UNHAIRING,LIMIMG,DELIMING

& BATING

SUBMITTED TO : DR. OMER JAVID

SUBMITTED BY : UM-E-KALSOOM
ROLL NO : 01
COURSE TITLE : INDUSTRIAL PROCESS CHEMISTRY
COURSE CODE : CHEM-534
 LEATHER PROCESSING

UNHAIRING:
The aim of unhairing (depilation) and liming is to remove the hair, epidermis and to some degree
the inter-fibrillary proteins, and to prepare the hide for removal of loose flesh and fat by the
fleshing process.
The removal of the epidermis system, ie the hair, wool, or bristles, and pigmentry matter, is
achieved with the aid of depilatory agent. The epidermal system consists mainly of protein keratin,
which is different from collagen of the fibre structure in many important aspects. The most
important is that it includes sulphur-containing amino acid cystine and strong cross-link are formed
by sulphur. Oxidizing and reducing agents readily attack this link and thus form the main
depilatory agents. It is also known that certain proteolytic enzymes attack keratin, and other
enzymes attack the substrate in which keratin is found. The process of depilation can be carried
either as a separate process prior to liming, or the depilation and liming effects are combined into
a single simultaneous operation .
Methods of hair removing can be divided into two groups:
(i) methods based on destruction or modification of the epidermis tissue surrounding the hair, so
that it can be loosened and removed, and
(ii) methods in which the hair itself is attacked and its structure is destroyed (use of alkali Ca(OH)2
or NaOH and Na2S).

Enzyme
Base(NaOH)
Reducing agent

Sulphide crosslinking of cystin in keratin of hair break into cysteine on action of enzyme or base and reducing agent.

1. Enzyme unhairing:
Enzyme preparations that preferentially attack the keratin cells at base of hair roots or epidermis
are available. Enzymes are specific in their action and are active within a narrow range of
temperature and pH. Since optimum temperature for unhairing enzymes are close to those for
bacterial growth, it is essential to use some disinfectant to prevent bacterial putrefaction. Enzyme
unhairing has been used commercially for many years on goatskins and is now being seriously
considered as other types of unhairing material, in order to eliminate the nuisance of sulphide in
tannery effluent disposal. Enzyme preparations are available which preferentially attack the young
keratin cells at the base of hair roots or epidermis. They give very clean flat grain. The soaked
skins are paddled or drained in a water float 28-30°C with 1-2 % (base on skin weight) of specific
enzyme preparation at pH 8-9 for 4 hours. Adding 0.2 % sodium chlorite may prevent bacterial
contamination.
 a. soaked sheepskin, b unhairing enzyme manually applied as paste on flesh side, and c unhaired sheepskin after 6 h
2. Paint unhairing:
The washed or soaked skins are piled to drain off the surplus water and then painted, or sprayed
on the flesh side with a "paint" which may be made from approximately 50 parts hydrated lime,
50 parts water and 5-2- parts sodium sulphide (fused). The sodium sulphide and lime dissolve in
the water and penetrate through the corium and dissolve the keratin cells, which enclose the hair
roots. The process may take 5-12 hours depending on thickness of the skin, tightness of fiber
structure, and amount of fat and flesh left on the skin. Green fleshing before painting can be good.
After washing and further treatment in lime liquor, the skins are sorted into group according to
weight and size prior to tanning. Mechanical unhairing and re-liming are necessary.
3. Pulping techniques:
An alternative method of depilation is complete immersion of the stock in sulphide solution, with
or without addition of lime. The sodium sulphide treatment my be incorporated into the general
liming procedure; alternatively it may be short sharp pretreatment followed by washing and further
plumping in alkaline liquors. For calf and wet salted hides the best method is to apply the sodium
sulphide during liming, but for sun-dried hide and goatskins sharp pretreatment is preferable. For
calf and wet salted hides, between 3% and 4% of sulphide (62%) on the weight of stock is used
for a period of 24 – 48 hours. With total float 400% water on pelt weight, the effective
concentration of sodium sulphide is 0.75 – 1 % by volume. In sun dried hides and goat skins it
may be increased to 2.5% by volume to similar periods, or increased up to 5% for solution
treatments of one or two hours duration.
4. Oxidation unhairing:
As has been previously stated, the cystine cross link in keratin can be broken by oxidizing agents,
and the use of sodium chlorite plus hydrogen peroxide has been investigated in Germany. The
advantages are an alkali sulphide free effluent and firm clear white pelt.

LIMING:
Liming is a process in which the hide or skin are immersed in solutions of lime, to which sodium
sulphide and some enzymes maybe added. The aim of liming is primary to loosen the hair, and
destroy epidermis; at the same time the fibrous structure becomes swollen plumped with a partial
separation of the fibre. Methods of liming vary both in the chemicals used and in procedures.
Unhairing and liming can be carried out simultaneously by immersing the skins in the lime and
water mixture, often with the addition of other chemicals known as sharpeners, e.g., sodium
sulphide.
Objectives of lime:
The objectives of lime as reported by Sarkar (1981) are as follow:
(i) Liming removes the epidermis together with the hair and are thus separated from the corium or
true skin.
(ii) Dissolution of the cementing substance of the corium. This removal of cementing substance
makes the final leather pliable and soft.
(iii) Splitting up of the fibre bundles into individual fibres and also splitting up of individual fibres
into fibrils: this is necessary for satisfactory tannage. By splitting up and consequent separation of
the individual fibres and fibrils their surface all round them is exposed to the action of the tan
liquor from which the fibres and fibrils absorb tannin and become converted into leather. The
opening up of the fibres is also due partially to rupture of the elastin bands holding them together.

(iv) Saponification of grease: Hide and skins contain natural fat. This fat is saponifided and is
converted into lime soap by action of lime. The lime soap is not removed by washing the limed
hides. It is mechanically removed by scudding. Unless this natural fat is removed the final leather
will have patches of fat (known as fat spue) in grain and a light and uniform finished surface will
not be obtained.

(v) Swelling and plumping

1. Straight lime liquors:
Water dissolves a relatively small amount of lime. Approximately 1/8 parts lime per 100 parts
water gives a clear solution. And lime is unusual because it dissolves less with increasing
temperature. The alkali solution causes the collagen fiber of the corium to swell by absorbing more
water. The hair and epidermis swell to a lesser extent, and the interfibrillary proteins become more
soluble and are loosened from the fibre structure. These effects occur with all soluble alkalis and
the stronger the alkalinity, the greater the effect. As lime has a limited solubility compared with
other alkalis, it is considered safe for hides and skins.
The alkali modifies and breaks down the collagen fibre of the skin, but much more slowly than the
keratin. Therefore, if skins are limed too long they suffer from thinness, looseness and weakness.
For skins that have already been unhaired; straight lime liquors of 2 parts lime per 100 parts water
are used. The skins are immersed in about 5-6 times their weight of this liquor, for 12-60 hours at
13-18º C. This quantity of lime is in excess of that needed to get the necessary alkalinity (pH 12-
13), plus the lime, which it’s chemically fixed to the hide. The surplus may be spent by adsorption
on grease, loose protein or by carbonation. It also makes handling of the hides slippery. However
this excess lime often requires expensive effluent treatment.
2. Paddles liming:
The use of paddles for liming is wildly practiced, it gives well overall results. A shallow running
paddle is preferred and it should be turned for only one or two minutes hourly, this method is
more rapid than pit liming and labour costs are lower.

DELIMING & BATING:

During the liming and bating processes the swollen collagen structure is dramatically opened up
and cleaned from unwanted substances; solid lime is still present in the interstitial spaces of the
fibres and the pH is equivalent in all the cross section (around 12.5- 13.0). The aim of the deliming
stage is to solubilise residual lime and deflate the structure by lowering the pH down to 8.5-9.0,
ideal for the enzymatic digestion that will occur during the next bating step.
By treatment. with ammonium salts:
Deliming is safely achieved, for instance, by treatment. with ammonium salts (chloride or
sulphate) that have an appreciable buffering effect at the pH of interest and quickly penetrate into
the cross-section of the pelts.
2NH4Cl + Ca (OH)2 ------------> CaCl2 + 2NH3 + 2H2O
(NH4)2SO4 + Ca (OH)2 ------------> CaSO4 + 2NH3 + 2H2O
3Ca (OH)2 + 2H3BO3 ------------> Ca3(BO3)2 +6H2O
However, the employment of ammonium sulphate salts has two important drawbacks. In the first
place, ammoniacal nitrogen concentration in the effluent should be limited due to its toxicity to
aquatic life. Secondly, sulphate anions may form sparingly soluble CaSO4 by reaction with
calcium cations or limeblast left over from the previous liming step. In situ formed calcium
sulphate crystals produce a distortion of the fibre structure and negatively affects the quality of
dyeing. On the other hand, chloride ions have a greater lyotropic effect and can further open up
the collagenous structure.
CO2-deliming:
CO2-deliming is an alternative to conventional ammonium salt deliming. The mechanism of CO2-
deliming is simple. By dissolving carbon dioxide in water, it partly converts to carbonic acid. The
carbonic acid species acidify the float and remove calcium. the salt-free CO2-deliming enables an
accelerated deliming of animal hides without any ammonium nitrogen emission. In combination
with the CO2-intensified low chromium and sulfate emission tanning, CO2-deliming has high
potential to enable environmental friendly industrial beamhouse and tanning operations.
Bating:
This process helps to make a finished leather which is smooth, flat, flexible, soft and stretchy. It
involves the addition of proteolytic enzymes. These proteolytic enzymes open the fibrous structure
of the pelt to make it softer. Bating also removes the remaining lime in the pelt. Scuds are loosened
and other unwanted proteins are removed and this increase the degree of stretch. Bating de-swells
swollen pelts and prepares pelt for tanning. The process is performed at optimum temperatures for
the enzymes 35-40 ˚C. pH should range in the interval 8.0-9.0. Bating is stopped by lowering pH
and temperature when the desired degree of softening is reached.
REFERENCES:

 Ramesh, R. R., Muralidharan, V., & Palanivel, S. (2018). Preparation and application of
unhairing enzyme using solid wastes from the leather industry—an attempt toward
internalization of solid wastes within the leather industry. Environmental Science and
Pollution Research, 25(3), 2121-2136.
 Mohamed, K. (2003). Recycling of unhairing-liming solution. M. Sc. University of
Khartuom. Faculty of Animal Production.
 Beghetto, V., Zancanaro, A., Scrivanti, A., Matteoli, U., & Pozza, G. (2013). The leather
industry: a chemistry insight Part I: an overview of the industrial process. Sciences At
Ca'Foscari, (1| 2013).
 Maina, P., Ollengo, M. A., & Nthiga, E. W. (2019). Trends in leather processing: A
Review.
 Prokein, M., Chrobot, A., Renner, M., & Weidner, E. (2020). Free of salt high-pressure
deliming of animal hides. Environmental Science and Pollution Research, 27(28), 35567-
35579.