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Journal of Scientific & Industrial Research J SCI IND RES VOL 66 SEPTEMBER 2007

710
Vol. 66, September 2007, pp.710-715

Industrial applications of keratins A review


R Karthikeyan, S Balaji and P K Sehgal*

Bio Products Laboratory, Central Leather Research Institute (CLRI), Adyar, Chennai 600 020

Received 20 October 2006; revised 02 April 2007; accepted 16 April 2007

Keratin, a fibrous protein forming main structural constituent of feather, hair, wool, horn, hoof etc., is abundantly available
as a by-product from poultry, slaughterhouse, tanning and fur processing industry. Keratins though find applications in food,
pharmaceutical, cosmetic and fertilizer industry, considerable amount of these products is wasted repeatedly. Keratins are
difficult to degradation and their disposal leads to environmental problems. Research is being done globally to utilize these
wastes. Keratin hydrolysates find potential application in leather tanning industry.

Keywords: Fibrous protein, Keratin, Leather tanning industry

Introduction Feather (90% keratin) is used as animal feedstuff in the


India has a large livestock population, which produce form of feather meal18-21. Acid, alkali or enzymes
annually: goatskins, 82; sheep skins, 30; cattle hides, 23; hydrolyze keratin and hydrolysates have number of
and buffalo hides, 28 million1. World production of bovine applications22-27. Cosmetics based on keratin preparations
and ovine skins during 2000 was 1,192 million pieces2. have been reported for the treatment of human hair and
Feathers constitute up to 8-10% of total chicken weight skin28-33. Keratinous materials are used as additive in
and it is estimated that several million tons of feathers the preparation of concrete and ceramics34,35. Sulfur
are produced annually. Bovine and ovine hair is obtained bound amino acid solution is used to prepare organic
as a by-product from the tanneries during hair-saving fertilizer, which enhances plant metabolism36. Fire
unhairing process and it is estimated that about 5% of fighting composition is prepared from a solution of organic
dry hair is recovered based on the raw hide weight3,4. colloid derived from the hydrolysis of horns and hoofs37.
But still most of the tanneries are following hair-burning Oxidization of keratinous materials cleaves and oxidizes
process, which destroy the hair completely and contribute some of the disulfide linkages to form water-soluble
high amount of COD, BOD, TDS etc., to the effluent5-8. peptides and this material is used as a wound healing
Microbial proteases offer potential solution to remove agent38. An attempt has been made for the first time in
the hair completely from the raw skins9-12. Central Leather Research Institute (CLRI), Chennai to
utilize keratin wastes successfully in leather tanning
An enormous quantity of keratins in the form of hairs,
processes39,40,92-95,102,103. Successful attempts have been
feathers, horns and hoofs are wasted each year13.
made to convert keratinous wastes like poultry feathers,
Keratins are broadly classified as hard (5% sulfur) and
animal hair, horns and hoofs into keratin hydrolysate (KH)
soft (1% sulfur) keratins. Keratin is mechanically robust
by controlled alkali hydrolysis. KH has been successfully
and chemically unreactive due to tight packing of protein
employed in leather processing particularly during chrome
chain in the form of -helix or -sheet into a super coiled
tanning and rechroming operations to enhance the uptake
polypeptide chain crosslinked with disulfide bonds. In
of chromium salt by leather. KH is also successfully
horns, hoofs and hair, keratin is in the form of -keratin,
employed in filling cum retanning operation in leather
whereas in feathers it is in the form of -keratin14-17.
processing. The process of KH preparation was upscaled
*Author for correspondence in CLRI pilot plant and technology was transferred to a
E-mail: sehgal_pk@yahoo.co.in company for commercial exploitation.
KARTHIKEYAN et al : INDUSTRIAL APPLICATIONS OF KERATINS A REVIEW 711

Fig. 1Rendering plant located in Bioproducts Pilot Plant (CLRI)

Recently, authors at CLRI subjected raw horns and to losses of essential amino acids (lysine, methionine and
hoofs of slaughtered cattle and buffaloes collected from tryptophan) and causes the formation of non-nutritive
the local slaughterhouse at Chennai to high steam pressure amino acids48,49 (lysinoalanine, lanthionine, etc). Merits
(40 psi) in a rendering plant (FMC, Australia) for 3 h and demerits of alkali versus acid hydrolysis50 have been
(raw horn: water ratio: 100:30 w/v). The resulting material reported.
(Fig. 1) was dried in a dryer (BHL, Ahmedabad) and
Microbial Treatment
pulverized in pulverizer (FMC, Australia) to get horn meal
Microbial conversion of keratin wastes is a potential
(60%).
technique for degradation and utilization of keratin as a
hydrolysate in terms of cost-effective and
Approaches to Convert Keratin Protein into
environmentally benign processing 51-54. Presence of
Keratin Hydrolysate
disulfide bonds in keratins hinders their degradation by
Hydrothermal Treatment
proteolytic enzymes55-58 (trypsin, pepsin and papain),
Hydrothermal process usually employs high
which can be efficiently degraded by soil
steam pressure (10-15 psi) and/or high temperature
microorganisms59,60, actinomycetes, bacteria and fungi
(80-140C) in the presence of acid41 (HCl, H 2SO4,
by synthesis of keratinolytic proteases-keratinases61-71.
HCOOH etc.) or alkali42,43 (NaOH, KOH, Na 2CO3,
Keratinases are robust enzymes with a wide temperature
K2CO3, NaSiO2 etc.). Treatment with acid or alkali at
and pH activity range and are largely serine or
the boiling temperature for over 2-3 h opens disulfide
metalloproteases. Keratinases attack keratin residues72,73
linkages of keratin and yields water soluble polypeptides,
(feather, wool, steam hydrolyzed horn powder etc.) and
oligopeptides or even amino acids44-46. The effect of
convert them into degradative and cost effective
change in pressure, temperature, chemicals and pH
products. Application of keratinase-producing
during thermo-chemical treatment has been studied to
microorganisms is being explored in feed, fertilizer,
analyze the nutritional value of feather meal18,19,47. Main
detergent, leather and pharmaceutical industries where
drawback in hydrothermal process is that hydrolysis may
there is great need for materials derived from alternative
result in partial or even complete destruction of amino
raw materials specifically animal wastes derived from
acids, which contain peptides with varying molecular
meat processing plants, poultry units, marine and slaughter
weight and nutritional improvement. These methods leads
houses.
712 J SCI IND RES VOL 66 SEPTEMBER 2007

Applications of Keratin Hydrolysate in Leather based syntans, polymers of various types, such as
Processing Industry acrylates, urethanes and melamine resins98-100. Most of
Keratin Hydrolysate in Tanning these retanning agents are still suspected in their
In leather processing, tanning converts putrescible skin application due to release of high COD, TDS, free phenol
collagen into stable leather74. At present, chromium sulfate and free formaldehyde. Protein based retanning agents
is widely used world over75 as a tanning agent due to its offer better prospects as they fill loose areas such as
versatile nature to produce different types of leathers belly, flanks and poor substance materials without
with required properties and uses76,77. But this tanning contributing much load to tannery effluent. Chicken
system is under increased pressure from the green groups feathers and hairs can be converted into water soluble
due to its polluting and toxic nature78-88. One of the peptides using lime and sodium hydroxide at elevated
constraints reported in conventional chrome tanning temperature and pressure in an autoclave and hydrolysate
practices is of the exhaustion of Cr in the tanning bath, has been successfully employed as a retanning-cum-filling
which does not exceed 60-65% in commercial agent in leather processing102,103. KH has selective filling
tanneries89,90. Due to this, very large quantity of chromium action, upgrades the poor substance skins and it can be
is discharged into the effluent causing environmental used along with other retanning agents. Besides, the use
pollution. The discharge limit of chromium in the waste of KH in retanning process influences lubricating effect
stream should not exceed 2.0 ppm in most of the that enhances grain smoothness and softness
countries91 necessitating treatment of discharge in characteristics of leathers.
Common Effluent Treatment Plant (CETP) before it let
out for usage. This leads to increase in cost of leather Conclusions
processed in tanneries. Hence, CLRI studies conducted This review provides base material towards the
to improve exhaustion of Cr in tanning bath by using KH establishment of environmentally friendly technology for
prepared from poultry feathers and tannery hairs92-94. the treatment of keratin wastes and throws light on
KH (2-3%) was used in chrome tanning (based on skin conversion of non-edible slaughterhouse and tannery
weight) and the exhaustion of chromium in tanning bath waste (hair, feather, horn and wool) into value-added
could be more than 90%. KH prepared from horn meal products. The use of KH in leather processing has two-
by acid hydrolysis (using HCl) and microbial hydrolysis fold advantage. Initially, bio waste is converted into KH,
(using Bacillus subtilis strain) could also be successfully which is used as exhaustive aid in chrome tanning to
employed in chrome tanning process to improve reduce the pollution load, and finally it is used as filler-
exhaustion95. The reaction of water-soluble keratin cum-retanning agent to replace existing retanning-cum-
peptides in chrome tanning involves two-step reaction. filling material used by the leather industry.
Initially, low molecular weight peptides react with
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