Fibers and Polymers 2017, Vol.18, No.

10, 1969-1974 ISSN 1229-9197 (print version)

DOI 10.1007/s12221-017-1241-3 ISSN 1875-0052 (electronic version)

Application of Liquid Organic Salt to Cotton Dyeing Process with

Reactive Dyes
Deshuai Sun*, Xiaodong Zhang, Hui Du, Long Fang, and Peng Jiang
College of Chemical Engineering, Qingdao University, Qingdao 266071, China
(Received December 23, 2016; Revised July 28, 2017; Accepted July 31, 2017)

Abstract: Reactive dyes are used widely in cotton dyeing process. Reactive dyeing uses high amounts of inorganic salts to
accelerate dye exhaustion. These salts are then discharged to the effluent, leading to serious environmental problems.
Biodegradable organic salts can alternatively be used in the dyeing process. In this paper, a new liquid organic salt was
synthesized by acid-base neutralization, which was used to replace inorganic salts in reactive dyeing. Dye exhaustion in
organic salt dyeing was similar to the values in conventional dyeing. However, dye fixations were slightly lower in organic
salt dyeing than in conventional dyeing. The washing fastness of dyed fabrics with organic salt was excellent. Experimental
results showed that dye exhaustion reached the maximum value when the concentration range of organic salt was from 20 g/l
to 40 g/l. In addition, the optimal alkali concentration in organic salt dyeing was found to be about 30 g/l. These parameters
suggested organic salt could replace inorganic salt in reactive dyeing process.
Keywords: Triethanolamine citrate, Cotton dyeing, Reactive dyes, Fastness, Biodegradable organic salts

Introduction another method that could increase the dyeability of cotton

Reactive dyes are widely used for dyeing cotton because
they have bright shade, high strength, and excellent fastness
properties. The amounts of reactive dyes consumed are
expected to increase more rapidly than that of many other
cotton dyes. However, there are many drawbacks for their
application. Dyeing cotton with reactive dyes is performed
in an alkaline condition. Cotton acquires a negative charge
because of the ionization of hydroxyl in cellulose in the
dyeing bath. There are strongly static repulsion between the
cotton fiber and the anionic reactive dyes, which can be
reduced by adding an electrolyte, such as sodium chloride or
sodium sulfate. The salt usage varies from 30 g/l to 150 g/l
depending on the color depth and dye structure [1]. Sufficient
salt accelerates the transfer of dyes from the dyeing solution
to the surface of the cotton fiber, and consequently improves
dye exhaustion. The fixations of reactive dyes on cotton rely
on the formation of a covalent bond between the dye molecule
and the hydroxyl of cotton fiber at high pH (>10.5). Moreover,
some parts of dyestuff molecules can react with OH− in the
alkaline bath, resulting in the low fixations of dye [2].
Therefore, high salt usage and low fixation of reactive dye
have caught great attention of the dyeing chemists [3]. The
strongly colored effluents with great chemical complexity in
the dyeing process have caused serious environmental
problems [4,5].
A number of approaches have been made to reduce salt
usage and increase dye fixation. New reactive dyes have
been developed, such as bifunctional dyes with higher dye
fixation [6,7], reactive cationic dyes with zero salt dyeing
[8,9], and “low-salt” dyes with higher substantivity [6]. The
modification of cellulose fiber with cationic group was
*Corresponding author: luckysds@163.com
with reactive dyes [10-12]. However, the application of
reactive dyes to cellulosic fiber continued to be costly for the
dyehouse in terms of the amounts of dye wasted, electrolyte
and alkali used and, in addition, presented a large pollution
load for the environment [6].
Biodegradable organic salt was recently found to be an
effective alternative to the non-biodegradable inorganic salts
used in reactive dyeing. Trisodium citrate is an eco-friendly
organic salt, used as an exhausting agent in dyeing bleached
cotton fabrics with reactive, direct, and solubilized vat dyes.
Reactive and solubilized vat dyed samples provide better
dye uptake and have better fastness properties than direct
dyed fabrics [13]. Polycarboxylic acid salts were another
organic salts used in dyeing cotton with reactive dye. The
K/S value and fastness were good in dip-dyeing process
while these values were excellent in pad-dry dyeing [14].
Betaine was a potential exhausting agent to reduce the
amount of inorganic salt in the reactive dyeing of cotton
[15]. In another study, biodegradable alkaline organic salts,
such as trisodium nitrilo triacetate [16], tetrasodium N,N-
bis(carboxylatomethyl)-L-glutamate [17,18] and sodium
edate [19,20], were found effective as a replacement for
conventionally used inorganic electrolyte and alkali for the
reactive dyeing of cotton. Although some documents have
reported the application of organic salts in dyeing process,
the study of organic salt was still in pilot stage.
The present paper discusses the application of liquid
organic salt composed of organic cation and anion. The salt
was presented in a molten state at or close to room
temperature and easy to solve in water, which was used as an
exhausting agent in dyeing cotton fabrics with reactive dyes.
The different factors affecting the dyeability were also
discussed in detail.

1969
1970 Fibers and Polymers 2017, Vol.18, No.10
Experimental
Materials
Citric acid, triethanolamine, sodium chloride, sodium
carbonate, ethanol, and acetic ether were purchased from
Sinopharm Chemical Reagent Co., Ltd. (China). All the
reagents used were analytically pure.
Scoured and bleached 100 % plain weave cotton fabrics
(132 g/m2) were used in this test. Three commercial
monochlorotriazine reactive dyes, reactive yellow K-4G,
reactive orange K-7R, and reactive red K-2G, were supplied
by Zhangjiagang Jiada Chemical Co., Ltd. and used without
purification. The basic properties were given in Table 1. A
non-ionic detergent, Detergent 209, was supplied by Baodao
Chemical Engineering Co., Ltd.
Preparation of Organic Salt
Organic salt was prepared by acid-base neutralization of
citric acid with triethanolamine [21,22], as shown in Scheme
1. Triethanolamine (0.3 mol) and ethanol (50 ml) were
combined in a 250 ml three-neck round-bottomed glass flask
equipped with a condenser. The mixture was stirred with a
mechanical agitator and heated to 60 oC. Citric acid solution
(0.1 mol) in ethanol (50 ml) was slowly added into the flask
drop by drop. The reaction mixtures then were warmed to
80 oC and stirred for 12 h. After the reaction, the sticky
solution was transferred into a separatory funnel to perform
liquid-liquid separation. The primrose yellow viscous liquid
in the lower level was collected and dried at 50 oC in a
vacuum oven. Finally, the liquid organic salt, named as
triethanolamine citrate, was obtained with the yield of 93.6 %.
Dyeing
In order to investigate the exhaustion effects of organic
salt, the dyeing of fabrics were performed first using a
control method (Figure 1). The dyebath composed of dyes
Table 1. Basic properties of the reactive dyes
Commercial name C.I. generic name λmax (nm)a
Reactive yellow K-4G Reactive yellow 118 413
Reactive orange K-7R Reactive orange 15 494
R reactive red K-2G Reactive red 24 510
a
Maximum absorption wavelength were measured from dye solu-
tion of 0.037 g/l for K-4G and 0.020 g/l for K-7R and K-2G.
Scheme 1. Synthesis of organic salt.
Deshuai Sun et al.
Figure 1. Dyeing method.
(4 % owf) and sodium chloride (40 g/l) or organic salt (20 g/l)
were prepared unless otherwise specified. The fabrics were
dyed in a liquor ratio of 10:1 at 60 oC for 50 min. Dyeing
temperature was raised to 90 oC and sodium carbonate (10 g/l
to 50 g/l) was added into the dye-bath. The fixation time
lasted for another 50 min at 90 oC. The dyed fabrics were
rinsed twice with cold water and washed in a bath with a
liquor ratio of 40:1 using 3 g/l non-ionic detergent 209 for
30 min at 95 oC, then rinsed and finally dried at ambient
temperature.
Measurement
The structure of organic salt was characterized by IR
spectra and elemental analyzer. IR spectra were recorded by
a Nicolet 6700 fourier transform infrared spectrometer
(FTIR) using KBr disk. The measurements were performed
at 20 oC and a 45 % relative humidity. Elemental analyzer
data were measured by VARIO EL III.
Dye Exhaustion
Dye exhaustion was measured by determining the absorbance
of dye solution at the maximum wavelength (λmax) by a UV-
2102PC UV-visible spectrometer (Unicol Instrument Co.,
Ltd.). The percent dye exhaustion was calculated according
to equation (1) [14].
A
%E = ⎛ 1 – -----0⎞ × 100 (1)
⎝ At ⎠
where A0 and At were the initial absorbance and absorbance
at time t, respectively.
Dye Fixation
The fixation of the reactive dye on cotton was evaluated
by measuring the color strength (K/S values) of the dyed
fabrics at the maximum wavelength (λmax) using SF600
Application of Organic Salt to Dyeing Process Fibers and Polymers 2017, Vol.18, No.10 1971

color photometer (Datacolor) with 10 o view field under a the strong absorption band located in 1722 cm-1 was
D65 standard lamp, before and after soaping. The dye attributed to the stretching vibration of the C=O double bond
fixation was defined by equation (2) [11]. of the carboxyl groups in the citric acid. The wide bands
( K/S ) between 3422 cm-1 and 2610 cm-1 were the characteristics of
%F = ---------------a × 100 (2) hydrogen bond in the polycarboxylic acid of citric acid,
( K/S )b
which covered up the weak absorption band of -CH2- of
where (K/S)b and (K/S)a were the color strengths of the dyed citric acid. These bands disappeared in bio-salt as shown in
samples before and after soaping, respectively. Figure 2(b). Two new bands at 1560 cm-1 and 1480 cm-1
clearly appeared in Figure 2(b) [21,26], which corresponded
Fastness Properties to the carbonyls in carboxylate of bio-salt. Also, the
The determination of washing properties was performed
using an SW-12 (Dongyuan testing Machinery) washing
machine according to the standard, ISO 105-C06. Rubbing
fastness properties were performed according to the standard,
ISO 105-X12 on a Y571B (Changzhou Textile Instrument
Co., Ltd.) rubbing machine [23].

Results and Discussion

Citrate compounds are widely used in the food, drug, and

cosmetics industry. Citrates are readily degraded when they
come in contact with a variety of microorganisms found in
soil, natural waters, or sewage treatment systems. For
example, aquatic biodegradability data show that sodium
citrate dehydrate can be readily degraded in days [24].
Ethanolamine appears to have minimal or no adverse effects
on the environment, except possibly for algal growth
inhibition. Ethanolamine has a very low soil sorption tendency
and low toxicity in fish. Ethanolamine degrades anaerobically
and aerobically with acetaldehyde as an intermediate degradation
product [25]. The synthesized organic salt was triethanolamine
citrate, which could help reduce the environmental pollution
of inorganic salt in dyeing process.

Characterization of Organic Salt

The structure of the triethanolamine citrate was confirmed
by FTIR spectrum, as shown in Figure 2. From Figure 2(a),

Figure 3. Effect of organic and inorganic salt on the dye

Figure 2. FT-IR spectrum of synthesized organic salt. absorbance spectrum.
1972 Fibers and Polymers 2017, Vol.18, No.10
absorbance of triethanolamine citrate formed by the tertiary
amine was located in 3151 cm-1. The characteristic peaks
near 2932 cm-1 in Figure 2(b) belonged to stretching vibration
of -CH2CH2- in triethanolamine [26]. Moreover, The measuring
data of carbon, hydrogen and nitrogen percentages of organic
salt were 44.28 %, 3.75 % and 6.84 %, respectively. These
values were in good with the calculated data (C, 45.07 %; H,
3.605; N, 6.57 %). Based on these results, we concluded that
triethanolamine citrate has been synthesized from the reaction
between the citric acid and triethanolamine.
Effect of Organic Salt on Dye Absorbance
The organic salt synthesized in this paper was a molten
salt in room temperature and easy to dissolve in water. In
order to investigate the interaction between triethanolamine
citrate and dyes, the absorbance of the dye solution with
triethanolamine citrate was determined, as illustrated in
Figure 3. The maximum wavelength shifted towards the
long waves from 1 nm to 2 nm with the addition of
triethanolamine citrate and 3 nm to 4 nm with the addition of
sodium chloride. In addition, no obvious change in the
intensity of the absorbance was observed for the three dyes.
These findings suggest that the structure of the dye was not
affected by the addition of triethanolamine citrate.
Effect of Organic Salt on Dye Exhaustion
The effect of organic salt on dyeing exhaustion is shown in
Figure 4. Effect of organic salt on dyeing exhaustion.
Deshuai Sun et al.
Figure 4. For the first 50 min, the dye exhaustion in organic
salt dyeing was higher than that in conventional dyeing.
These results were consistent with the study of Prabu and
Sundrarajan [13]. However, with the addition of sodium
carbonate, the uptakes of K-4G and K-7R were gradually
lower in organic salt dyeing than in conventional dyeing. For
K-2G, organic salt was an effective exhaustion agent. The
good adsorption of dyes in organic salt dyeing suggests that
it could be used as an alternative inorganic salt. However,
the chemical structure of dyes affected the dye exhaustion in
organic salt dyeing process [17,20].
Effect of Organic Salt Concentration on Dye Exhaustion
In this test, the concentration of organic salt was performed
from 5 g/l to 70 g/l, as shown in Figure 5. It was clear that
increasing organic salt concentration from 5 g/l to 20 g/l lead
to increased dye exhaustion. Maximum dye uptake occurred
at organic salt concentration range of 20 g/l to 40 g/l. When
the organic salt concentration was further increase, the dye
uptake decreased gradually for K-4G and K-7R, and
increased slightly for K-2G. Compared with previous reports
[16,17,20], the concentration of triethanolamine citrate was
smaller than the value of alkaline organic salts. Although
organic salt used in this work is expensive, the amount of
organic salt in dyeing was less than that of sodium chloride,
which would offset some cost of raw materials.
The observed effect of organic salt could be explained by
Application of Organic Salt to Dyeing Process Fibers and Polymers 2017, Vol.18, No.10 1973

Figure 6. Effect of alkali concentration on dye exhaustion and pH

value of the dyeing bath.
Figure 5. Effect of organic salt concentration on dye exhaustion.

the following facts. Generally, the cation in inorganic salt

can aggregate around the sulfonic acid groups of reactive
dyes and decreases the negative charge on the dye molecule,
which can favor the adsorption of dyes on the fiber. The
ammonium generated from the dissolution of organic salt
might perform similar functions. Moreover, the new combination
of dyes and ammonium reduce the solubility of the dye in
water, which accelerated the transfer of dyes from the dyeing
solution to the surface of cotton fabrics [14].

Effect of Alkali Concentration on Dye Exhaustion

Sodium carbonate was used as a fixation agent, which
affected the covalent bond between the fiber and dyes. High
pH encouraged the dye exhaustion and fixation reaction of
reactive dyes on fiber [16,23]. At the same time, excessively
high pH led to the rapid hydrolysis of reactive dyes. However,
the organic salt may affect the hydrolysis of sodium carbonate.
The pH values of the dyeing bath (K-4G) at dyeing time of
60 min and 100 min are indicated in Figure 6. It can be
observed that the pH is below 10 at 60 min if the amount of
sodium carbonate was less than 20 g/l. The pH values of the
dyeing solution could only exceed 10.5 when the concentration
of sodium carbonate was more than 30 g/l. Consequently,
the minimum concentration of alkali was about 30 g/l.
The effect of alkali concentration on dye exhaustion is also
shown in Figure 6. As expected, dye exhaustion increased
with the incremental alkali concentration from 15 g/l to 30 g/l.
However, the continuous improvement in alkali concentration
did not affect the exhaustion values for the three reactive
dyes. For the selected reactive dyes, the optimal alkali
concentration was about 30 g/l, which was higher than that
in conventional dyeing (20 g/l). This result was similar to the
reactive dyeing with betaine [15].
Effect of Organic Salt on Dye Fixation
Dye fixation is an important factor in every dyeing process.
Figure 7. Effect of organic salt on dye fixation.
Figure 7 illustrates the effect of organic salt on dye fixation.
The dye fixations in organic salt dyeing were slightly lower
than that in conventional dyeing, even though the degree of
dye exhaustion is similar in the two methods. This is
probably caused by the internal diffusion of the different
cations. The radii of ammonium and sodium ion were 0.435 nm
(calculated by CHEMSKECH12.0) and 0.095 nm, respectively.
The large radium of ammonium prevented the fast diffusion
into the fiber, which resulted in the low efficiency of
decrements in the repulsive force between the dye molecule
and cellulose. Some dyes were only adsorbed on the surface
of cotton, resulting in low fixation.
Fastness Properties
The washing and rubbing fastness values of the dyed
samples are shown in Table 2. The rubbing fastness values
of the samples dyed with organic salt in the dyeing solution
was similar to that of dyed fabric with sodium chloride in the
dyeing solution. These results accorded with previous
reports [16,17,20]. However, the samples dyed with organic
1974 Fibers and Polymers 2017, Vol.18, No.10 Deshuai Sun et al.

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