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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

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

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 Other threatening factor is the increasing
production of leather and other products influence of vegan lifestyle.
made thereof. Indeed, Europe plays a
significant role in international leather Nevertheless, Europe is still considered to
trading, being one of the most ancient and be leader in this industry. Its main
dynamic markets. In fact, according to FAO strengths are the high quality of its
data [1], EU27 countries shared 37% (in products, its environmental and social
value) of worldwide exports in 2013. commitment, its involvement in fashion
Besides, according to Eurostat database, trends and its willingness to the
the EU28 tanning industry in 2014 was implementation of technologies in order
made up of about 3,328 companies with to improve processes and products.
an estimated turnover of 11,000 million Figure 1.2 summarises the main strengths,
Euros and employed about 42,070 people. weaknesses, opportunities and threats
However, the global economic crisis, along (SWOT) for the European tanning industry.
with the competence form third countries
1.2. Tanneries and the Environment
with lower-wages and more tolerant
environmental legislation, have negatively Even though this sector is considered to
affected the European leather sector, and play an important environmental role
the local economies of the tanning areas, because it reuses the by-products of the
in terms of both production and meat industry, the processes carried out in
employment. the different stages have in turn an
important environmental impact.
According to the European Confederation
Environmental issues at tanneries deal
of the Leather Industry (COTANCE),
with resources consumption (water,
competition from countries with loose
chemicals and energy) and the generation
social and environmental standards causes
of wastewater, solid waste and
socio-economic damage equivalent to
atmospheric emissions, such as volatile
dumping [2].
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 have implications for the leather industry:
sector is affected by different measures
concerning the Environment, the use of Regulation (EC) No 1907/2006 on the
chemicals, the marketing and use of Registration, Evaluation, Authorisation
certain hazardous substances as well as and restriction of Chemical substances
the use of animal by-products. (REACH) [4], as the industry is an

From leather waste to functional leather 5

 important downstream user of a wide beamhouse operations in the tanning
range of chemical preparations. process. In fact, it is estimated that the
yield of finished leather hardly reaches
Regulation (EU) No 1069/2009 on
25% by weight of raw salted hides [7]. In
animal by-products and derived
addition, other solid wastes are also
products not intended for human
produced, including preserving salts,
consumption [5], as hides and skins are
buffing dust and sludge from wastewater
materials of animal origin that are used
treatment, among others.
outside the food chain.
Directive 2010/75/EU on industrial Figure 1.3 shows a general overview of
emissions [6] according to which permit inputs and outputs in a conventional
conditions, including emission limit tannery, as estimated for the
values, must be based on the Best transformation of bovine salted hides into
Available Techniques (BAT). The BAT leather [7].
reference document (BREF) for tanning
According to the List of Waste (LoW),
of hides and skins was adopted in 2013
established in Commission Decision
[7].
2014/955/EU [8], wastes deriving from
During the transformation of hides and tanning operations are classified as shown
skins into leather, big quantities of solid in Box 1.1. Only wastes containing solvents
organic waste are generated in that a have a hazardous entry.
percentage of the raw material is rejected
This means that, for the time being, the
due to either a lack of properties or
European legislation does not consider
because of aesthetic reasons.
untanned waste to be hazardous, and
Furthermore, hair, wool, fleshings and therefore it has been long disposed of in
sebum are removed from the skins during 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 and aims to recover tannery waste to be
organic waste disposal. Furthermore, the reused by other industries.
European Union is promoting waste
recovery and valorisation through the In particular, the project’s purpose is to
transformation into added-value products valorise untanned waste. Specifically, the
that can be recycled or reused by other project intends to obtain gelatines to be
industries, contributing to a circular used as a shell-forming material for the
microencapsulation of active substances.
economy model.
Thus, LIFE microTAN deals with
valorisation of tannery waste to produce
1.3. LIFE microTAN proposal
functional materials, used in different
This is how the LIFE microTAN project consumer products intended to optimising
emerged in the framework of the EU’s user’s well-being.
financial instrument for the Environment
In short, LIFE microTAN is an
and Climate.
environmental project that envisages the
It is an initiative of Spanish and Italian recovery of tannery waste rich in collagen,
partners – countries gathering more than contributing to a circular economy model
64% of the European leather industry – and entailing socio-economic advantages.
 From hides/skins to leather

2. From hides/skins to leather skins are stabilised so that they are longer
susceptible to putrefaction or rotting.
2.1. General overview of the tanning
In the post-tanning area, several
processes
operations known as wet-finishing
The transformation of animal skins and processes are carried out in order to
hides into valuable materials used in the provide leathers with certain
manufacture of products such as shoes, characteristics. These features include
leather goods, etc. requires a series of colour or feel at touch, as well as
chemical and mechanical processes. functional properties such as water
repellence or resistance, oleophobicity,
The very first operations are performed in gas permeability, flame retardance,
the slaughterhouse, whereas the abrasion resistance or antistatic
subsequent operations take place in properties.
tanneries.
Finally, leathers are subjected to different
The processes carried out since the skins mechanical and/or chemical finishing
or hides reach the tannery until tanning operations in order to modify their final
takes place, constitute the so-called appearance.
beamhouse operations.
Figure 2.1 shows a diagram of the main
Subsequently, several operations are stages of the process as it takes place in
carried out at the tanyard area of the most tanneries.
tannery, where collagen fibres in hides and

From leather waste to functional leather 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.
 Form hides/skins to leather

2.2. Preparation operations sides). Once dried, skins are kept at

temperature below room temperature.
2.2.1. Flaying
Salting: Sodium chloride has been used to
This process takes place in the
preserve skins and hides since the middle
slaughterhouse and consists in removing
19th Century. 35-50% w/w of salt with
the skin or hide from the animal. Special
respect to skin/hide is spread on its
care is required in this step, since an
surface. Salt removes moisture from the
inappropriate procedure can inflict defects
skin/hide and provides an unfavourable
on skins and hides, thus reducing their
medium for most microorganisms’ growth.
value and increasing the amount of solid
This treatment allows skins/hides to be
waste at tanneries.
stored for weeks or months. Currently, this
2.2.2. Preservation methods is still the most commonly used method.

In order to ensure that skins and hides Chilling: Temperature is reduced as fast as
reach tanneries in suitable conditions, a possible from 36ºC to 2ºC. When done in a
series of preservation or curing operations short period of time, a correct
are necessary, which prevent hide or skin preservation and quality of the product is
degradation and putrefaction that can be ensured. Once chilled, skins and hides can
caused by external factors as well as by be stored at 2ºC for 15-20 days.
their own enzymes. Moisture content of
fresh-flayed skins and hides is close to
2.3. Stages before tanning:
60%, which favours degradation. The
following preservation methods can be Beamhouse operations
applied. “Beamhouse operations” is a term that
Air drying: The best option for skins is to refers to the chemical, chemical-physical,
place them in the open air, in a breezy enzymatic and mechanical processes that
place. It is important that drying takes are aimed to prepare the stored raw hides
place quickly on both sides (grain and flesh and skins for the tanning process. The

From leather waste to functional leather 11

solid wastes generated in these steps operation facilitates the saponification and
were explored as a raw material for LIFE elimination of fats.
microTAN project.
Most commonly used methods for hair
Below, the different steps of beamhouse loosening are chemicals, mainly sodium
operations, as performed at Spanish and sulphide and lime. They act as swelling
Italian tanneries, are described. agents on the skin collagen. It is important
to tune the swelling of the skins according
2.3.1. Soaking or stripping to the type of leather that is being
This is the first operation, and it mainly produced. Sulphide acts also as a shaving
consists in a treatment with water that agent separating the keratin groups. A
involves two steps. First, the skin/hide is solution of sodium sulphide at a relatively
washed to remove dirt as well as salt from high concentration destroys both hair and
preservation stages. In the second step, epidermis. The liming phase modifies also
the fibre is rehydrated. To this end, the content of natural fats present in the
bactericides, sodium hydroxide, skin which become easily removable.
proteolytic enzymes and moisturising Furthermore during this phase most of
agents are also added. This process allows globular proteins are removed. Some
salts and other soluble materials to be amine-based chemicals are often used in
removed, leading to clean, soft and this stage in order to facilitate the
rehydrated skins/hides. loosening of the epidermis fibres and to
control the swelling of the skin.
2.3.2. Unhairing or liming
Some tanneries are replacing these
In this step, the hair or the wool is chemicals by new thiol-based products
removed along with the epidermis. In this that allow hair recovery. This system gives
process, the corium-epidermis union is good results both in terms of quality of the
cleaved and the hair root is softened, final product and from the environmental
allowing their separation. Besides, this point of view, reducing the amount of
pollutants in the sludge.
 Form hides/skins to leather

Other tanneries are replacing the tanneries are advised to split hides/skins
traditional method by an enzymatic beforehand (“after liming”) so that wastes
treatment with bacterial alkaline are free from chemicals used in tanning
proteases, thus reducing the processes, reducing the environmental
environmental impact of effluents from impact. Furthermore, from the LIFE
this step, as well. microTAN project point of view, following
this recommendation will enable a higher
It is important to point out that, after this recovery of collagen from untanned
operation, hides and skins are no longer
wastes.
subject to animal by-products controls
[7]. 2.3.5. Deliming

2.3.3. Fleshing As above described, most tanneries carry

out the unhairing process by means of
At this stage, residual flesh, subcutaneal lime and sulphide baths. Part of the lime
and adipose tissues, are removed in a (especially that between the fibres and on
mechanical way. Wastes obtained in this top of the fibres) is removed by washing
process are called “fleshings”. the skins with water, but some lime is
2.3.4. Splitting retained on the skin/hide, making it highly
alkaline.
The aim of splitting is to make the
skin/hide thickness even, allowing tanning The remaining lime makes hides and skins
and staining to be more homogeneous. If a highly alkaline and can have deleterious
hide is too thick, it is split into two layers: effects at further stages at the tannery. In
the grain layer and the flesh split. The the deliming operation, acids are used in
grain layer is the outermost, and maintains order to reduce alkaline swelling, remove
the whole dermis structure. The split layer the remaining lime from hides/skins and
is the innermost and only maintains the lower the pH, so that enzymes used in the
reticular dermis. Some tanneries carry out bating stage (a process that sometimes is
this operation after tanning. Nevertheless,

From leather waste to functional leather 13

carried out simultaneously to deliming) porosity, thus enabling tanning agents to
can act in optimal conditions. penetrate the skin/hide.

2.3.6. Bating
2.4. Waste generated
In order to get leather with a soft, smooth
touch, and a thin, silky grain layer, As previously stated, in the production of
hides/skins have to be subjected to the leather, a high percentage of raw material
bating process. This consists in an is rejected as solid waste. Besides,
enzymatic treatment that cleans the grain processes carried out at the different
layer and removes proteins other than stages have an important environmental
collagen (albumin, globulin, etc.) that are impact. Table 2.1 summarises the above
not suitable for leather production. described stages, the chemicals used and
Specific enzymes acting on proteins are the main environmental impacts
called proteases, and the most common in associated to each of them. Wastes in
the bating stage are pancreatic proteases bold have been considered as a raw
(trypsin), fungal proteases, bacterial material in the LIFE microTAN project.
proteases and mixtures of them. Bating
provides hides and skins with higher
 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 In this study, a catalogue of solid waste
studies of the environmental and socio- generated at these tanneries, as well as
economic impact in two Italian tanneries the cost of their management was
located in Santa Croce sull'Arno (Italy) prepared. Table 2.2 summarises the
were carried out. 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 More recently, the European Commission

has expressed its intention to enhance
circular economy at
Europe's ecological resilience and
tanneries transform the EU into an inclusive and
sustainable green economy. To this end,
3.1. EU policies on Green and
the EU 7th Environment Action Programme
Circular Economy (7th EAP, [11]) has established the
Environment and Economy are terms that following three thematic priorities:
traditionally seemed to have nothing to do Priority objective 1: To protect, conserve
with one another, or even to confront.
and enhance the Union’s natural capital.
Nevertheless, current European policies
enforce that both concepts go hand in Priority objective 2: To turn the Union into
hand. Thus, the term Green Economy has a resource-efficient, green and
arisen, which is defined by the European competitive low-carbon economy.
Environment Agency (EEA) as an economy
“in which policies and innovations enable Priority objective 3: To safeguard the
society to use resources efficiently, Union’s citizens from environment-related
pressures and risks to health and well-
enhancing human well‑being in an
being.
inclusive manner, while maintaining the
natural systems that sustain us” [9]. In a circular economy, the value of
products, materials and resources is
In its Communication Europe 2020 – A
maintained in the economy for as long as
strategy for smart, sustainable and
possible, and the generation of waste is
inclusive growth [10], the European
minimised [12]. Circular economy is thus
Commission established the priority
considered as an instrument in achieving
“Sustainable growth: promoting a more
the second objective of the 7th EAP, and
resource efficient, greener and more
can be represented as the core of a green
competitive economy” as a strategy to
economy perspective (see Figure 3.1).
help Europe emerge from the crisis.

From leather waste to functional leather 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 reduction, and establish a road map for
released its Communication Closing-the- waste management and recycling. A key
loop - An EU action plan for the Circular element of the revised waste proposal
Economy [12]. This document established includes specific measures to promote re-
an ambitious Circular Economy Package use by turning by-products into raw
with the aim of encouraging both materials, which will also stimulate
European businesses and consumers to industrial symbiosis.
make a more sustainable use of resources
Figure 3.2 shows a simplified model of
by implementing a circular economy.
circular economy for both energy (outer
This Circular Economy Package establishes circle) and materials (middle circle). The
a precise and ambitious program of inner circle represents reuse, repair,
actions, with measures that include a redistribution, refurbishment and
revision of Directive 2008/98/EC remanufacture as eco-design enabling
[14] on waste and Directive 1999/31/EC factors [13].
[15] on the landfill of waste [16, 17],
among others. Besides, this action plan In the implementation of this circular
covers the whole cycle: from production economy, one of the industrial sectors to
and consumption to waste management pay attention to is the tanning industry. As
and use as secondary raw materials. In previously stated, even though this sector
contrast to the traditional, linear “extract- is considered to play an important
environmental role because it reuses the
transform-use-dispose” economy model,
the European Commission proposes by-products of the meat industry,
"closing the loop" of products’ lifecycles processes carried out at the different
by increasing recycling and re-use, in stages generate a large quantity of solid
favour of both the Environment and waste. For this reason, the European
economy. tanning sector needs to implement new,
greener strategies and solutions to provide
The revised legislative proposals on waste a cleaner, more sustainable and more
set clear targets for waste and landfill competitive industry.

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

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 Figure 3.4. Microcapsule structure. Shell: polymeric
instance for the preparation of organic cover; Core: encapsulated active chemical.
fertilisers, the production of biomaterials,
gelatines or collagens, and the production
of bio fuel [18]. Microencapsulation is an effective method
to prevent reactive, sensitive or volatile
The gel-forming properties of gelatine, a chemicals from reacting with moisture,
collagen derivative, are the basis for its light and oxygen. Besides, this technology
classical application in food, photographic, not only enhances stability against
cosmetic and pharmaceutical industries. external factors, but also allows controlled
Besides, new applications have arisen, release of the active substance. Indeed,
such as its use as a shell-forming polymer microcapsules, when firmly anchored to a
for microencapsulation applications [22- material such as leather, can add new
24]. smart functionalities without affecting
Microencapsulation consists of a coating look and feeling at touch.
technology by which active substances are Therefore, this technology holds great
encapsulated in a polymeric shell, leading promise for the future of tanneries and
to core-shell particles called microcapsules leather end-user industries, such as
(see Figure 3.4). 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. materials, such as leather, with functional
properties. Thus, LIFE microTAN is a
In this context, LIFE microTAN (LIFE12 proposal for “closing the loop” within the
ENV/ES/000568) focuses on the recovery tanning industry. Figure 3.5 shows the
of collagen derivatives from untanned general overview of the circular economy
solid wastes. More specifically, it deals approach of the LIFE microTAN project.
with the isolation of gelatine in order to
use it as a natural microencapsulating

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

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

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

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

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

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 alkaline or an acid treatment to achieve
suffered by the by-product may affect the the cleavage of collagen crosslinks
gelatine extraction process. followed by extraction with warm water.
The diagram in Figure 1.2 summarises the
main techniques commonly used for
4.2. Current gelatine production obtaining gelatines from slaughterhouses
process and animal by-products industry wastes.

Collagen is the main protein component of However, such procedures should be

mammalian and fish skins, bones and improved in order to save time, energy
connective tissues. It is a water-insoluble and water consumption. Bones pre-
protein of great industrial interest that can treatment and gelatine drying stages are
only be extracted by hydrolysis. A partial high energy consuming processes.
hydrolysis of this protein leads to gelatine. Furthermore, demineralisation, liming and
A stronger hydrolysis leads to low hydrolysis steps require large quantities of
molecular peptides known as collagen water, and the resulting wastewater must
hydrolysates. be conveniently treated.

Currently, the gelatine industry obtains In addition, according to the BREF

both hydrolysed collagen and gelatine document on Best Available Techniques in
directly from Category 3 bones, hides and slaughterhouses and animal by-products,
skins. high protein levels are found in
wastewater, which means that more
Collagen hydrolysates are commonly
efficient processes for the recovery of this
produced by enzymatic hydrolysis.
protein fraction should be developed.
In general, gelatine extraction
requirements of can be summarised in an
 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 The use of this kind of enzymes for the
microTAN conditioning of hides prior to gelatine
extraction was proposed by the LIFE
The LIFE microTAN project focused on the microTAN project as a new enzymatic pre-
valorisation of untanned bovine hide by- treatment, alternative to the alkaline and
products. As previously stated, this kind of acid pre-treatments, in order to minimise
by-products is conventionally pre-treated the environmental impact, as well as to
by the alkaline procedure. reduce processing time.

However, alkaline pre-treatment is a long- Thus, in the LIFE microTAN project, both
term process that can take several weeks, the pre-treatment and extraction stages
even months, and which requires big were optimised in order to produce
volumes of water and alkali, thus gelatine with suitable properties for
generating large quantities of wastewater. microencapsulation applications.

Nowadays, the enzymatic pre-treatment Figure 4.4 shows a diagram of the

as an alternative to the alkaline pre- proposed procedure, as carried out at
treatment for gelatine manufacture is laboratory scale.
raising interest in order to save costs by
reducing wastewater and time [23, 27]. This enzymatic procedure proved to
provide the following advantages:
Proteolytic enzymes (proteases) are
commonly used in the detergent industry Appropriate: When the pre-treatment
for breaking down proteinaceous matter reaction is carried out under optimised
caused by body secretions, food stuff, and conditions, by-products are transformed
blood. Such type of enzymes are also being into gelatine with adequate properties for
employed in the leather industry as an microencapsulation applications.
alternative to conventional agents used in
Efficient: Depending on the type of by-
unhairing, bating and soaking processes
product, the process allows the recovery
[30].
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- Figure 4.5 shows the LIFE microTAN
treatment allows a reduction of treatment demonstration plant.
length from weeks to hours.
It mainly consists of a 100-L, jacketed main
reactor with a heating system by means of
4.4. Demonstration plant recirculating water. It includes the
necessary components and ancillaries to
Throughout the project, a demonstration ensure the appropriate control of
plan was built, where gelatines were processing conditions such as pH,
produced with suitable properties to be temperature and time.
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.
 From leather by-products…

A filtering system is located at the bottom Automated control of processing

of the vessel and at the product outlet conditions.
pipe, and an input for compressed air
exerts a positive pressure that facilitates By selecting the appropriate conditions,
gelatine extract discharge. the LIFE microTAN process is able to
produce different grade gelatines,
The demonstration plant includes a suitable for different applications.
switchboard for automated control
systems for the temperature and heating Table 4.1 compares the properties of
unit, pH and acid/alkalis dosing pumps, gelatines produced at the demonstration
water inlet, load and level, upper cover plant with those of commercial gelatines
lifting, stirring, vacuum, filtering, piping obtained by the conventional alkaline
valves, centrifugal pumps, cleaning process process (B-type gelatines). Gelatines with
and product discharge. very similar properties to those of type-B
commercial gelatines can be produced in
In short, the demonstration plant allows: the demonstration plant.

Treatment of 25 kg of untanned solid In the case of gelatines with medium-high

waste per batch. Bloom values (suitable for
microencapsulation), the demonstration
Pre-treatment and extraction processes
plant key performance data are
to be carried out in a single reactor.
summarised in Box 1.1.

Table 4.1. microTAN gelatine main properties. Comparison with commercial B-type gelatines.

Properties microTAN gelatine Commercial B-type gelatine

Isoelectric point (pI) 4.9 – 5.2 4.7 – 5.2
Gel strength. Bloom value (g) 10 -260 50 - 300

From leather waste to functional leather 33

 Amount of by-product processed 25 kg/batch
Yield of valorisation (depending on the hide by-product batch) 65-90% collagen
Amount of valorised product 2-4 Kg gelatine
Whole process duration 8 h/batch
3
Water consumption 0.2 m

Box 4.1. Demonstration plant key performance data.

4.5. Environmental benefits As a consequence, a significant reduction

in wastewater generation is also achieved.
An important conclusion of the project is An analysis of the wastewater generated
that gelatine from bovine untanned hide in this pre-treatment process has shown
wastes can be successfully extracted as a that it can be completely recovered as a
valuable co-product using an enzymatic fertiliser. Alternatively, it could be also
pre-treatment, alternative to the valorised in a biogas production plant.
conventional alkaline one. The main
environmental benefits of the new process
are derived from this pre-treatment step. 4.6. Economic feasibility

When comparing both processes, the Gelatine prices are governed by their
proposed enzymatic pre-treatment gives a properties and final use. Depending on
series of advantages, from both the their Bloom value, prices of commercial
environmental and the economic point of gelatines (industrial grade) can range from
view. Significant savings in time and water 5.30 €/kg (125 g Bloom) to 5.77 €/kg (250
consumption are achieved with the g). Prices of gelatines for use as a
enzymatic process. A comparison between laboratory reagent reach values over 300
both processes is outlined in Figure 4.6. €/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 years, 231 working days per year and a
process developed was made, considering single batch per day were considered.
different plant capacities. Costs of gelatine
A conservative yield of 70% of collagen
production were estimated taking into
recovery.
account the following considerations:
The analysis was made at three levels:
Estimation of gelatine production costs,
a) The project demonstration plant;
considering energy, chemicals and
water consumption, labour costs and b) A potential production plant to be set
equipment depreciation. up in the tannery, with a capacity
according to waste generation

From leather waste to functional leather 35

 reported in the case studies (100 (industrial grade, 260 g Bloom), and after
tonnes/year); deducting current costs for the
management of the recovered untanned
c) A potential production plant with
wastes (approx. 10,000 €/year), it was
higher capacity, to be set up in a
estimated that benefits for a tannery
waste management company.
recovering 100 tonnes of by-products per
According to this analysis, cost of gelatine year would be:
production would range from 48 €/kg to
• Revenues: 102,600 €/year.
2.69 €/kg, depending on the facility size. In
the case of tanneries participating in the • Profit: 30,000 €/year.
case studies, on-site gelatine recovery
from their untanned wastes would have a In the case of waste managers, benefits
cost of 4.59 €. Gelatine costs could be would be higher due to their higher
reduced when 2-3 batches are processed production capacity and, therefore, lower
in the company (shift-work). production costs per kg of gelatine.

Considering these estimated production

costs, applying a sales price of 5.7 €/kg
 … to functional leather

5. … to functional leather capable of improving the quality of our

lives.
5.1. Microencapsulation
Biopolymers, such as gelatine, are suitable
Microencapsulation technology could be as shell-forming materials for the synthesis
defined as a process by which active of natural and biodegradable
substances are coated with materials of microcapsules that mean an alternative to
different natures, generally polymeric other artificially produced substances
shells, to obtain micrometric particles deriving from synthetic polymers, like
known as microcapsules or sub- melamine-formaldehyde, polyurethane, or
micrometric particles known as polystyrene.
nanocapsules.

Microencapsulation provides protection 5.2. Gelatine in microencapsulation

and masking of the encapsulated
substance whilst facing unstable or harsh One microencapsulation method which
mediums, allowing its subsequent uses gelatine as a shell-forming polymer is
progressive release. These factors have complex coacervation. This process is
prompted certain industrial sectors, such based on the phase separation that takes
as the medical, pharmaceutical, cosmetics, place spontaneously when in an aqueous
food and nutrition, agriculture industries, medium, two or more colloids of opposite
etc. to base some of their most innovative charges (a polycation and a polyanion) are
products on this technology. mixed in the presence of a dispersion of an
active substance.
In other sectors, such as the footwear
industry, microencapsulation is regarded Gelatine is an amphoteric macromolecule,
as a technology to obtain innovative which is positively charged at a pH below
shoes, since it can transform everyday its isoelectric point (pI). Thus, it is suitable
traditional footwear into smart products, to be used as a polycation in complex
coacervation reactions. As a polyanion, a

From leather waste to functional leather 37

polysaccharide is generally used, such as were selected as a shell-forming material
sodium carboxymethylcellulose (CMC). for the preparation of microcapsules.
Gelatine extracts were directly used,
In the LIFE microTAN project, several
without being subjected to drying.
essences were microencapsulated by
means of this method: rosemary, violet, The microencapsulation of the different
jasmine, aloe, orange, magnolia, lavender, oils was confirmed by microscopy.
permetrine, ivy, orange blossom, lemon Aqueous suspensions of the microcapsules
and tree tea oil. These essential oils were were observed under optical microscopy
selected because of their antimicrobial (OM). Freeze-dried microcapsules were
and/or fragrant properties. evaluated under Scanning Electron
Microscopy (SEM). Figure 5.1 shows, by
Gelatines obtained at the demonstration way of example, the morphology of
plant, with high-medium gelling properties microcapsules containing violet essential
(Bloom values ranging from 120 g to 230 g) 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 modified materials with enhanced
of microcapsules by this method had been properties. Microcapsules concentration in
confirmed, better results were obtained by the process liquor has to be optimised.
direct application like coating (spraying). Besides, other parameters in the process
need to be modified in order to avoid
The preparation of functional leather premature rupture of the microcapsules or
during the retanning process is to be oil migration during the process.
optimised in order to produce highly
 Long-term benefits

6. Long-term benefits about 13 m3 wastewater when treated by

the conventional alkaline process, whereas
6.1. Environmental benefits less than 0.5 m3 wastewater would be
generated by means of the enzymatic
It is estimated that European tanneries process. If the total amount of the
produce over 650,000 tonnes of untanned estimated untanned waste generated in
waste annually, which can be recovered Europe was recovered as gelatine, the
and turned into gelatine. implementation of the enzymatic process
If all this waste was recovered through the instead of the conventional one (alkaline)
enzymatic process suggested, the amount would lead to a reduction of ca. 81.8 106
of chemicals and water consumption in m3 wastewater generated per year. This
the process would be considerably volume is equivalent to 32,720 Olympic-
reduced. It is estimated that the recovery size swimming pools.
of 100 kg of untanned waste requires
Moreover, the wastewater generated
about 1 tonne NaOH, 120 L acetic acid
during the enzymatic process can also be
(glacial) and 12.4 m3 water when treated
reused in the production of fertilisers.
by the conventional alkaline process. In
turn, when treating 100 kg of untanned From the point of view of gelatine
waste, the enzymatic process only requires producers, it is estimated that the
1 kg NaOH, 300 mL acetic acid (glacial), proposed enzymatic process could mean
0.23 kg enzymes and 420 L water. that about 61 kg chemicals and 665 L
water could be saved per kilogramme of
In terms of wastewater generated, this
gelatine produced. Generated wastewater
means a considerable reduction with
could be reduced by ca. 700 L per kg
respect to the conventional alkaline pre-
gelatine.
treatment that is being currently used in
gelatine production. On the basis of Such environmental benefits could be
current results of the LIFE microTAN extrapolated, in the long term, to the
project, it is estimated that the recovery of recovery of other types of collagen-
100 kg of untanned waste can generate

From leather waste to functional leather 43

containing waste (i.e. waste produced in 6.2. Support to EU policies
slaughterhouses or by the fish industry).
This project meets the objective of Life+
The Reference Document on Best Environment Policy and Governance in
Available Techniques in the that its results will contribute to the
Slaughterhouses and Animal By-products development and demonstration of
Industries states that, out of the 47 million innovative technologies, thus enhancing
tonnes of animals slaughtered for meat the knowledge of the most
production in Europe every year, 17 environmentally-friendly techniques in the
million tonnes of animal by-products are European footwear and tanning industries.
produced. Hides, skins and bones are sold In this sense, LIFE mictoTAN contributes to
to the leather industry or to gelatine the implementation, update and
producers. About 14-15 million tonnes development of the European Union
(some 15% of which are proteins) are Environmental policy and legislation
processed by renderers and fat melters.
An unspecified amount of waste is left to In a legal context, this project supports the
rot or illegally dumped. The enzymatic principles of Directive 2010/75/EU of the
treatment proposed in LIFE microTAN European Parliament and of the Council on
project could be implemented as a industrial emissions (Integrated Pollution
procedure alternative to the rendering Prevention and Control – IPPC) [6], which
process, as well as a way to reduce illegal promotes measures allowing the reduction
dumping. of pollution at source, as well as all EU
environmental policies as, for instance, the
Furthermore, current gelatine producers Waste Framework Directive 2008/98/EC
could implement the enzymatic process in [14] or the Water Framework Directive
their companies as an alternative to the 2000/60/EC [31].
conventional systems. This would lead to a
significant reduction in water and Furthermore, the LIFE microTAN project
chemicals requirements at their facilities, supports the Commission’s Flagship
as well as in production times. 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: of the key enabling technologies of
interest in medical and health-related
More sustainable processes applications.
Besides, the environmental benefits of the Last but not least, the new business
project are expected to benefit also the opportunity for tanneries brought about
health and wellbeing of the population in by the recovery of gelatine can also
general. What is more, micro/ benefit the employability in this industrial
nanoencapsulation (intended application sector.
of recovered gelatines) is regarded as one
 Glossary

7. Glossary IPPC: Integrated Pollution Prevention and

Control.
7.1. Abbreviations
LoW: List of Waste.
BAT: Best Available Techniques.
OM: Optical Microscopy.
BREF: Best Available Techniques Reference
pI: Isoelectric point.
Document.

CGS: C.G.S. di Coluccia Michele & C. sas. REACH: Regulation on the Registration,
Evaluation, Authorisation and Restriction
Associated Beneficiary of the LIFE
of Chemical Substances.
microTAN project.
SEM: Scanning Electron Microscopy.
CMC: Carboxymethylcellulose.

COTANCE: European Confederation of the

Leather Industry. 7.2. Glossary of keywords

EAP: Environmental Action Plan. 7.2.1. Tanning processes and materials

EC: European Commission. Raw hide/skin: Haired hide/skin without

any treatment, obtained after the removal
EEA: European Environment Agency. of the skin from the animal in the
slaughterhouse. Hide: The outer covering
EU: European Union. of a mature or fully grown large mammal,
e.g. cattle, horse, etc. Skin: The outer
FAO: Food and Agriculture Organization of
covering of small mammals and other
the United Nations.
vertebrates, e.g. pigs, sheep, goats, fishes,
INESCOP: Centre for Technology and etc.; or of the immature animal of the
Innovation. Coordinating Beneficiary of the larger species, i.e. calves and colts.
LIFE microTAN project.

From leather waste to functional leather 47

Beamhouse operations: Sequence of Splitting: The horizontal splitting of hides
treatment processes that take place at the and skins into a grain layer and, if the hide
tannery since the skin/hide arrives at the is thick enough, a flesh (split) layer.
facility and before the tanning process. It Splitting is carried out on splitting
consists of mechanical, chemical and/or machines, fitted with a band knife.
enzymatic processes aiming to remove Splitting can be done in the limed
every undesired component (hair, wool, condition or in the tanned condition. Two
fat, blood, etc.), as well as to prepare the layers are produced: The grain layer is the
collagen structure for tanning. outermost, and maintains the whole
dermis structure; the split layer is the
Trimming: Cutting off some of the edges innermost and only maintains the reticular
of the hides and skins, such as legs, tails, dermis.
face, udders, etc. This process is generally
carried out during the sorting process, but Bating: Manufacturing step, carried out at
is also conducted in other stages in the the beamhouse, which follows liming. Its
tanning process. The residues arising from purpose is to clear the grain, reduce
this operation are called trimmings. swelling, peptise fibres and remove
protein degradation products.
Fleshing: Mechanical removal of excess
flesh and fatty substances. The residues Tanning: Stabilisation of collagen fibres by
arising from this operation are called tanning agents so that the hide or skin is
fleshings and consist of residual flesh, no longer susceptible to putrefaction or
subcutaneal and adipose tissues. rotting.

Liming: Also known as “unhairing”. Retanning: Process carried out after the
Process that causes a controlled alkaline tanning stage. It is intended to improve
hydrolysis of collagen in order to remove leather properties such as feeling at touch,
hair or wool, epidermis and subcutaneous embossability and breaking strength, as
tissue and thus to give a certain flexibility well as to provide a tight and uniform
to leather. grain surface for leather finishing. Besides,
at this stage, leather is subjected to
 Glossary

various treatments in order to provide it structure is stabilised by hydrogen bonds

with special features such as colour, and represents the basic building blocks of
waterproofness, fire resistance, etc. collagen tissue.

Leather: A general term for a hide or skin Collagen microfibril: Arrangement of

with its original fibrous structure more or successive layers of four to eight
less intact, tanned to be imputrescible; the tropocollagen molecule aggregates. A
hair or wool may or may not have been microfibril is in turn the basic unit to form
removed. the so-called collagen fibrils.

7.2.2. Collagen and gelatine Collagen fibril: Arrangement of microfibrils

that is stabilised and reinforced by cross-
Scleroprotein: A type of protein
links in the form of covalent bonds.
characterised by being fibrous and the
function of which is to provide a protective Collagen fibre: Aggregation of collagen
and structural support in connective fibrils that is further cross-linked to form
tissues. They are usually water-insoluble. the basic structure of tissues such as skin
Examples of scleroproteins include and bones.
collagen, keratin, elastin and fibroin.
Hydroxyproline: 4-Hydroxyproline (4-Hyp)
Native collagen: Primary protein of the is a non-proteinogenic (non-coded)
connective tissue in humans and animals aminoacid that is produced by post-
and the most abundant protein in translational hydroxylation of proline
mammals. Type I collagen is an insoluble residues. It is a non-essential amino acid
scleroprotein that is found as linear, fibre- found only in collagenous proteins. For
like hierarchical structures. It is the main this reason, it is widely used as a factor to
fibrous protein in the corium of a hide or estimate collagen content in biological
skin that, after tanning, yields leather. specimens.

Tropocollagen: Collagen molecule made Gelatine: High molecular weight collagen

up from up to three polypeptide chains oligopeptides produced by partial
that are combined in a triple helix. This

From leather waste to functional leather 49

hydrolysis of native collagen. Gelatine This property affects the
shows gelling power. Type A gelatine: microencapsulation process.
Gelatine produced by acid hydrolysis. Type
B gelatine: Gelatine produced by basic Hydrolysis: A reaction where chemical
(alkaline) hydrolysis. compounds are cleaved by water.
Hydrolysis takes place by increasing the
Hydrolysed collagen: Low molecular temperature or by the effect of acids,
weight collagen oligopeptides produced by bases or enzymes.
the enzymatic hydrolysis of collagen.
Hydrolysed collagen shows no gelling Enzyme: High molecular weight protein
power. that acts as a biocatalyst. Protease:
Enzyme that cleaves peptide bonds in
Gel: A semi-rigid, non-fluid, jelly-like proteins. Collagenase: Protease that
material consisting in a three-dimensional specifically cleaves the peptide bonds in
network structure that is produced when a collagen. Lipase: Enzyme that catalyses the
high molecular weight polymer is swollen hydrolysis of fats.
by a solvent. A hydrogel is a gel in which
7.2.3. Microencapsulation
the swelling agent is water.
Microencapsulation: Process by which
Gelling power: Ability of a certain amount
small solid particles, liquid droplets or gas
of gelatine to form a gel of a specific
bubbles are coated with a thin film of an
firmness. The measure of the gelatine gel
inert coating or shell material. It leads to
firmness is known as Bloom value. The
core-shell particles called nanocapsules,
Bloom value for standard commercial
microcapsules or macrocapsules
gelatine ranges between 50 and 280 g.
depending on their size, which in turn
Isoelectric point: pH value at which the isolate and protect the core substance
net electric charge of an amphoteric from the external environment.
molecule, such as a protein or an amino
Core: Particles or droplets of a substance
acid, is zero. Proteins are positively
(usually an essential oil or an active
charged at a pH below its isoelectric point.
 Glossary

substance) that are covered and protected Complex coacervate: It is an aggregate of

by the shell in a microcapsule. colloidal droplets held together by
electrostatic attractive force.
Shell: External polymeric coating in a
microcapsule. 7.2.4. Green and circular economy

Multi-core microcapsule: Microcapsules in Green Economy: Economy in which

which the shell material coats individual policies and innovations enable society to
particles of the core material, and which use resources efficiently, enhancing
then aggregate and form a cluster. human well‑being in an inclusive manner,
while maintaining the natural systems
Complex coacervation: It is a
(EEA, [9]).
microencapsulation method based on the
phase separation that takes place Circular Economy: Economy in which the
spontaneously when colloids of opposite value of products, materials and resources
charges (that is, a polycation and a is maintained for as long as possible, and
polyanion) are mixed together, producing the generation of waste is minimised.
a non miscible complex coacervate that
envelops the oil droplets to be
encapsulated.

From leather waste to functional leather 51

 Glossary

8. Bibliography [5] European Parliament and Council,

“Regulation (EC) No 1069/2009 of the
European Parliament and of the
Council of 21 October 2009 laying
[1] Intergovernmental Group on Meat
down health rules as regards animal
and Dairy Products Sub-group on
by-products and derived products not
Hides and Skins, “World statistical
intended for human consumption and
compendium for raw hides and skins,
repealing Regulation (EC) No
leather and leather footwear 1999-
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