421
365 possible an extremely short fixing time, which is important in not represent an environmental risk as regards their toxicity 422
366 continuous dyeing requiring levelness dyeing without spot for- and biodegradability, they still colour the wastewater. 423
367 mation. On the other hand, sodium dithionite is very easily A further group of reducing agents [20] was discovered in 424
368 oxidised by atmospheric oxygen and its stability in aqueous al- the class of iron(II) complexes with triethanolamine, triisopro- 425
TE

369 kaline solution declines very rapidly with increasing tempera- panolamine and also aliphatic hydroxy compounds containing 426
370 tures even in the absence of oxygen, so it is necessary to use an a number of hydroxyl groups. The reducing effect of iron(II) 427
371 excess of sodium dithionite (up to 70% of the total required) to complex is the result of a negative redox potential in an alka- 428
372 compensate their loss for dye re-vatting. In some cases the line solution at a molar ratio of iron(II) and iron(III) from 0.8:1 429
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373 very great reductive power of sodium dithionite may lead to to 2:1. One mole of oxidised dye which takes up two electrons 430
374 excessive reduction and to destruction of the dye, so an ap- per molecule to convert into the leuco form requires 2 mol of 431
375 proach using a mixture of sodium dithionite with a derivative a mediator iron complex system, based on the redox-active 432
376 of ammonia containing the radical of an alkali metal salt or metal ion supplying one electron [21]. However, all the men- 433
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377 ammonium salt of an alkylsulphinic acid having 1e4 C atoms tioned mediator systems have certain disadvantages, like not 434
378 or a hydroxyalkylsulphinic acid having 2e4 C atoms, attached having a sufficiently negative redox potential for dye reduc- 435
379 via nitrogen, has been proposed. The addition of sulphinic acid tion, not being sufficiently stable in the more weakly alkaline 436
380 derivates to sodium dithionite not only increases the stability region, or having a relatively too large fraction of iron(II) com- 437
381 at elevated temperature but also increases the stability of so- plex to achieve the redox potential required. Furthermore, the 438
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382 dium dithionite with respect to oxidative influences of atmo- large fraction of iron(II) complex required is a particular prob- 439
383 spheric oxygen. The dyeings obtainable according to the lem in producing indigo-dyed denim, because the textile ma- 440
384 new process are distinguished from dyeings developed with terial is dyed layer by layer by repeated immersion in the 441
385 sodium dithionite alone by improved levelness, higher bril- dyebath and subsequently oxidised in air. With this method, 442
386 liance and improved purity of shade [19]. the mediator in the dyebath is completely oxidised with every 443
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387 The generation of non-regenerable oxidation products air passage and first has to be reduced again for the next dye- 444
388 causes various problems in the disposal of the dyeing bath ing cycle. Additional problem presents wastewaters with high 445
389 and the washing water, because the sodium dithionite is finally content of metal ions. 446
390 oxidised into compounds (sodium sulphate (Na2SO4), sulphite 447
391 ions (SO2 2
3 ) and thiosulphate ions (S2O3 )) whose release af-
448
392 fect the environment detrimentally due to their toxicity. In 2. Ecological alternatives of reduction and oxidation 449
393 mechanisms 450
394 451
395 In the last decade, many attempts have been made to re- 452
396 D S S D
reduction
2D SH
alkali
2 D SNa
place the environmentally unfriendly reduction and/or oxida- 453
397 tion agents by ecologically more attractive alternatives using 454
sulphur dye insoluble form soluble form
398 advanced chemical, electrochemical, electrocatalytic hydroge- 455
399 Scheme 4. nation and biological methods. 456
Please cite this article in press as: Bozic M, Kokol V, Ecological alternatives to the reduction and oxidation processes in dyeing with vat and sulphur dyes, Dyes
and Pigments (2007), doi:10.1016/j.dyepig.2006.05.041
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M. Bozic, V. Kokol / Dyes and Pigments xx (2007) 1e9 5

457 2.1. Upgraded chemical approaches 2.2.2. Direct electrochemical reduction of dye pigment 514
458 via the radical process [2,36] 515
459 In order to reduce the use of environmentally unfavourable This reduction process is based on a reaction mechanism in 516
460 reducing agents, a research was focused on improving dyeing which an indigo anion radical is formed by a comproportiona- 517
461 with vat dyes in 1990. BASF has developed Compress C plus, tion reaction between the dye and the leuco dye, followed by 518
462 a process which applies special Caledon SF dyes in conjunc- the electrochemical reduction of this radical. The leuco dye is 519
463 tion with a newly developed auxiliary system (Zetex CCP1, acting as an electron-shuttle between the electrode and the sur- 520
464 Zetex CCP2, sodium sulphate decahydrate and catalyst) with- face of the dye pigment, as shown in Scheme 5. Anyhow, the 521
465 out using sodium dithionite. The process is suitable for dyeing electrochemical reaction rate is limited by the diffusion trans- 522
466 with vat dyes on dry-span as well as on thermo-sol machine port of the intermediate radical anion and at potentials more 523
467 with drying at 100e140  C, and thermo-fixing for 20e30 s negative than 1100 mV the current density increases due to 524

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468 at 170e190  C. The process is economical, easy, without es- the cathodic liberation of hydrogen. In order to start the pro- 525
469 sential loading of the wastewaters, and suitable for dyeing cot- cess an initial amount of the leuco dye is generated by a con- 526

OO
470 ton fabrics and blends with polyester. The limitation of the ventional reaction, i.e. by adding a small amount of a soluble 527
471 process is that it allows dyeing only of pale shades [5,22]. An- reducing agent (sodium dithionite). 528
472 other attempt to achieve optimal application of chemicals for 529
473 reduction and oxidation was made in 1999 in cooperation of 2.2.3. Direct electrochemical reduction of dye pigment 530
474 companies Thies GmbH and DyStar [5]. The developed sys- on graphite electrodes [17] 531

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475 tem pro VAT plus enables the measuring of the smallest quan- Graphite as a cheap and stable high-surface-area material 532
476 tity of chemicals. The regulation of the whole dyeing system is (working cell) can act as electrode material for the direct elec- 533
477 entirely automated and is based on continuous on-line mea- trochemical reduction of indigo/vat dyes in aqueous suspen- 534
478 surement of redox potential changes in the vat dye reduction sion. The leuco dye is produced (in contrast to the process 535
479 system. based on the electrochemical reduction of the dye radical) di- 536
480 537
ED
rectly from the dye suspension, thus direct electron transfer
481 2.2. Electrochemical techniques between the dye and the graphite is obtained. Much of the 538
482 chemical activity of the carbon surface is connected with ox- 539
483 Different electrochemical reduction techniques, especially ygen functionalities (i.e. quinone and hydroquinone). To en- 540
484 for indigo dyes, have been investigated. Electrochemistry hance the chemical activity of the carbon surface (i.e. 541
CT

485 seems to offer a reduction method that could minimise the increase the content of oxygen-containing groups on the sur- 542
486 consumption of chemicals [23e25]. face of carbon), an oxidative pre-treatment approach or an ap- 543
487 proach based on the covalent bounding of quinoid molecules 544
488 2.2.1. Indirect electrochemical process using a onto the graphite surface are proposed. In the particular case 545
E

489 mediator [26e31] of indigo reduction, anthraquinones have been used as re- 546
490 The process is mediated by an electron-carrier whereby re- dox-active molecules. Scheme 6 shows the resulting material: 547
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491 duction takes place between the separated surfaces of the elec- covalently modified with redox-active quinones, which are at- 548
492 trode and the insoluble dye molecules and not by direct tached to the carbons particles through the eOH groups on the 549
493 contact between both surfaces [20]. Mediators are reversible surface [37]. 550
494 redox systems which reduce the dye and are themselves oxi- 551
495 dised in the process. After conversion back to the reduced 2.2.4. Electrocatalytic hydrogenation 552
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496 form at the cathode, they are then available for further dye re- The process consists of a sequence of reduction steps in- 553
497 duction. However, reduction of the total amount of indigo nec- volving electron transfer from the cathode to either a mediator 554
498 essary for dyeing requires enormous amounts of electrical 555
499 energy and large electrode surfaces [32]. Among the already 556
500 mentioned transition regenerable metal complexes (i.e. 557
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501 iron(II/III) complex), ironesaccharic acid complexes, selected 558

502 anthraquinone compounds such as anthraquinonesulphonic 559
503 acids and hydroxyanthraquinones are of important interest 560
504 [33,34]. A great advantage of this technique is that the process 561
505 can be monitored by measuring the redox potential [35]. After 562
506 reduction and prior to the dyeing process, the mediator has to 563
507 be separated from the soluble leuco dye by ultrafiltration, and 564
508 the concentration of the mediator in the filtrate is increased by 565
509 nanofiltration. Such filtration considerably increases the costs 566
510 for this vatting process and introduces several technical prob- 567
511 lems like big pressure drop built up during the filtration and 568
512 the persistent danger of blocking the reactor (electrochemical 569
513 cell). Scheme 5. 570
Please cite this article in press as: Bozic M, Kokol V, Ecological alternatives to the reduction and oxidation processes in dyeing with vat and sulphur dyes, Dyes
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571 Besides, it seems that the electrochemical techniques can 628

572 be used also for stabilization or regeneration of sodium di- 629
573 thionite. By appropriate cathodic reduction, it is possible to 630
574 generate from sodium hydrosulphite a powerful reducing spe- 631
575 cies with a redox potential higher than that of hydrosulphite 632
576 itself, which should reduce dithionite consumption by 30% 633
577 [3,42]. 634
578 635
579 2.3. Biodegradable organic compounds as reducing 636
Scheme 6.
580 agent 637
581 638

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582 or the leuco radical anion of the vat dye [38]; adsorbed hy- After several decades of research and development there is 639
583 drogen, produced in situ by electrolysis of water, reacts still no commercial reducing technology (including electro- 640
584 with adsorbed organic substrates (i.e. vat dye) at the electrode chemical processes) available today that can replace sodium 641
585 surface (Scheme 7). The leuco dye prepared by catalytic hy- dithionite in all areas of vat dye applications. There have been 642
586 drogenation is converted back into the pigment form in a con- previous attempts to replace sodium dithionite as a reducing 643

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587 ventional manner by air oxidation [39]. There are severe agent for dyeing with vat dyes wholly or partly by small 644
588 drawbacks in this technique, such as the big pressure drop amounts of organic water-miscible (hydrophilic) solvents, 645
589 built up, the persistent danger of blocking the reactor and i.e. enediols [43]. The enediols are in general a-hydroxycar- 646
590 low performance [3]. bonyl compounds having a strongly reducing action (negative 647
591
592
It has been reported recently that vat and sulphur dyes can
be reduced in alkaline media by H2 using an appropriate sys-
DP redox potentials) in an alkaline medium. Typical compounds
which form enediols (enediolates) in an alkaline medium are
648
649
593 tem involving the production of environmentally safe water in particular low molecular weight (C2eC6)-a-hydroxyke- 650
594 [40]: tones and a-hydroxyaldehydes. The standard potential for 651
595 catalyst 2,3-butanedione is 1718 mV in acetonitrile with 0.1 M tet- 652
596 dye þ H2 ƒƒƒ! leuco form þ H2 O raethylammonium perchlorate measured with a mercury work- 653
TE

597 ing electrode, whereas the corresponding value for 2,2,5,5- 654
598 The low reactivity of hydrogen as reducing agent was re- tetramethylcylohexane-1,3-dione is 2903 mV; the standard 655
599 solved by using a hydrogenation metal catalyst (Pd) which, potential of 1,2-cyclohexanedione lies between these two 656

600 predictably, induces homolytic (H2 / 2H ) or heterolytic values [44]. The ability of a-hydroxyketones to reduce vat 657
EC

601 splitting of the HeH bond (H2 / Hþ þ H). The potential dyes is demonstrated in Scheme 8 [45]. Replacement of so- 658
602 risk of fire and explosion because of the gaseous hydrogen dium dithionite in the vat-dyeing process by a-hydroxyketones 659
603 was solved by Pd catalyst where Pd adsorbs hydrogen and seems to meet the requirements in terms of reductive effi- 660
604 forms a bulk hydride phase with an H/Pd. The bulk hydride ciency and biodegradability. However, work on the reduction 661
RR

605 guarantees constant surface activity of hydrogen and therefore of vat dyes, in particular indigo, with enediols gave unsatisfac- 662
606 the maintenance of catalytic activity even when the hydrogen tory results, since the reduction process was incomplete and 663
607 is diluted within an inert gas carrier that it loses its inflamma- the dyeings obtained were unable to meet the high require- 664
608 bility. Different behaviour of vat and sulphur dyes towards the ments, for example with respect to constancy of shade and lev- 665
609 same reducing agent comes from electrolytic hydrogenation of elness. Besides, some substances are expensive and the use of 666
CO

610 organic substances. Some organic functions are easily reduced some a-hydroxyketones is restricted to closed systems because 667
611 by hydrogen, whereas the others, e.g. quinones, can only be re- they form strong-smelling condensation products in alkaline 668
612 duced by electrons. Leuco indigo prepared by catalytic hydro- solution. 669
613 genation as a product of dyestuff manufacturers is used in the Some other reducing systems, based on sulphur containing 670
614 patent for the process of dyeing cellulose-containing textile substances, have also been recommended (i.e. hydroxyalkyl 671
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615 material with hydrogenated indigo [41]. sulphinate, thiourea, etc.) [46]. The relatively low sulphur con- 672
616 tent and lower equivalent mass than that of hydrosulphite lead 673
617 to lower amounts of sodium sulphates and toxic sulphide in 674
618 the effluent. Another proposal has used thiourea dioxide 675
619 (1000 mV) in vat dyeing, it recommends continuous applica- 676
620 tion with a mixing pump that combines dye dispersion with li- 677
621 quor containing thiourea dioxide, sodium dithionite, 678
622 formaldehyde and caustic soda. Another system uses thiourea 679
623 dioxide in combination with aliphatic ketones or alicyclic ke- 680
624 tones or ketocarboxylic acids. Solid, pasty formulations of 681
625 leuco indigo, in which oxidation to indigo is prevented by 682
626 a mixture of alkali and a stabilizer based on sugar-derived 683
627 Scheme 7. polyhydroxy compounds, have also been used. When these 684
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and Pigments (2007), doi:10.1016/j.dyepig.2006.05.041
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685 742
686 743
687 744
688 745
689 746
690 747
691 748
692 749
693 750
694 751
695 Scheme 8. 752

OF
696 753
697 formulations are used for dyeing, the sodium sulphate content activity on the temperature and pH, and the toxicity of some 754
698 of the dyehouse wastewater can be effectively lowered, but the of them [51]. 755
699 wastewater contains high concentrations of dissolved organic Before the introduction of chemical methods, indigo was 756
700 hydroxyl compounds, measured as TOC (total organic car- reduced in a woad vat, by the anaerobic fermentation of 757

RO
701 bon), COD (chemical oxygen demand) or BOD (biochemical treated (couched) woad leaves. Recent findings show Clostrid- 758
702 oxygen demand). For the delicate dyestuffs, where over-reduc- ium isatidis to be a unique indigo-reducing bacterium isolated 759
703 tion can occur, the use of isomaltulose [47] (a-D-glucopyrano- from a woad dye vat that could be employed in a biotechnolog- 760
704 syl-(1,6)-D-fructofuranose monohydrate) 13, particularly of an ical indigo-reduction process [52,53] C. isatidis cultures gen- 761
705
706
707
isomaltulose mixture containing also trehalulose (a-D-gluco-
pyranosyl-(1,1)-D-fructofuranose), as the reducing agent in
the reduction of sulphur and vat dyestuffs has the advantage
DP erate redox potentials from 476 mV to 602 mV, which is
about 100 mV more negative than those of the other bacteria
examined [54]. The mechanism of bacterial indigo reduction
762
763
764
708 since the redox potential equilibrium of isomaltulose is remains unknown, but the unique features of the indigo-reduc- 765
709 reached considerably more rapidly than with the convention- ing C. isatidis indicate possible mechanisms for biotechnolog- 766
710 ally used sugars (fructose, mannose or glucose) [48]. Isomal- ical indigo-reduction process. 767
TE
711 tulose is a naturally occurring disaccharide composed of a- Dehydrogenases are another class of the enzymes that 768
712 1,6-linked glucose and fructose [49]. When used as a reducing could be used for the reduction of vat dyes [55]. Dehydroge- 769
713 agent, it has the advantage that the detrimental environmental nases are enzymes that catalyze the reduction of carbonyl 770
714 effects, which result from the release of sulphide (S2) ions, groups. To exhibit catalytic activities, the enzymes require 771
EC

715 are avoided. a coenzyme such as nicotinamide adenine dinucleotide phos- 772
716 phate (NAD(P)H) from which a hydride is transferred to the 773
717 substrate with carbonyl group (Scheme 9). The most elegant 774
718 2.4. Biotechnological (enzymatic) approaches and simple approach makes use of a single enzyme, which si- 775
RR

719 multaneously transforms the substrate with carbonyl group 776

720 The replacement of the existing chemical reduction and ox- plus co-substrate with hydroxyl group (Scheme 9(a)). Scheme 777
721 idation processes with enzymatic technologies could be a very 9(b) shows the more complex ‘coupled-enzyme’ approach 778
722 attractive alternative from the ecological point of view. It is where cofactor-recycling is performed by using a second 779
723 also economically attractive because of the possible reduction (and preferably irreversible) enzymatic reaction. The most ad- 780
CO

724 in the cost of treating the effluent. The main advantages of en- vanced regeneration systems use innocuous hydrogen and ox- 781
725 zyme-catalyzed reactions are mild temperatures of processing, ygen as reductant and oxidant, respectively. In addition, the 782
726 absence of by-products, and most of the enzyme processes are coupled-substrate system may be used in the oxidation and re- 783
727 claimed to be environment-friendly [50]. The main disadvan- duction mode, whereas separate cofactor-recycling systems 784
728 tage of the enzyme process is the dependence of enzyme are required for the coupled-enzyme approach [55]. 785
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729 786
730 787
731 788
732 789
733 790
734 791
735 792
736 793
737 794
738 795
739 796
740 797
741 Scheme 9. 798
Please cite this article in press as: Bozic M, Kokol V, Ecological alternatives to the reduction and oxidation processes in dyeing with vat and sulphur dyes, Dyes
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799 Matsuda [56] reviewed the use of alcohol dehydrogenases dissolving and vatting processes can thus be significantly 856
800 (cells of fungus, Geotrichum candidum) in supercritical CO2 shortened making the possibility to carry out the dyeing pro- 857
801 for the reduction of various ketones. Supercritical fluids have cess in a continuous procedure. 858
802 the unique properties to present a grand opportunity to dis- 859
803 cover a range of novel chemical processes. They differ from 2.6. Magnetic field [63e66] 860
804 ordinary solvents in having both their gas-like low viscosities 861
805 and high diffusivities and their liquid-like solubilizing power. The application of magnetic field is another promising 862
806 Instead of employing an isolated enzyme, the whole resting physico-chemical method influencing the textile materials 863
807 cell was used for reduction, thus avoiding the need for an ex- and/or the treating solution components. The use of permanent 864
808 pensive coenzyme. The use of dehydrogenases in supercritical magnetic fields has shown to be importantly advantageous 865
809 CO2 is also under intensive investigation [56]. over other physical methods of intensification: besides low 866

OF
810 However, there is still no method for replacing the reduc- material and energy consumption as well as ecological safety 867
811 tion process in vat dyeing by a system that uses a biological of the method, a variety of resulting effects due to the selectiv- 868
812 approach, but there is enzymatic re-oxidation process that is ity influence of magnetic field on different substances and pro- 869
813 already patented [57]. Oxidoreductases are enzymes that cata- cesses have been proposed. The influence of the magnetic field 870
814 lyze the oxidation of various aromatic compounds, specifically 871

RO
on the processes of quinoneehydroquinone transitions of vat
815 phenols and anilines [58]. Two classes of oxireductases are dyes was determined [67]. It has been established that the 872
816 proposed for oxidation of vat and sulphur dyes: (1) laccases, magnetic field increases the rate of sodium dithionite oxida- 873
817 multi-copper containing enzymes (with a redox potential of tion and quinone-transformation of vat dyes and stabilizes 874
818 780 mV), that catalyze the oxidation of phenols and related the sodium dithionite composition when dyeing with vat 875
819
820
compounds, and (2) peroxidases which oxidise compounds
in the presence of hydrogen peroxide. The reduced vat or sul-
DP dyes. Besides, the magnetic treatment during soaking in-
creases the sorption and depth of dye penetration into the fibre.
876
877
821 phur dye, adsorbed onto the treated material, is oxidised with It is advisable to activate the interactions between the mole- 878
822 laccase or peroxidase. To enhance the activity of laccase, cules of dye and the reducer in the solution penetrating into 879
823 a chemical redox mediator agent (e.g. ABTS (2,20 -azino- the pores of the fibres. 880
824 bis(3-ethylbenzthiazoline-6-sulphonic acid) diammonium 881
TE

825 salt) is added, which represents effective shuttle electrons be- 882
826 tween the enzymes and the dye. The enzymatic re-oxidation 2.7. UV application 883
827 process has lot of advantages, like the mild process conditions 884
828 resulting in less damage of the fibres, lower energy consump- Modern universal equipment makes it possible to treat tex- 885
EC

829 tion due to lower temperature and shorter time of treatment tile materials by UV and IR irradiations ranging in the wave- 886
830 needed. length from 300 to 1200 nm. Research work proves that it is 887
831 possible to carry out photochemical colouration of fabrics by 888
832 2.5. Ultrasonic energy vat dyes and the thermal treatment in conventional dyeing 889
and finishing [68]. Pobedinskij [69] presented an ambient,
RR

833 890
834 Ultrasound has been shown to improve the dyeing vat pro- friendly photochemical technology of dyeing with leuco ethers 891
835 cesses by increasing the dye uptake of the substrate and reduc- of vat dye using UV irradiation. 892
836 ing the amount of the reducing agent and other components 893
837 used, as well as by reducing the time and energy required to 3. Conclusions 894
CO

838 obtain a desired colour [59e61]. The effect of cavitation en- 895
839 ergy of the ultrasound is attributed to the production of inten- Chemical, ecological and economical advantages of the lat- 896
840 sive movement of molecules in the liquor, which considerably est research inventions related to the dyeing of vat and sulphur 897
841 accelerates fibre wetting, the rapid diffusion of dye molecules dyes applying reduction and oxidation mechanisms at dyeing 898
842 inside the fibre structure as well as the promotion of dye mol- processes are reviewed in the article. Special intention is 899
UN

843 ecules’ de-aggregation. Influence of ultrasound on the vatting paid to methods not using sodium dithionite as the most appro- 900
844 degree of indigo with a-hydroxyacetone has shown to increase priate reducing agent, which would ideally give complete vat- 901
845 the vatting degree by a factor of approximately 4e5 [62]. It is ting and lead to dyeings with the stated high requirements. 902
846 well known that ultrasound enhances the degree of reduction Electrochemical reduction methods offer tremendous environ- 903
847 by disintegrating dispersed water-insoluble dye aggregates mental and economic benefits by minimising the consumption 904
848 into smaller particles and by forming significantly more ho- of chemicals and effluent load. 905
849 mogenous and stabile dispersion of dye molecules in the dye- The physical activation of processes and/or fibres employ- 906
850 bath or printing paste (especially at higher concentration of ing ultrasound, magnetic field or UV applications has shown to 907
851 vatted/soluble dyes) leading to higher dye yield on the sub- be practical (parallel) application enabling to solve ecological 908
852 strate [63]. Besides, the increase of the dye surface and simul- problems due to the reduction in consumption of chemicals. 909
853 taneous shortening of the dye diffusion interfaces, the The economical benefit shows in the reduction in time of tech- 910
854 probability for collisions between reducing agent and dye mol- nological processes and the increased rate of absorption and 911
855 ecules increases resulting to the faster reaction rate [3]. The diffusion of the dye molecules into the fibre. 912
Please cite this article in press as: Bozic M, Kokol V, Ecological alternatives to the reduction and oxidation processes in dyeing with vat and sulphur dyes, Dyes
and Pigments (2007), doi:10.1016/j.dyepig.2006.05.041
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913 References [35] Bechtold T, Burtscher E, Bobleter O, Blatt W, Schneider L. Chem Eng 975
914 Technol 1998;21:877e80. 976
915 [36] Roessler A, Dossenbach O, Marte W, Rys P. J Appl Electrochem 977
[1] Luke JE. A fiber trilogy. Textile World May 2005.
916 2002;32(6):647e51. 978
[2] Roessler A, Crettenand D, Dossenbach O, Marte W, Rys Paul. Electro-
917 [37] Ramesh P, Sampath S. Analyst 2001;126:1872e7. 979
chim Acta 2002;47:1989e95.
918 [38] Roessler A, Dossenbach O, Marte W, Rys P. Dyes Pigments 980
[3] Roessler A, Jin X. Dyes Pigments 2003;59:223e35.
919 2002;54:141e6. 981
[4] Zollinger H. Color chemistry: syntheses, properties and applications of
920 [39] Schnitzer G, Suetsch F. Dyeing cellulose-containing textile material with 982
organic dyes and pigments. Federal republic of Germany: Verlag
921 hydrogenated indigo. U.S. 5,586,992; 1996. 983
GmbH & Co; 1987. p. 197e9.
922 [40] Comisso N, Mengoli G. Environ Chem Lett 2004;229e32. 984
[5] Završnik T. Tekstilec 2002;3e4:69e77.
923 [41] Schnitzer G, Suetsch F, Schmit M, Kromm E, Schluete H, Kruger R. 985
[6] Aspland JR. Text Chem Color 1992;24:22e4.
924 et al. Dyeing cellulose-containing textile material with hydrogenated in- 986
[7] Polenov YuV, Pushkina VA, Budanov VV, Khilinskaya OS. Russ J Appl
925 digo. WO 94/23114; 1994. 987
Chem 2001;74:1301e4.

F
926 [42] Daruwalla EH. Text Asia 1975;9:165e9. 988
[8] Etters JN. Am Dyest Rep 1998;87:15e7.
927 [43] Marte W, Rys P. Dyeing and printing of cellulosic fibre materials with vat 989
[9] Adesanya Ibidapo T. Chem Eng J 1992;49:73e8.
928 dyes with mono- or di-hydroxyacetone as reducing agent. U.S. 990

OO
[10] Radugin MV, Zakharov AG, Lebedeva TN, Kolov AL. Russ J Appl Chem
929 4,950,306; 1990. 991
1996;69:709e11.
930 [44] Petersen RA, Evans DH. J Electroanal Chem 1987;222(1e2):129e50. 992
[11] Radugin MV, Zakharov AG, Lebedev VV, Lebedeva TN. Thermochim
931 [45] Wilhelm Bolinger R. Investigation using examples of a-hydroxyketones 993
Acta 1994;231:49e54.
932 systems and oregonator, Ph.D. thesis no. 13637, Zurich; 2000. 994
[12] Zanoni Maria Valnice B, Sousa Wellington R, de Lima Juliana P,
933 [46] Baumgarte U. Rev Prog Color 1987;17:29e38. 995
Carneiro Patricia A, Fogg Arnold G. Dyes Pigments 2006;68:19e25.
934 [47] Application for the approval of isomaltulose. Regulation (EC) No 258/97 996

PR
[13] Govaert F, Temmerman E, Kiekens P. Anal Chim Acta 1990;385:307e
935 of the European Parliament and of the Council of 27th January 1997 con- 997
14.
936 cerning novel foods and novel food. 998
[14] Hunger K, editor. Industrial dyes, chemistry, properties, applications,
937 [48] Grull DR, Begli AH, Kubadinow N, Kunz M, Munir M. Process for re- 999
vols. 35e43. Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA;
938 ducing sulphur and vat dyes. WO 98/24967; 1999. 1000
2003. p. 187e218.
939 [49] Lina BA, Jonker D, Kozianowski G. Food Chem Toxicol 2002;40(10): 1001
[15] Christie RM. Colour chemistry. Cambridge CB4 0WF, UK; 2001. p.
940 1375e81. 1002
70e7.
ED
941 [50] Artur Cavaco-Paulo. Enzymatic processing with enzymes. Fifth World 1003
[16] Ullmann’s encyclopedia of industrial chemistry: anthraquinone dyes and
942 Conference AUTEX; 2005, p. 425e8. 1004
intermediates. Wiley-VCH Verlag GmbH & Co. KGaA; 2000.
943 [51] Cavaco-Paulo A, Gübitz GM. Textile processing with enzymes. England: 1005
[17] Roessler A, Crettenand D. Dyes Pigments 2004;63(1):29e37.
944 Woodhead Publishing Ltd; 2003. p. 3e6. 1006
[18] Ullmann’s encyclopedia of industrial chemistry: sulfites, thiosulfates, and
945 [52] Padden AN, John P, Colins MD, Hutson R, Hall AR. J Archaeol Sci 1007
dithionites. Wiley-VCH Verlag GmbH & Co. KGaA; 2000.
CT

946 2000;27:953e6. 1008

[19] Janson A, Wilhelm E, Schober E, Schlueter H. Dyeing textile material
947 [53] Yumoto I, Hirota K, Nodasaka Y, Yokota Y, Hoshino T, Nakajima K. Int J 1009
with vat and sulphur dyes. GB 1015626; 1966.
948 Syst Evol Microbiol 2004;54:2379e83. 1010
[20] Bechtold T, Burtscher E. Mediator systems based on mixed metal com-
949 [54] Nicholson SK, John P. Biocatal Biotransform 2004;22(5e6):397e400. 1011
plexes, used for reducing dyes. U.S. 6,790,241; 2001.
950 [55] Kroutil W, Mang H, Edegger K, Faber K. Curr Opin Chem Biol 1012
[21] Ruettiger W, Krueger R. Vat-dyeing cellulose at textiles with water insol-
951 2004;8:120e6. 1013
E

uble dye-comprises red to leuco-dye in aqueous alkali medium using

952 [56] Matsuda T, Watanabe K, Harada T, Nakamura K. Catal Today 1014
complex of ferrous compound. and aliphatic hydroxy compound with
953 2004;96:103e11. 1015
carbonyl group and oxidation. DE 4206929; 1993.
RR

954 [57] Deussen HJW, Lund H, Xu F, Salmon S. Enzymatic methods for dyeing 1016
[22] Schortt W, Laws R, Hiebsch W, Wilder G. Int Text Bull 2000;5:66e74.
955 with reduced vat and sulphur dyes. WO 0031333; 2000. 1017
[23] Roessler A, Rys P, Marte W. Method for the electrochemical reduction of
956 [58] Zille A, Munteanu FD, Gubitz GM, Paulo AC. J Mol Catal B Enzym 1018
vat and sulphur dyes. AU 2003273714; 2004.
957 2005;33:23e8. 1019
[24] Bechtold T, Burtscher E, Gmeiner D, Bobleter O. Melliand Textilber
958 [59] Singh S, Das S, Patil S. Improving dye uptake of natural fibers. Ind Text J 1020
1991;72:50e4.
959 2001;9e16. 1021
CO

[25] Roessler A. New electrochemical methods fort the reduction of vat dyes.
960 [60] Klutz DS. Fundamental interactions of ultrasound with cotton fibres and 1022
Switzerland; 2003.
961 vat dyes, Ph.D. thesis, North Carolina State University; 1997. 1023
[26] Bechtold T, Burtscher E, Gmeiner D, Bobleter O. Melliand Textilber
962 [61] Marte W, Marte A, Marte E. Process and apparatus fort he preparation of 1024
1990;25:221e6.
963 a dyeing solution and their use in textile colouration. EP 0373119; 1990. 1025
[27] Bechtold T, Burtscher E, Turcanu A, Bobleter O. Text Res J
964 [62] Poulakis K, Bach E, Knittel D, Schollmayer E. Textilveredlung 1026
1997;67(9):635e42.
965 1996;31:110e3. 1027
UN

[28] Chakraborty JN, Chavan RB. AATCC Rev 2004;4(7):17e20.

966 [63] Zakharov AG, Maximov AI, Koksharov SA. The properties of physical 1028
[29] Blatt W, Schneider L. Melliand Textilber 1999;80:624e6.
967 effect applications under textile material treatment. 17th IFVTCC Con- 1029
[30] Bechtold T, Burtscher E, Turcanu A, Bobleter O. J Appl Electrochem
968 gress, Vienna, Austria; June 5e7 1966. p. 173e6. 1030
1997;27:1021e8.
969 [64] Koksharov SA. Review, Moscow, TsNIITEILegprom, no. 6; 1989. 60 pp. 1031
[31] Bechtold T, Burtscher E, Turcanu A. Text Chem Color 1998;30(8):72e7.
970 [65] Koksharov SA, Ivanov VV. J Gen Chem 1997;40:69e73. 1032
[32] Thomas Bechtold, Rudolf Krueger. Method for producing aqueous alka-
971 [66] Koksharov SA. Text Chem 1998;1(13):64e74. 1033
line solutions or reduced indigoid dyes. U.S. 6,767,448; 2004.
972 [67] Ivanov VV, Koksharov SA, Melnikov BN. Text Chem 1992;2(2):42e8. 1034
[33] Bechtold T, Turcanu A, Burtscher E, Bobleter O. Textilveredlung
973 [68] Pobedinskij VS, Ryzhakov AV. Text Chem 1997;2(11):85e8. 1035
1997;32:204.
974 [69] Pobedinskij VS. Text Chem 1998;1(13):88e95. 1036
[34] Bechtold T, Burtscher E, Turcanu A. J Electroanal Chem 1999;465:80e7.

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