Mulungushi University

School of Science Engineering and Technology

CHE 492 – Industrial Chemistry

Leather Processing
Introduction
• Leather is a material created by tanning animal raw hides and skins.
• Tanning; a process of converting animal hides or skins into leather
• Raw material; Hides and skins from sheep, goat, cow, buffalo etc.
• The unwanted components of the skin or hades are removed and skin/hide
brought into a condition by suitable processes where it can resist bacterial,
thermal, chemical and hydrolytic influences.
• Leather is used to make a variety of articles, including footwear, automobile
seats, clothing, bags, book bindings, fashion accessories, and furniture.
Leather products
STAGES IN THE LEATHER PROCESSING
• Three main stages of operations involved;
1. Beamhouse or pre-tanning operations; the skins and hides in the wet salted
conditions are processed to remove unwanted materials such as hair, flesh
and other proteinous materials
2. Tanning process; the skins and hides are converted into semi-finished
leather (the process imparts resistance to the putrescible skins and hides
against bacterial degradation.
3. Post-tanning operations; the tanned semi-finished leathers are dyed to give a
colour and fatliquored to impart the degree of softness and retanned to
impart the filling, grain tightening and improve the uniformity in substance.
PRE-TANNING OPERATIONS
Soaking;
• The skins and hides are received mostly in salted conditions. Why?
• Soaking involve the removal of salt and rehydration of the skins and hides to
their original condition.
• Process can be done either in pits or paddles.
• Water is changed several times to bring back raw material to is original state.
• Duration vary from 3 hours to overnight, even longer for sundried stock.
• To prevent damage of the skin by bacterial growth during the soaking period,
biocides, typically dithiocarbamates, may be used. Fungicides such as
2-thiocyanomethylthiobenzothiazole may also be added later in the process, to
protect wet leathers from mold growth. After 1980, the use of
pentachlorophenol and mercury-based biocides and their derivatives was
forbidden. Why?
Soaking paddles
Liming;

• After soaking, the hides are treated with milk of lime Ca(OH)2 (a basic agent)
typically supplemented by "sharpening agents" (disulfide reducing agents) such
as sodium sulfide, cyanides, amines, etc.
Primary objectives of the liming process are
i. to remove the hair and flesh
ii. to open up the fibre structures of the skins and hides by suitable plumping
and swelling.
• In addition, part of the natural fat or grease and other unwanted proteins such
as sweat glands, blood vessels, nerve tissues are removed.
Two stages are involved in liming;

• In stage 1, the unhairing process, the soaked stock is treated with a mixture of
lime and sodium sulphide either in pit or paddles or indeed in paint liming
system which is used for sheep and goat skins as a hair shaving method.
• In stage 2, reliming is perforemed in order to suitably open up the fibre
structure.
• Reliming is carried out either in pits or paddles mostly with 300- 400% water
and lime. Soda ash or sodium hydroxide may be used in small quantities to
improve swelling to obtain better opening up of fibre structure in shorter
duration.
Deliming & Bating:

• These are done in the same vessels(milling drums, mixers etc.) that are to be
used for tanning

• Deliming:

• After unhairing, the lime in the skin is no longer needed & if left it has
detrimental effect on subsequent tannage
• With chrome tanning, the lime give a hard green inflexible leather & prevents
proper tannage
• With vegetable tanning, the lime slows down or reduces tannage & gives
a dark colour
• Deliming can be done through washing or by use of chemicals

Deliming by washing:

• The skins are put in a paddle or drum & run with continuous flow of cold
clean water

• Undissolved lime on the surface & some dissolved lime between the
fibres is quickly removed

• The lime that is chemically held by the fibres (about 0.4% of the skin wt) is
removed very slowly necessitating prolonged washing
• Prolonged washing may lead to lime blast if the water used is hard (soluble Ca or
Mg bicarbonates or carbonic acid react with lime to precipitate CaCO3)
• Prolonged washing allows further alkali breakdown of the skin giving loose
leather particularly if the water is warm

Chemical deliming:

• The loose lime is removed by quick washing followed by addition of controlled

amounts of weak acids or acid producing salts to neutralize the alkali

• Too much acid damages the skin by causing violent swelling & dissolving protein,
therefore weak acids are used
• Weak organic acids used include: Boric, lactic or acetic acid

• Acid salts that can be used include: sodium bisulphite, salts of weak alkalis such
as ammonium chloride or sulphate

• The lime is converted into readily soluble salts that are rinsed out (deliming
subsides the alkali swelling caused by the liming chemicals)
• Deliming is tested by dropping a few drops of phenophthalein onto a cross-
section of the pelt (if the process is complete – colourless; if not it becomes red)
• Delimed pelts must be taken to the next process immediately since putrefying
bacteria can cause a slimy feel & loose leather with damaged structure will result
PRE-TANNING OPERATIONS
Bating;
• The main reason of this operation is to purify the pelts by removing the
unwanted components consisting of the proteinous products, epidermis, short
hair, the scud and interfibrillary proteins loosened by liming using enzymes

• Enzymatic bating agents are used which attack non-structured collagen &
noncollagenic proteins in a controlled manner to make them soluble
• Bating opens up the pelt for the ensuing tannage, improves softness, grain
elasticity & colour levelness of the leather
• Intensive bating does not impair tensile strength of the leather & may even
improve the tear strength by increasing elasticity of the fibres
• Originally enzymes used for bating were pepsin & trypsin from dog dung & fowl
• droppings (cause soft smooth & silky grain)

• Today two main types of bates are used:

• 1. Pancreatic bates – digestive enzymes from the pancreas
• 2. Bacterial bates – digestive enzymes of bacteria
PRE-TANNING OPERATIONS
Pickling;
• Pickling is carried out to bring down the pH to 2.5-3.0 so as to get quicker
penetration and more uniform distribution in chrome tanning.
• In the case of rapid method of vegetable tanning, a partial pickling is done to a
pH 4-4.5.
• The pelt is treated with a mixture of formic and sulphuric acids, and 10%
sodium chloride is used to suppress the acid swelling due to rapid drop in pH.
• 80% water based on pelt weight is used in pickling process.
PRE-TANNING OPERATIONS
Degreasing;
• Degreasing is most relevant in processing sheepskins, where the natural fat
content is about 10 – 20 % of dry weight. Degreasing as a separate process step
is not usual for bovine hides. The nature of this fat makes it difficult to remove
because of the presence of glycerides and a high melting temperature.
• Excessive amounts of grease in the skin may interfere with uniform penetration
of tan or dye, causing difficulties in the finishing processes and creating dark
and greasy patches on the finished leather. Degreasing of greasy skins is
particularly important before chrome tannage as the chromium salts can react
with the greases and form insoluble chromium soaps, which are very difficult to
remove subsequently
• The process may be carried out either after deliming or after pickling, though it
would be more effective after pickling.
• Due to washing, the pH of pickled pelt increases and hence repickling is done to
bring down the pH to 2.8 before commencing chrome tanning.

The three different methods commonly used for degreasing are:

• 1. degreasing in an aqueous medium with an organic solvent and a non-
ionic surfactant
• 2. degreasing in an aqueous medium with a non-ionic surfactant
• 3. degreasing in a solvent medium.

Look at each method: lookout for advantages disadvantages of each

quality of leather, pollution, usefulness of the grease produced
TANNING PROCESS
• Tanning process is the most important because it imparts the resistance
against bacterial degradation and improves the durability.
• Tannage
• Converts the unstable natural fibre network of the hide collagen into a stable
material (leather)
• The tanning materials react with the polypeptide chains of the collagen, the
• individual tanning material particles each forming several bonds with the
different reactive groups of the collagen molecules
• The collagen molecules become cross-linked and strengthened both
individually & collectively leading to great stability

• Differences of leather from untanned hide:

(i) Increased resistance to hot H2O

(ii) Resistance to micro organisms when wet
(iii) Less swelling in H2O
(iv) Better shape retention
(v) Dries leather-like (i.e. not ‘bony’)
• Tannage can be effected by means of very different types of tanning material
which react poly-functionally with the hide collagen in different ways
• Therefore there is a vast array of tanning methods and materials
Tanning methods and materials

• The tanning agent or materials that are used for tanning of skins and hides are;
• vegetable tanning materials,
• mineral tanning agents (chrome, aluminium and zirconium salts),
• aldehydes (formaldehyde and glutaraldehyde),
• oils such as fish oil etc
• The most common tanning agents are trivalent chromium and vegetable
tannings extracted from specific plant products.
Vegetable tanning
• Vegetable Tanning is oldest tanning method and still in use nowdays.
• Process could be either;
1. Pit tannage
2. Accelerated tannage
3. Rapid tannage (BASF RAPITAN process)
• the pelts are treated with extracts of bark, nuts, leaves or heartwoods of certain
plants.
• The most commonly used tanning materials are wattle, avaram, konnam, myrobalan,
babul,quebracho, cutch, etc.,
• The vegetable tanning materials are polyphenolic compounds and form colloidal
dispersions in water.
• In convectional old methods, the tanning was be carried out in a series of pits
containing the liquors in the increasing order of concentrations.
• Pelts used to stay in each pit for 2-3 days and the total duration was taking around 30-
60 days.
TANNING PROCESS
• Vegetable Tanning Process cont
• short pre-tanning at a pH 4.2 for 6 days followed by drum tanning is the usual
tanning method followed nowadays.
• To cut down the time and drudgery, only drum tanning method can be used.
• In the rapid method, a treatment with phenolic pre-tanning syntan is given
before commencing vegetable tanning to quicken the penetration and it is also
common to use sulphated vegetable fatliquor during tanning.

• Vegetable tanned leathers have a characteristic colour (vary from pale yellow-
brown to intensive red-brown depending on the type of vegetable tanning
material used & conditions applied); the colour darkens indaylight
• Vegetable tanned leather is used for making soles, sandals, straps, belts,
upholstery, bags, decorations, shoe lining & book binding leather etc.

• Characteristics of vegetable tanned leather:

(i) good strength

(ii) shape retention
(iii) low heat conductivity
Mineral tanning

• Basic salts of chromium, zirconium & aluminium are used

• Very soft leather is produced compared to vegetable tanning
• Leather colour is white for aluminium & zirconium but pale green or blue for
chromium tannage
• Little change of colour in daylight
• Chromium tan does not wash out but Al does wash out
• Alum tans are used for gloves or fur-skins
Chrome Tanning;
• Chrome tanning is generally popular (80% of leather) because chrome tanned
leather is used for different applications due to its relative stability to higher
temperature compared with vegetable tanned leather
• Process is done using wooden drums.
• 8 - 10% chrome in the form of Basic Chromium Sulphate (BCS) along with a
cationic or multicharged fat liquor or acid and electrolyte stable fat liquors.
• Chrome tanning is started at a pH around 2.8 and finally after ensuring
complete penetration, the pH is raised to 3.8-4.0 during basification to
complete chrome tanning.
• A mixture of sodium formate and bicarbonate is used for basification.
• Total duration of tanning process is about 6-8 hrs
A modern electric tanning drum in
Germany
Advantages of chrome over vegetable tannage
a) Chrome leather has favourable properties (high mechanical strength,
outstandin gdyeing properties, absolute light fastness)

b) Ideal as semi-finished product (wet blues) with good storage stability for
subsequent processing into all types of leather

• c) Heat resistant (can withstand modern drying & steaming processes used in
finishing & shoe manufacture)

• d) Chrome tannage offers wide scope for streamlining

• e) Less capital is required because of quicker turn-over of raw materials &
more modest space requirements
• f) Production times are shorter & tanning material costs lower
 Synthetic tans (Syntans):
• Include substances which were manufactured to replace partially or completely,
the natural vegetable extracts, to accelerate production & make it cheaper. They
may be of various chemical structures
• Syntans give leather that is paler than vegtans, may darken in daylight, does not
washout with water
• Uses are white leathers & specialty leather
Aldehyde tannage:
• Uses formaldehyde or gluteraldehyde
• Produces soft white leather that does not wash out
• The leather is water absorbent
• Used for water washable gloves & clothing
Oil tannage:
• Cod liver oil is used
• Produce light, soft, air-permeable leather that is resistant to washing
• The leather is pale yellow that bleaches in sunlight
• Used for wash leathers & washable gloves
Other tanning processes:

1. Oil & sulphur tannage

2. Isocyanate tannage
3. Sulphochloride tannage
4. Quinone tannage
POST-TANNING OPERATIONS
Semi - chroming
• Vegetable tanned leathers possess many good qualities but lack in
hydrothermal stability and affinity for dyes and fatliquors.
• So usually a retanning with chrome is carried out to improve these properties
before they are processed into different finished leathers.
• This is called semi-chroming.
• semi-chroming involve the following;
1. Stripping; to remove unfixed or unwanted tannins from the leather and also
to remove oils and greases from the leather using alkalis such as borax or
sodium bicarbonate with sodium sulphite and degreasing agent.
2. bleaching with oxalic acid and bleaching syntan with about 300 to 400% float
to remove iron stains formed during the shaving operation and to get a
uniform Colour and washing with about 600% water
POST-TANNING OPERATIONS
3. Souring to pH 3.0 - 3.3 with 300% water and formic acid and then chrome
tanning is commenced in the same bath. Cationic or mulitcharge fatliquors
are also used along with chrome and the tanning is completed at pH 3.8
4. basification stage using sodium formate and sodium bicarbonate mixture.
POST-TANNING OPERATIONS
 Neutralisation;
• Neutralisation is meant to neutralise the excess acid present in wet blue/semi-
chrome leathers, which interferes with subsequent operations like dyeing,
fatliquoring and retanning.
• The extent of neutralisation would depend on the desired properties of the
finished leathers.
• The agents commonly used for neutralisation are sodium formate, sodium
bicarbonate, sodium sulphite, ammonium bicarbonate,neutralising syntan, etc
POST-TANNING OPERATIONS
 Retanning;
• Retanning is done to impart;
I. filling of the loose portions
II. fullness, round feel and body to the leather
III. tightness of the grain.
• main retanning materials;
• vegetable tanning materials, phenolic syntans, acrylic and other resin tanning
materials, protein based tanning agents, whitening syntans and polyurethane
syntans.
• Note: ‘semi-chrome’ tannage refers to complete vegetable tanning followed by
retannage with chrome
• ‘chrome-retan’ is a full chrome tannage
POST-TANNING OPERATIONS
 Dyeing;
• Leathers are dyed to impart colour.
• Leather dyeing is a transition process between tanning & finishing
• Some leathers require penetration of dyestuff into collagen network while
others need surface application
• Synthetic dyestuffs are used & any colour shade can be applied
• Leather is dyed discontinuously in rotating vessels (drums or Y-shaped dyeing
units) or continuously (through-feed dyeing, dyeing by roll coating or spray
dyeing)
The most commonly used dyes are acid, direct and metal complex dyes.
POST-TANNING OPERATIONS;
Fat liquoring
• This is the last operation in the aqueous phase of tanning before drying
• The process involves the introduction of oil into the leather so that individual
fibres become uniformly coated
• Fatliquoring separate the fibres in the wet state so that they do not stick
together too much during drying
• This is the process that determines the mechanical & physical properties of the
leather
• Fatliquoring of leather imparts softness,flexibility, feel, drape, run, etc.
• Leather dried before or with little fatliquoring becomes hard & bony; such
leather may crack in use
• Over lubrication results in excessive softness & raggy leather
POST-TANNING OPERATIONS
 Fatliquoring
• Fatliquors are oil in water emulsions.
• The oils and fats are converted into emulsions by a process of sulphation,
sulphonation, sulphitation or sulphochlorination.
• The fatliquors, based on their charge characteristics are classified into;
i. anionic
ii. cationic
iii. non-ionic and
iv. multi charged fatliquors
Fatliquoring

•They are also classified based on the origin of the oils as;
I. vegetable oils
II. animal oils which include marine based oils and
III. synthetic oils based on long chain hydro carbons, long
IV. chain fatty esters and long chain fatty alcohols etc.
•All the three unit operations are carried out together in the same bath mostly
and the dyes and fatliquors will have to be fixed by the addition of formic acid.

• After these unit operations, the leathers are dried.

Finishing
POST-TANNING OPERATIONS
 Finishing;
• Finishing of leather consists of the application of a firm forming material to the
grain to provide aesthetic appeal and to improve the sale value of the leather.

• It also provides surface protection against rubbing, abrasion and staining.

• The defects of the grain are covered by the protective coat and hence the
cutting value is also very much enhanced.
• Finishing formulations contain :
i) pigments and dyes for colouring,

ii) binders based on casein or acrylates or polyurethane for binding,

Formaldehyde is used for fixing for casein based finishes.

• Formaldehyde is used for fixing for casein based finishes.

iii) wax emulsions for feel modification,

iv) fillers for readjustment in optical property and

v) nitro cellulose or cellulose acetate butyrate or other hard resins for surface
coat protection.
Environmental Impact
• Air pollution
• – ammonia gas, hydrosulphuric gas and volatile organic compounds
• Water contamination
– residual baths for hide treatment and washings containing chemical
products
• Contamination of the soil
–flesh, hairs, hide chippings and scrapings
• Large amount of water consumption
• Chrome has high level of contamination
Chemical Consumption Pattern in Leather Industry
• The chemicals used in leather processing are classified as bulk and
performance chemicals.
• Bulk chemicals are sodium chloride, lime, sodium sulphide, ammonium salts,
formic acid, sulphuric acid, sodium formate, sodium bicarbonate, ammonia
etc., which are used in many other industries as well.
• tanning materials, formulations of fatliquors, retanning, finishing agents etc.,
are performance chemicals. These are used to add to the performance of
leather in usage and limited to use in leather sector alone.