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JournalofEngineering,Computers&AppliedSciences(JEC&AS)ISSNNo:23195606

Volume2,No.5,May2013
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www.borjournals.comBlueOceanResearchJournals17
Preparation of Eco-Friendly Leather by Process
Modifications to Make Pollution Free Tanneries

M.Sathiyamoorthy, Research Scholar, Department of Chemical Engineering, CMJ University, Shillong,


Meghalaya, India
V.Selvi, Assistant Professor, Department of Chemical Engineering, Annamalai University, Chidambaram,
Tamilnadu, India,
Derese Mekonnen, Lecturer, Department of Chemical Engineering, Adama Science & Technology University,
Adama, Ethiopia,
Shewarega Habtamu, Lecturer, Department of Chemical Engineering, Adama Science & Technology
University, Adama, Ethiopia,

ABSTRACT
The term eco friendly leather meant the chrome free leather. Around 80% of leather is tanned using
chromium. The chromium used in the tannery may be in the form of chromium III, IV and chromium VI
compounds. The chromium tanned leathers use chromium III salts (Trivalent chromium) in the form of
chromium sulfate. This form of chromium is found naturally in the environment and is necessary nutrient for the
human body. However the chromium III oxidizes to chromium VI (Hexavalent chromium) in the presence of
oxygen combined with other factors, such as extremes in pH. This happens during the tanning process. The
hexavalent chromium produces allergic reaction and easily moves across the membranes such as skin, and it is
a major cause for many diseases. This research work suggests using silicate tanning process by eliminating the
chrome tanning process to make eco friendly leather. The present tanneries which use chrome tanning process
can be modified in to silicate tanning process to make pollution free tanneries and the future generations can be
protected from very dangerous environmental impacts caused by chromium compounds.

Key words: Eco friendly leather, Chrome free leather, tanning, trivalent chromium, hexavalent chromium,
chrome tanning, silicate tanning.


1. INTRODUCTION
A. Leather tanning
Tanning is the process of making leather, which
does not easily decompose, from the skins of
animals, which decomposes. Often this uses tannin,
an acidic chemical compound. Coloring may occur
during tanning. A tannery is the term for a place
where these skins are processed. Tanning leather
involves a process which permanently alters the
protein structure of skin so that it cannot ever
return to rawhide. Making rawhide does not require
the use of tannin and is made simply by removing
the flesh and fat and then the hair by way of
soaking in an aqueous solution (often called liming
when using lime and water or bucking when using
wood ash (lye) and water), then scraping over a
beam with a dull knife, and then leaving to dry,
usually stretched on a frame so that it dries flat.
The two aforementioned solutions for removing the
hair also act to clean the fiber network of the skin
and therefore allow penetration and action of the
tanning agent.
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. 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.
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B. Types of Tanning process
Chrome tanning most leather produced is chrome
tanned. Chrome tanning produces leather better
suited for certain applications, particularly for the
upper parts of boots and shoes, and requires less
processing time than traditional vegetable tanning.
No two tanneries are identical; each has its unique
characteristics and sub processes; some perform
only some of the processes shown and ship their
goods to another tannery to complete the
processing. Hides and skins are received from meat
packing plants by truck or railroad car. Each cattle
hide is tied in a bundle weighing approximately 25
kg. The bundles are cut open and the hides
unfolded, inspected, and usually split along the
backbone, producing two sides from each hide,
which is followed by a sequence of wet operations.
The sides are soaked in water to return some of the
lost natural moisture. The remaining flesh or fatty
substance adhering to the inside or flesh surface of
the side is removed; these fleshing are usually
either rendered in the tannery or sold. The cattle
hides are then soaked in a lime and sulfide solution
which either loosens or dissolves the attached hair.
In some operations, the hair is only loosened
through the caustic action of the lime, with the hair
removed mechanically, followed by washing,
drying and sold as a by-product (for carpet pads
and similar uses). However, the more common
approach for hair removal is to completely dissolve
the hair and discharge it to the wastewater stream.
Following hair removal, the hides are ready to be
prepared for the actual tanning operation. The hides
are placed in large rotating drums and treated in
turn with an enzyme solution and then a salt-acid
solution. These operations (respectively called
bating and pickling) prepare the hide for the
tanning process. While still in the drum after
discharge of the pickling solution, the hides are
tanned. A chromium sulfate solution is added to the
drum and the hides and chrome solution are mixed
for periods of up to 24 hours. Following the
chrome tanning process, all hides have a
characteristic blue color caused by the chrome
tanning solution. Upon removal from the tanning
drums, excess moisture is removed from the hides
through a wringing operation.

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 used in modern times are chestnut,
oak, redoul, tanoak, hemlock, quebracho,
mangrove, wattle 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.
Tawing is a method that uses alum and aluminum
salts, generally in conjunction with other products
such as egg yolk, flour, and other salts. The leather
becomes tawed by soaking in warm potash alum
and salts solution, between 20C and 30C. The
process increases the leather's pliability,
stretchability, softness, and quality. Adding egg
yolk and flour to the standard soaking solution
further enhances its fine handling characteristics.
Then, the leather is air dried ("crusted") for several
weeks, which allows it to stabilize. Tawing is
traditionally used on pigskins and goatskins to
create the whitest colors. However, exposure and
aging may cause slight yellowing over time and, if
it remains in a wet condition, tawed leather will
suffer from decay. Technically, tawing is not
tanning. Depending on the finish desired, the hide
may be waxed, rolled, lubricated, injected with oil,
split, shaved and, of course, dyed.

C. Hexavalent Chromium
Hexavalent chromium (chromium VI) refers to
chemical compounds that contain the element
chromium in the +6 oxidation state. Virtually all
chromium ore is processed via Hexavalent
chromium, specifically the salt sodium dichromate.
Other Hexavalent chromium compounds are
chromium trioxide and various salts of chromate
and dichromate. Hexavalent chromium is used for
the production of stainless steel, textile dyes, wood
preservation, leather tanning, and as anti-corrosion
and conversion coatings as well as a variety of
uses.

D. Toxicity
Hexavalent chromium is transported into cells via
the sulfate transport mechanisms, taking advantage
of the similarity of sulfate and chromate with
respect to their structure and charge. Trivalent
chromium, which is the more common variety of
chromium compounds, is not transported into cells.
JournalofEngineering,Computers&AppliedSciences(JEC&AS)ISSNNo:23195606
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Inside the cell, Cr (VI) is reduced first to Meta
stable pentavalent chromium (Cr (V)) and then to
trivalent chromium (Cr (III)). Chromate-dyed
textiles or chromate-tanned leather shoes can cause
or exacerbate contact dermatitis. Vitamin C and
other reducing agents combine with chromate to
give Cr (III) products inside the cell.
Chromium Hexavalent Cr (VI) compounds, often
called Hexavalent chromium, exist in several
forms. Industrial uses of Hexavalent chromium
compounds include chromate pigments in dyes,
paints, inks, and plastics; chromates added as
anticorrosive agents to paints, primers, and other
surface coatings; and chromic acid electroplated
onto metal parts to provide a decorative or
protective coating. Hexavalent chromium can also
be formed when performing "hot work" such as
welding on stainless steel or melting chromium
metal. In these situations the chromium is not
originally Hexavalent, but the high temperatures
involved in the process result in oxidation that
converts the chromium to a Hexavalent state.

E. Chromium hazards to humans
Workers in many different occupations are
exposed to chromium. Occupational exposures
occur mainly among workers who handle pigments
containing dry chromate, spray paints and coatings
containing chromate, operate chrome plating baths,
and weld or cut metals containing chromium, such
as stainless steel. The following references aid in
recognizing hazards and health effects associated
with chromium. Workers who breathe Hexavalent
chromium compounds at their jobs for many years
may be at increased risk of developing lung cancer.
Irritation or damage to the eyes and skin can occur
if Hexavalent chromium contacts these organs in
high concentrations or for a prolonged period of
time.
Cancer: All forms of hexavalent chromium are
regarded as carcinogenic to workers. The risk of
developing lung cancer increases with the amount
of hexavalent chromium inhaled and the length of
time the worker are exposed. Studies of workers in
chromate production, chromate pigment, and
chrome electroplating industries employed before
the 1980s show increased rates of lung cancer
mortality. Certain hexavalent chromium
compounds produced lung cancer in animals that
had the compounds placed directly in their lungs.
Eyes: Direct eye contact with chromic acid or
chromate dusts can cause permanent eye damage.
Hexavalent chromium can irritate the nose, throat,
and lungs. Repeated or prolonged exposure can
damage the mucous membranes of the nasal
passages and result in ulcers. In severe cases,
exposure causes perforation of the septum (the wall
separating the nasal passages). Breathing small
amounts of hexavalent chromium even for long
periods does not cause respiratory tract irritation in
most people. Some employees become allergic to
hexavalent chromium so that inhaling the chromate
compounds can cause asthma symptoms such as
wheezing and shortness of breath.
Skin: Prolonged skin contact can result in
dermatitis and skin ulcers. Some workers develop
an allergic sensitization to chromium. In sensitized
workers, contact with even small amounts can
cause a serious skin rash.

2. PROCESS DESCRIPTION
A. Silicates
Silicon dioxide consists of 60% of earths crust,
either in the free form or in the combined form
with other silicates.
Composition of silicates:
Soluble silicates contain three components
1. Silica-this is the primary constituent of all
silicates
2. Alkali-a key component of soluble
silicates. It can either be sodium oxide or potassium
oxide form
3. Water
B. Physical properties of silicates
The raw materials needed to produce soluble
silicates are silica sand, soda ash/potash and water.
Alkali is determined using pH or total titrate able
alkali content.
1. Total solid is the sum of silica and alkali.
2. Weight ratio is the most important silicate
variable. Ratio determines the product solubility,
reactivity and physical properties.
3. Ratio is either the weight or molar
production of silica to alkali.
4. Density is an expression of total solids and
is typically determined using hydrometer. As
temperature density increases and as solid content
increases density increases.
5. pH is a function of silicate composition
and solid concentration. The pH value of silicates
does not truly reflect the alkali content of solution.
C. Silica chemistry
Sodium Silicates (Na
2
O.XSiO
2
) are metal oxides
of silica. All soluble silicates can be differentiated
by their ratio, defined as the weight proportion of
silica to alkali (SiO
2
/Na
2
O) ratio determines the
physical and chemical properties of product. Using
silicates to tie up metal ions is an inexpensive way
to enhance the performance of many processes.
Soluble silica reacts with all multivalent cationic
metal ions to form the corresponding insoluble
metal silicates. Silicates will precipitate these
metals out of solution and render them insoluble or
non reactive. The reactant by-product normally
displays long term stability.
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D. Advantages of silicate tanning process
1. It reduces the pollution load of chrome
2. Cost wise it is cheaper than Cr and it is
easily available
3. It possesses tanning property and
facilitates buff ability in case of suede leather
4. Bright shades could be obtained with
sodium silicate tanned leather on dyeing.
5. Silicate tanned leather retains soft even on
washing, perhaps due to the lubricating nature of
silicates.
6. Fullness of the leathers is improved
considerably.
7. It imparts high tensile strength to the
leather.
E. Chemicals used in leather processing
The below table shows a list of chemicals and
specialty chemicals used for leather processing and
dyeing.

Table 1: List of chemicals used in tanning

S.No Chemicals used Process
1 Wetting agent Soaking
2 Soap nut
Wetting agent in
Soaking
3
Lime & sodium
sulphide
Liming
4 Ammonium Sulphate Deliming
5 Carbon dioxide
Deliming eco
process
6 Sodium formate Neutralization
7 Sodium bi carbonate Neutralization
8 Formic acid Fixation
9 Synthetic liquor
Dyeing -
lubrication
10 Sodium silicate Tanning
11
Basic chrome
Sulphate
Tanning
12 Bate De liming
13 Sodium chloride Pickling
14 Syntans Dyeing

Soap nut: Soap nut is a natural surfactant of plant
origin. It serves the purpose to substitute wetting
and degreasing agent.

Bate: Bate is basically consisting of ammonium
chloride, enzyme and saw dust.

Fat liquor: Fat liquors are used in leather
processing for following purposes.
a) Softness
b) Pliability
c) Stretch
d) Ability to take up or resist water
e) As an aid to the resistance to abrasion
f) To improve tensile strength ,color
g) As an aid to the resistance to chemical
attack
Table 2: Types fat liquors used

Type pH Application

SAF (Synthetic fat
liquor waxing
type)

6.5-7.5
It is a light fast fat
liquor suitable for
white color to
black/dark shade
to get extra
ordinary softness
with waxy feel to
the leather,

SA ( Synthetic fat
liquor non waxing
type )


6.5- 7

Upholstery (4-5%)
Nappa (6-8%),
Softy lining,
Fur skin (12%)

FB(Vegetable fat
liquor)

7
A semi - synthetic,
anionic fat liquor.
It can be used for
fat liquoring of all
kinds of soft
leather.

Syntans: Syntans are high molecular organic
compounds or mixtures of such compounds which
convert decomposable protein animal hide to
permanently conserved substance called leather.
Even though syntans differ structurally from
naturally vegetable tanning, they react similarly to
the natural tanning agents in their reaction with
gelatin, hide or skin.
Syntans help to improve the various physical,
chemical and antimicrobial properties of leathers.
The type of syntans used has a considerable effect
on the resultant leather. Some of the syntans are
introduced mainly to substitute or supplement
natural vegetable tannins. In the case of syntans
meant for purposes other than tanning like syntans
for bleaching, filling, etc, the criteria of converting
animal hide or skin into leather, and thereby
increasing shrinkage temperature of leather, are not
required. Also syntans meant for filling should not
have film forming properties in the leather, for
example, binders.

3. SILICATE TANNING METHOD
The conventional tanning process involved
different steps to make leather from the raw skins
and hides. In the conventional leather making
process uses the chromium compounds. The
different processes used in the tanning process
should be changed accordingly to avoid using of
the chromium compounds.
JournalofEngineering,Computers&AppliedSciences(JEC&AS)ISSNNo:23195606
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The below table mentioned the list of chemicals
used in the normal conventional chrome tanning
process for the leather and the modern silicate
tanning process for the eco-friendly leather.

Table 3: Preparation of eco friendly leather
Process
Conventional procedure for
Leather processing
Modern silicate tanning for
Eco friendly leather
Soaking I
Water : 300%
Wetting agent : 0.5% - 30
Water : 300%
Soap nut : 8% - 30
Soaking II
Water : 300%
Wetting agent :0.5%-over night
Water : 300%
Wetting agent : 0.5%-over night
Next day washing Water : 200% Water : 200%
Liming
Water :150%
Lime :10%
Sodium sulfide :2%
Left for three days in a pit
Water :150%
Lime :10%
Sodium sulfide :2%
Left for three days in a pit
Fleshing and scudding is done on limed pelts
Washing Water : 200% Water : 200%
De-liming
Water : 200%
Ammonium sulfate : 2%
Bate : 0.5% - run for 2 hours
Water : 200 %
Carbon dioxide : -one day
Soap nut : 8%
Washing Water : 100% Water : 100%
Pickling
Water : 80%
Sodium chloride : 8%
Formic acid : 1% -10 mins
Sulphuric acid : 1.5% pH:3
Water : 80%
Sodium chloride : 8%
Formic acid : 1% -10 mins
Sulphuric acid : 1.5% pH:3
Next day the pelts are drummed for 30 mins. pH across the cross section is made to be 2.8 3.0 then 50 % of pickled
bath is drained.
Tanning
Chromium Sulphate : 8%
Fat Liquor :1%
Sodium Formate :1%
Sodium bicarbonate :2%
Water : 50%
Basyntan : 3%
Wattle : 3%
Fat Liquor : 1%
Formic acid : 1%
Sodium silicate :10%
GS powder : 5%
Then the leather was neutralized to pH of 5.5 and taken for dyeing.

The conventional leather processing by chrome
tanning can be modified by the above mentioned
silicate tanning process to make the eco friendly
leather which contains no chromium and the very
dangerous environmental impacts caused by
chromium can be protected.

G. Shrinkage test
In this research work many parameters has been
tested for the different types of leather The
shrinkage temperature which is measure of
hydrothermal stability of leather is determine using
a shrink of test shrinkage tester. A 2cm 2 sample cut
out from the tanned leather was clamped between
the jaws of the clamp, which in turn was immersed
in a mixture of glycerol and water (3:1) and the
solution was stirred vigorously using mechanical
stirrer. The temperature of the solution was
gradually increased and the temperature at which
the sample shrinks was noted.
Table 4: Leather shrinkage temperature

Leather Shrinkage temperature
Chrome tanned 110
0
C
JournalofEngineering,Computers&AppliedSciences(JEC&AS)ISSNNo:23195606
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Silicate tanned 95
0
C
Vegetable tanned 65
0
C
As expected chrome tanned leather posses higher
shrinkage followed by silica tanned leather.
Vegetable tanned leather has slightly lower
shrinkage temperature.

4. CONCLUSION
The detailed research study has been made on
leather processing. Almost all tanneries uses
chrome tanning process to make good quality
leather. In chrome tanning process, the different
chromium salts are used. These chromium salts and
its derivatives are very dangerous to human health
and to the environment. This research suggests,
replacing the chrome tanning process with silicate
tanning process, so that the dangerous
environmental impacts caused by the chromium
compounds can be eliminated. Since the properties
of chrome and silicate leathers are almost same, it
is better to use silicate tanning process instead of
chrome tanning. This yields the tanneries and
tannery products will be eco friendly and pollution
free tanneries.

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