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From leather waste to functional leather

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 M.J. Escoto-Palacios
M.A. Pérez-Limiñana
F. Arán-Ais

INESCOP, Instituto Tecnológico del Calzado y Conexas

 Edited by:

INESCOP, Instituto Tecnológico del Calzado y Conexas

Authors:

María José Escoto Palacios

María Ángeles Pérez Limiñana

Francisca Arán Ais

Contributor:

C.G.S. di Coluccia Michele & C. s.a.s.

“From leather waste to functional leather” was edited in the framework of the LIFE microTAN
project (LIFE12 ENV/ES/000568), a project that was partially funded by the European
Commission through the LIFE+ Programme.

ISBN 978-84-934261-9-4

2016 INESCOP, Elda

 Contents

Contents

1. Introduction ............................................................................................................................. 3
1.1. The European tanning industry ....................................................................................... 3
1.2. Tanneries and the Environment ...................................................................................... 4
1.3. LIFE microTAN proposal ................................................................................................... 8
2. From hides/skins to leather ..................................................................................................... 9
2.1. General overview of the tanning processes .................................................................... 9
2.2. Preparation operations .................................................................................................. 11
2.3. Stages before tanning: Beamhouse operations............................................................. 11
2.4. Waste generated ........................................................................................................... 14
3. LIFE microTAN: Towards a circular economy at tanneries .................................................... 17
3.1. EU policies on Green and Circular Economy .................................................................. 17
3.2. The circular economy approach of LIFE microTAN ........................................................ 21
4. From leather by-products… ................................................................................................... 25
4.1. From collagen to gelatine .............................................................................................. 25
4.2. Current gelatine production process ............................................................................. 28
4.3. Alternative process: LIFE microTAN ............................................................................... 30
4.4. Demonstration plant...................................................................................................... 32
4.5. Environmental benefits.................................................................................................. 34
4.6. Economic feasibility ....................................................................................................... 34
5. … to functional leather ........................................................................................................... 37
5.1. Microencapsulation ....................................................................................................... 37
5.2. Gelatine in microencapsulation ..................................................................................... 37

From leather waste to functional leather 1

 5.3. Leather functionalisation ............................................................................................... 39
6. Long-term benefits................................................................................................................. 43
6.1. Environmental benefits.................................................................................................. 43
6.2. Support to EU policies.................................................................................................... 44
6.3. Socio-economic benefits................................................................................................ 45
7. Glossary .................................................................................................................................. 47
7.1. Abbreviations ................................................................................................................. 47
7.2. Glossary of keywords ..................................................................................................... 47
8. Bibliography ........................................................................................................................... 53
 Introduction

1. Introduction demand for milk and meat, gave rise to

1.1. The European tanning industry
According to FAO [1], the worldwide cattle
population raised to over 3,800 million
heads in 2014, out of which 195 million
were grown in the EU27. This livestock,
which is grown in order to meet the
the worldwide production of over 1,400
million pieces of raw hides and skins (see
Figure 1.1). This by-product of the meat
industry is recovered and processed by the
tanning industry to produce leathers that
are used in the manufacture of footwear,
leather goods and clothing.

Figure 1.1. Distribution of the production of raw hides and skins in 2014. Data [1] expressed in thousands of pieces.

From leather waste to functional leather 3

Europe has a long tradition in the
production of leather and other products
made thereof. Indeed, Europe plays a
significant role in international leather
trading, being one of the most ancient and
dynamic markets. In fact, according to FAO
data [1], EU27 countries shared 37% (in
value) of worldwide exports in 2013.
Besides, according to Eurostat database,
the EU28 tanning industry in 2014 was
made up of about 3,328 companies with
an estimated turnover of 11,000 million
Euros and employed about 42,070 people.
However, the global economic crisis, along
with the competence form third countries
with lower-wages and more tolerant
environmental legislation, have negatively
affected the European leather sector, and
the local economies of the tanning areas,
in terms of both production and
employment.
According to the European Confederation
of the Leather Industry (COTANCE),
competition from countries with loose
social and environmental standards causes
socio-economic damage equivalent to
dumping [2].
Other threatening factor is the increasing
influence of vegan lifestyle.
Nevertheless, Europe is still considered to
be leader in this industry. Its main
strengths are the high quality of its
products, its environmental and social
commitment, its involvement in fashion
trends and its willingness to the
implementation of technologies in order
to improve processes and products.
Figure 1.2 summarises the main strengths,
weaknesses, opportunities and threats
(SWOT) for the European tanning industry.
1.2. Tanneries and the Environment
Even though this sector is considered to
play an important environmental role
because it reuses the by-products of the
meat industry, the processes carried out in
the different stages have in turn an
important environmental impact.
Environmental issues at tanneries deal
with resources consumption (water,
chemicals and energy) and the generation
of wastewater, solid waste and
atmospheric emissions, such as volatile
organic compounds.
 Introduction

Figure 1.2. SWOT analysis of the European leather industry. Based on [3].

Thus, although there is no specific EU Accordingly, the following EU regulations

legislation for the leather industry, this
sector is affected by different measures
concerning the Environment, the use of
chemicals, the marketing and use of
certain hazardous substances as well as
the use of animal by-products.
have implications for the leather industry:
Regulation (EC) No 1907/2006 on the
Registration, Evaluation, Authorisation
and restriction of Chemical substances
(REACH) [4], as the industry is an

From leather waste to functional leather 5

 important downstream user of a wide
range of chemical preparations.
Regulation (EU) No 1069/2009 on
animal by-products and derived
products not intended for human
consumption [5], as hides and skins are
materials of animal origin that are used
outside the food chain.
Directive 2010/75/EU on industrial
emissions [6] according to which permit
conditions, including emission limit
values, must be based on the Best
Available Techniques (BAT). The BAT
reference document (BREF) for tanning
of hides and skins was adopted in 2013
[7].
During the transformation of hides and
skins into leather, big quantities of solid
organic waste are generated in that a
percentage of the raw material is rejected
due to either a lack of properties or
because of aesthetic reasons.
Furthermore, hair, wool, fleshings and
sebum are removed from the skins during
beamhouse operations in the tanning
process. In fact, it is estimated that the
yield of finished leather hardly reaches
25% by weight of raw salted hides [7]. In
addition, other solid wastes are also
produced, including preserving salts,
buffing dust and sludge from wastewater
treatment, among others.
Figure 1.3 shows a general overview of
inputs and outputs in a conventional
tannery, as estimated for the
transformation of bovine salted hides into
leather [7].
According to the List of Waste (LoW),
established in Commission Decision
2014/955/EU [8], wastes deriving from
tanning operations are classified as shown
in Box 1.1. Only wastes containing solvents
have a hazardous entry.
This means that, for the time being, the
European legislation does not consider
untanned waste to be hazardous, and
therefore it has been long disposed of in
landfills.
 Introduction

Figure 1.3. Input/output overview in a conventional tannery. Processing of bovine salted hides (Based on [7])

04 01 wastes from the leather and fur industry

04 01 01 fleshings and lime split wastes
04 01 02 liming waste
04 01 03* degreasing wastes containing solvents without a liquid phase
04 01 04 tanning liquor containing chromium
04 01 05 tanning liquor free of chromium
04 01 06 sludge, in particular from on-site effluent treatment containing chromium
04 01 07 sludge in particular from on-site effluent treatment free of chromium
04 01 08 waste tanned leather (blue sheetings, shavings, cuttings, buffing dust) containing chromium
04 01 09 wastes from dressing and finishing
04 01 99 wastes not otherwise specified

Box 1.1. Classification of wastes from the leather and fur industry. Wastes marked with an asterisk have a
hazardous entry.

From leather waste to functional leather 7

Yet, restrictions are becoming stricter for
organic waste disposal. Furthermore, the
European Union is promoting waste
recovery and valorisation through the
transformation into added-value products
that can be recycled or reused by other
industries, contributing to a circular
economy model.
1.3. LIFE microTAN proposal
This is how the LIFE microTAN project
emerged in the framework of the EU’s
financial instrument for the Environment
and Climate.
It is an initiative of Spanish and Italian
partners – countries gathering more than
64% of the European leather industry –
and aims to recover tannery waste to be
reused by other industries.
In particular, the project’s purpose is to
valorise untanned waste. Specifically, the
project intends to obtain gelatines to be
used as a shell-forming material for the
microencapsulation of active substances.
Thus, LIFE microTAN deals with
valorisation of tannery waste to produce
functional materials, used in different
consumer products intended to optimising
user’s well-being.
In short, LIFE microTAN is an
environmental project that envisages the
recovery of tannery waste rich in collagen,
contributing to a circular economy model
and entailing socio-economic advantages.

2. From hides/skins to leather
2.1. General overview of the tanning
processes
The transformation of animal skins and
hides into valuable materials used in the
manufacture of products such as shoes,
leather goods, etc. requires a series of
chemical and mechanical processes.
The very first operations are performed in
the slaughterhouse, whereas the
subsequent operations take place in
tanneries.
The processes carried out since the skins
or hides reach the tannery until tanning
takes place, constitute the so-called
beamhouse operations.
Subsequently, several operations are
carried out at the tanyard area of the
tannery, where collagen fibres in hides and
From leather waste to functional leather
From hides/skins to leather
skins are stabilised so that they are longer
susceptible to putrefaction or rotting.
In the post-tanning area, several
operations known as wet-finishing
processes are carried out in order to
provide leathers with certain
characteristics. These features include
colour or feel at touch, as well as
functional properties such as water
repellence or resistance, oleophobicity,
gas permeability, flame retardance,
abrasion resistance or antistatic
properties.
Finally, leathers are subjected to different
mechanical and/or chemical finishing
operations in order to modify their final
appearance.
Figure 2.1 shows a diagram of the main
stages of the process as it takes place in
most tanneries.
9
 Figure 2.1. Main operations in the transformation of skins and hides into leather. (*) Splitting stage can be
performed either before or after tanning.

The LIFE microTAN project focuses on the the tanning phase. The main operations
recovery of untanned wastes. For this included in the preparation and
reason, the main processes of interest for beamhouse phase are briefly explained
the project are those carried out prior to below.

2.2. Preparation operations
2.2.1. Flaying
This process takes place in the
slaughterhouse and consists in removing
the skin or hide from the animal. Special
care is required in this step, since an
inappropriate procedure can inflict defects
on skins and hides, thus reducing their
value and increasing the amount of solid
waste at tanneries.
2.2.2. Preservation methods
In order to ensure that skins and hides
reach tanneries in suitable conditions, a
series of preservation or curing operations
are necessary, which prevent hide or skin
degradation and putrefaction that can be
caused by external factors as well as by
their own enzymes. Moisture content of
fresh-flayed skins and hides is close to
60%, which favours degradation. The
following preservation methods can be
applied.
Air drying: The best option for skins is to
place them in the open air, in a breezy
place. It is important that drying takes
place quickly on both sides (grain and flesh
From leather waste to functional leather
Form hides/skins to leather
sides). Once dried, skins are kept at
temperature below room temperature.
Salting: Sodium chloride has been used to
preserve skins and hides since the middle
19th Century. 35-50% w/w of salt with
respect to skin/hide is spread on its
surface. Salt removes moisture from the
skin/hide and provides an unfavourable
medium for most microorganisms’ growth.
This treatment allows skins/hides to be
stored for weeks or months. Currently, this
is still the most commonly used method.
Chilling: Temperature is reduced as fast as
possible from 36ºC to 2ºC. When done in a
short period of time, a correct
preservation and quality of the product is
ensured. Once chilled, skins and hides can
be stored at 2ºC for 15-20 days.
2.3. Stages before tanning:
Beamhouse operations
“Beamhouse operations” is a term that
refers to the chemical, chemical-physical,
enzymatic and mechanical processes that
are aimed to prepare the stored raw hides
and skins for the tanning process. The
11
solid wastes generated in these steps
were explored as a raw material for LIFE
microTAN project.
Below, the different steps of beamhouse
operations, as performed at Spanish and
Italian tanneries, are described.
2.3.1. Soaking or stripping
This is the first operation, and it mainly
consists in a treatment with water that
involves two steps. First, the skin/hide is
washed to remove dirt as well as salt from
preservation stages. In the second step,
the fibre is rehydrated. To this end,
bactericides, sodium hydroxide,
proteolytic enzymes and moisturising
agents are also added. This process allows
salts and other soluble materials to be
removed, leading to clean, soft and
rehydrated skins/hides.
2.3.2. Unhairing or liming
In this step, the hair or the wool is
removed along with the epidermis. In this
process, the corium-epidermis union is
cleaved and the hair root is softened,
allowing their separation. Besides, this
operation facilitates the saponification and
elimination of fats.
Most commonly used methods for hair
loosening are chemicals, mainly sodium
sulphide and lime. They act as swelling
agents on the skin collagen. It is important
to tune the swelling of the skins according
to the type of leather that is being
produced. Sulphide acts also as a shaving
agent separating the keratin groups. A
solution of sodium sulphide at a relatively
high concentration destroys both hair and
epidermis. The liming phase modifies also
the content of natural fats present in the
skin which become easily removable.
Furthermore during this phase most of
globular proteins are removed. Some
amine-based chemicals are often used in
this stage in order to facilitate the
loosening of the epidermis fibres and to
control the swelling of the skin.
Some tanneries are replacing these
chemicals by new thiol-based products
that allow hair recovery. This system gives
good results both in terms of quality of the
final product and from the environmental
point of view, reducing the amount of
pollutants in the sludge.

Other tanneries are replacing the
traditional method by an enzymatic
treatment with bacterial alkaline
proteases, thus reducing the
environmental impact of effluents from
this step, as well.
It is important to point out that, after this
operation, hides and skins are no longer
subject to animal by-products controls
[7].
2.3.3. Fleshing
At this stage, residual flesh, subcutaneal
and adipose tissues, are removed in a
mechanical way. Wastes obtained in this
process are called “fleshings”.
2.3.4. Splitting
The aim of splitting is to make the
skin/hide thickness even, allowing tanning
and staining to be more homogeneous. If a
hide is too thick, it is split into two layers:
the grain layer and the flesh split. The
grain layer is the outermost, and maintains
the whole dermis structure. The split layer
is the innermost and only maintains the
reticular dermis. Some tanneries carry out
this operation after tanning. Nevertheless,
From leather waste to functional leather
Form hides/skins to leather
tanneries are advised to split hides/skins
beforehand (“after liming”) so that wastes
are free from chemicals used in tanning
processes, reducing the environmental
impact. Furthermore, from the LIFE
microTAN project point of view, following
this recommendation will enable a higher
recovery of collagen from untanned
wastes.
2.3.5. Deliming
As above described, most tanneries carry
out the unhairing process by means of
lime and sulphide baths. Part of the lime
(especially that between the fibres and on
top of the fibres) is removed by washing
the skins with water, but some lime is
retained on the skin/hide, making it highly
alkaline.
The remaining lime makes hides and skins
highly alkaline and can have deleterious
effects at further stages at the tannery. In
the deliming operation, acids are used in
order to reduce alkaline swelling, remove
the remaining lime from hides/skins and
lower the pH, so that enzymes used in the
bating stage (a process that sometimes is
13
carried out simultaneously to deliming)
can act in optimal conditions.
2.3.6. Bating
In order to get leather with a soft, smooth
touch, and a thin, silky grain layer,
hides/skins have to be subjected to the
bating process. This consists in an
enzymatic treatment that cleans the grain
layer and removes proteins other than
collagen (albumin, globulin, etc.) that are
not suitable for leather production.
Specific enzymes acting on proteins are
called proteases, and the most common in
the bating stage are pancreatic proteases
(trypsin), fungal proteases, bacterial
proteases and mixtures of them. Bating
provides hides and skins with higher
porosity, thus enabling tanning agents to
penetrate the skin/hide.
2.4. Waste generated
As previously stated, in the production of
leather, a high percentage of raw material
is rejected as solid waste. Besides,
processes carried out at the different
stages have an important environmental
impact. Table 2.1 summarises the above
described stages, the chemicals used and
the main environmental impacts
associated to each of them. Wastes in
bold have been considered as a raw
material in the LIFE microTAN project.
 Form hides/skins to leather

Table 2.1. Main environmental impacts in preparation and beamhouse operations.

Chemicals Action Wastes

Preservation
Salting or draying treatment to Contaminated salt
Salt
prevent skin/hide putrefaction Raw hide/skin trimmings
Soaking
Water/Surfactants/
Salted and contaminated
Enzymes Skin/hide cleaning and rehydrating
wastewater
Bactericides
Unhairing (liming)
Hair
Water/sodium sulphide
Alkaline water and water rich in
or sulphydrate Hair removing
sulphur, with a high organic
Lime/Enzymes
content
Fleshing
Water Mechanical operation where adipose Fleshings
Mechanical processes tissue is removed using blades Alkaline water
Splitting
Skin/hide Skin thickness evening Limed hide/skin grain and split
Deliming
Water
Removing lime retained on the
Ammonium sulphate Slightly acidic wastewater
skin/hide
Weak acids
Bating
Enzymatic degradation of fibres in the Neutral/slightly alkaline
Enzyme
dermis wastewater

During the project development, two case
studies of the environmental and socio-
economic impact in two Italian tanneries
located in Santa Croce sull'Arno (Italy)
were carried out.
In this study, a catalogue of solid waste
generated at these tanneries, as well as
the cost of their management was
prepared. Table 2.2 summarises the
results obtained in this analysis.

From leather waste to functional leather 15

Table 2.2. Case studies in two Italian tanneries. Solid waste generated and environmental costs.

Average amount Environmental costs

Waste type
(tonnes/year) (€/tonne)
Milling salts 110 100
Raw skin trimmings 100 100
Fleshings 535 80
Tanned scraps 225 65
Sludge 1,460 100
 LIFE microTAN: Towards a circular economy at tanneries
3. LIFE microTAN: Towards a
circular economy at
tanneries
3.1. EU policies on Green and
Circular Economy
Environment and Economy are terms that
traditionally seemed to have nothing to do
with one another, or even to confront.
Nevertheless, current European policies
enforce that both concepts go hand in
hand. Thus, the term Green Economy has
arisen, which is defined by the European
Environment Agency (EEA) as an economy
“in which policies and innovations enable
society to use resources efficiently,
enhancing human well‑being in an
inclusive manner, while maintaining the
natural systems that sustain us” [9].
In its Communication Europe 2020 – A
strategy for smart, sustainable and
inclusive growth [10], the European
Commission established the priority
“Sustainable growth: promoting a more
resource efficient, greener and more
competitive economy” as a strategy to
help Europe emerge from the crisis.
From leather waste to functional leather
More recently, the European Commission
has expressed its intention to enhance
Europe's ecological resilience and
transform the EU into an inclusive and
sustainable green economy. To this end,
the EU 7th Environment Action Programme
(7th EAP, [11]) has established the
following three thematic priorities:
Priority objective 1: To protect, conserve
and enhance the Union’s natural capital.
Priority objective 2: To turn the Union into
a resource-efficient, green and
competitive low-carbon economy.
Priority objective 3: To safeguard the
Union’s citizens from environment-related
pressures and risks to health and well-
being.
In a circular economy, the value of
products, materials and resources is
maintained in the economy for as long as
possible, and the generation of waste is
minimised [12]. Circular economy is thus
considered as an instrument in achieving
the second objective of the 7th EAP, and
can be represented as the core of a green
economy perspective (see Figure 3.1).
17
Figure 3.1. Circular economy in the context of green economy. Adapted from [13].
 LIFE microTAN: Towards a circular economy at tanneries
In 2015, the European Commission
released its Communication Closing-the-
loop - An EU action plan for the Circular
Economy [12]. This document established
an ambitious Circular Economy Package
with the aim of encouraging both
European businesses and consumers to
make a more sustainable use of resources
by implementing a circular economy.
This Circular Economy Package establishes
a precise and ambitious program of
actions, with measures that include a
revision of Directive 2008/98/EC
[14] on waste and Directive 1999/31/EC
[15] on the landfill of waste [16, 17],
among others. Besides, this action plan
covers the whole cycle: from production
and consumption to waste management
and use as secondary raw materials. In
contrast to the traditional, linear “extract-
transform-use-dispose” economy model,
the European Commission proposes
"closing the loop" of products’ lifecycles
by increasing recycling and re-use, in
favour of both the Environment and
economy.
The revised legislative proposals on waste
set clear targets for waste and landfill
From leather waste to functional leather
reduction, and establish a road map for
waste management and recycling. A key
element of the revised waste proposal
includes specific measures to promote re-
use by turning by-products into raw
materials, which will also stimulate
industrial symbiosis.
Figure 3.2 shows a simplified model of
circular economy for both energy (outer
circle) and materials (middle circle). The
inner circle represents reuse, repair,
redistribution, refurbishment and
remanufacture as eco-design enabling
factors [13].
In the implementation of this circular
economy, one of the industrial sectors to
pay attention to is the tanning industry. As
previously stated, even though this sector
is considered to play an important
environmental role because it reuses the
by-products of the meat industry,
processes carried out at the different
stages generate a large quantity of solid
waste. For this reason, the European
tanning sector needs to implement new,
greener strategies and solutions to provide
a cleaner, more sustainable and more
competitive industry.
19
Figure 3.2. Simplified model of the circular economy for materials and energy. Credit: EEA [13].
 LIFE microTAN: Towards a circular economy at tanneries

3.2. The circular economy approach
of LIFE microTAN
The tanning processes carried out during
the different stages involved in the
transformation of hides and skins into
leather generate significant amounts of
both liquid (wastewater) and solid (tanned
and untanned waste and sludge) waste.
Several approaches have been suggested
for the minimisation, treatment and
valorisation of effluents and solid wastes
generated by the leather industry. Figure
3.3 shows several proposals for
valorisation of solid wastes from tanneries
and slaughterhouses [7, 18-21].

Figure 3.3. Proposals for valorisation of solid wastes from tanneries and slaughterhouses.

From leather waste to functional leather 21

An important part of the waste generated
at tanneries is rich in collagen. The
advancement of European policies and
legislation protecting the environment has
prompted the transformation of tannery
solid waste materials into valuable
collagen derivatives that can be recycled
or employed in other industries, for
instance for the preparation of organic
fertilisers, the production of biomaterials,
gelatines or collagens, and the production
of bio fuel [18].
The gel-forming properties of gelatine, a
collagen derivative, are the basis for its
classical application in food, photographic,
cosmetic and pharmaceutical industries.
Besides, new applications have arisen,
such as its use as a shell-forming polymer
for microencapsulation applications [22-
24].
Microencapsulation consists of a coating
technology by which active substances are
encapsulated in a polymeric shell, leading
to core-shell particles called microcapsules
(see Figure 3.4).
Figure 3.4. Microcapsule structure. Shell: polymeric
cover; Core: encapsulated active chemical.
Microencapsulation is an effective method
to prevent reactive, sensitive or volatile
chemicals from reacting with moisture,
light and oxygen. Besides, this technology
not only enhances stability against
external factors, but also allows controlled
release of the active substance. Indeed,
microcapsules, when firmly anchored to a
material such as leather, can add new
smart functionalities without affecting
look and feeling at touch.
Therefore, this technology holds great
promise for the future of tanneries and
leather end-user industries, such as
footwear. It can transform a traditional
leather-made item into an active one by
 LIFE microTAN: Towards a circular economy at tanneries

incorporating microencapsulated products agent in the production of active

with active properties.
In this context, LIFE microTAN (LIFE12
ENV/ES/000568) focuses on the recovery
of collagen derivatives from untanned
solid wastes. More specifically, it deals
with the isolation of gelatine in order to
use it as a natural microencapsulating
materials, such as leather, with functional
properties. Thus, LIFE microTAN is a
proposal for “closing the loop” within the
tanning industry. Figure 3.5 shows the
general overview of the circular economy
approach of the LIFE microTAN project.

Figure 3.5. Circular Economy approach of the LIFE microTAN project.

From leather waste to functional leather 23

 From leather by-products…

4. From leather by-products… known, which differ in chemical and

4.1. From collagen to gelatine
Collagen is the most frequently occurring
protein class in both animals and humans.
Furthermore, along with cellulose and
lignin, it is one of the three dominant
biopolymers, from a quantitative point of
view.
Collagen is not a single substance but a
family. Several types of collagen are
structural properties as well as in their
function in the living organism. Type I is
the most abundant type of collagen, and is
a primary component of the skeleton and
the skin.
In contrast to spherical globular proteins,
Type I collagen is a scleroprotein that is
found as linear, fibre-like hierarchical
structures (see Figure 1.1).

Figure 4.1. Hierarchical microstructure of Type I collagen. Based on [25].

From leather waste to functional leather 25

Type I collagen is composed of three left-
handed α-helix chains, two of which are
identical (α1) and one is slightly different
(α1). The three α-chains are then twisted
around each other into a right-handed
super-helix to form a rigid structure called
tropocollagen. This structure is stabilised
by hydrogen bonds and represents the
basic building blocks of the collagen tissue.
Due to their charge distribution, these
basic structures are assembled into groups
of four to eight tropocollagen units.
Successive layers of such assembly
constitute a microfibril, which is in turn the
basic unit to form the so-called collagen
fibrils. The entire structure is stabilised
and reinforced by cross-links in the form of
covalent bonds. Many of these collagen
fibrils are then further cross-linked to form
the basic structure for tissues such as skin
and bones.
Such structure makes native collagen be
water-insoluble. For this reason, in the
manufacture of gelatine, treatment of the
animal raw material needs to be carried
out in order to partially cleave cross-links,
leading to “warm water-soluble collagen”:
gelatine.
This collagen denaturation and hydrolysis
is known as “conditioning process or pre-
treatment” within the gelatine industry. In
the subsequent extraction step, i.e.
melting out of gelatine from the raw
material, an additional thermal hydrolysis
step takes place. This reduces the
molecular weight still further.
Gelatine shows a wide range of properties
such as gel strength, film-forming
capability, and emulsion properties,
among others, which determine its final
application. The gel-forming properties of
gelatine are the basis for
microencapsulation applications.
In turning collagen into gelatine, the effect
of the conditioning process parameters
(acid, alkali or enzymatic, as well as
thermal energy) leads to different types of
collagen fragments, so a mixture
comprising different molecular weights is
obtained.
Therefore, a controlled partial hydrolysis
of the crosslinks and peptide bonds of the
original collagen structure (untanned hide
wastes) is necessary to obtain suitable
properties for the application envisaged.
 From leather by-products…

Gelatine properties are also governed by by-product. Considerable topographical

extraction conditions (temperature, pH,
time, etc). Therefore, the optimisation of
the transformation process of collagen
into gelatine is necessary in order to
obtain specific properties suitable to their
use in added value applications, for
instance as a shell forming biopolymer for
microencapsulation [23, 26-28].
differences exist among the different
layers within hides and skins, in terms of
weave density, angle of the collagen
fibres, etc. Such differences can affect the
extraction conditions and the properties of
gelatines. Figure 4.2 shows the different
layers that can be found in hides and skins.

Last but not least, collagen properties vary

as a function of the different layers of
hides and skins and, therefore, the type of

Figure 4.2. Different layers of hides and skins. Adapted from “Section of animal skin” in [29] (original image in the
public domain).

From leather waste to functional leather 27

Furthermore, any previous treatment
suffered by the by-product may affect the
gelatine extraction process.
4.2. Current gelatine production
process
Collagen is the main protein component of
mammalian and fish skins, bones and
connective tissues. It is a water-insoluble
protein of great industrial interest that can
only be extracted by hydrolysis. A partial
hydrolysis of this protein leads to gelatine.
A stronger hydrolysis leads to low
molecular peptides known as collagen
hydrolysates.
Currently, the gelatine industry obtains
both hydrolysed collagen and gelatine
directly from Category 3 bones, hides and
skins.
Collagen hydrolysates are commonly
produced by enzymatic hydrolysis.
In general, gelatine extraction
requirements of can be summarised in an
alkaline or an acid treatment to achieve
the cleavage of collagen crosslinks
followed by extraction with warm water.
The diagram in Figure 1.2 summarises the
main techniques commonly used for
obtaining gelatines from slaughterhouses
and animal by-products industry wastes.
However, such procedures should be
improved in order to save time, energy
and water consumption. Bones pre-
treatment and gelatine drying stages are
high energy consuming processes.
Furthermore, demineralisation, liming and
hydrolysis steps require large quantities of
water, and the resulting wastewater must
be conveniently treated.
In addition, according to the BREF
document on Best Available Techniques in
slaughterhouses and animal by-products,
high protein levels are found in
wastewater, which means that more
efficient processes for the recovery of this
protein fraction should be developed.
 From leather by-products…

Figure 4.3. Current main procedures for obtaining gelatine. 1: Cut pigskin; 2: Cut and defatted hides/skins; 3: Hair-
free hides; 1’: Crushed bones; 2’: Tallow/water mixture; 3’: Defatted bones and sinews; 4’: Ossein; 5: Gelatine.

From leather waste to functional leather 29

4.3. Alternative process: LIFE
microTAN
The LIFE microTAN project focused on the
valorisation of untanned bovine hide by-
products. As previously stated, this kind of
by-products is conventionally pre-treated
by the alkaline procedure.
However, alkaline pre-treatment is a long-
term process that can take several weeks,
even months, and which requires big
volumes of water and alkali, thus
generating large quantities of wastewater.
Nowadays, the enzymatic pre-treatment
as an alternative to the alkaline pre-
treatment for gelatine manufacture is
raising interest in order to save costs by
reducing wastewater and time [23, 27].
Proteolytic enzymes (proteases) are
commonly used in the detergent industry
for breaking down proteinaceous matter
caused by body secretions, food stuff, and
blood. Such type of enzymes are also being
employed in the leather industry as an
alternative to conventional agents used in
unhairing, bating and soaking processes
[30].
The use of this kind of enzymes for the
conditioning of hides prior to gelatine
extraction was proposed by the LIFE
microTAN project as a new enzymatic pre-
treatment, alternative to the alkaline and
acid pre-treatments, in order to minimise
the environmental impact, as well as to
reduce processing time.
Thus, in the LIFE microTAN project, both
the pre-treatment and extraction stages
were optimised in order to produce
gelatine with suitable properties for
microencapsulation applications.
Figure 4.4 shows a diagram of the
proposed procedure, as carried out at
laboratory scale.
This enzymatic procedure proved to
provide the following advantages:
Appropriate: When the pre-treatment
reaction is carried out under optimised
conditions, by-products are transformed
into gelatine with adequate properties for
microencapsulation applications.
Efficient: Depending on the type of by-
product, the process allows the recovery
of up to 90% collagen as gelatine.
 From leather by-products…

Figure 4.4. Diagram of the proposed procedure, on a laboratory scale, for non-tanned by-products pre-treatment
and gelatine extraction.

Versatile: By adjusting pre-treatment Environmentally-friendly: The enzymatic

conditions, the process allows the process gives rise to a significant reduction
recovery of different grades of product, in water and chemicals consumption,
from hydrolysed collagen to gelatines with when compared with the conventional
high-medium gelling power (Bloom value). alkaline process.

From leather waste to functional leather 31

Quick: The proposed enzymatic pre-
treatment allows a reduction of treatment
length from weeks to hours.
4.4. Demonstration plant
Throughout the project, a demonstration
plan was built, where gelatines were
produced with suitable properties to be
used as a shell polymer in the
microencapsulation of substances.
Figure 4.5. LIFE microTAN demonstration plant located at INESCOP’s facilities, next to a microencapsulation plant.
Figure 4.5 shows the LIFE microTAN
demonstration plant.
It mainly consists of a 100-L, jacketed main
reactor with a heating system by means of
recirculating water. It includes the
necessary components and ancillaries to
ensure the appropriate control of
processing conditions such as pH,
temperature and time.

A filtering system is located at the bottom
of the vessel and at the product outlet
pipe, and an input for compressed air
exerts a positive pressure that facilitates
gelatine extract discharge.
The demonstration plant includes a
switchboard for automated control
systems for the temperature and heating
unit, pH and acid/alkalis dosing pumps,
water inlet, load and level, upper cover
lifting, stirring, vacuum, filtering, piping
valves, centrifugal pumps, cleaning process
and product discharge.
In short, the demonstration plant allows:
Treatment of 25 kg of untanned solid
waste per batch.
Pre-treatment and extraction processes
to be carried out in a single reactor.
Table 4.1. microTAN gelatine main properties. Comparison with commercial B-type gelatines.
Properties microTAN gelatine
Isoelectric point (pI)
Gel strength. Bloom value (g)
From leather by-products…
Automated control of processing
conditions.
By selecting the appropriate conditions,
the LIFE microTAN process is able to
produce different grade gelatines,
suitable for different applications.
Table 4.1 compares the properties of
gelatines produced at the demonstration
plant with those of commercial gelatines
obtained by the conventional alkaline
process (B-type gelatines). Gelatines with
very similar properties to those of type-B
commercial gelatines can be produced in
the demonstration plant.
In the case of gelatines with medium-high
Bloom values (suitable for
microencapsulation), the demonstration
plant key performance data are
summarised in Box 1.1.
Commercial B-type gelatine
4.9 – 5.2 4.7 – 5.2
10 -260 50 - 300
From leather waste to functional leather 33
 Amount of by-product processed
Yield of valorisation (depending on the hide by-product batch)
Amount of valorised product
Whole process duration
Water consumption
Box 4.1. Demonstration plant key performance data.
4.5. Environmental benefits
An important conclusion of the project is
that gelatine from bovine untanned hide
wastes can be successfully extracted as a
valuable co-product using an enzymatic
pre-treatment, alternative to the
conventional alkaline one. The main
environmental benefits of the new process
are derived from this pre-treatment step.
When comparing both processes, the
proposed enzymatic pre-treatment gives a
series of advantages, from both the
environmental and the economic point of
view. Significant savings in time and water
consumption are achieved with the
enzymatic process. A comparison between
both processes is outlined in Figure 4.6.
25 kg/batch
65-90% collagen
2-4 Kg gelatine
8 h/batch
3
0.2 m
As a consequence, a significant reduction
in wastewater generation is also achieved.
An analysis of the wastewater generated
in this pre-treatment process has shown
that it can be completely recovered as a
fertiliser. Alternatively, it could be also
valorised in a biogas production plant.
4.6. Economic feasibility
Gelatine prices are governed by their
properties and final use. Depending on
their Bloom value, prices of commercial
gelatines (industrial grade) can range from
5.30 €/kg (125 g Bloom) to 5.77 €/kg (250
g). Prices of gelatines for use as a
laboratory reagent reach values over 300
€/kg.
 From leather by-products…

Figure 4.6. Comparison between conventional alkaline pre-treatment and microTAN enzymatic process.

A financial feasibility assessment of the A medium production capacity for seven

gelatine produced by the enzymatic
process developed was made, considering
different plant capacities. Costs of gelatine
production were estimated taking into
account the following considerations:
Estimation of gelatine production costs,
considering energy, chemicals and
water consumption, labour costs and
equipment depreciation.
years, 231 working days per year and a
single batch per day were considered.
A conservative yield of 70% of collagen
recovery.
The analysis was made at three levels:
a) The project demonstration plant;
b) A potential production plant to be set
up in the tannery, with a capacity
according to waste generation

From leather waste to functional leather 35

 reported in the case studies (100
tonnes/year);
c) A potential production plant with
higher capacity, to be set up in a
waste management company.
According to this analysis, cost of gelatine
production would range from 48 €/kg to
2.69 €/kg, depending on the facility size. In
the case of tanneries participating in the
case studies, on-site gelatine recovery
from their untanned wastes would have a
cost of 4.59 €. Gelatine costs could be
reduced when 2-3 batches are processed
in the company (shift-work).
Considering these estimated production
costs, applying a sales price of 5.7 €/kg
(industrial grade, 260 g Bloom), and after
deducting current costs for the
management of the recovered untanned
wastes (approx. 10,000 €/year), it was
estimated that benefits for a tannery
recovering 100 tonnes of by-products per
year would be:
• Revenues: 102,600 €/year.
• Profit: 30,000 €/year.
In the case of waste managers, benefits
would be higher due to their higher
production capacity and, therefore, lower
production costs per kg of gelatine.

5. … to functional leather
5.1. Microencapsulation
Microencapsulation technology could be
defined as a process by which active
substances are coated with materials of
different natures, generally polymeric
shells, to obtain micrometric particles
known as microcapsules or sub-
micrometric particles known as
nanocapsules.
Microencapsulation provides protection
and masking of the encapsulated
substance whilst facing unstable or harsh
mediums, allowing its subsequent
progressive release. These factors have
prompted certain industrial sectors, such
as the medical, pharmaceutical, cosmetics,
food and nutrition, agriculture industries,
etc. to base some of their most innovative
products on this technology.
In other sectors, such as the footwear
industry, microencapsulation is regarded
as a technology to obtain innovative
shoes, since it can transform everyday
traditional footwear into smart products,
From leather waste to functional leather
… to functional leather
capable of improving the quality of our
lives.
Biopolymers, such as gelatine, are suitable
as shell-forming materials for the synthesis
of natural and biodegradable
microcapsules that mean an alternative to
other artificially produced substances
deriving from synthetic polymers, like
melamine-formaldehyde, polyurethane, or
polystyrene.
5.2. Gelatine in microencapsulation
One microencapsulation method which
uses gelatine as a shell-forming polymer is
complex coacervation. This process is
based on the phase separation that takes
place spontaneously when in an aqueous
medium, two or more colloids of opposite
charges (a polycation and a polyanion) are
mixed in the presence of a dispersion of an
active substance.
Gelatine is an amphoteric macromolecule,
which is positively charged at a pH below
its isoelectric point (pI). Thus, it is suitable
to be used as a polycation in complex
coacervation reactions. As a polyanion, a
37
polysaccharide is generally used, such as
sodium carboxymethylcellulose (CMC).
In the LIFE microTAN project, several
essences were microencapsulated by
means of this method: rosemary, violet,
jasmine, aloe, orange, magnolia, lavender,
permetrine, ivy, orange blossom, lemon
and tree tea oil. These essential oils were
selected because of their antimicrobial
and/or fragrant properties.
Gelatines obtained at the demonstration
plant, with high-medium gelling properties
(Bloom values ranging from 120 g to 230 g)
were selected as a shell-forming material
for the preparation of microcapsules.
Gelatine extracts were directly used,
without being subjected to drying.
The microencapsulation of the different
oils was confirmed by microscopy.
Aqueous suspensions of the microcapsules
were observed under optical microscopy
(OM). Freeze-dried microcapsules were
evaluated under Scanning Electron
Microscopy (SEM). Figure 5.1 shows, by
way of example, the morphology of
microcapsules containing violet essential
oil, as observed under OM and under SEM.

Figure 5.1. Morphology of microcapsules containing violet essential oil. A: Microcapsule suspension observed by
optical microscopy; B: Freeze-dried microcapsule observed by Scanning Electron Microscopy (SEM).
 … to functional leather

Besides, when comparing the thermal 5.3.1. Direct application

decomposition of microencapsulated and
Microcapsules solutions (diluted at 50%)
free essential oils, the successful
were sprayed on finished leather. Their
encapsulation of the essential oils was
successful incorporation was confirmed by
proved.
microscopy (see Figure 5.2 A).
By way of example, a shift on the rosemary
This analysis proved that direct application
oil decomposition temperature from
allows gelatine-based microcapsules to be
154 ºC (free oil) to 269.9 ºC
satisfactorily incorporated into materials,
(microencapsulated oil) took place. This
since direct application ensures that
indicates that an increase in thermal
encapsulated essential oils remain
stability had been achieved thanks to the
unaltered throughout the process.
protection offered by the gelatine shell.
This kind of microcapsules is intended to
obtain a flash effect, easy rupture of the
5.3. Leather functionalisation
microcapsule and a great aromatic
Leather can be functionalised by means of sensation for the user.
the addition of microencapsulated active
This means that, when using gelatine as a
substances.
shell material, the active substance (the
Therefore, microcapsules containing essential oil) can be released by hand
different essential oils were incorporated rubbing.
into leather, using two different methods:
Figure 5.2 compares the appearance of the
Direct application by spraying. incorporated microcapsules before and
after being rubbed to release the active
Incorporation in laboratory drums substance.
during the retanning process of leather.

From leather waste to functional leather 39

 Figure 5.2. Functional leather. Microcapsules incorporated by direct spraying. Appearance of incorporated
microcapsules before (A) and after (B) rubbing.

production, different treatments are

5.3.2. Incorporation during the retanning applied to leather in order to provide it
process
with special features such as colour,
During the process of transforming animal waterproofness or fire resistance, among
skins into leather, a tanning process takes others.
place where collagen fibres are stabilised.
Trials were carried out, where
In general, a further retanning process is
microencapsulated lemon and rosemary
necessary to improve leather properties
solutions at different concentrations were
such as feeling at touch, embossability and
incorporated during the retanning process,
breaking strength, as well as to provide a
more specifically during the dyeing
tight and uniform grain surface for leather
operation. This incorporation was carried
finishing. Besides, at this stage of leather
out in laboratory drums (see Figure 5.3).
 … to functional leather

Figure 5.3. Leather functionalisation during the retanning process on a laboratory scale. Incorporation of
microencapsulated lemon (A) and rosemary (B) oils.

From leather waste to functional leather 41

Even though the successful incorporation
of microcapsules by this method had been
confirmed, better results were obtained by
direct application like coating (spraying).
The preparation of functional leather
during the retanning process is to be
optimised in order to produce highly
modified materials with enhanced
properties. Microcapsules concentration in
the process liquor has to be optimised.
Besides, other parameters in the process
need to be modified in order to avoid
premature rupture of the microcapsules or
oil migration during the process.

6. Long-term benefits
6.1. Environmental benefits
It is estimated that European tanneries
produce over 650,000 tonnes of untanned
waste annually, which can be recovered
and turned into gelatine.
If all this waste was recovered through the
enzymatic process suggested, the amount
of chemicals and water consumption in
the process would be considerably
reduced. It is estimated that the recovery
of 100 kg of untanned waste requires
about 1 tonne NaOH, 120 L acetic acid
(glacial) and 12.4 m3 water when treated
by the conventional alkaline process. In
turn, when treating 100 kg of untanned
waste, the enzymatic process only requires
1 kg NaOH, 300 mL acetic acid (glacial),
0.23 kg enzymes and 420 L water.
In terms of wastewater generated, this
means a considerable reduction with
respect to the conventional alkaline pre-
treatment that is being currently used in
gelatine production. On the basis of
current results of the LIFE microTAN
project, it is estimated that the recovery of
100 kg of untanned waste can generate
From leather waste to functional leather
Long-term benefits
about 13 m3 wastewater when treated by
the conventional alkaline process, whereas
less than 0.5 m3 wastewater would be
generated by means of the enzymatic
process. If the total amount of the
estimated untanned waste generated in
Europe was recovered as gelatine, the
implementation of the enzymatic process
instead of the conventional one (alkaline)
would lead to a reduction of ca. 81.8 106
m3 wastewater generated per year. This
volume is equivalent to 32,720 Olympic-
size swimming pools.
Moreover, the wastewater generated
during the enzymatic process can also be
reused in the production of fertilisers.
From the point of view of gelatine
producers, it is estimated that the
proposed enzymatic process could mean
that about 61 kg chemicals and 665 L
water could be saved per kilogramme of
gelatine produced. Generated wastewater
could be reduced by ca. 700 L per kg
gelatine.
Such environmental benefits could be
extrapolated, in the long term, to the
recovery of other types of collagen-
43
containing waste (i.e. waste produced in
slaughterhouses or by the fish industry).
The Reference Document on Best
Available Techniques in the
Slaughterhouses and Animal By-products
Industries states that, out of the 47 million
tonnes of animals slaughtered for meat
production in Europe every year, 17
million tonnes of animal by-products are
produced. Hides, skins and bones are sold
to the leather industry or to gelatine
producers. About 14-15 million tonnes
(some 15% of which are proteins) are
processed by renderers and fat melters.
An unspecified amount of waste is left to
rot or illegally dumped. The enzymatic
treatment proposed in LIFE microTAN
project could be implemented as a
procedure alternative to the rendering
process, as well as a way to reduce illegal
dumping.
Furthermore, current gelatine producers
could implement the enzymatic process in
their companies as an alternative to the
conventional systems. This would lead to a
significant reduction in water and
chemicals requirements at their facilities,
as well as in production times.
6.2. Support to EU policies
This project meets the objective of Life+
Environment Policy and Governance in
that its results will contribute to the
development and demonstration of
innovative technologies, thus enhancing
the knowledge of the most
environmentally-friendly techniques in the
European footwear and tanning industries.
In this sense, LIFE mictoTAN contributes to
the implementation, update and
development of the European Union
Environmental policy and legislation
In a legal context, this project supports the
principles of Directive 2010/75/EU of the
European Parliament and of the Council on
industrial emissions (Integrated Pollution
Prevention and Control – IPPC) [6], which
promotes measures allowing the reduction
of pollution at source, as well as all EU
environmental policies as, for instance, the
Waste Framework Directive 2008/98/EC
[14] or the Water Framework Directive
2000/60/EC [31].
Furthermore, the LIFE microTAN project
supports the Commission’s Flagship
Initiative “A resource-efficient Europe”
 Long-term benefits

under its Europe 2020 Strategy [32] as well treatment, to a few hours in the case of
as the EU Circular Economy Package [12]. the proposed enzymatic pre-treatment.
The project focuses on the recovery of
collagen derivatives from untanned solid It is expected that the LIFE microTAN
waste. More specifically, it deals with the project will not only contribute to the
isolation of gelatine in order to use it as a protection of the Environment, but will
natural microencapsulating agent in the also bring about socio-economic
production of active materials, such as advantages including:
leather, with functional properties. Thus, Increase in sales and income
the LIFE microTAN project is a proposal for
“closing the loop” within the tanning High added-value products for different
industry. industrial sectors
Improvement of European companies’
competitiveness
6.3. Socio-economic benefits
Differentiation of European products
The recovery of gelatine from untanned and brands
hide waste will represent a new business
opportunity for European tanneries. Materials and products contributing to
well-being
Furthermore, as far as the gelatine
industry is concerned, the achievement of In fact, the following business
shorter production cycles along with low opportunities have been identified,
production costs is expected to be one of according to stakeholders’ groups:
the key driving factors for this market [33]. Tanneries:
In this sense, LIFE microTAN the use of an
enzymatic pre-treatment allowing a Own waste management
noticeable reduction in production cycle
Functional and sustainable additives for
times from several weeks or months, in
leather
the case of alkaline or acidic pre-

From leather waste to functional leather 45

Waste-management undertakings:
More sustainable processes
Besides, the environmental benefits of the
project are expected to benefit also the
health and wellbeing of the population in
general. What is more, micro/
nanoencapsulation (intended application
of recovered gelatines) is regarded as one
of the key enabling technologies of
interest in medical and health-related
applications.
Last but not least, the new business
opportunity for tanneries brought about
by the recovery of gelatine can also
benefit the employability in this industrial
sector.

7. Glossary
7.1. Abbreviations
BAT: Best Available Techniques.
BREF: Best Available Techniques Reference
Document.
CGS: C.G.S. di Coluccia Michele & C. sas.
Associated Beneficiary of the LIFE
microTAN project.
CMC: Carboxymethylcellulose.
COTANCE: European Confederation of the
Leather Industry.
EAP: Environmental Action Plan.
EC: European Commission.
EEA: European Environment Agency.
EU: European Union.
FAO: Food and Agriculture Organization of
the United Nations.
INESCOP: Centre for Technology and
Innovation. Coordinating Beneficiary of the
LIFE microTAN project.
From leather waste to functional leather
Glossary
IPPC: Integrated Pollution Prevention and
Control.
LoW: List of Waste.
OM: Optical Microscopy.
pI: Isoelectric point.
REACH: Regulation on the Registration,
Evaluation, Authorisation and Restriction
of Chemical Substances.
SEM: Scanning Electron Microscopy.
7.2. Glossary of keywords
7.2.1. Tanning processes and materials
Raw hide/skin: Haired hide/skin without
any treatment, obtained after the removal
of the skin from the animal in the
slaughterhouse. Hide: The outer covering
of a mature or fully grown large mammal,
e.g. cattle, horse, etc. Skin: The outer
covering of small mammals and other
vertebrates, e.g. pigs, sheep, goats, fishes,
etc.; or of the immature animal of the
larger species, i.e. calves and colts.
47
Beamhouse operations: Sequence of
treatment processes that take place at the
tannery since the skin/hide arrives at the
facility and before the tanning process. It
consists of mechanical, chemical and/or
enzymatic processes aiming to remove
every undesired component (hair, wool,
fat, blood, etc.), as well as to prepare the
collagen structure for tanning.
Trimming: Cutting off some of the edges
of the hides and skins, such as legs, tails,
face, udders, etc. This process is generally
carried out during the sorting process, but
is also conducted in other stages in the
tanning process. The residues arising from
this operation are called trimmings.
Fleshing: Mechanical removal of excess
flesh and fatty substances. The residues
arising from this operation are called
fleshings and consist of residual flesh,
subcutaneal and adipose tissues.
Liming: Also known as “unhairing”.
Process that causes a controlled alkaline
hydrolysis of collagen in order to remove
hair or wool, epidermis and subcutaneous
tissue and thus to give a certain flexibility
to leather.
Splitting: The horizontal splitting of hides
and skins into a grain layer and, if the hide
is thick enough, a flesh (split) layer.
Splitting is carried out on splitting
machines, fitted with a band knife.
Splitting can be done in the limed
condition or in the tanned condition. Two
layers are produced: The grain layer is the
outermost, and maintains the whole
dermis structure; the split layer is the
innermost and only maintains the reticular
dermis.
Bating: Manufacturing step, carried out at
the beamhouse, which follows liming. Its
purpose is to clear the grain, reduce
swelling, peptise fibres and remove
protein degradation products.
Tanning: Stabilisation of collagen fibres by
tanning agents so that the hide or skin is
no longer susceptible to putrefaction or
rotting.
Retanning: Process carried out after the
tanning stage. It is intended to improve
leather properties such as feeling at touch,
embossability and breaking strength, as
well as to provide a tight and uniform
grain surface for leather finishing. Besides,
at this stage, leather is subjected to

various treatments in order to provide it
with special features such as colour,
waterproofness, fire resistance, etc.
Leather: A general term for a hide or skin
with its original fibrous structure more or
less intact, tanned to be imputrescible; the
hair or wool may or may not have been
removed.
7.2.2. Collagen and gelatine
Scleroprotein: A type of protein
characterised by being fibrous and the
function of which is to provide a protective
and structural support in connective
tissues. They are usually water-insoluble.
Examples of scleroproteins include
collagen, keratin, elastin and fibroin.
Native collagen: Primary protein of the
connective tissue in humans and animals
and the most abundant protein in
mammals. Type I collagen is an insoluble
scleroprotein that is found as linear, fibre-
like hierarchical structures. It is the main
fibrous protein in the corium of a hide or
skin that, after tanning, yields leather.
Tropocollagen: Collagen molecule made
up from up to three polypeptide chains
that are combined in a triple helix. This
From leather waste to functional leather
Glossary
structure is stabilised by hydrogen bonds
and represents the basic building blocks of
collagen tissue.
Collagen microfibril: Arrangement of
successive layers of four to eight
tropocollagen molecule aggregates. A
microfibril is in turn the basic unit to form
the so-called collagen fibrils.
Collagen fibril: Arrangement of microfibrils
that is stabilised and reinforced by cross-
links in the form of covalent bonds.
Collagen fibre: Aggregation of collagen
fibrils that is further cross-linked to form
the basic structure of tissues such as skin
and bones.
Hydroxyproline: 4-Hydroxyproline (4-Hyp)
is a non-proteinogenic (non-coded)
aminoacid that is produced by post-
translational hydroxylation of proline
residues. It is a non-essential amino acid
found only in collagenous proteins. For
this reason, it is widely used as a factor to
estimate collagen content in biological
specimens.
Gelatine: High molecular weight collagen
oligopeptides produced by partial
49
hydrolysis of native collagen. Gelatine
shows gelling power. Type A gelatine:
Gelatine produced by acid hydrolysis. Type
B gelatine: Gelatine produced by basic
(alkaline) hydrolysis.
Hydrolysed collagen: Low molecular
weight collagen oligopeptides produced by
the enzymatic hydrolysis of collagen.
Hydrolysed collagen shows no gelling
power.
Gel: A semi-rigid, non-fluid, jelly-like
material consisting in a three-dimensional
network structure that is produced when a
high molecular weight polymer is swollen
by a solvent. A hydrogel is a gel in which
the swelling agent is water.
Gelling power: Ability of a certain amount
of gelatine to form a gel of a specific
firmness. The measure of the gelatine gel
firmness is known as Bloom value. The
Bloom value for standard commercial
gelatine ranges between 50 and 280 g.
Isoelectric point: pH value at which the
net electric charge of an amphoteric
molecule, such as a protein or an amino
acid, is zero. Proteins are positively
charged at a pH below its isoelectric point.
This property affects the
microencapsulation process.
Hydrolysis: A reaction where chemical
compounds are cleaved by water.
Hydrolysis takes place by increasing the
temperature or by the effect of acids,
bases or enzymes.
Enzyme: High molecular weight protein
that acts as a biocatalyst. Protease:
Enzyme that cleaves peptide bonds in
proteins. Collagenase: Protease that
specifically cleaves the peptide bonds in
collagen. Lipase: Enzyme that catalyses the
hydrolysis of fats.
7.2.3. Microencapsulation
Microencapsulation: Process by which
small solid particles, liquid droplets or gas
bubbles are coated with a thin film of an
inert coating or shell material. It leads to
core-shell particles called nanocapsules,
microcapsules or macrocapsules
depending on their size, which in turn
isolate and protect the core substance
from the external environment.
Core: Particles or droplets of a substance
(usually an essential oil or an active

substance) that are covered and protected
by the shell in a microcapsule.
Shell: External polymeric coating in a
microcapsule.
Multi-core microcapsule: Microcapsules in
which the shell material coats individual
particles of the core material, and which
then aggregate and form a cluster.
Complex coacervation: It is a
microencapsulation method based on the
phase separation that takes place
spontaneously when colloids of opposite
charges (that is, a polycation and a
polyanion) are mixed together, producing
a non miscible complex coacervate that
envelops the oil droplets to be
encapsulated.
From leather waste to functional leather
Glossary
Complex coacervate: It is an aggregate of
colloidal droplets held together by
electrostatic attractive force.
7.2.4. Green and circular economy
Green Economy: Economy in which
policies and innovations enable society to
use resources efficiently, enhancing
human well‑being in an inclusive manner,
while maintaining the natural systems
(EEA, [9]).
Circular Economy: Economy in which the
value of products, materials and resources
is maintained for as long as possible, and
the generation of waste is minimised.
51

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