Leather is a material produced from animal skins (or hides).

- is used for making shoes, upholstery, clothing, gloves, hats,

books, handbags, etc

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 Tanning is the process of making leather, which does not easily decompose,
from the skins of animals.

 It involves chemically binding of the organic or inorganic materials to the

protein structure of the hide and preserve it from deterioration.

 The substances generally used to accomplish the tanning process are

chromium or tannin, an acidic chemical compound which is extracted from the
bark of trees, such as chestnut, oak, etc.

 These processes prevent putrefaction and rotting of hide under humid

conditions and permanently alters the protein structure of skin to leather, so
that it can not ever return to rawhide or raw skin.

 Different types of hides (or skins) are used for leather production including
those of the cow, ox, pig, sheep, goat, horse, buffalo, crocodile and other
animals.

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 Leather tanning and finishing industry

Raw hides delivered to tannery

Soaking, liming & unhairing,

Fleshing & splitting, scudding

Deliming, bating

pickling

Vegetable tanning Chrome tanning

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Vegetable tanning chrome tanning

neutralization splitting

dyeing & fat liquoring shaving

drying
Re-tanning
Dyeing, Fat-liquoring
Conditioning
(buffing & sanding)
drying
Finishing & spraying
Conditioning
Finished leather (buffing & sanding)
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Tanning process
The first stage is the preparation for tanning. The second stage is the actual
tanning and other chemical treatment. The third stage, known as retanning,
applies retanning agents and dyes to the material to provide the physical strength
and properties desired depending on the end product. The fourth and final stage,
known as finishing, is used to apply finishing material to the surface or finish the
surface without the application of any chemicals if so desired.
Preparing hides begins by curing them with salt. Curing is employed to
prevent putrefaction of the protein substance (collagen) from bacterial growth
during the time lag that might occur from procuring the hide to when it is
processed. Curing removes excess water from the hides and skins using a
difference in osmotic pressure. The moisture content of hides and skins gets
greatly reduced. In wet-salting, the hides are heavily salted, then pressed into
packs for about 30 days. In brine-curing the hides are agitated in a salt water bath
for about 16 hours. Generally speaking, curing substantially reduces the chance of
spoilage by bacteria. Curing can also be done by preserving the hides and skins at
a very low temperature.
In a process known as soaking, the hides are then soaked in clean water to
remove the salt and increase the moisture so that the hide or skin can be further
treated. soaking in water over a period of 6 hours to 2 days. To prevent damage of
the skin by bacterial growth during the soaking period, biocides is added. Now it is
forbidden to add in soaking.
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 After soaking, the hides and skins are taken for liming: treatment
with milk of lime (a basic agent) that may involve the addition of
"sharpening agents" (disulfide reducing agents) like sodium sulfide,
cyanides, amines etc. The objectives of this operation are mainly to:

• Remove the hairs, nails and other keratinous matter

• Remove some of the interfibrillary soluble proteins like mucins
• Swell up and split up the fibres to the desired extent
• Remove the natural grease and fats to some extent
• Bring the collagen in the hide to a proper condition for satisfactory
tannage

The weakening of hair is dependent on the breakdown of the

disulfide link of the amino acid called cystine, which is the characteristic of
the keratin class of protein that gives strength to hair and wools (keratin
typically makes up 90% of the dry weight of hair). The hydrogen atoms
supplied by the sharpening agent weaken the cystine - cysteine molecular
link, and the covalent disulfide bond links are ruptured. This weakens the
keratin. To some extent, sharpening also contributes to "unhairing," as it
tends to break down the hair proteins.

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Unhairing agents used during liming are:
• Sodium sulfide
• Sodium hydroxide
• Sodium hydrosulfite
• Arsenic sulfide
• Calcium hydrosulfide
• Dimethyl amine
• Sodium sulfhydrate
The majority of hair is then removed using a machine, with remaining hair
being removed by hand using a dull knife, a process known as scudding.
Depending on the end use of the leather, hides may be treated with
enzymes to soften them in a process called "bating." But before bating,
the pH of the collagen is brought down to a lower level so that enzymes
may act on it. This process is known as "deliming."
Once bating is complete, the hides and skins are treated with a mixture of
common (table) salt and sulfuric acid, in case a mineral tanning is to be
done. This is done to bring down the pH of collagen to a very low level so
as to facilitate the penetration of mineral tanning agent into the
substance. This process is known as "pickling." The common salt (sodium
chloride) penetrates the hide twice as fast as the acid and checks the ill
effect of sudden drop of pH.

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Vegetable tanning uses tannin (this is the origin of the name of the process). The
tannins (a class of polyphenol astringent chemical) occur naturally in the bark and
leaves of many plants. Tannins bind to the collagen proteins in the hide and coat
them causing them to become less water-soluble, and more resistant to bacterial
attack. The process also causes the hide to become more flexible. The primary
barks, processed in Bark Mills and used in modern times are chestnut, oak, redoul,
tanoak, hemlock, quebracho, mangrove, wattle (acacia; see catechu), and
myrobalan. Hides are stretched on frames and immersed for several weeks in vats
of increasing concentrations of tannin. Vegetable tanned hide is flexible and is
used for luggage and furniture.

Mineral tanning usually uses chromium in the form of basic chromium sulfate. It is
employed after pickling. Once the desired level of penetration of chrome into the
substance is achieved, the pH of the material is raised again to facilitate the
process. This is known as "basification". In the raw state chrome tanned skins are
blue and therefore referred to as "wet blue." Chrome tanning is faster than
vegetable tanning (less than a day for this part of the process) and produces a
stretchable leather which is excellent for use in handbags and garments.

Depending on the finish desired, the hide may be waxed, rolled, lubricated, injected
with oil, split, shaved and, of course, dyed.

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Waste water characteristics

(Composite untreated wastewater)

20–80 m3/t of hide or skin treated
Highly turbid, colored, and foul smelling.
consists of acidic and alkaline liquors,
chromium levels of 100–400 mg/l;
sulfide levels of 200–800 mg/l;
Nitrogen levels of 200–1,000 mg/l;
BOD levels of 160 to 24,000 mg/l;
COD ranging from 2,400 to 14,000 mg/l;
Chloride ranging from 5,600 to 27,000 mg/l
high levels of fat
Suspended solids are usually half (1/2) of chloride levels.

Wastewater may also contain residues of pesticides used to preserve hides during
transport, as well as significant levels of pathogens.

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Solid waste
Significant volumes of solid wastes are produced, including trimmings, degraded hide,
and hair from the beamhouse processes. The solid wastes can represent up to 70%
of the wet weight of the original hides.
Sludges
In addition, large quantities of sludges are generated (rich in chromium): 3% on dry
basis

Atmospheric emission
Decaying organic material produces strong odors. Hydrogen sulfide is released during
dehairing, and ammonia is released in deliming. Volatile solvents escape to
atmosphere during spraying and oiling in finishing stage.

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Pollution Prevention and Control
• Process fresh hides or skins to reduce the quantity of salt in wastewater, where
feasible.
• Reduce the quantities of salt used for preservation.
• When salted skins are used as raw material, pretreat the skins with salt elimination
methods.
• Use salt or chilling methods to preserve hides, instead of persistent insecticides
and fungicides.
• When antiseptics or biocides are necessary, avoid toxic and less degradable ones,
especially those containing arsenic, mercury, lindane, or pentachlorophenol or
other chlorinated substances.
• Flesh green hides instead of limed hides.
• Use sulfide and lime as a 20–50% solution to reduce sulfide levels in wastewater.
• Split limed hides to reduce the amount of chrome needed for tanning.
• Consider the use of carbon dioxide in deliming to reduce ammonia in wastewater.
• Use only trivalent chrome when required for tanning.
• Inject tanning solution in the skin using highpressure nozzles; recover chrome from
chrome-containing wastewaters, which should be kept segregated from other
wastewaters. Recycle chrome after precipitation and acidification.
• Improve fixation of chrome by addition of dicarboxylic acids.
• Recycle spent chrome liquor to the tanning process or to the pickling vat.

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• Examine alternatives to chrome in tanning, such as titanium, aluminum,
iron, zirconium, and vegetable tanning agents.
• Use inorganic solvents for dyeing and finishing.
• Recover hair by using hair-saving methods to reduce pollution loads. For
example, avoid dissolving hair in chemicals by making a proper choice of
chemicals and using screens to remove hair from wastewater.
• Use batch washing instead of continuous washing
• Recycle liming, pickling, and tanning floats.
• Recycle sulfide in spent liming liquor after screening to reduce sulfide losses
and lime loss
• Reuse wastewaters for washing—for example, by recycling lime wash water
to the soaking stage. Reuse treated wastewaters in the process to the
extent feasible (for example, in soaking and pickling).

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Solid waste reduction
• Waste reduction measures should include the following:
• Recover hide trimmings for use in the manufacture of glue, gelatin, and
similar products.
• Recycle wastes to the extent feasible in the manufacture of fertilizer,
animal feed, and tallow, provided the quality of these products is not
compromised.
• Use tanned shavings in leather board manufacture.
• Control odor problems by good housekeeping methods such as minimal
storage of flesh trimmings and organic material.

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