CONTENTS:

1) Introduction

2) Definition of Leather Tanning

3) Preparatory steps prior to tanning

4) Leather Tanning Process

5) Post Processing

6) Environment and Health Concerns

7) Pollution Prevention And Control

8) Tanning Industry in Pakistan

9) References
Introduction:
The story of leather is long and colorful. Many years before recorded history people wrapped themselves in
dried animal pelts. The fact that the skins turned stiff and rotted was a problem, but ways of softening and
preserving the hides were discovered. This was the beginning of leather processing. At first the hides or skins
were probably dried in air and sunlight. Later they may have been soaked in water and dried over a fire. Still
later it was discovered that certain twigs, barks and leaves soaked with the hides in water helped to preserve
them. As civilization advanced, preserving hides and tanning them into leather became an important industry. In
the 18th century tanning was an old and respectable trade and a tedious one. Nearly a year was spent
manipulating a hide before it was delivered as leather to the saddle maker, harness maker or other craftsmen.

Definition of Leather Tanning:

The English word for tanning is from Medieval Latin tannāre, deriv. of tannum (oak bark), related to Old High
German tanna meaning oak or fir (related to modern Tannenbaum). This refers to use of the bark of oaks (the
original source of tannin) in some kinds of hide preservation.

Tanning is the process of treating skins of animals to produce leather, which is more durable and less
susceptible to decomposition. Tanning hide into leather involves a process which permanently alters the protein
structure of skin.

Preparatory steps prior to tanning:

The hides and skins of animals are the source of leather. The skins of large animals such as cattle and horses are
referred to as hides. Those of smaller animals such as sheep, goats and calves are called skins. After the hide
has been removed it is fleshed removing any remaining meat tissue or fat. Freshly fleshed hides are shipped in
refrigerated trucks to a tannery for immediate processing into leather. If this is not possible, the fleshed hides
are cured or preserved by immersion in agitated salty water or brine for 12 hours. After curing, the hides can be
stored for several months without rotting and can be shipped to tanneries throughout the world.

The steps below shows you what tanneries do to prepare hide for tanning:

a) Curing:

Raw hides and skins must be preserved to stop them deteriorating before the leather-making process can begin.
Methods of preservation include salting, chilling, freezing and the use of biocides.

b) Soaking:

Cured hides or skins are soaked in water for several hours to several days. This allows them to reabsorb any
water they may have lost in the curing process or during transportation. It also helps to clean them of salt and
dirt.

c)Painting:

Painting is a method by which wool can be removed from sheepskins using a sulphide based mixture.

d)Liming;

Liming removes the epidermis and hair. This also results in alkaline swelling of the pelt to cause a controlled
breaking of some of the chemical crosslinks of the collagen.
e)Fleshing:

After liming the pelt is passed through a machine to remove fleshy tissue from the flesh side. Hides may be split
into layers at this stage or after tanning.

f) DE liming:

The principal action of deliming is to gradually neutralize the alkali in the pelt, avoiding rapid changes in pH
which could lead to distortion or disruption of the tissues.

g) Bating:

A long delime can significantly improve the removal of any remaining lime, scud (miscellaneous debris) and
residual components broken down during liming. Bating - based on the use of enzymes - completes this process
so that the pelt is flat, relaxed, clean and ready for pickling and tanning.

h) Pickling:

Weak acid and salt solutions are used to bring the pelt to the weakly acid state required for most tanning
processes. Stronger pickling solutions are used to preserve pelts so that they can be stored or transported in a
stable form over periods of several months.

i) Degreasing:

Solvents or water-based systems can be used to remove excess grease before tanning.

Leather Tanning Process:

Tanning is the final process in turning hides and skins into leather. Tanning converts the protein of the raw hide
or skin into a stable material, which will not putrefy and is suitable for a wide variety of purposes. Tanning
materials form crosslinks in the collagen structure and stabilize it against the effects of acids, alkalis, heat, water
and the action of micro-organisms.

The main types of tanning methods are:

a)Chrome tanning:

Chromium(III) sulfate ([Cr(H2O)6]2(SO4)3) has long been regarded as the most efficient and effective tanning
agent.The pH must be very acidic when the chromium is introduced to ensure that the chromium complexes are
small enough to fit in between the fibers and residues of the collagen. 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 step 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.

b) Aldehyde and oil tanning:

Tanning with aldehydes and oils produce very soft leathers and this system can be used to produce dry
cleanable and washable fashion leathers and also chamois leather.
c) Vegetable tanning:

Vegetable tanning uses tannin. 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 and myrobalans from Terminalia spp., such as Terminalia
chebula. 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 various products such as shoe soles, luggage, saddler,
belt leathers and upholstery, luggage and furniture.

d) Wet white tanning:

It based on alum, zirconium, titanium, iron salts, or a combination thereof, lead to skins known as wet white.
Wet white is also a semi-finished stage like wet blue, but is much more eco friendly. The shrinkage temperature
of wet white varies from 70 to 85 degree Celsius, while that of wet blue varies from 95 to 100 degree Celsius.
This fairly new method of tanning has been gaining popularity, partially due to increased concern for the
environment. Wet white tanned leathers are free of chrome and recyclable.

Post Processing:
The steps mentioned below follows tanning:

a) Splitting:

A splitting machine slices thicker leather into two layers. The layer without a grain surface can be turned into
suede or have an artificial grain surface applied.

b) Shaving:

A uniform thickness is achieved by shaving the leather on the non-grain side using a machine with helical
blades mounted on a rotating cylinder.

c) Neutralization:

Neutralising removes residual chemicals and prepares the leather for further processing and finishing.
Additional tanning material may be applied to give particular properties which are required in the finished
leather.

d)Dyeing:

The dyeing of leather into a wide variety of colours plays an important part in meeting fashion requirements.
Some leathers are only surface dyed, while others need completely penetrated dyeing’s, as is the case with
suede leathers.

e)Fat liquoring:

Fat liquoring introduces oils to lubricate the fibers and keep the leather flexible and soft. Without these oils the
leather will become hard and inflexible as it dries out.
f) Samming:

This process reduces water content to about 55% and can be achieved by a number of machines, the commonest
being like a large mangle with felt covered rollers.

g) Setting out:

The leather is stretched out and the grain side is smoothed. This process also reduces the water content to about
40%.

h) Final drying:

Leather is normally dried to 10-20% water content. This can be achieved in a number of ways and each method
has a different effect on the finished leather:

i) Staking and dry drumming:

A staking machine makes the leather softer and more flexible by massaging it to separate the fiber’s. To finish
off the leather may be softened by the tumbling action inside a rotating drum.

j) Buffing and Brushing:

The flesh surface is removed by mechanical abrasion to produce a suede effect or to reduce the thickness. In
some cases the grain surface is buffed to produce a very fine nap, e.g. nubuck leathers. After buffing the leather
is brushed to remove excess dust.

k) Finishing:

The aims of finishing are to level the colour, cover grain defects, control the gloss and provide a protective
surface with good resistance to water, chemical attack and abrasion.

l) Final grading:

Leather will be graded before dispatch to the customer. This grading may consider the colour intensity and
uniformity, the feel of the leather, softness, visual appearance, thickness, design effects and natural defects such
as scratches.

m) Measurement;

The area of each piece of leather is measured by machine. Nearly all leather is sold by area so accurate
measurement is important.

Environmental and Health Concerns:

Environmental issues associated with tanning and leather finishing include the following:

1) Industrial Process wastewater

2) Air Emissions
3) Solid Waste
4) Hazardous Material
5) Odors
a) Industrial Process Wastewater;

Process water consumption, and consequently wastewater effluent discharges, varies greatly between tanneries,
based on the processes involved, raw materials, and products. Generally, water consumption is greatest in the
pre-tanning areas, but significant amounts of water are consumed also in the post tanning processes. Wastewater
from the beam house processes (e.g. soaking, fleshing, detailing, and liming) and from associated rinsing is
generally collected together. It may contain hide substance, dirt, blood, or dung and therefore have significant
loads of organic matter and suspended solids. Wastewater from tan yard processes, deliming and bating may
contain sulfides ammonium salts, and calcium salts and is weakly alkaline.

b) Salts and Total Dissolved Solids:

Salting and other tannery processes contribute to the presence of salts / electrolytes in wastewater streams,
measured as Total Dissolved Solids (TDS). Approximately 60 percent of total chloride is produced from salt
used for curing, which is subsequently released in the soaking effluent. The rest is generated mainly from
pickling and, to a lesser extent, tanning and dyeing processes. Additional contributors to TDS include the use of
ammonium chloride and sodium sulfate. The TDS concentrations may reach 15,000 mg/l in tannery effluents.
Disposal of waste-neutral electrolyte is a significant challenge for leather manufacturing, particularly for those
facilities located in land-locked areas.

c) Chromium and Other Tanning Agents;

Trivalent chromium salts (Cr III) are among the most commonly used tanning agents, accounting for the
majority (approximately 75 percent) of the chromium in the wastewater stream. The remainder is typically
generated from post-tanning wet processes, from stock drainage, and wringing. The reducing characteristics of
tannery sludge serve to stabilize Cr (III) with respect to hexavalent chromium (Cr VI) content, as a result of the
presence of organic matter and sulfide5.

d) Air Emissions:

Air emissions from tanning facilities include organic solvents from tanning and leather finishing operations;
sulfides from the beam house and wastewater treatment; ammonia from the beam house, tanning, and post-
tanning operations; dust / total particulate from various process operations; and odors. Emissions of sulfur
dioxide may occur during bleaching, post tanning operations, or CO2 deliming, but they are not typically a
significant source of emissions.

e) Odors:

Odors may result from raw hides and skins, putrefaction, and from substances including sulfides, mercaptans,
and organic solvents.

Health Concerns:

Tannery workers may be exposed to chemical hazards during loading, unloading, handling, and mixing of
chemicals; during the washing, and disposing of chemical containers; and during the management and disposal
of chemical waste and effluent. Workers may be exposed to disease-agents such as bacteria, fungi, mites, and
parasites which may be present in the hides or as part of the manufacturing process. Common diseases found
among workers include lung cancer, leukemia, skin diseases, diarrhea, anthrax etc. Preventive measures need to
implemented to address these issues.
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/biocides are necessary, avoid toxic and less degradable ones especially those containing
arsenic, mercury, linden, pentachlorophenol or other chlorinated substances.
• Fleshing of 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 high pressure nozzles and implement chrome recovery 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.
• Examine alternatives to chrome in tanning, such as titanium, aluminum, iron zirconium, and vegetable
tanning agents.
• Use non organic solvents for dyeing and finishing.
• Recover hair by using hair saving methods (for example, avoid dissolving hair in chemical both by proper
choice of chemicals and use screens to remove them from wastewater) to reduce pollution loads.

• Batch washing instead of continuous washing -- reductions of up to 50%.

• Use low float methods such as having 40-80% floats. Recycle liming, pickling, and tanning floats. Recycle
sulfide in spent liming liquor after screening to reduce sulfide losses (say by 20-50%) and lime loss (say by 40-
60%).
• Use of drums instead of pit for immersion of hides.
• Reuse of wastewaters for washing—for example, by recycling lime wash water to the soaking stage. Reuse
treated wastewaters in the process to the extent feasible (such as in soaking and pickling).

Waste reduction measures should include the following:

• Recover hide trimmings for use in the manufacture of glue, gelatin, and similar products.
• Recover grease for rendering. Use aqueous degreasing methods.
• Recycle wastes to the extent feasible in the manufacture of fertilizer, animal feed, and tallow
provided the quality of these is not compromised.
• Use tanned shavings in leather board manufacture.
• Control odor problems by good housekeeping, such as minimal storage of flesh trimmings and organic
material.
• Recover energy from the drying process to heat process water

Tanning industry in Pakistan:
No one can deny the importance of tanning industry in the national economy of a country; it supplies the most
essential requirements of the people during the days of war and peace alike.
Pakistan occupies a predominant place in the production of raw hides and skins. It is estimated that our annual
production is as follows:

Buffalo hides.............. 8, 11, 000

Cow hides.............. 44, 73,000
Goat skins and.............. 53, 50,000
Sheep skins.............. 20, 75,000

Most of these hides and skins are exported to U. K., U. S. A., India and other countries. Pakistan enjoys one
great advantage. It has almost a monopoly of the best varieties known to the world trade of “slaughter” hides
and skins. As the slaughter of cows is prohibited in India, she has to depend on “Fallen” hides, i.e., animals that
die a natural death. The hides are, therefore, of inferior quality and fetch lower prices. The leather made of these
hides known as chrome, lacks elasticity and is comparatively less durable. The availability of skilled labor is
another great advantage enjoyed by the industry in Pakistan.

In Pakistan tanning materials like lime, fish and vegetable oil, Mangrove bark and babul bark are also available.
The wattle bark is imported from South Africa and East Africa. We are short of tan stuffs like myrabolams and
avaram bark which at present is imported from India but it has been found by the tanning experts that babul,
kikar and mangrove bark which are abundantly found in Pakistan are fairly good substitutes. For chemicals and
dyes we are dependent on foreign countries. Summing up the argument, Pakistan possesses almost all the
requirements that are necessary for the growth of the industry.

But this does not mean that the problems facing the industry are small or few. The industry remains under a
constant threat of foreign competition, both in buying hides and skins and in selling tanned leather. Frequently
this competition leads to abnormally high price of hides and skins and the chances of profits for the producer’s
decline. Also diseases of livestock and deplorable working conditions of tanneries pose problems. Pakistan
Government fully realizes the importance of this industry and is taking keen interest in its development.

Of all the countries of the East, Pakistan is best suited to become the chief producer of tanned leather. The
industry being on the decline in India, there is a chance for Pakistan to step in the place left vacant by India. We
have all the necessary requirements for developing this industry. What is required is to implement the programs
that have been already chalked out.

References:

1) Hayat Tanning Industries In Pakistan.pdf

2) Charles Thomas Davies. The Manufacture of Leather. 1899. Henry Carey Baird & Co.
3) Leather Tanning-Environmental Protection Agency.pdf
4) James E. Churchill, The Complete Book of Tanning Skins and Furs
5) Gustafson, K.H. "The Chemistry of Tanning Processes" Academic Press Inc., New York
6) Heinemann, E.; Leather. Ullman’s Encyclopedia of Industrial Chemistry,2005
7) Covington, A. "Modern Tanning Chemistry" Chemical Society Review