Chapter -1

Leather Industry
Introduction
• The leather industry is an integral part of our agricultur
al economy. The largest industry, the meat industry, has
the hides and skins of the slaughtered animals as one of i
ts by-products.
• The leather industry is a chemical processing industry.
• Processing is largely carried out in a water medium and
as such, there is potential for a number of environmental
concerns.
• The first leather was produced in pre-historic times.
• It was discovered quite by accident that a skin
which has been soaked for some time in water
which had been infused with the bark of trees d
id not rot or dry up like other skins, but remain
ed soft and lasted for a long time.
• The new material had many applications: it wa
s useful for clothing, foot protection, for tying a
nd binding and for tool making.
• This discovery of the secret of making leather, like tha
t of making fire, was one of the more important in earl
y human history.
• From the initial accidental discovery until quite recen
t times, leather-making has remained a craft industry.
• However, as we obtain a better understanding of the c
hemistry of collagen, keratin and the various tanning
materials used, the results obtained are becoming mor
e predictable and more controllable.
• Leather-making is now a scientifically based industry,
but still retains some of the charm and mystery of the
original craft.
• As such, it holds a constant challenge for the chemist wh
o, through research and an understanding of the underlyin
g principles, can control the quality of the final product to
a much greater degree.
Animals skin
 Animal skin that has been processed to retain its flexibilit
y, toughness, and waterproof nature is known as leather,
and the leather industry is largest industry throughout the
world.
 Leather is made by processing the skins of animals slaugh
tered in the meat processing industry, and hence the majori
ty of skins tanned are those of sheep and cattle.
 The use of hides and skins, tanned or untanned, as useful a
rticles has been with us for thousands of years.
 The Oxford Dictionary refers to leather as "material made
from the hide or skin of an animal by tanning".
 Tanning, in simple terms, refers to the treatment of raw hid
es and skins with tanning substances to render the materia
l immune to bacterial attack, i.e. to produce leather.
 Additional changes introduced in the process of tanning a
re secondary and are related to the tanning and retanning c
hemicals used.
 There are hundreds of different leather types and tens of t
housands of different chemicals to choose from when pro
ducing these leathers.
 The most important chemicals in the tanning process are t
he tanning agents as they define the process of leather ma
nufacture as a whole.
 In this modern day and age, tanners will choose tanning c
hemicals based on price, convenience of use, environme
ntal issues, and by matching the physical and aesthetic pr
operties introduced by the tanning chemicals to the desir
ed leather properties of the end product.
 Preparation of skin for tanning
 The leather manufacturing process is divided into three
sub-processes: preparatory stages, tanning and crusting.
 All true leathers will undergo these sub-processes.
 A further sub-process, surface coating may be added into t
he sequence.
 The list of operations that leathers undergo vary with the t
ype of leather.
Preparatory stages
 The preparatory stages are when the hide/skin is prepared
for tanning.
 During the preparatory stages many of the unwanted raw
skin components are removed.
 Many options for pretreatment of the skin exist.
 Not all of the options may be performed.
 Preparatory stages may include:
 Preservation- the hide/skin is treated with a m
ethod which renders it temporarily unputrescibl
e.
 Soaking - water for purposes of washing or rehy
dration is reintroduced.
 Liming - unwanted proteins and "opening up" is
achieved.
 Unhairing - the majority of hair is removed.
 Fleshing - subcutaneous material is removed.
 Splitting - the hide/skin is cut into two or mo
re horizontal layers.
 Reliming - the hide/skin is further treated to
 Deliming - liming and unhairing chemicals are removed
from the pelt.
 Bating - proteolytic proteins are introduced to the skin to
remove further proteins and to assist with softening of the
pelt.
 Degreasing - natural fats/oils are stripped or as much as is
possible from the hide/skin.
 Frizing - physical removal of the fat layer inside the skin.
Also similar to Slicking.
 Bleaching - chemical modification of dark pigments to
yield a lighter coloured pelt.
 Pickling - lowering of the pH value to the acidic region.
Must be done in the presence of salts. Pickling is normally
done to help with the penetration of certain tanning agents,
e.g., chromium (and other metals), aldehydic and some
polymeric tanning agents.
 Depickling - raising of the pH out of the acidic region to as
sist with penetration of certain tanning agents.
Tanning
 Tanning is the process that converts the protein of the raw h
ide or skin into a stable material which will not putrefy and
is suitable for a wide variety of end applications.
 The principal difference between raw hides and tanned hide
s is that raw hides dry out to form a hard inflexible material
that can putrefy when re-wetted (wetted back), while tanne
d material dries out to a flexible form that does not become
putrid when wetted back.
 A large number of different tanning methods and materials
can be used; the choice is ultimately dependent on the end
application of the leather.
 The most commonly used tanning material is chromium, whi
ch leaves the leather, once tanned, a pale blue colour (due to t
he chromium), this product is commonly called “wet blue”.
 The acidity of hides once they have finished pick
ling will typically be between pH of 2.8-3.2.
 At this point the hides are loaded in a drum and
immersed in a float containing the tanning liquo
r.
 The hides are allowed to soak (while the drum slo
wly rotates about its axle) and the tanning liquo
r slowly penetrates through the full substance of
the hide.
 Regular checks will be made to see the penetration by cutting
the cross section of a hide and observing the degree of penetra
tion.
 The pH of the leather when chrome tanned would typically finish
Crusting:
• Crusting is when the hide/skin is thinned, retanned and lubri
cated.
• Often a coloring operation is included in the crusting sub-pr
ocess.
• The chemicals added during crusting have to be fixed in plac
e.
• The culmination of the crusting sub-process is the drying and
softening operations.
 Crusting may include the following operations:
• wetting back - semi-processed leather is rehydrated.
• sammying -Chromium-tanned leather contains between 90-10
0% of water, but in order for the leather to be adequately split
and shaved, it must not contain more than 50-55%. 45-55%(m
/m) water is squeezed out the leather.
• This operation is carried out making the leather go
through two rollers covered with filter nets.
• splitting - the leather is split into one or more horiz
ontal layers.
• shaving -The leather is passed through a cutting m
achine subjecting it to a knife that adjusts its final t
hickness, generating waste called shavings. Or the
leather is thinned using a machine which cuts leath
er fibres off.
• neutralisation - the pH of the leather is adjusted to
a value between 4.5 and 6.5.
• retanning - additional tanning agents are added to impart pr
operties.
• dyeing - the leather is coloured.
• fatliquoring - fats/oils and waxes are fixed to the leather fibr
es.
• filling - heavy/dense chemicals that make the leather harder
and heavier are added.
• stuffing - fats/oils and waxes are added between the fibres.
• stripping - superficially fixed tannins are removed.
• whitening - the colour of the leather is lightened.
• fixation - all unbound chemicals are chemically bonded/trap
ped or removed from the leather
• setting - area, grain flatness are imparted and excess water r
emoved.
• drying - the leather is dried to various moisture levels (commo
nly 14-25%).
• conditioning - water is added to the leather to a level of 18-28
%.
• softening - physical softening of the leather by separating the l
eather fibres.
• buffing - abrasion of the surfaces of the leather to reduce nap o
r grain defects.
 Surface coating:
• For some leathers a surface coating is applied. Tanners refer to
this as finishing. Finishing operations may include:
• Oiling, brushing, padding impregnation , buffing ,
spraying , roller coating
• curtain coating , polishing , plating , embossing
, ironing , combing (hair-on),glazing
 Vegetable tanning
 Vegetable tanning is a traditional craft process that tanneri
es have handed down from father to son for over 200 year
s, using both ancient recipes and state-of-the-art technolo
gy.
 With vegetable tanned products, you can really see the ski
ll that has gone into producing them.
 The transformation from raw hides into a material that wil
l last a long time is a process that happens slowly in wood
en drums, while respecting the environment.
 It is an astonishing process based on the use of natural tan
nins, on modern technologies and machineries but mainly,
on the slow passage of time.
 Among the various tanning methods, the vegetable
tanning is the most classical, the most traditional, t
he most recognizable, the only one able to give lea
ther unique characteristics, the most natural and th
e most environmental-friendly.
 It is able to join comfort and look, fashion and trad
ition, uniqueness and versatility in the product.
 Raw materials used for vegetable tanning are 
natural tannins, available in liquid or powder for
m, obtained from different part of plants including
woods, barks, fruits, fruit pods and leaves.
 Advantages of vegetable tanning
 Vegetable tanning is environmentally friendly; meaning any
leather products that have been vegetable tanned can be recy
cled.
 Vegetable tanning is an age old tradition, so most tanneries h
ave very skilled craftsmen producing and dyeing the leather.
 Due to the natural tannins used, vegetable tanned products ar
e unique and have their own life, they are not the same for th
eir entire life, but they change, continuously, for the better.
 The colours that vegetable tanning produces are rich and wa
rm tones that look completely natural.
 Vegetable tanned leathers are more valuable and thus sold at
a higher average price compared to chrome tanned leathers.
 Disadvantages of vegetable tanning
 The average process time of vegetable tanning is q
uite similar to chrome tanned leather but it can tak
e up to 60 days to produce sole leather.
 It can stain easily in the presence of iron.
 Products that have been vegetable tanned are more
expensive.
 They require much more skill to tan the hides, this
means they are of better quality.
 Direct heat can cause vegetable tanned products to
shrink or crack.
 Chrome tanning
 The most common tanning method in the world.
 Today, 80-90% of leathers in the world are tanned by chrom
e tanning.
 Chrome tanning uses a solution of chemicals, acids and salt
s (including chromium sulphate) to tan the hide.
 It’s a very quick process, taking about a day to produce a pi
ece of tanned leather.
 First hide are limed to remove hair and then are “pickled” b
y being left in the acid salt mixture, before being placed in t
he chromium sulphate.
 All hides then come out looking light blue (known as “wet
blue”).
 About 2% of it has been used for the pro
duction of chromium sales, such as chrom
ium sulphate, for the making of leather
tanning materials but also for the produ
ction of dyestuffs and plastics.
 The most important chrome deposits are f
ound in South Africa accounting for 33%
of production, while India and Kazakhsta
n provided 20% and 17% respectively.
 Brazil, Finland, Oman, Russia, and Turke
y together contributed a further 21%, wh
ile some 12 smaller producer countries b
rought the balance of 9%.
 Main advantages of chrome tanning
• Quick and easy to produce, usually only taking up to
a day.
• Water can roll off the surface easily with appropriate
retanning and finishing processes.
• Soft and supple to the touch.
• It is possible to obtain leather with a stable colour.
• It is cheaper to buy than vegetable tanned leather, w
hich means it is also easier to find.
• It has a high degree of thermal resistance.
Disadvantages of chrome tanning
• Chrome tanning is very bad for the environment.

• It’s produced with little craftsmanship and very

often mass produced.
• It doesn’t wear well with time.
• Chrome tanning often smells of chemicals.
• It doesn’t appear (neither is it) very natural.

• Lacks of charm and warmth.

Trimming salted hides
Pickled hides
Trimming pickled hide
s
Spent tanning fluid inside a tanning drum
A tanning drum in operation.
Curing tanned hid
es
 How tanning works
• Animal skins are made up of protein called collagen (amo
ng other things).
• This protein is readily degraded by bacteria and fungi.
• When tannins bond to the collagen, the cross linked fibers
are no longer susceptible to attack.
• The tannin must effectively crosslink the protein, but mus
t also have desirable color properties and meet many other
requirements.
 Tanning of hides:
 Hides are usually salted to prevent decomposition. The hide
s are first soaked in lime (or enzymes) to remove hair (depil
atories).
 The proper concentration of tannin solution must be used be
cause if it is too concentrated, it seals the outside of the hide
and the inside portions don't get tanned.
 After tanning for an appropriate period, the hides are was
hed, dried and then treated with oil or grease for softness.
 The leather is finished and coated with a layer of gum, w
ax, or resin.
 About 15% of all tanning in the U.S. is initially carried o
ut with vegetable tanning.
 Almost all thick leather products are still vegetable tanne
d. Shoe soles, brief cases, luggage, and belts are made in
this manner.
 On the other hand, shoe uppers, are tanned with chrome a
lum.
 However, most of these inorganically tanned products are
later retanned with vegetable tannins.
 Generally, Animal skins are converted to leather in an eig
ht step process as follows:
Step 1 - Unhairing
 The animal skins are steeped in an alkali solution that breaks d
own the structure of the hair at its weakest point (the root) and
so removes the hair.
 The keratin of hair and wool is subject to attack by alkali, whi
ch will break (by hydrolysis).
 The sulphur-sulphur bond in the cystine linkage of the keratin.
 The hair is attacked first at the root, where it is in its immature
form.
 After a certain time of being steeped in a solution of alkali (so
dium or calcium hydroxide) and a reducing agent, normally so
dium sulphide, the hair roots are dissolved, and the hair may b
e removed and saved.
 In the processing of sheep and lambskins, the solution of
alkali and sulphide is applied on the inside of the skin, all
owing the solution to penetrate through the skins, attacki
ng the wool roots, which can then be removed by 'pulling'
them from the skin.
Step 2 - Liming
 The hairless skin is immersed in a solution of alkali and sul
phide to complete the removal of the hair and to alter the pr
operties of the skin protein (collagen).
 The collagen becomes chemically modified and swells, lea
ving a more open structure.
 The process of liming is a combination of chemical and physi
cal action on the skin structure.
 The chemicals involved are similar to those in the unhairing
operation.
 A solution of lime and sodium sulphide is used and the
skins are immersed in this solution for whatever time i
s necessary to produce the desired effects.
 The process of unhairing is taken to completion during
the liming process, and there is appreciable modificati
on of the collagen due to the action of alkali.
Skin protein (collagen) alkali →
1) Hydrolysis of amide groups
2) Modification of guanide groups
3) Hydrolysis of keto-imide links in protein chains
4) Swelling
 Step 3 - Deliming and Bateing
 The skin structure is then opened further by treatment with en
zymes, and further unwanted material is removed.
 After the strong alkaline action, the skin structure is further op
ened up during the deliming and bateing process.
 Bateing is an enzyme digestion process which continues the cl
eaning up process begun by the alkaline action.
 Bateing is carried out at pH 9-10.
 This is achieved by treatment with acid salts (ammonium chlo
ride or ammonium sulphate) or carbon dioxide until the desire
d pH is reached.
 Hydrolysis is continued by the enzyme process and further dis
solution of unwanted material occurs.
 The main fibrous network is then cleaned up and the swelling
is reduced.
 Step 4 - Pickling
 The skins are then treated with acid to preserve them for up to tw
o years.
 The main acidification process is that of pickling.
 The skins are agitated in a solution of salt and sulphuric acid unti
l they are at or near equilibrium at a pH value of 3.0 - 3.5.
Step 5 – Tanning (the treatment process
- tanning )
 This is the most chemically complex step.
 During tanning, the skin structure is stabilised in its open form by r
eplacing some of the collagen with complex ions of chromium.
 Depending on the compounds used, the colour and texture of the le
ather changes.
 When leather has been tanned it is able to 'breathe' and to withstand
100 oC boiling water, as well as being much more flexible than an u
ntreated dead skin.
 Step 6-Neutralising, Dyeing and Fat Liquoring
After tannage, leather must be neutralized to
remove unwanted acids to prevent deterioration
during the drying process, and to prepare the
leather for the next stages in processing:
Dyeing and fat liquoring.
Neutralising is often carried out using mild a
lkalis which have some effect on the chromium co
mplex (sodium formate is a good example).
Next is dyeing, using a variety of dyestuff ty
pes. Commercial dyes are essentially mixtures o
f chemical compounds which can be fixed (combine
d) to the material to be dyed and which have app
reciable resonance within the molecule giving co
 The leather is then treated with alkali to neutralize it and s
o prevent deteroration, and then dyed.
 This involves fixing a variety of compounds onto the chro
mium, as that is the most reactive site present.
 Once the leather is dyed, it is treated with reactive oils tha
t attach themselves to the fibrous structure, improving sup
pleness and flexibility.
 Its colour comes from the presence of the hydroxide grou
p in conjunction with the azo group, allowing a high degr
ee of resonance. It can be fixed to the material to be dyed
by means of the sulphonic acid group.
 In chrome tanned leathers the most reactive sites are the c
hromium nuclei, and these form the main points of fixatio
n for dyestuffs.
 As with other processes, the main factors controlli
ng dyeing are the physical one of locating the dye
in the required position within the leather structur
e and the chemical one of controlling the conditio
ns so that reasonable penetration and fixation are
achieved.
 A wide range of dyes are used in leather processin
g and some examples are:Direct dyes, Acid dye
s, Pre- metallized dyes.
 Step 7 - Drying
• Water is removed from the leather, and its chemical prop
erties stabilised.
• Vacuum drying: the leather is spread out on a heated hori
zontal plate, the machine’s airtight hood is placed over th
e leather and a strong vacuum is applied to quickly remo
ve moisture from the leather.
• The drying duration depends on the thickness of the leat
her and will take several minutes.
• Currently, this is the most commonly used method.
 Figure 1:Vacuum drying.
• Finally, as water is removed from the system, the
chemical condition is stabilised and the final properties
of the leather are determined.
 Step 8 – Finishing
 The main purpose of finishing is to provide different ty
pes of leather with characteristics that satisfy the requir
ements of a continuously evolving global market.
 These characteristics include the following: Colour,
brightness, matting, feel, softness, water r
esistance, special physical properties.
 Finishing consists of applying a surface coa
ting - pigments or dyes bound in an organic
(acrylic, butadiene or polyurethane) or prot
ein (casein) medium.
 This enhances the natural qualities of the s
kin and covers such defects as scars, horn d
amage, seed scars etc., as may be present.
 In the case of suede leather, the suede is bu
ffed to prepare a 'nap' and to produce a gene
rally even texture.
 The main requirements for finishing are evenn
ess and the reproducibility of colour and ade
quate wear and feel properties.
 Almost all types of hides and skins can be finished.
 The final uses of the different leathers is wide and includ
es shoe uppers, furniture and automotive upholstery, gar
ments and leather goods.
 It is therefore very important for finishing in the best wa
y.
 The range of chemical products used in finishing is consi
derable, and combinations of these products can produce