BM DAS Lecture 2010

BM DAS MEMORIAL LECTURE 2010
Sustainable Leather Manufacture –

Realistic Objective
or Wishful Thinking?
Heinz-Peter Germann
Lederinstitut Gerberschule Reutlingen
(LGR) - GERMANY
LERIG Symposium
CLRI, Chennai – India, January 29-30, 2010
Prof. B.M. Das
Prof. E. Stiasny
& Prof. A. Küntzel
Prof. E. Heidemann
Definition of
“Sustainable development”
…according to the World Commission on

Environment and Development:
= development that “meets the needs of

the present without compromising the
ability of future generations to meet
their own needs”
Scheme of sustainable development –
at the confluence of three constituent parts
Social
Bearable Equitable
Sustai-
nable
Environment Viable Economic
Historical development
– past progress made by chance
• some hundred thousand years ago:
– discovery of a stabilized animal skin by chewing
(principle of chamois tannage)
– smoke tannage following to the discovery of fire
• more recent evidence dating back to

the 4th Millenium BC (Copper age):
– the “Iceman” (found in the Alps on the icy
heights of the Schnalstal Glacier frontier
area between Italy and Austria) wearing
fur clothes “tanned” by a special fatliquor procedure
Historical development
– past progress made by chance
• (main) interest: stabilisation of hides and
skins – available from animals hunted for the
need of nourishment – for the use of personal
protection
• implying also the first attempt for “pollution

prevention and control” by avoiding
uncontrolled rotting of hunting/slaughtering
waste in the environment!?
Leather manufacturing
… is in itself recycling
… is a sustainable environmental solution to

the disposal problem of hides and skins that
originate from the meat industry
Principle of the unhairing
by lime-sulphide systems
1. Step: attack of disulphide crosslinks in keratin
-CH2-S-S-CH2- -CH2-SH + HS-CH2-
+ 2 NaSH + Na2S2
2. Step: splitting of peptide bonds
CO CO-O–
NH + OH– pH > 10.5 +
RCH RCH-NH2
Principle of hair immunization
NH NH
HC-CH2-SH C=CH2 + H2S
C=O C=O
cysteine dehydroalanine
+
NH NH NH
C=CH2 HC-CH2-S-CH2-CH
C=O C=O C=O
dehydroalanine lanthionine
Figure: High-Speed Penetrator
LGR‘s investigations on high-pressure
injection of process chemicals
… with the following objectives:

– set-up a throughfeed process
– rapid penetration and uniform distribution of the

process chemicals
– avoidance of any residual process liquors
– conducting e.g. chrome tannage without pickling

Limitations observed in semi-technical
scale trials which impeded an
industrial application
• partially incomplete penetration of process chemicals
in the case of heavier bovine hides
• enzyme unhaired skins need an additional reliming
step for opening up the fibre structure and to guarantee
complete removal of short hair
• wet-blues require a subsequent storage (up to 2 h) for
a good chrome fixation
• especially, in the case of woolled sheepskins clogging
of the filtering units by e.g. sand and fibres turned out
to be a problem
Tanning techniques employed
in the pre-industrial period
• Vegetable tannage
or
• Aluminium tannage (tawing)
depending on the intended use

of the resulting leather – based
on the leather characteristics
(e.g. heavy & stiff ./. light & soft)
Dating from the end of the 19th Century:
Chrome tannage
• discovery of the tanning effect of chromium
salts is attributed to Friedrich Knapp (“On the
nature and essential character of the tanning
process and of leather”, 1858)
• two-bath tanning process of August Schultz
in 1884
• practical one-bath chrome tannage was
patented by Martin Dennis in 1893
Dating from the end of the 19th Century:
Chrome tannage
at the beginning, no environmental concerns
main interest: rationalisation of the tanning
process
• benefits in cost and speed of the reaction
• significant cut of throughput time
• highly versatile basis for
leather manufacture
major step towards
industrialisation
Ref.: www.vallero-international.com
Within the last 50 years:
Different approaches for an improved
chrome management
• chrome recycling techniques
• better understanding on the influence of process
parameters:
– mechanical action – temperature – pH
– concentration – processing time – Cr offer
• development of high exhausting chrome tanning

systems … based on the general principles of:
low chrome offer, optimised process parameters and
application of special auxiliaries
Alternatives to chrome tanning?
Amount of tanning agent required for a bovine hide
kg (40 kg pelt weight)
Chrome:
8% tan.ag. = 2% Cr-oxide
Vegetable (Mimosa):
25% tannins (70% tan.cont.)
Chamois (Oil):
25% offer
White-tan. (Syntan):
20% tan.ag. (95% tan.cont.)
Importance of tanning methods, today
• Chromium Tannage:
ca. 80 – 85 %
• Chrome-free Tannages:
ca. 15 – 20 %
– Percentage of chrome-free Automotive
Leather (FOC)
ca. 25 – 30 %
Worldwide leather production
– in % of industrial application field –
60
50
40
% 30
20
10
0
Footwear Furniture Clothing Others
+Auto
Source: Estimation on
basis of FAO- &
other statistical
data
Chrome-free leathers (“FOC-leathers”)
– mainly in the automotive sector –
Principle:
• Wet-white pre-tannage by glutaraldehyde-

tanning agents (partially modified) or THPS
• Retanning by polyphenols
(vegetable and syntan tanning agents)
and other organic-synthetic retanning agents
Advantages + Disadvantages in comparison

to chrome leathers
Advantages:
no “heavy metal”
less problems in solid waste disposal
(including sludge)
improved dry-shrinking behaviour
Advantages + Disadvantages in comparison

to chrome leathers
Disadvantages:
higher COD in the effluent

reduced fixation of dyestuffs and fatliquoring agents
extremely difficult hydrophobing
more difficult “handling” in production and processing
lower stability and mould resistance of semi-finished
products (wet-white)
The course of tanning
in modern processing
Pre-tanning/Main Tanning Retanning/Filling
stabilisation for adjustment of the

mechanical treatment required leather
(sammying, shaving) characteristics
production of a storable (e.g. fullness, shape-
and transportable semi- retention ability, grain
finished leather product firmness, embossability,
(wet-white, wet-blue) buffability)
Retanning/Filling
• Application of
– vegetable tannins – syntans
– resins – polymers
– mineral tanning agents – aldehydes
Recent research & developments
… concerning
“Pre-tanning”
search for new, ecologically beneficial methods of

pre-tanning / resp. stabilising of the skin (collagen
matrix)
e.g.:
wasserglass stabilisation
enzymatic crosslinking
application of natural plant
crosslinkers (from olive waste)
Main objectives
To establish an innovative, sustainable and

environmentally friendly tanning system – as an
appropriate complement to the existing tanning methods
The stabilisation/pre-tanning of the skin material – under

the avoidance of conventional chemical tanning agents –
so that a satisfactory mechanical processability
(shaveability) can be achieved
To obtain by-products/waste (shavings), enabling

practically unlimited usage
Wasserglass stabilisation
Skin stabilisation by Wasserglass results in a white,

stable and shaveable material.
Stabilised pelts are storable for months

However, there is no (significant) increase in the
shrinkage temperature
hesitations / reluctance for technical application
Basis of the biotechnological
tanning system
• application of an enzyme from the group of
Transglutaminases
• technical applications already exist in the field of

food-technology
• the effect of crosslinking results in the formation of

high-molecular protein aggregates with modified
characteristics (e.g. increased thermal stability)
• irreversible crosslinking by covalent isopeptide bonds

between Glutamine- and Lysine-side chains.
Enzymatic crosslinking
C=O O=C
HN NH
–(CH2)2–CO–NH2 NH2–(CH2)4–
O=C Glutamine Lysine C=O
NH Transglutaminase + H+ HN
R– – NH4+ –R
C=O O=C
Enzymatic crosslinking
C=O O=C
HN NH
-CH2-CH2-CO-NH-CH2-CH2-CH2-CH2-
O=C Glutamine Lysine C=O
NH HN
R– –R
C=O O=C
Status and limitations
By the application of Transglutaminase, sufficient
stabilisation (significant increase in the shrinkage
temperature) – as required for leather manufacturing –
could not be achieved.
Transglutaminase (TG) produces, however, irreversible
crosslinking with denaturated collagen (gelatine).
Why collagen-crosslinking without denaturation is not

adequate?
- TG is too large?
- No diffusion into the „right position“?
- sterical conditions / crosslinking distance of liable
groups are inappropriate?
Natural plant crosslinkers
Application of an activated extract from

olive solid waste produced technically Olea europea
promising results:
a stable leather intermediate (“wet-green®”)

with good shaveability
and TS > 70°C
forming an excellent basis
for crust leather production
Economical feasibility –
raw material availability
• Olive solid waste material: leaves, pomace/residue,
effluent from olive oil- and table olive production
• In Europe (> 95% of world cultivation area for olive trees)
approximately 30 mio. tons of olive-solid waste materials
are produced
• Future research work with our partners

will focus on practical application and
improvements in the economics of the
new („wet-green-tanning“) process
The issue of mould growth in a
(semi-processed) leather
• A delay of further processing in the wet-blue or

wet-white stage can lead to mould growth and
hence a potential loss in quality and value
• Avoiding such losses includes the use of effective

preservatives (fungicides) in the (pre-)tanning
system
Future investigations
“Pre-tanning”
NEW additional objective:
an universal intermediate stage

requiring no preservation
i.e. an intermediate stage of leather which can be

- subjected to drying a n d
- subsequently wetted-back
without any problems
Future investigations
Aims:
– avoiding losses from mould attack
– avoiding the application of undesirable chemical
agents
Tasks:
– appropriate stabilisation / crosslinking and
sufficient increase in the shrinkage temperature to
enable sammying and shaving
– appropriate “fibre separation” (e.g. by the filling
effect of certain tanning agents or fatliqours) to
enable drying without sticking within the fibrous
collagen structure
Sustainable leather manufacture
– future challenges
In principle, leather manufacturing is in itself ‘recycling’
– i.e. it is a sustainable solution to the disposal problem
of a by-product that originates from the meat industry
The concept of ‘globalization’ in leather production has

to be updated / adjusted by taking more into account
additional factors like e.g. raw material sourcing that is
also relevant to the subject of sustainability
Sustainability of leather manufacture can be further

increased by using resources (i.e. water, fossil fuels
and other natural resources) sparingly, and giving
priority to the use of renewable resources
Thank you very much
for listening

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BM DAS MEMORIAL LECTURE 2010

Sustainable Leather Manufacture –

…according to the World Commission on

= development that “meets the needs of

• more recent evidence dating back to

• implying also the first attempt for “pollution

… is a sustainable environmental solution to

-CH2-S-S-CH2- -CH2-SH + HS-CH2-

2. Step: splitting of peptide bonds

… with the following objectives:

– rapid penetration and uniform distribution of the

– avoidance of any residual process liquors

– conducting e.g. chrome tannage without pickling

depending on the intended use

• development of high exhausting chrome tanning

• Wet-white pre-tannage by glutaraldehyde-

Advantages + Disadvantages in comparison

Advantages + Disadvantages in comparison

higher COD in the effluent

Pre-tanning/Main Tanning Retanning/Filling

stabilisation for adjustment of the

search for new, ecologically beneficial methods of

To establish an innovative, sustainable and

The stabilisation/pre-tanning of the skin material – under

To obtain by-products/waste (shavings), enabling

Skin stabilisation by Wasserglass results in a white,

Stabilised pelts are storable for months

• technical applications already exist in the field of

• the effect of crosslinking results in the formation of

• irreversible crosslinking by covalent isopeptide bonds

Why collagen-crosslinking without denaturation is not

Application of an activated extract from

a stable leather intermediate (“wet-green®”)

• Future research work with our partners

• A delay of further processing in the wet-blue or

• Avoiding such losses includes the use of effective

NEW additional objective:

an universal intermediate stage

i.e. an intermediate stage of leather which can be

The concept of ‘globalization’ in leather production has

Sustainability of leather manufacture can be further

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