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Journal of Bioresources and Bioproducts.

2016, 1(1): 30-35 Peer-Reviewed


ORIGINAL PAPER

Poultry keratin based decolorants for dyeing wastewater treatment


Bi Chena,b* Long Yan a,b Xia Liua, Jessica L. Worrallc

a) School of Chemistry and Chemical Engineering, Yulin University, Yulin,719000,China.


b) Key laboratory of Industries Wastewater Treatment, Yulin University, Yulin,719000, China
c) University of New Brunswick, Fredericton, NB, Canada, E3B 5A3
*Correspondence author: Bi Chen (chenbi_110@163.com)

ABSTRACT
One of the challenges in wastewater treatment is the low efficiency in decoloring dyeing wastewater. Chicken feather, as a waste material,
has a great potential in decoloring the dyeing wastewater. In this study, a lab synthesized dyeing wastewater prepared with acid blue-A dye
was treated with a chicken feather keratin-based composite decolorant KA (keratin agent) using batch decoloration techniques. A modified
KA (MKA) was also developed to improve the decoloration efficiency. The decoloration performance of the two decolorants was then
evaluated in terms of decoloring rate, at various decolorant dosages, pH, reaction temperature and time. Under optimal conditions, the
decoloration rates of the KA and MKA in treating the dyeing wastewater were 91.8% and 94.3%, respectively. IR and TEM results
indicated that the KA and MKA decolorants removed the dye stuff from the dyeing wastewater by physical adsorption as well as chemical
reactions.

Keywords: Keratin; Poutry feather; Decolorant; Dye; Dyeing wastewater; Decoloring; Treatment

1. INTRODUCTION properties in relation to the disulphide bonds and cross-


linkages of feathers.
Water pollution caused by the color effluents discharged In this study, two kinds of composite decolorants were
from textile dye manufacturers and textile dyeing mills is prepared by hydrolyzing the poultry feather in sodium
one of the major environmental concerns in the world hydroxide solution to extract the kerating protein which was
todays.1 Textile dyeing wastewater is difficult to treat. modified to have improved decoloring properties. The
Color removal2 of the dyeing wastewater is especially performance of the feather keratin based decolorants in
difficult due to its complex characteristics, large volume, treating a simulated dyeing wastewater was assessed by the
high content of organic pollutants, dark color, and unstable absorbance and decoloring rate of the treated wastewater.
properties. A number of techniques have been developed to The process parameters including decolorant dosage, pH,
remove different types of dyes from wastewater.3,4 One temperature and contact time were investigated to optimize
technique, a physicochemical method, removes different the decoloring process. The treated dyeing wastewater,
types of dyes through adsorption,5,6 electrocoagulation,7 feather keratin decolorants and resulting sludge were
oxidation8 and photocatalytic decolourization9.9 Recently, examined by infrared spectrum (IR), transmission electron
the adsorption technique has been gaining more attention microscopy (TEM), and the underlining decoloring
since it can be widely used in different dyeing wastewater mechanism was discussed.
treatments, and it is versatile and easily to be
implimented.10 Various potential adsorbents have been 2. MATERIALS AND METHODS
studied, such as activated carbon,11,12 clays,13 agricultural
solid wastes14,15 and fly ash.16 However, more research is 2.1 Materials
needed to develop more cost-effective dye absorbents. Chicken feathers were collected from a slaughterhouse in
Poultry Feather is a solid waste produced from Yulin. An acid blue-A dye sample was obtained from a dye
slaughterhouses. It is estimated that the annual production chemical plant in Shanghai of China, and a dye-fixing agent
of poultry feather is more than 8.5 billion tons in the (DE) from Shanghai Tiantan Auxiliaries Co., Ltd.
world.17 Traditionally, the majority of the feather is being Analytical reagent grade hydrochloric acid (HCl), sodium
dumped into landfills, which is expensive to operate and dithionite (NaHSO3) and sodium hydroxide (NaOH) were
has harmful impacts on the environment. In addition, purchased from Chemicals Ltd, Xian (China).
poultry feather is reach in protein which breeds flies and
viruses. For these reasons, there has been an increased 2.2 Experimental procedures
interest in the utilization of feather keratin.18 For instance, Two different composite decolorants were prepared for
feather was used to decolor or filtrate toxic pollutants19and the lab trials in this study. The first decolorant (KA) was
dyes from dyeing wastewater.20 The poultry feather may be prepared by following steps: 1) the feathers were treated
activated and used directly without extracting the keratin.21 first with 40% hydrochloric acid at 75 C for 90 min; 2) and
Limited studies have been found in the literature on the then with 30% sodium bisulfite solution at 75 C for 90
extraction of keratin and its chemical and physical min; 3) and then hydrolyzed with 20% sodium hydroxide

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Journal of Bioresources and Bioproducts. 2016, 1(1): 30-35 Peer-Reviewed

solution at 80C for 40 min. The liquid extract from the last acidic dyeing wastewater. In contrast, the results for MKA
step contained 0.8 g/L of poultry keratin, and it was were completely different, with the optimum performance
designated as KA. obtained in the neutral to alkaline range (pH from 6 to 12),
The second decolorant (MKA) was prepared by mixing indicating that MKA was suitable for treating neutral or
the KA (0.8 g/L) with DE (0.6 g/L) in a rotary reactor (500 alkaline wastewater. When the pH was lower than the
mL) at 80 C for 30min, at a rotating speed of 120 r/min. isoelectric point of KA, its amine groups were protonized to
DE was a positively charged cationic polymeric quaternary impart positive charges to KA to absorb the anionic dye
ammonium salt with an epoxy group, and the KA had polar molecules by electrostatic attraction. For MKA, the reactive
groups in the main chain such as -COOH, -NH2, -OH and epoxy functional groups and cationic quaternary groups of
peptide bond (-CONH-).22,23 Thus, the epoxy group of DE DE enabled it to absorb dye molecules even under basic
can readily react with the amino and hydroxy groups of KA conditions. However, the MKA had lower efficiency in an
to produce MKA, which can absorb or embed dye acidic medium as shown in Figure 1.
molecules in micelles by electrostatic attraction, hydrogen
bonding, Van der Waals' force and hydrophobic force.24
100
The decoloration experiment was carried out in glass
beakers with 100 mL synthesized dyeing wastewater of 60
mg/L dye concentration, according to the National Standard 80

Decoloring rate(%)
Method and relative literature.16 The pH of the mixture was
adjusted to a desired level by adding hydrochloric acid or 60 KA
sodium hydroxide solutions, and it was maintained at the MKA
level throughout the whole reaction period. A PHS-3C 40
model pH meter was used to monitor the pH value. The
reaction temperature was also maintained at a constant level
20
as desired. After the decoloration treatment, the wastewater
was filtered and measured for absorbance. The absorbance
of the original and treated dyeing wastewater was 0
0 2 4 6 8 10 12
determined at 635 nm wavelength with a UV-2401PC series
spectrophotometer (SHIMADZU Co., Ltd). All experiments pH
were repeated three times for each condition, and the
average value was reported. Fig.1 Effect of pH on the decoloring rate
The decoloring rate of the treatment was calculated from
the change in the absorbance of the synthesized dyeing 3.1.2 Effect of decolorant dosage
wastewater before and after the treatment. The decoloring In Figure 2, the decolorant dosage was varied from 40 to
rate was calculated as 1000 mg/L for KA at pH 2, and 400 to 1600 mg/L for MKA
nAi at pH 8, and the temperature was fixed at 20C. The results
R = (1 ) 100%
mA0 show that the decoloring rate increased first with increasing
Where R is the decoloring rate; A0 and Ai are the decolorant dosage, and then started to decrease when the
absorbance of the dyeing wastewater before and after the dosage was higher than 400 mg/L for the KA system, and
treatment at 635 nm; m and n are dilution factors for the 1400 mg/L for the MKA system. The maximum decoloring
dyeing wastewater. rate was 91% and 92.8% for the KA and MKA systems,
respectively.
3. RESULT AND DISCUSSION
3.1.3 Effect of reaction temperature
3.1 Optimization of process parameters Figure 3 shows the impact of reaction temperature on the
decoloring rate from 20C to 70C, with 400 mg/L KA at
3.1.1 Effect of pH pH 2, or with 1000 mg/L at pH 8. The results show that as
The pH of an adsorption process is an important process the temperature increased from 20 to 30 C, the decoloring
parameter to be controlled to obtain maximum rate increased slightly, and then decreased rapidly when the
performance.25 Figure 1 shows the effect of pH on the temperature increased further from 30 to 70 C. The
decoloring rate in a wide range from pH 1 to pH 12, with maximum decoloring rates were 92% for KA and 93% for
600 mg/L KA or 600 mg/L MKA, under ambient MKA, both of which were obtained at 30C. A moderately
temperature (20 C) for 30 min. For KA, the decoloring rate higher temperature (e.g. 30 C) might favour the interaction
maintained at about 85% between pH of 1 to 4, and between the dye molecules and the decolorants, without
decreased dramatically to below 10% as the pH increased ruining the flocs formed in the absorption process.
from 5 to 10. This means, KA was suitable for treating However, when the temperature was too high (above 30

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Journal of Bioresources and Bioproducts. 2016, 1(1): 30-35 Peer-Reviewed

C), the flocs formation might be disturbed, resulting in a


lower decoloring rate.

3.1.4 Effect of contact time 94


Figure 4 compares the decoloring rate of KA and MKA

Decoloring rate(%)
at various reaction times, in the range from 5 to 120 92
minutes. The decolorant dosage and reaction pH were fixed
at 400 mg/L and 2 for the KA system, and 1000 mg/L and 90
pH 8 for the MKA system. The results show that the
decoloring rate increased rapidly with the increase of the KA
reaction time in the first 30 minutes, and then leveled off 88
MKA
and reached a plateau at 90 minutes, which was true for
both the KA and MKA processes. 86

0 20 40 60 80 100 120
Time(min)
95
Fig.4 Effect of contact time on the decoloring rate
90
Decoloring rate(%)

3.2 Decoloring Mechanism


85
3.2.1 IR spectra
80 KA Infrared spectra of the KA and MKA decolorants are
MKA shown in curve 5 and curve 4, respectively, in Figure 5. The
absorption peaks at 3377.7 cm-1 and 1638.3 cm-1 were
75 attributed to the O-H and C=O vibration. The vibration
absorption of the C-H on the peptide chain and the N-H
70 bending vibration peaked at 1463.1 cm-1 and 1409.7 cm-1,
0 200 400 600 800 1000 1200 1400 1600
respectively, both of which intensified and shifted slightly
Dosage(mg/L) to the lower wave numbers. The absorption peak at 1650
cm-1 was responsible for the S-H groups in the spectrum for
Fig.2 Effect of MKA and KA dosages on the decoloring rate KA disappeared in the spectrum for MKA, indicating that
the dye-fixing agent DE had reacted with KA in the
decolorant preparation process.
The IR spectra for the sludge samples from the
treatments of the dyeing wastewater with KA or MKA are
95
shown by the curves 2 and 3 in Figure 4, respectively. In
KA both cases the absorption bands were intensified and
MKA
Decoloring rate(%)

90 slightly shifted to lower wave numbers. Both spectra had


the characteristic absorption peak of the acid blue A at
2359.5 cm-1, which shows that the decolorant KA and
85 MKA had interacted with the acid blue dye.8,11
The DE fixing agent had a plurality of reactive epoxy
functional groups, which can interact with the amine and
80 hydroxyl groups under alkaline conditions. The DE fixing
agent also contained multiple quaternary ammonium
75
cationic groups. It was expected that DE would crosslink
keratin and impart cationic charges to the decolorant. The
20 30 40 50 60 70
introduction of the cationic groups to the protein molecules
Temperature(C) of the keratin decolorant increased the electrostatic
attraction between the keratin decolorant and anionic dye
Fig.3 Effect of treating temperature on the decoloring rate molecules,12 and thus facilitated the absorption and
flocculation of the dye stuff in decoloration process.

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Journal of Bioresources and Bioproducts. 2016, 1(1): 30-35 Peer-Reviewed

D SO3 Na + P O CH2 CH CH2 N(R)3Cl


OH

D SO3 P O CH2 CH CH2 N(R)3 + NaCl


OH

These chemical reactions, as well as the electrostatic


attraction, Van der Waals force and hydrogen bonds
between the decolorant and the anionic dye molecules
played important roles in the decoloration of the dyeing
wastewater with MKA.

3.2.2 TEM analyses


The KA decolorant particles shown in the transmission
electron microscopic (TEM) image in Figure 6a were in
separate granule form, while the MKA decolorant particles
were in cluster form (Figure 6b). The network structure of
the MKA decolorant provides further evidence for the
1-Acid Blue-A; 2-MKA sludge; 3-KA sludge; 4-.MKA; 5- KA
strong physical/chemical interaction between KA and DE.
Fig.5 The IR spectra of the decolorants and the decoloring sludge This also explains the improved decoloring performance of
MKA in treating the dyeing wastewater. The TEM image of
The chemical structural of DE: the sludge from the decoloring process with MKA (Figure 6
d) had more compact structure than that from the KA
process (Figure 6c), which explains the much faster
settlement of the flocs formed in the decoloring process
with MKA than with KA.

Its simplified form:

H2C CH CH2 N(R)3Cl


O

The reactions of DE with the hydroxyl and amine groups


of KA may be described as:

P NH2 + H2C CH CH2 N(R3)Cl P NH CH2 CH CH2 N(R3)Cl


OH
O

P OH + H2C CH CH2 N(R)3Cl P O CH2 CH CH2 N(R)3Cl


O
OH

The dye (Acid Blue A) contained sulfonate groups and


was an anionic dye. The reactions of MKA with the anionic
dye may be described as follows.

D SO3 Na + P NH CH2 CH CH2 N(R)3Cl


OH

Fig.6 TEM images of KA, MKA and the corresponding sludge


D SO3 P NH CH2 CH CH2 N(R)3 + NaCl samples from the decoloration processes of the dyeing wastewater
OH with KA or MKA

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Journal of Bioresources and Bioproducts. 2016, 1(1): 30-35 Peer-Reviewed

4. CONCLUSIONS central composite design. Coloration Technology, 2014.


130(3): p. 226-235.
Two poultry keratin-based decolorants (KA and MKA) 8. Asghar, A., A.A.A. Raman, and W.M.A.W. Daud,
were successfully prepared in the lab and evaluated in Advanced oxidation processes for in-situ production of
treating a dyeing wastewater synthesized with an acid blue- hydrogen peroxide/hydroxyl radical for textile
A dye. It was found that the modified keratin decolorant wastewater treatment: a review. Journal of Cleaner
MKA had a superior decoloring performance than the Production, 2015. 87: p. 826-838.
original keratin decolorant KA extracted from poultry 9. Chun, H. and W. Yizhong, Decolorization and
feather. The decoloring rate of the dyeing wastewater was biodegradability of photocatalytic treated azo dyes and
up to 90% with KA, and up to 92.5% with MKA, under the wool textile wastewater. Chemosphere, 1999. 39(12): p.
conditions in current study. It was also found that the KA 2107-2115.
was more effective in acidic conditions. While the MKA 10. Crini, G., NonConventional Adsorbents for Dye
performed better in a neutral to alkaline medium. The IR Removal. Green Chemistry for Dyes Removal from
and TEM results support the hypothesis that there were Wastewater: Research Trends and Applications, 2015:
strong physical/chemical interaction between the KA p. 359-407.
decolorant and the DE dye fixing agent. 11. Juang, R.-S., F.-C. Wu, and R.-L. Tseng,
Characterization and use of activated carbons prepared
ACKNOWLEDGEMENT from bagasses for liquid-phase adsorption. Colloids and
Surfaces A: Physicochemical and Engineering Aspects,
The authors gratefully acknowledge the financial support 2002. 201(1): p. 191-199.
from Science Foundation of Department of Shaanxi 12. Valix, M., W. Cheung, and G. McKay, Preparation of
Province (2014K10-25). We are also full of gratitude for activated carbon using low temperature carbonisation
the support provided by the Produce-learn-research project and physical activation of high ash raw bagasse for acid
of Yu Lin (2015CXY14-04). And thanks Ju Chen from dye adsorption. Chemosphere, 2004. 56(5): p. 493-501.
Polytechinique Montreal for her generous help. 13. Ranelovi, M., et al., Structural, textural and
adsorption characteristics of bentonite-based composite.
REFERENCE Microporous and Mesoporous Materials, 2014. 195: p.
67-74.
1. Mittal, A., L. Kurup, and J. Mittal, Freundlich and 14. Banat, F., S. Al-Asheh, and L. Al-Makhadmeh,
Langmuir adsorption isotherms and kinetics for the Evaluation of the use of raw and activated date pits as
removal of Tartrazine from aqueous solutions using hen potential adsorbents for dye containing waters. Process
feathers. Journal of hazardous materials, 2007. 146(1): Biochemistry, 2003. 39(2): p. 193-202.
p. 243-248. 15. ZHANG, Z., Q. KUANG, and X. JIA, Study on the
2. Xue, Z., H. Jinxin, and Z. Yizhen, Research progress of kinetics and thermodynamics of Pb2+, Cu2+, Cr3+,
the dyeing wastewater treatment technologies [J]. Cd2+, Ni2+ adsorption onto peanut hull. Ecology and
Journal of Chemical Industry & Engineering, 2009. 2: p. Environmental Sciences, 2010. 19(12): p. 2973-2977.
014. 16. Yan, L., et al., Feasibility of fly ash-based composite
3. Mittal, A., J. Mittal, and L. Kurup, Utilization of hen coagulant for coal washing wastewater treatment.
feathers for the adsorption of indigo carmine from Journal of hazardous materials, 2012. 203: p. 221-228.
simulated effluents. J. Environ. Prot. Sci, 2007. 1: p. 17. Agrahari, S. and N. Wadhwa, Degradation of chicken
92-100. feather a poultry waste product by keratinolytic bacteria
4. Rajkumar, D., B.J. Song, and J.G. Kim, isolated from dumping site at Ghazipur poultry
Electrochemical degradation of Reactive Blue 19 in processing plant. Int J Poult Sci, 2010. 9(5): p. 482-489.
chloride medium for the treatment of textile dyeing 18. Sun, P., Z.-T. Liu, and Z.-W. Liu, Chemically modified
wastewater with identification of intermediate chicken feather as sorbent for removing toxic
compounds. Dyes and pigments, 2007. 72(1): p. 1-7. chromium (VI) ions. Industrial & Engineering
5. Low, K., C. Lee, and S. Liew, Sorption of cadmium Chemistry Research, 2009. 48(14): p. 6882-6889.
and lead from aqueous solutions by spent grain. Process 19. Ghosh, A. and S.R. Collie, keratinous Materials as
Biochemistry, 2000. 36(1): p. 59-64. novel absorbent systems for toxic Pollutants. Defence
6. iban, M., M. Klanja, and B. krbi, Modified Science Journal, 2014. 64(3): p. 209-221.
softwood sawdust as adsorbent of heavy metal ions 20. Mittal, A., V. Thakur, and V. Gajbe, Evaluation of
from water. Journal of Hazardous Materials, 2006. adsorption characteristics of an anionic azo dye
136(2): p. 266-271. Brilliant Yellow onto hen feathers in aqueous solutions.
7. Kobya, M., et al., Treatment of textile dyeing Environmental Science and Pollution Research, 2012.
wastewater by electrocoagulation using Fe and Al 19(6): p. 2438-2447.
electrodes: optimisation of operating parameters using

www.Bioresources-Bioproducts.com 34
Journal of Bioresources and Bioproducts. 2016, 1(1): 30-35 Peer-Reviewed

21. Mittal, J., V. Thakur, and A. Mittal, Batch removal of 24. Beak, M.H., C.O. Ijagbemi, and D.S. Kim, Treatment
hazardous azo dye Bismark Brown R using waste of malachite green-containing wastewater using poultry
material hen feather. Ecological Engineering, 2013. 60: feathers as adsorbent. Journal of Environmental
p. 249-253. Science and Health Part A, 2009. 44(5): p. 536-542.
22. Sehgal, P., T. Sastry, and M. Kumar, Studies on 25. nl, N. and M. Ersoz, Adsorption characteristics of
solubilised keratins from poultry feathers. Leather Sci, heavy metal ions onto a low cost biopolymeric sorbent
1986. 33: p. 333. from aqueous solutions. Journal of Hazardous Materials,
23. Rivera-Torres, V., J. Noblet, and J. Van Milgen, 2006. 136(2): p. 272-280.
Changes in chemical composition in male turkeys 26. Wang, C., Practical techniques of Biochemistry and
during growth. Poultry science, 2011. 90(1): p. 68-74. Molecular Biology. 2003: Hubei Science and
Technology Press.

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