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Enzyme Technology-An Eco Friendly approach towards Leather

making:

One of the important criteria determining the sustainability of an


industrial activity is the ecological acceptability of the processing methods.
Eco-friendliness of the processing methods employed in industrial production
has gained paramount importance. In this regard, pre-tanning process has in
particular raised serious ecological concerns in leather sector. The leather
industry world over is coming under pressure from environmental regulations to
comply with the pollution and discharge legislation. The chemicals mainly
responsible for pollution in pre-tanning processes are lime, sodium sulphide,
and caustic soda apart from common salt and degreasing chemicals. In fact, one
third of the pollution caused by the leather industries results from the wastes
generated during dehairing operations. Therefore the current activity in the area
of leather processing is shifting towards the design and utilization of cleaner and
softer technology like enzymatically enhanced processes. The use of enzymes as
a viable alternative has been resorted to in pre-tanning operations such as
soaking, dehairing, fiber opening, bating and degreasing. The enzymes can also
be used for the treatment of byproducts (offal) from the hide or skin.

Conventional Process:

Conventional leather processing is associated with the discharges


of significant amount of environmental contaminants. They contribute to
biological oxygen demand (BOD), chemical oxygen demand (COD), total
dissolved solids (TDS), Sulphides, chlorides, sulphates, chromium, lime, etc.
The Pre-tanning process produces about 95% of total Suspended Solids
(SS), 80% of total COD, 85% of total BOD and 100% of the toxicity. A
brief description about the wastes generated from a tannery and their impact
on the environment would be appropriate to understand the problem
associated with it.

Soaking:

Soaking is the first of the beamhouse process wherein the hides and
skins are cleaned and softened with water. Soaking is necessary for
solubilization and elimination of salts and globular proteins contained within
the fibrous structure of hides and skins. Sodium hydroxide and sodium
sulphide as well as wetting agents, emulsifiers and surfactants are added to
facilitate soaking and prepare hides and skins for the next stage.

The salted skins/hides are soaked in the water for 17 to 48 hours to


wet back and remove the salts, blood and dirt. The environmental impact of
soaking may be discerned by the quality of waste water produced by this
operation. Table 1 indicates that soaking produces a particularly heavy load
of dissolved solids (DS).

Dehairing/Liming:

Dehairing is one of the main operations in the beamhouse. Paint


liming process is preferred for skins, where as pit and paddle methods are
preferred for hides. Hides and skins are treated with lime and sodium
sulphide to remove the hairs and open-up the fibers. In this process the
effluent will generally contain sulfides, caustic alkali and solid wastes (hair
and flesh). This operation results in the generation of high biochemical
oxygen demand (BOD) and chemical oxygen demand (COD) load. The hair
removal efficiency is very good but it has lot of disadvantages.
Significant disadvantages are:

1. It is responsible for 84% of BOD, 75% of the COD, 92% of suspended


solids and 100% of the toxicity.

2. Sulphide is highly toxic with unpleasant odor. If left untreated, it can


cause major problems in the sewers.

3. Enhance the level of nitrogen-bearing organic pollutants in the effluent.

4. The severe alkaline condition is a health hazard for the workers.

Deliming and Bating:

The hides/skins are processed with ammonia salts, enzymes


(pancreatic) and mild organic acids to remove lime, scuds and some protein
cementing substances to make the pelt softer and cleaner. The spent liquor
usually contains neutral salts, ammonia, soluble skin proteins and high
organic matter, which result in high organic, load and can create
nitrogeneous pollution.

Degreasing:

Degreasing, the final stage in beamhouse operations, is performed to


remove the grease from pelt, thus improving the quality and durability of the
final leather product. During the degreasing operation in the pretanning
process, the fat or grease is removed from the interfibrillary spaces of the
skins to facilitate the even penetration of tanning materials, fat liquors, and
dyes, etc.
Degreasing is carried out using aqueous emulsification with
detergents, or by solvent extraction. Kerosene, chlorinated hydrocarbons,
and white spirit are used in the degreasing system which adds to the toxicity
of the environment and effluents. It is well known that organic solvents like
kerosene, petrol and trichloroethylene are highly unsafe and hazardous to the
workers and heavily pollute the environment. The detergents, though not
hazardous, while handling and storing cause serious pollution problems.
These detergents and solvents add to the BOD load of the pickling effluent,
and the chlorinated hydrocarbons and solvents add to the toxicity of the
effluent.

Table 1: Characteristics of tannery waste water:

Parameter pH Volume of TS DS SS BOD COD


s effluent (mg/l) (mg/l) (mg/l) (mg/l) (mg/l)
(meter3)

Soaking 7.5 - 6–9 3500 - 32000 - 3000 - 1100 - 3000 -


8 5500 48000 7000 2500 6000

Liming 10 - 3–4 30000 - 24000 - 6000 - 5000 - 5000 -


12.8 50000 30000 20000 10000 25000

Deliming 7.2 - 1–2 4000 - 2500 - 1500 - 1000 - 2500 -


& Bating 9 10000 6000 4000 3000 7000

Source: UNIDO & UNEP, Industrial Pollution Prevention and


Abatement, chapter on “Leather tanning and finishing”, draft report (June
1994)
Table 2: Relative Contributions of the Pre-tanning Operations to
Waste Loading (Percentages)

Operation Waste water BOD Solids Sulphides Ether


Soluble
material

Soaking 18 8 30 - 25

Dehairing 24 80 40 99 50

Fleshing 2 3 10 Traces 20

Bating 20 5 10 Traces Traces

Source: Adapted from Profit from Pollution Prevention: A Guide to


Industrial Waste Reduction and Recycling, a project of the Pollution
Probe Foundation (LELP, 0021)

Enzymes in Pre-tanning process:


Enzymes are natural protein molecules that act as highly efficient
catalysts in biochemical reactions, that is, they help a chemical reaction take
place quickly and efficiently. Enzymes not only work efficiently and rapidly,
they are also biodegradable. The use of enzymes helps in reducing COD
load by 80%, TDS load by 85%, and chromium load by 80% compared to
the conventional processes.
The main advantages of the use of enzymes are specificity, stereo
specificity, activity under mild conditions, possibility of producing ‘natural’
products, non-pollutants, and biodegradability. The use of enzymes results
in many benefits that cannot be obtained with traditional chemical process.
These include higher product quality and lower manufacturing cost, and less
waste and reduced energy consumption. The processing time and water
consumption are also reduced drastically. Since enzymes are catalysts, the
amount required to accomplish a reaction is relatively small. Enzymes also
contribute to safer working conditions during production processes.

Enzymes in soaking:

Soaking can be done by using a cocktail of proteolytic, amylolytic and


lipolytic enzymes. Enzyme used in soaking reduces the need for the liming
chemicals by 30–60%. Use of enzyme will result in a decrease in soaking
time. For enzymatic soaking, the average soaking period for salted raw stock
is about 4 h and for dried raw stock is about 8–10 h. A water soak without
auxiliary agents takes 24 h for salted hides, and 36–48 h for dried hides.

The advantages of enzymatic soaking

1. Loosening of the scud.

2. Initiation of the opening of the fiber structure.

3. Production of leather with less wrinkled grain.

4. Improves the softness and elasticity, and increases the area yield of the fur
by 3.3%.

Enzymes in dehairing:

Enzymatic dehairing is suggested as an environmentally friendly


alternative to the conventional chemical process. Proteolytic enzymes can be
used here. This enzyme digests the basal cells of the hair bulb and the cells
of the epidermis. This is followed by loosening of hair with an attack on the
outermost sheath and subsequent swelling and breakdown of the inner root
sheath and parts of the hair that are not keratinized. In dehairing, the hair
loosening is effected at pH 10.0. Using enzymes, the treatment period will
be approximately 12–16 h, followed by hair removal using mechanical
means. Enzymatic hair loosening processes play a role wherever high-
quality hair, wool or bristles are to be recovered.

Advantages of enzymatic dehairing are:

1. Complete elimination of the use of sodium sulphide.

2. Recovery of hair of good quality and strength with a good selling price.

3. An ecologically contributing atmosphere for the workers.

4. Leathers have better strength properties and greater surface area.

5. A significant nature of the enzymatic dehairing process is the time factor


involved. The lime-sulphide process takes about 16 h, whereas the
enzymatic dehairing would be also completed between 12 and 20 h.

Enzymes in Fiber opening:

Fiber opening is another important step in the beamhouse process. In


conventional process lime is employed for fiber opening. Lime is
responsible for the fact that leather industry is considered as a black sheep
industry because of its pollution load. The enzymes that can be used in fiber
opening are carbohydrases that degrades specifically the proteoglycans.
Conventional liming mechanism:
Lime mechanism of fiber opening is by osmotic pressure created in
the leather matrix. Lime usage is approximately 10 - 20% of the raw weight,
which is not fully used. Most of the lime will not diffuse into the skin and
results in large amount of lime sludge. The diffused lime is again removed in
deliming. And also in this process the thickness increases and area decreases
which we try to regain in other operations. It requires long time usually more
than 2 days.
Fiber Opening Enzyme (FOE) mechanism:
Generally collagen is bound by gummy material, the proteoglycans
which has a protein & glucose linked by glycosidic linkages. They occupy
approximately 0.5% on raw weight. The more the proteoglycans removed
the more is the softness. These linkages are removed by this enzyme i.e., the
cementing material is lost and the fiber is opened up and water gets into the
fiber hence we get the swelling.
The advantages of enzymatic fiber opening are;

1. No need of lime hence no lime sludge problem.

2. Fiber opening could be achieved in 3-4 hrs therefore significant

reduction in time.

3. Provides about 4-5% area yield.

4. Net reduction in pollution load.

Enzymatic Unhairing and Fiber opening:


Current studies are undergoing in exploring a single step unhairing
and fiber opening process by the use of enzymes. Liming/Unhairing and
reliming/fiber opening processes are two inevitable steps in leather
processing and also generate significant pollution up to 60 – 70%. The time
taken to achieve for this will take from minimum of 3 days to 1 week. But
using a cocktail of proteolytic and amylolytic enzymes, there are
possibilities for achieving the unhairing and fiber opening in a single
process.

The significant advantage

1. Both unhairing and fiber opening could be achieved in 24 hrs.

2. There is about 73% reduction in time consumption.

3. 50% reduction in energy consumption because of the integrated


process.
4. Another major advantage of this process is that it involves the use of

enzymes both in unhairing and fiber opening, which will increase the
area of the final leather by 3%.

Enzymes in bating:

Bating is a very important process in which enzymes have been


successfully employed for centuries. The main object of bating is to remove
some of the nonleather-forming proteinous materials like albumins, globulin,
and mucoids from hides and skins, and to allow splitting up of collagen
fibers to facilitate the penetration of tanning materials and other processing
chemicals, thereby giving the finished leather the desired characteristic
properties like feel, softness, pliability. Proteolytic enzyme finds a major
usage in this application.

Enzymes in degreasing

Enzymatic degreasing is a viable alternative to combat the pollution


problems caused by the use of solvents and detergents. Fat degrading or
lipolytic enzymes which are alternatives for solvents and detergents catalyze
the breakdown of fats and can be obtained from animal, microbial and plant
sources.

The advantages of using enzymes for degreasing are;

1. Elimination of solvents

2. Reduction in surfactants

3. Possible recovery of valuable by-products.

Enzymes for by-products utilization and effluent treatment:

When raw hides are processed to leather, a number of by-products


such as native hide material (claws, tails, necks, fleshings), pelt waste
(trimmings, machine fleshings, gluestock, pelt cuts), and tanned material
(shavings, leather cuts, buffing dust, chrome cuttings) are obtained.

Enzymes could be used in the treatment of fleshings and effluent from


tannery processes. A combination of hydrolytic enzymes, viz. proteases,
carbohydrases and lipases can be used. The advantages to be realised include
a protein by-product suitable for animal feed as well as energy conservation
and fat recovery.
The enzymatic conversion of glue stock and other hide offal to
technically useful byproducts by hydrolysing the pulverised hide wastes
with an alkaline protease, pH 9.0–13.0, in the presence of urea, and then at
pH 2.0–5.0 in the presence of a strong acid. The treating fleshings with
pancreatic enzymes instead of heat treatment for separating the fat from the
proteinaceous matter requires much less energy, and the yield is increased
from 60–65% to over 90%. The utilization of fleshings which consists of the
enzymatic hydrolysis of the proteins, conditioning of the resulting liquid,
and separating the fats and solids present in the hydrolysate. The outstanding
feature of the process is a recovery of 91% of the fat in the fleshings and the
application of the hydrolysate directly to the soil, as a fertilizer.

Fig: Comparison between conventional and Enzymatic tanning:


Table 3: Input–output audit of chemicals and bioproducts:
Parameter Conventional Process Enzymatic Process Reduction
(kg/t) (kg/t) (%)
Input 438 90 ↓ 80
Output
Effluent 257 33 ↓ 87
Sludge 149 14 ↓ 91
Leather(Uptake 40 43
)

Conclusion

Ecological concerns have become key issues in the present global


industrial activities. By adopting the enzymatic processes the pollution load
will decrease significantly. After all, “a journey of thousand miles will begin
with a single step”. Therefore cleaner leather processing using enzyme
technology will help our leather industry to gain its eco-friendly status and
its sustainability.

References:

1. United Nations “Environmentally Sound Technologies in the Tanning


Industry”, 1997.

2. R B Choudhary, A K Jana & M K Jha “Enzyme technology

applications in leather processing”, Indian Journal of Chemical


Technology, Vol 11, pp 659-671, Sep 2004.

3. N. R. Kamini, C. Hemachander, J. Geraldine Sandana Mala and R.


Puvanakrishnan “Microbial enzyme technology as an alternative to
conventional chemicals in leather industry”, Current science, Jul 10.

4. P. Thanikaivelan, C. K. Bharath, S. Saravanabhavan, J. R. Rao, N.K

Chandrababu “Integrated hair removal and fiber opening process


using mixed enzymes”, Clean Technology Environmental Policy, pp
61 - 68, 2007.

5. P. Thanikaivelan, J. R. Rao, B. U. Nair, T. Ramasami “Zero


Discharge Tanning: A shift from Chemical to Biocatalytic Leather
Processing”, Environmental Science Technology, pp 4187 – 4194,
2002

6. P. Thanikaivelan, J. R. Rao, B. U. Nair, T. Ramasami “Enzymes and

biotechnology for cleaner leather processing” Current science, vol. 96,


no. 11, June 2009

7. S. Saravanabhavan, R. Aravindan, P. Thanikaivelan, J. R. Rao, B. U.

Nair “ Green Solution for tannery pollution: effect of enzyme based


lime-free unhairing and fiber opening in combination with pickle free
chrome tanning” Green Chemistry, pp 707 – 714, 2003

8. J. Ludvik UNIDO “The scope for decreasing pollution load in leather

processing”

9. L. Ahlstrom, L. Mathiasson, C. K. Bharath, J. R. Rao and B. U. Nair


“Single step hair removal and fiber opening process”, JALCA, Vol
101, pp 388 – 398, 2006