Journal of Applied Electrochemistry (2006) 36:287–293 Ó Springer 2005

DOI 10.1007/s10800-005-9068-9

On-site formation of hypochlorite for indigo oxidation – Scale-up and full scale
operation of an electrolyser for denim bleach processes

T. BECHTOLD1,*, A. TURCANU1, R. CAMPESE2, P. MAIER3 and W. SCHROTT4

1
Institute for Textile Chemistry and Textile Physics, University of Innsbruck, Hoechsterstrasse 73, A-6850 Dornbirn,
Austria
2
Research Departement, Tonello srl, 36030 Sarcedo, Italy
3
Lilienweiß GmbH Textile Dienstleistungen, D-73639 Remshalden, Germany
4
DyStar Textilfarben GmbH&Co, D-65926 Frankfurt a. M., Germany
(*author for correspondence, e-mail: textilchemie@uibk.ac.at)

Received 2 December 2004; accepted in revised form 8 September 2005

Key words: denim, electrolysis, hypochlorite, indigo, textile bleach

Abstract

On-site production of hypochlorite for denim bleach was investigated using undivided unipolar electrolysers. The
current efficiency of the electrolysis process was studied at laboratory scale with up to 20 A cell current and at the
technical scale using a 1200 A electrolyser. NaCl solutions in the concentration range 0.236–0.944 M NaCl (13.8–
55.2 g l)1) were used. Anodic current densities up to 400 A m)2 were used. Hypochlorite solutions with active
chlorine concentration c(Cl)=0.10–0.12 M were obtained with current efficiency of 58–70%. For denim bleach
processes a concentration of active chlorine up to c(Cl)=0.12 M is required. This corresponds to approximately
30 ml l)1 of commercial hypochlorite solution. Electrical energy consumption calculated per kg of active chlorine
formed ranges from 5.7 to 8.6 kWh kg)1. By coupling the electrolyser to a commercial 30 kg capacity drum
washing machine the electrochemically prepared oxidant was successfully used in bleach processes. The technique
overcomes problems of insufficient reproducibility of bleach, chemical costs and released wasted water due to the
use of commercial NaOCl solution.

List of symbols
I cell current, A g1,2 current efficiency, %
id current density, A m)2 Q charge flow, Ah
Uz cell voltage, V nth mol Cl theoretically formed,
T electrolyte temperature, °C mol
t1,2 duration of experiment, cexp analytically determined
min conc. of chlorine, M

1. Introduction Table 1 gives an overview on relevant processes and

bleach chemicals in denim wash-down.
The production of indigo dyed textiles for Denim (jeans) As can be seen, use of oxidising agents forms the
holds an almost unique position in the worldwide textile chemical basis of the main part of treatments applied.
market. The annual production is in the magnitude of Within these sodium hypochlorite is used in more than
approximately 2.0 billion m2 of denim fabric, mainly 80% of the bleach processes. NaOCl offers a broad
dyed with indigo. The indigo dyestuff production can be variety of bleach effects, simple handling and relative
estimated at more than 30,000 t per year. low costs and thus still forms the chemical basis of the
A central step in the processing of indigo dyed textiles is standard processes in denim bleach. However, problems
the wash/bleach process of the garments to obtain the can arise from insufficient chemical stability during
final wash down effect. To remove/destroy the ring dyed storage of NaOCl particularly at higher temperatures
indigo dyestuff a combination of both mechanical agita- which results in unsatisfactory reproducibility of bleach
tion in drum washing machines and addition of chemicals effects. Further, total costs for chemicals and transpor-
to oxidize/reduce the dyestuff are used at present [1, 2]. tation of the hazardous material are considerable.
288
In other textile bleach processes hypochlorite has been Table 1. Relevant processes in denim wash-down
replaced by other chemicals because of the AOX Chemical Formula Reaction Market
released in the waste water (AOX adsorbable haloge- share/%
nated organic compounds).
In the last decade substantial research has been done Hypochlorite NaOCl Oxidative >85
Persulphate K2/Na2S2O8 Oxidative <5
to investigate electrochemical processes for reduction of Permanganate K/NaMnO4 Oxidative <2
indigo and vat dyes in textile dyeing processes [3–5]; Enzymes Oxidoreductases Oxidative <2
however, recently use of anodic processes for oxidative Ozone O3 Oxidative No relevance
bleach processes has been studied more intensively. Peroxocompounds ÆÆ–O–O–ÆÆ Oxidative No relevance
DyStar Textilfarben GmbH&Co Deutschland KG Glucose C6H12O6 Reductive <5
Sulfinic acids R–S(O)OH Reductive <1
and the Institute for Textile Chemistry and Textile
Physics of the University of Innsbruck, Austria have
been working together for many years on the develop- lyser to a 30 kg drum washing machine is discussed in
ment of electrochemical processes for the textile industry detail. Current efficiency for hypochlorite formation and
which they aim to commercialise. The main focus of this results from full scale tests are summarised.
work is on electrochemical dyeing but also includes
decolouration of textile effluent and bleaching of textiles. 2. Experimental
Processes for electrochemical production of bleach
chemicals have been studied for delignification of pulp 2.1. Chemicals
and for textile bleach processes [6–13]. The electrochem-
ical formation of hydrogen-peroxide on-site has been NaCl used as electrolyte was technical grade quality.
investigated [14, 15]. The use of electrochemical methods Chemicals used for the analytical determination of the
to form organic oxidizing agents for denim bleach has NaOCl content were analytical grade chemicals.
been described [13]. Limited scientific information is
available about the electrochemical in-situ formation of 2.2. Laboratory scale experiments
hypo-halogenites for bleach operations [9, 10, 16, 17].
The in-house preparation of NaOCl also has been An undivided monopolar cell was used for the electrol-
described, however the efficiency of the bleach process ysis experiments. A Pt-mixed oxide coated titanium
has been described as rather low [12].
The use of electrochemical processes for on-site or in-
situ formation of oxidizing agents e.g. hypochlorite,
offers interesting new aspects for denim bleach:
– improved process control, better reproducibility
leading to processing cost reduction
– higher reproducibility of bleach result
– lowered total costs for chemicals
– regeneration of used bleach baths improves the eco-
logical profile.
The chemical reaction of the bleach process can be
formulated according to Equations (1)–(3). Figure 1
shows a general scheme for the oxidation reaction of
indigo in presence of hypochlorite [18, 19].
2 H2 O þ 2 e
! 2OH
þ H2 cathode ð1Þ

Cl
þ H2 O ! OCl
þ 2Hþ þ 2e
anode ð2Þ

m

2OCl
þ indigo ! 2Cl
þ isatin solution ð3Þ

In this work results from laboratory experiments to

design a simple and robust electrolyser for anodic
formation of hypochlorite for denim bleach are pre-
sented and the scale-up to full technical operation is
described. Performance tests of the technical scale
hypochlorite electrolyser are presented and data from
tests in full operation of the 1200 A cell current Fig. 1. Scheme for the oxidation of indigo by hypochlorite to yield
electrolyser are presented. The coupling of an electro- isatin [18, 19].
 289
electrode (DE NORA, Rodenbach, Germany) was used For the electrolysis a volume of 145 l of electrolyte
as anode and a stainless steel fabric served as cathode. was filled in the cell and electrolysed at constant current.
Dimensions are given in Table 2. Both, formation of oxidant in the bleach solution and
The redox potential of the electrolyte was measured decrease of NaOCl concentration during bleach process
with a Pt-electrode vs. a (Ag/AgCl, 3 M KCl) reference. in the washing machine, were monitored by redox
The pH of electrolyte was measured with a glass titration with Na2S2O3.
electrode (Hamilton-flush-trode, Orion 720 A, Orion After a defined concentration of oxidant had been
Research Inc. Boston, MA). The electrolyte flow was formed in the electrolyte, the bleach bath was pumped
parallel to the direction of the current flow (20 l min)1, into the washing machine for processing the garment.
flow approx. 0.8 cm s)1). Indigo dyed jeans were used for the full scale bleach
Experiments were performed in galvanostatic batch experiments.
electrolysis mode. Samples of the bleach solution were The result of the bleach step was evaluated visually
analysed for hypochlorite as function of electrolysis time and by measuring CIELab-coordinates. The colours are
by redox titration with sodium thiosulphate. 5 ml of described in CIELab-coordinates, L corresponding to
10% KI solution and 10 ml of 10% HCl were added to a the brightness (100 = white, 0 = black), a to the red–
volume of 50 ml of electrolyte and titration was per- green coordinate (positive sign = red, negative sign =
formed with 0.1 M Na2S2O3 by means of a titroproces- green) and b to the yellow–blue coordinate (positive
sor (Orion Autochemistry System 960, Orion, Boston, sign = yellow, negative sign = blue). Details for the
MA). bleach effect are given elsewhere [11, 20].
For comparison and standardisation reference wash-
2.3. Technical scale process down procedures were performed with 24.4–28.2 mM
NaOCl (addition of 13–15 ml l)1 of commercial 1.88 M
For full scale tests a undivided cell manufactured by NaOCl).
DE NORA Elektrochemie (HKE-4-H, DE NORA
Deutschland, Rodenbach, Germany) was used. The
cell was a monopolar cell and equipped with parallel
electrodes (5 cathodes and 4 anodes). Titanium anodes 3. Results and discussion
coated with Pt-mixed oxide were used. Titanium
cathodes were used for initial tests, and were later 3.1. Laboratory scale electrolysis
replaced by stainless steel electrodes due to severe
corrosion of the titanium. In discussions with denim experts a concentration of
For full scale operation tests a Tonello G1 150 drum 0.86 M NaCl (50 g l)1) had been evaluated as the upper
washing machine with a load capacity of 30 kg textiles limit for NaCl concentration acceptable for the technical
and a fill of 300 l of bleach bath was coupled to the cell process. To keep the number of variations limited this
(Tonello, Sarcedo, Italy). concentration was used in the electrolyte and the
A scheme of the installation is given in Figure 2. The formation of hypochlorite was studied in galvanostatic
operation cycle of the unit was as following batch electrolysis experiments.
– filling of electrolyser with NaCl solution Experimental conditions and results of the turnover
– electrochemical formation of NaOCl bleach solution experiments in laboratory scale are given in Table 3.
– pumping of bleach solution into washing machine Electrolysis was performed with an anodic current
– wash/bleach process. density of 64–500 A m)2. The total duration of a batch

Table 2. Geometric data of the laboratory scale electrolyser and general experimental conditions

Experimental parameter Laboratory scale Technical scale

Anode Material 1 Electrode 4 Electrodes

Pt-mixed oxide coated 0.4 m2 Pt-mixed oxide coated
titan expanded mesh titan expanded mesh
Geometric area 400 cm2 40.4 m2=1.6 m2
(both sides considered) 240.4 m2=3.2 m2
Cell current Total current 5–20 A 250–1200 A
Anodic current density 12.5–50 mA cm)2 7.8–37.5 mA m)2
125–500 A m)2 78–375 A m)2
Cathode Material 1 Electrode 5 Electrodes
Stainless steel fabric 0.4 m2 Stainless steel
expanded mesh
Geometric area 360 cm2 50.4 m2=2.0 m2
Cathodic current density 140–560 A m)2 125–600 A m)2
(both sides considered) 62.5–375 A m)2
Distance Anode/cathode 12 cm 2.5 cm
Electrolyte Volume 11 l 160 l
290

Fig. 2. Scheme of the coupling between electrolyser and drum washing machine: a anode, b cathode, c power supply, d electrolyte, e denim
fabric, f bleach bath, g filling pump, h drum washing machine, i bleach bath regeneration, j drain.

electrolysis was fixed at approx. 150 min. Within this Thus NaOCl solutions with sufficient concentration to
time an average current efficiency of 56–67% was be applicable for denim bleach operations can be
determined. A current efficiency of apparently more produced in the cell.
than 100% is observed at the beginning of the exper-
iment which can be explained by the influence of small 3.2. Technical scale process
experimental errors causing considerable effects partic-
ularly at the initial phase of the experiment. As a The size of the electrolyser was defined by the technical
function of cell current the applied cell voltage, Uz , requirement to produce the chlorine bleach within the
ranged from 3.7 to 13.4 V. The rather high cell voltage cycle time of a bleach in the drum washer. Assuming a
was caused by the considerable geometric distance of current efficiency of 50% a cell current of 1210 A was
12 cm between anode and cathode. Experiments were calculated to deliver 22.6 mol of oxidant within 60 min.
started at room temperature. During electrolysis the This amount corresponds to 200 l 56.4 mM NaOCl,
temperature of the electrolyte increased to values near equivalent to 30 ml l)1 commercial 1.88 M NaOCl
40 °C. The final temperature reached was dependent on solution.
the cell current. pH values typically remained below pH Before the electrolyser was coupled to the drum
of 9, e.g. at the end of experiment (8) a final pH value of washer a set of batch experiments was performed to
8.9 was measured in the electrolyte. The formation of characterise the performance of the cell (c(NaCl)
the oxidant, current efficiency and electrolyte tempera- =0.86 M, 50 g l)1). The formation of hypochlorite as
ture as function of time for experiment (8) are shown in function of electrolysis time and the corresponding
Figure 3. current efficiencies were determined. Figure 4 shows the
The highest concentration of active chlorine c(Cl) was concentration of oxidizing equivalents formed and the
observed in experiment (8) with c(Cl)=0.0914 M; this current efficiency measured at cell currents of 250, 500
corresponds to 24 ml l)1 commercial NaOCl solution and 750 A. At the begin of the tests high current
(c(NaOCl)=1.88 M). A concentration of 0.1 M NaOCl efficiency of 80–100% is observed, which decreases with
can be seen as upper limit for a technical bleach process. increased concentration of oxidant. An increase in

Table 3. Experimental conditions and results of the electrochemical bleach experiments in laboratory scale: Composition of electrolyte 0.86 M
NaCl (50 g l)1), volume electrolyte 11 l, distance anode–cathode 12 cm

Expt. No. I/A id/A m)2 Uz/V T/°C Flow/l min)1 t1/min g1/% t2/min Q/Ah nth(Cl)/mol cexp(Cl)/M g2/%

1 2.6 64 3.7–3.6 20.6–24.8 20 60 77.3 150 6.4 0.239 0.014 62.4

2 5.0 125 4.8–4.7 20.7–25.9 20 60 79.7 150 12.5 0.466 0.029 67.6
3 5.5 138 5.0–4.8 18.7–23.9 4 60 69.5 140 11.7 0.435 0.027 67.3
4 7.0 175 5.8–5.6 20.9–26.8 20 60 87.0 135 15.8 0.588 0.040 63.5
5 10 250 6.9–6.6 20.8–28.9 20 50 73.5 155 25.8 0.964 0.057 64.4
6 15 375 10.1–8.6 19.3–33.4 20 50 76.9 135 33.8 1.259 0.074 64.6
7 15 375 10.7–9.0 21.3–34.1 20 45 72.3 – 33.8 1.259 – –
8 20 500 13.4–10.3 19.0–41.1 20 45 77.9 143 47.7 1.778 0.091 56.5
 291

Fig. 3. (Left scale:) (n) temperature T and (right scale:) (d) current efficiency g, ( n ) concentration of oxidant c(Cl) as function of electroly-
sis time t for experiment (8) (cell current I 20 A).

current efficiency from 74 to 86% was observed with The cell voltage Uz increased from 2.75 V at 100 A to
increase of anodic current density from 156 to 4.12 V at 600 A and 5.2 V at a cell current of 1200 A. A
468 A m)2 . The upper value corresponds to 750 A cell linear correlation between Uz and I was observed in the
current. 100–1200 A range.
A considerable decrease of current density is
observed at rather low concentrations of hypochlorite 3.3. Preparation of denim bleach solution
of c(Cl)=0.015 M which corresponds to a turn-over
of less than 2% of the NaCl present in the For full scale tests the cell was coupled to a 30 kg
electrolyte. capacity drum washer which, technically, is used for

Fig. 4. Current efficiency g and concentration of equivalents of oxidant c(Cl) formed in galvanostatic tests as function of electrolysis time t,
cell current of 250, 500 and 750 A.
292
Table 4. Experimental conditions and results of the electrochemical bleach experiments in technical scale: volume electrolyte 145 l

Expt. No. c (NaCl)/M c (NaCl)/g l)1 I/A Uz/V t/min g/% Q/Ah nth/mol cth/M cexp/M

9 0.236 13.79 1000 6.8 40 57.7 667 28.9 0.172 0.10

10 0.354 20.69 1000 6.1 40 57.7 667 28.9 0.172 0.10
11 0.472 27.59 1000 5.4 41 69.5 683 25.5 0.176 0.12
12 0.708 41.38 800 4.5 85 45.7 1138 42.3 0.292 0.13
13 0.944 55.17 1000 4.5 55 48.9 917 34.2 0.236 0.12
14 0.944 55.17 1000 4.5 54 51.1 900 33.6 0.232 0.12

denim bleach. The filled load was 30 kg indigo dyed and For comparison with results obtained using commer-
stone washed garments. cial hypochlorite solution, standard bleach was
In Table 4 relevant data collected during the batch performed at 24.4–28.2 mM NaOCl, corresponding to
electrolysis are summarised. Hypochlorite concentration 13–15 ml l)1 of 1.88 M active chlorine. Details describ-
was monitored every 10 min. Different NaCl concen- ing bleach effects and comparison of bleach results are
trations of 0.24–0.94 M NaCl (14–55 g l)1) were used in given elsewhere [11, 20]. The comparison of the bleach
the experiments. The adjusted cell current was kept effects indicated that, under similar process conditions
constant during each experiment. Within the first 40– e.g. concentration of oxidant, pH, temperature and
54 min current efficiency ranged from 57 to 70%. In duration a more intensive bleach effect is observed using
experiments 12–14 the duration of electrolysis was electrochemically prepared bleach baths [11, 20]. This
prolonged. Due the higher concentration of OCl) finding may be explained as being due to partial
already present in the electrolyte current efficiency disproportionation of the commercial NaOCl solution
decreased to 45–52%. The increase in hypochlorite to less bleaching NaClO3 and NaCl during storage;
concentration almost ceased at a concentration of however, detailed studies are in progress.
approximately 0.10–0.13 M active chlorine.
For comparison the total amount of active chlorine 3.5. Energy consumption
formed in the electrolyte can be calculated in terms of
ml l)1 commercial 1.88 M hypochlorite solution A cell voltage of 4.5–6.8 V was required for a cell
(approx. 140 g l)1 NaOCl). In experiments 9–14 hypo- current of 1000 A. On the basis of an average current
chlorite concentrations corresponding 27–35 ml l)1 efficiency of 60%, production of 1 kg of chlorine
commercial 1.88 M NaOCl were produced in the cell. requires a charge flow of 1260 Ah and consumes 5.67–
8.57 kWh kg)1. This corresponds to a volume of 7.9 l
3.4. Bleach process commercial NaOCl solution (1.88 g l)1 NaOCl).
Production of chlorine in chlorine-alkali electrolysis
Following the formation of the bleach solution elec- requires approximately 2.7 kWh per kg [21]. The higher
trolysis was terminated and the filling of the electro- energy consumption of the present cell can mainly be
lyser (145 l) was transferred into the drum washing attributed both to lower current efficiency and non-
machine which was filled with 30 kg of denim goods. optimised cell geometry. However, for the described
Soft water was added to reach the required minimum technical application of in-site hypochlorite production
level of 300 l and the bleach procedure was started. energy costs are of minor relevance compared to the
Typical conditions for the bleach step were 40 °C expected savings due to improved reproducibility of the
temperature and agitation for 20 min, followed by bleach process and total chemical costs.
washing steps to eliminate residual oxidant from the
bleached goods.
The addition of water lowered the concentration of 4. Conclusions
hypochlorite in the washing machine to approximately
50% of the concentration determined at the end of In-site formation of hypochlorite solution for denim
electrolysis (Table 4). Thus reference bleach experiments bleach offers several advantages:
were performed with oxidant concentrations 24–30 mM – defined conditions of the bleach leading to better
NaOCl (equivalent to 13–16 ml l)1 commercial 1.88 M reproducibility and process cost saving
NaOCl). – no losses of activity of hypochlorite during storage
Analysis of the concentration of active chlorine in – better defined bleach process conditions
the bleach bath indicated an intensive reaction within – improved reproducibility of the bleach step
the first 5 min. During this period more than 50% of the – possible regeneration of the bleach bath.
oxidant is consumed. Dependent on the presence of The current efficiency of the electrolysis depends on the
oxidable matter in the bath an additional 20–40% of concentration of oxidant present in the undivided cell.
oxidant have reacted within the following 15 min. In Up to a concentration of c(Cl)=0.1 mol l)1 current
total 70–90% of the bleach chemicals are consumed efficiency is between 60 to 80%. In laboratory
within 20 min of the bleach. experiments using anodic current densities from 60 to
 293
500 A m)2 only small changes in current efficiencies den, Germany) and Tonello s.r.l. (Sarcedo, Italy) for
were found. supplying material, equipment, technical discussion
For denim bleach processes active chlorine concen- and assistance.
trations of c(Cl)=0.12 mol l)1 corresponding to
approximately 30 ml l)1 commercial NaOCl solution
are in use. The present undivided unipolar cell avoids
mechanically sensitive components. Using a cell current
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The authors thank the DyStar Textilfarben GmbH 216.
(Frankfurt, Germany), Lilienweiß GmbH, (Remshal-