Journal of Engineering, Computers & Applied Sciences (JEC&AS)                 ISSN No: 2319‐5606                  

 
Volume 2, No.5, May 2013 
_________________________________________________________________________________ 
 

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 retanning, applies retanning agents and dyes to the

A. Leather tanning material to provide the physical strength and
Tanning is the process of making leather, which properties desired depending on the end product.
does not easily decompose, from the skins of The fourth and final stage, known as finishing, is
animals, which decomposes. Often this uses tannin, used to apply finishing material to the surface or
an acidic chemical compound. Coloring may occur finish the surface without the application of any
during tanning. A tannery is the term for a place chemicals if so desired.
where these skins are processed. Tanning leather Preparing hides begins by curing them with salt.
involves a process which permanently alters the Curing is employed to prevent putrefaction of the
protein structure of skin so that it cannot ever protein substance (collagen) from bacterial growth
return to rawhide. Making rawhide does not require during the time lag that might occur from procuring
the use of tannin and is made simply by removing the hide to when it is processed. Curing removes
the flesh and fat and then the hair by way of excess water from the hides and skins using a
soaking in an aqueous solution (often called liming difference in osmotic pressure. The moisture
when using lime and water or bucking when using content of hides and skins gets greatly reduced. In
wood ash (lye) and water), then scraping over a wet-salting, the hides are heavily salted, then
beam with a dull knife, and then leaving to dry, pressed into packs for about 30 days. In brine-
usually stretched on a frame so that it dries flat. curing the hides are agitated in a salt water bath for
The two aforementioned solutions for removing the about 16 hours. Curing substantially reduces the
hair also act to clean the fiber network of the skin chance of spoilage by bacteria. Curing can also be
and therefore allow penetration and action of the done by preserving the hides and skins at a very
tanning agent. low temperature. In a process known as soaking,
The first stage is the preparation for tanning. The the hides are then soaked in clean water to remove
second stage is the actual tanning and other the salt and increase the moisture so that the hide or
chemical treatment. The third stage, known as skin can be further treated.

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Journal of Engineering, Computers & Applied Sciences (JEC&AS)                 ISSN No: 2319‐5606                  
 
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B. Types of Tanning process mangrove, wattle and myrobalan. Hides are

Chrome tanning most leather produced is chrome stretched on frames and immersed for several
tanned. Chrome tanning produces leather better weeks in vats of increasing concentrations of
suited for certain applications, particularly for the tannin. Vegetable tanned hide is flexible and is
upper parts of boots and shoes, and requires less used for luggage and furniture.
processing time than traditional vegetable tanning. Mineral tanning usually uses chromium in the
No two tanneries are identical; each has its unique form of basic chromium sulfate. It is employed
characteristics and sub processes; some perform after pickling. Once the desired level of penetration
only some of the processes shown and ship their of chrome into the substance is achieved, the pH of
goods to another tannery to complete the the material is raised again to facilitate the process.
processing. Hides and skins are received from meat This is known as "basification". In the raw state
packing plants by truck or railroad car. Each cattle chrome tanned skins are blue and therefore referred
hide is tied in a bundle weighing approximately 25 to as "wet blue." Chrome tanning is faster than
kg. The bundles are cut open and the hides vegetable tanning (less than a day for this part of
unfolded, inspected, and usually split along the the process) and produces a stretchable leather
backbone, producing two sides from each hide, which is excellent for use in handbags and
which is followed by a sequence of wet operations. garments.
The sides are soaked in water to return some of the Tawing is a method that uses alum and aluminum
lost natural moisture. The remaining flesh or fatty salts, generally in conjunction with other products
substance adhering to the inside or flesh surface of such as egg yolk, flour, and other salts. The leather
the side is removed; these fleshing are usually becomes tawed by soaking in warm potash alum
either rendered in the tannery or sold. The cattle and salts solution, between 20°C and 30°C. The
hides are then soaked in a lime and sulfide solution process increases the leather's pliability,
which either loosens or dissolves the attached hair. stretchability, softness, and quality. Adding egg
In some operations, the hair is only loosened yolk and flour to the standard soaking solution
through the caustic action of the lime, with the hair further enhances its fine handling characteristics.
removed mechanically, followed by washing, Then, the leather is air dried ("crusted") for several
drying and sold as a by-product (for carpet pads weeks, which allows it to stabilize. Tawing is
and similar uses). However, the more common traditionally used on pigskins and goatskins to
approach for hair removal is to completely dissolve create the whitest colors. However, exposure and
the hair and discharge it to the wastewater stream. aging may cause slight yellowing over time and, if
Following hair removal, the hides are ready to be it remains in a wet condition, tawed leather will
prepared for the actual tanning operation. The hides suffer from decay. Technically, tawing is not
are placed in large rotating drums and treated in tanning. Depending on the finish desired, the hide
turn with an enzyme solution and then a salt-acid may be waxed, rolled, lubricated, injected with oil,
solution. These operations (respectively called split, shaved and, of course, dyed.
bating and pickling) prepare the hide for the
tanning process. While still in the drum after C. Hexavalent Chromium
discharge of the pickling solution, the hides are Hexavalent chromium (chromium VI) refers to
tanned. A chromium sulfate solution is added to the chemical compounds that contain the element
drum and the hides and chrome solution are mixed chromium in the +6 oxidation state. Virtually all
for periods of up to 24 hours. Following the chromium ore is processed via Hexavalent
chrome tanning process, all hides have a chromium, specifically the salt sodium dichromate.
characteristic blue color caused by the chrome Other Hexavalent chromium compounds are
tanning solution. Upon removal from the tanning chromium trioxide and various salts of chromate
drums, excess moisture is removed from the hides and dichromate. Hexavalent chromium is used for
through a wringing operation. the production of stainless steel, textile dyes, wood
preservation, leather tanning, and as anti-corrosion
Vegetable tanning uses tannin (this is the origin of and conversion coatings as well as a variety of
the name of the process). The tannins (a class of uses.
polyphenol astringent chemical) occur naturally in
the bark and leaves of many plants. Tannins bind to D. Toxicity
the collagen proteins in the hide and coat them Hexavalent chromium is transported into cells via
causing them to become less water-soluble, and the sulfate transport mechanisms, taking advantage
more resistant to bacterial attack. The process also of the similarity of sulfate and chromate with
causes the hide to become more flexible. The respect to their structure and charge. Trivalent
primary barks used in modern times are chestnut, chromium, which is the more common variety of
oak, redoul, tanoak, hemlock, quebracho, chromium compounds, is not transported into cells.

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Journal of Engineering, Computers & Applied Sciences (JEC&AS)                 ISSN No: 2319‐5606                  
 
Volume 2, No.5, May 2013 
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Inside the cell, Cr (VI) is reduced first to Meta amounts of hexavalent chromium even for long
stable pentavalent chromium (Cr (V)) and then to periods does not cause respiratory tract irritation in
trivalent chromium (Cr (III)). Chromate-dyed most people. Some employees become allergic to
textiles or chromate-tanned leather shoes can cause hexavalent chromium so that inhaling the chromate
or exacerbate contact dermatitis. Vitamin C and compounds can cause asthma symptoms such as
other reducing agents combine with chromate to wheezing and shortness of breath.
give Cr (III) products inside the cell. Skin: Prolonged skin contact can result in
Chromium Hexavalent Cr (VI) compounds, often dermatitis and skin ulcers. Some workers develop
called Hexavalent chromium, exist in several an allergic sensitization to chromium. In sensitized
forms. Industrial uses of Hexavalent chromium workers, contact with even small amounts can
compounds include chromate pigments in dyes, cause a serious skin rash.
paints, inks, and plastics; chromates added as
anticorrosive agents to paints, primers, and other 2. PROCESS DESCRIPTION
surface coatings; and chromic acid electroplated A. Silicates
onto metal parts to provide a decorative or Silicon dioxide consists of 60% of earth’s crust,
protective coating. Hexavalent chromium can also either in the free form or in the combined form
be formed when performing "hot work" such as with other silicates.
welding on stainless steel or melting chromium Composition of silicates:
metal. In these situations the chromium is not Soluble silicates contain three components
originally Hexavalent, but the high temperatures 1. Silica-this is the primary constituent of all
involved in the process result in oxidation that silicates
converts the chromium to a Hexavalent state. 2. Alkali-a key component of soluble
silicates. It can either be sodium oxide or potassium
E. Chromium hazards to humans oxide form
Workers in many different occupations are 3. Water
exposed to chromium. Occupational exposures B. Physical properties of silicates
occur mainly among workers who handle pigments The raw materials needed to produce soluble
containing dry chromate, spray paints and coatings silicates are silica sand, soda ash/potash and water.
containing chromate, operate chrome plating baths, Alkali is determined using pH or total titrate able
and weld or cut metals containing chromium, such alkali content.
as stainless steel. The following references aid in 1. Total solid is the sum of silica and alkali.
recognizing hazards and health effects associated 2. Weight ratio is the most important silicate
with chromium. Workers who breathe Hexavalent variable. Ratio determines the product solubility,
chromium compounds at their jobs for many years reactivity and physical properties.
may be at increased risk of developing lung cancer. 3. Ratio is either the weight or molar
Irritation or damage to the eyes and skin can occur production of silica to alkali.
if Hexavalent chromium contacts these organs in 4. Density is an expression of total solids and
high concentrations or for a prolonged period of is typically determined using hydrometer. As
time. temperature density increases and as solid content
Cancer: All forms of hexavalent chromium are increases density increases.
regarded as carcinogenic to workers. The risk of 5. pH is a function of silicate composition
developing lung cancer increases with the amount and solid concentration. The pH value of silicates
of hexavalent chromium inhaled and the length of does not truly reflect the alkali content of solution.
time the worker are exposed. Studies of workers in C. Silica chemistry
chromate production, chromate pigment, and Sodium Silicates (Na2O.XSiO2) are metal oxides
chrome electroplating industries employed before of silica. All soluble silicates can be differentiated
the 1980s show increased rates of lung cancer by their ratio, defined as the weight proportion of
mortality. Certain hexavalent chromium silica to alkali (SiO2/Na2O) ratio determines the
compounds produced lung cancer in animals that physical and chemical properties of product. Using
had the compounds placed directly in their lungs. silicates to tie up metal ions is an inexpensive way
Eyes: Direct eye contact with chromic acid or to enhance the performance of many processes.
chromate dusts can cause permanent eye damage. Soluble silica reacts with all multivalent cationic
Hexavalent chromium can irritate the nose, throat, metal ions to form the corresponding insoluble
and lungs. Repeated or prolonged exposure can metal silicates. Silicates will precipitate these
damage the mucous membranes of the nasal metals out of solution and render them insoluble or
passages and result in ulcers. In severe cases, non reactive. The reactant by-product normally
exposure causes perforation of the septum (the wall displays long term stability.
separating the nasal passages). Breathing small

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e) As an aid to the resistance to abrasion

D. Advantages of silicate tanning process f) To improve tensile strength ,color
1. It reduces the pollution load of chrome g) As an aid to the resistance to chemical
2. Cost wise it is cheaper than Cr and it is attack
easily available Table 2: Types fat liquors used
3. It possesses tanning property and
facilitates buff ability in case of suede leather Type pH Application
4. Bright shades could be obtained with It is a light fast fat
sodium silicate tanned leather on dyeing. liquor suitable for
5. Silicate tanned leather retains soft even on white color to
washing, perhaps due to the lubricating nature of SAF (Synthetic fat
black/dark shade
silicates. liquor waxing 6.5-7.5
to get extra
6. Fullness of the leathers is improved type)
ordinary softness
considerably. with waxy feel to
7. It imparts high tensile strength to the the leather,
leather. Upholstery (4-5%)
E. Chemicals used in leather processing SA ( Synthetic fat Nappa (6-8%),
The below table shows a list of chemicals and liquor non waxing 6.5- 7 Softy lining,
specialty chemicals used for leather processing and type ) Fur skin (12%)
dyeing.
A semi - synthetic,
Table 1: List of chemicals used in tanning anionic fat liquor.
It can be used for
S.No Chemicals used Process FB(Vegetable fat
7 fat liquoring of all
1 Wetting agent Soaking liquor)
kinds of soft
Wetting agent in leather.
2 Soap nut
Soaking
Lime & sodium Syntans: Syntans are high molecular organic
3 Liming
sulphide compounds or mixtures of such compounds which
4 Ammonium Sulphate Deliming convert decomposable protein animal hide to
Deliming eco permanently conserved substance called leather.
5 Carbon dioxide
process Even though syntans differ structurally from
6 Sodium formate Neutralization naturally vegetable tanning, they react similarly to
7 Sodium bi carbonate Neutralization the natural tanning agents in their reaction with
8 Formic acid Fixation gelatin, hide or skin.
Dyeing - Syntans help to improve the various physical,
9 Synthetic liquor chemical and antimicrobial properties of leathers.
lubrication
10 Sodium silicate Tanning The type of syntans used has a considerable effect
Basic chrome on the resultant leather. Some of the syntans are
11 Tanning introduced mainly to substitute or supplement
Sulphate
12 Bate De liming natural vegetable tannins. In the case of syntans
13 Sodium chloride Pickling meant for purposes other than tanning like syntans
14 Syntans Dyeing for bleaching, filling, etc, the criteria of converting
animal hide or skin into leather, and thereby
increasing shrinkage temperature of leather, are not
Soap nut: Soap nut is a natural surfactant of plant
required. Also syntans meant for filling should not
origin. It serves the purpose to substitute wetting
have film forming properties in the leather, for
and degreasing agent.
example, binders.
Bate: Bate is basically consisting of ammonium
chloride, enzyme and saw dust. 3. SILICATE TANNING METHOD
The conventional tanning process involved
Fat liquor: Fat liquors are used in leather different steps to make leather from the raw skins
processing for following purposes. and hides. In the conventional leather making
a) Softness process uses the chromium compounds. The
b) Pliability different processes used in the tanning process
c) Stretch should be changed accordingly to avoid using of
d) Ability to take up or resist water the chromium compounds.

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The below table mentioned the list of chemicals process for the leather and the modern silicate
used in the normal conventional chrome tanning tanning process for the eco-friendly leather.

Table 3: Preparation of eco friendly leather

Conventional procedure for Modern silicate tanning for
Process
Leather processing Eco friendly leather
Water : 300% Water : 300%
Soaking I
Wetting agent : 0.5% - 30 Soap nut : 8% - 30
Water : 300% Water : 300%
Soaking II
Wetting agent :0.5%-over night Wetting agent : 0.5%-over night
Next day washing Water : 200% Water : 200%

Water :150% Water :150%

Lime :10% Lime :10%
Liming
Sodium sulfide :2% Sodium sulfide :2%
Left for three days in a pit Left for three days in a pit

Fleshing and scudding is done on limed pelts

Washing Water : 200% Water : 200%

Water : 200% Water : 200 %

De-liming Ammonium sulfate : 2% Carbon dioxide : -one day
Bate : 0.5% - run for 2 hours Soap nut : 8%

Washing Water : 100% Water : 100%

Water : 80% Water : 80%

Sodium chloride : 8% Sodium chloride : 8%
Pickling
Formic acid : 1% -10 mins Formic acid : 1% -10 mins
Sulphuric acid : 1.5% pH:3 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.
Water : 50%
Basyntan : 3%
Chromium Sulphate : 8%
Wattle : 3%
Fat Liquor :1%
Tanning Fat Liquor : 1%
Sodium Formate :1%
Formic acid : 1%
Sodium bicarbonate :2%
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 out from the tanned leather was clamped between
tanning can be modified by the above mentioned the jaws of the clamp, which in turn was immersed
silicate tanning process to make the eco friendly in a mixture of glycerol and water (3:1) and the
leather which contains no chromium and the very solution was stirred vigorously using mechanical
dangerous environmental impacts caused by stirrer. The temperature of the solution was
chromium can be protected. gradually increased and the temperature at which
the sample shrinks was noted.
G. Shrinkage test Table 4: Leather shrinkage temperature
In this research work many parameters has been
tested for the different types of leather The
Leather Shrinkage temperature
shrinkage temperature which is measure of
hydrothermal stability of leather is determine using
Chrome tanned 1100C
a shrink of test shrinkage tester. A 2cm 2 sample cut

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Silicate tanned 950C [6] Figveria MM et al, “The fate of

Chromium in water and soil”, Environmental
Vegetable tanned 650C science & technology, Vol. 33, pp. 1840-1846,
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4. CONCLUSION biotechnology, Vol.9 (21), pp. 3140-3143, May
The detailed research study has been made on 2010.
leather processing. Almost all tanneries uses [9] James Bruce R et al, “Chemical
chrome tanning process to make good quality transformations of chromium in soils”, Journal of
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environmental impacts caused by the chromium [11] M.Megharaj et al, “Toxicity of hexavalent
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