Environmental impact of Plastics:

Disposal and Recycling

 Where the plastics end their useful life:
At the beginning of the plastic age, poor attention was payed to the
environmental impact of a huge production of plastic materials. Plastic
material seemed to be very resistant and durable, chemically inert, able to
exert a scarce interaction with the environment.
The disposal of plastic items, therefore, was completely ignored.
As a consequence, an increasing amount of plastics was released in the
environment, and in particular in the oceans, with tremendous effects on
the environment (i.e. the fishes).
 Where the plastics end their useful life:
There are at least four big plastic islands, the first discovered, and the
biggest one, is located in the northern Pacific Ocean. The others: in
southern Pacific Ocean, in the Atlantic Ocean and in the Indian Ocean.
(Source: National Oceanographic and Atmosferic Administration).
In the northern part of the Pacific Ocean, a huge trash vortex (vortice di
rifiuti) has been formed, mainly composed by waste plastics. Each square
kilometer of water in that area contains approximately 750000 fragments of
waste plastics possessing microscopic dimensions that the fish can ingest,
thinking they are plankton (plastic floats on the sea).
 Where the plastics end their useful life:
The most of the plastics are not biodegradable. When they are trashed
away, they reduced in a enormous number of small pieces of plastic
(micro-plastic), able to occlude the intestine of fishes, birds and other
animals. (Also, plastic can provide a false sense of satiety, and then the
animals die for starvation).
Polyethylene is one of the most employed polymers for different usages
and probably the less biodegradable plastic. Even the green-PE
(produced by sugar-cane) is not biodegradable. About 29% of plastic waste
is composed by PE.
PE is not biodegradable since the microorganisms are not able to attack
and degrade its structure entirely formed by Carbon and Hydrogen atoms.
Its chain does not contain the groups (such as C=O) more easily degraded
by the enzymes. The only way to convert PE in a form easily eaten by the
microorganisms consists in its oxidation (thermal- or photo- oxidation).
Very recently, researchers discovered particular microorganisms (bacteria
and fungi) that produce enzymes able to digest and degrade also PE
without the necessity to oxidize the polymer (i.e. in Arabic sea).
 Where the plastics end their useful life:
Researchers in Japan have discovered the first PET-eating bacterium in the
world, a critter that uses PET as its major carbon and energy source.
To find microbes that could pull PET apart, a team led by Kohei Oda of
Kyoto Institute of Technology and Kenji Miyamoto of Keio University
screened 250 sediment, soil, wastewater and activated sludge samples from
a PET bottle recycling facility in Sakai, Japan.
After some careful microbial sleuthing, they found one bacterium that
thrived on PET films and named it Ideonella sakaiensis from the city
where it was found (Science, 2016).
Previously, some fungi able to break down PET were identified. However,
the bacterium identified by Oda and Miyamotos group appears to be more
efficient than the former. In fact, Ideonella sakaiensis fragment the polymer
at a surprisingly mild temperature (30C).
 Where the plastics end their useful life:
At the moment Ideonella sakaiensis and its enzymes need some additional
research before they will be ready to be used on the worlds PET waste.
The bacterium prefers to eat amorphous PET rather than the crystalline
one mainly used in products.
Furthermore, the enzymes work too slowly to be used industrially.
The researchers think that a PET pretreatment would make waste more
appetizing for the bacterium (enlarging the polymers amorphous areas).
Also, it might be possible to engineer the enzymes to make them faster
and more practical to be used in large scale plants.
 Life Cycle Assessment (LCA)

Life Cycle Assessment is a technique used to quantify the environmental

impact of products during their entire life cycle. The purposes of LCA are
as follows: (1) assess the energy for production and use of a material; (2)
examine the impacts of waste emissions on the environment; (3) seek
opportunities to improve the environment.
This evaluation method examines the processes and activities in the entire
product life cycle, including all stages of raw material extraction and
processing, product manufacturing, transportation and sales, product use,
reuse and maintenance, waste recycling and final waste disposal.
For each stage, an inventory is made of the energy and material
consumption and of any emissions to the environment. This makes it
possible to identify components where improvement can be made to
benefit the environment.
 Life Cycle Assessment (LCA)

This type of investigation of products may bring economic advantages, as

often material and energy consumption are reduced.
Environmentally friendly products also have a marketing advantage, as
consumers are becoming increasingly aware of 'green' issues.
In addition, legislation is being introduced across the world to enforce
environmentally friendly practices.
 Life Cycle Assessment (LCA)

There are many different types of environmental impact.

For example, plastics are generally produced from fossil fuels, which are
gradually becoming depleted.
The production process itself involves energy consumption and further
resource depletion:
Energetic demand for the production of different materials

PP
Polipropilene

PE
Polietilene petrolio
Oil
Consumed
energia energy inequivalente
in petrolio terms of equivalent oil
PVC

polistirene
PS

acciaio
Iron

Copper
rame

Aluminum
alluminio

0 2 4 6 8 10 12 14 16 18
of equivalent
Kg equivalenti oil for each
di petrolio per lt. of di
litro produced material
materiale
 Life Cycle Assessment (LCA)

During production, different emissions may occur in water, air or soil.

Emissions of concern include heavy metals, chlorofluorocarbons,
polycyclic aromatic hydrocarbons, volatile organic compounds (VOC),
sulfur oxides and dust.
These emissions have effects such as ozone depletion, carcinogenicity,
smog, acid rain, etc.
Thus, production of a plastic product can have adverse effects on
ecosystems, human health and the environment.
 Life Cycle Assessment (LCA)
There are many factors to consider for each environmental impact
assessment, so a method has to be used to highlight the most significant
factors for comparisons purposes. For instance: one major advantage of
plastic materials is their lightweight and strength: a thin polymer film may
perform as well as a thick layer of natural material, thus resulting in reduced
material use and reduced energy costs in transport.

(plastic bags have less net environmental effect than paper bags, requiring less energy to
produce, transport and recycle)

LCA is a crucial technique for the plastics industry in the 21st Century.
Manufacturers and suppliers need to demonstrate that they are acting
responsibly towards the environment in all aspects of production, from the
design phase through consumer use and abuse, to disposal of end of life
components.
*
**
**

* Very slow degradation rate

** Biodegradable in various environments, the rate of biodegradation depending
on many factors
 Impact of plastics processing on environment:
hazards in rubber and plastics industries
There are many (potential hazard) chemicals used in rubber and plastics
industries: from the raw materials to the monomers polymerized to form
plastics and rubbers, to the additives/modifiers used to enhance the
polymer properties. In addition, other potentially hazardous substances are
formed by reactions between these base chemicals with air. The formation
of suspected carcinogenic nitrosamine compounds by some rubber
formulations is an example. Chemicals present at low levels can still be
toxic. (E.g.: PVC)

Monitoring of exposure to chemicals in the workplace and in emissions

from factories is used to calculate exposure to possible chemical toxins
including carcinogens. Other factors must also be considered in chemical
monitoring, such as the actual risk of injury and possible areas of high
exposure, such as when opening ovens or dealing with specific equipment,
situations where an accumulation of (dangerous) chemicals can occur in an
enclosed environment.
 Polymers Grave
Recycling. Recycling means that we can reuse materials, such as
plastics. This means that no new natural resources need to be used,
saving also energy. Unfortunately, there are problems with recycling.
Firstly, it costs lots of money, as the materials need to be sorted and
cleaned. Secondly, every time a plastic is recycled, the molecules in
the plastic can be degraded and so the quality of the recycled plastic
decreases.
Incineration. Some materials, such as polymers, can be burnt. This
means that we can use the heat produced to create energy. The
problem is that burning polymers can produce air pollution and also
means that more natural resources need to be used to produce more
plastic containers.

Landfill. Sometimes (often)

materials just get thrown away
and end up being thrown into
landfill, with consequent huge
environmental concerns.
 3R Principle

Industrial companies have recently applied the 3R principle (reduce, reuse

and recycle) to the recovery processing system of their plastic products.

Environmental processing through resource recycling is not only beneficial

to the environment but also promotes technological innovation.
 Polymer recycling
Due to their valuable properties, such as good mechanical properties, low
density, rather low cost, ease of processing, polymers are the most widely used
materials in various fields.
The world plastic production in 2013 achieved 299 million tons (it was 1.7
million tons in 1950 and 169 million tons in 2003) and from Europe 57 million
tons (Source: PlasticsEurope).
The total production of plastics is expected to reach to 400 million tons in
2020 based on a conservatively annual growth rate.
Every year, large quantities of waste polymers are produced from industrial,
agricultural and household activities. In 2012, 25.2 million tons of post-
consumer plastics waste ended up in the waste upstream: plastics make up
more than 12% of municipal solid waste stream, a dramatic growth from 1960,
when plastics were only 1% of the waste stream.
Total collectable plastics waste in Europe in 2003 was 21.2 million tons of
which 61% was landfilled and incinerated without energy recovery.
Even though recycling and energy recovery processes have increased, in
2012 around 62% of waste was recovered through recycling (26%) and
energy recovery processes (36%), but 38% of plastic waste still goes to
landfill.
Polymer consumption
Polymer consumption
Polymer consumption
 Polymer recycling (last released data 2016)
In Europe (EU27+CH+NO), out of 25 million tons of polymer waste, 25%
are recycled mechanically and 36.5% used as an energy source (in combustion,
steel and cement production mostly). 38.4% still goes to landfills, varying
between 1% (CH), 50% (IT) and 70-80% (UK), while peaking at 87% for Malta
(according to PlasticsEurope).
In UK, 7% of plastic wastes are recycled while 8% directly burned.
In North America, the recycled fraction is 9% (USA) and 16% (Canada), with
about 60% going to landfills.
China, a hotspot of plastic waste treatment, manages 22%, out of more than
600 million tons, half of this being imported.
Only India manages to re-process more than half at a rate of 60%. (India
produces each year over 12 million tons pf plastics).
Consequences: bad resource management, difficulties in maintaining landfills,
increasing ocean pollution by plastic waste, hazard for animals that can
accidentally ingest plastic bags, entangle themselves in it, or suffocate from it.
Today, the most of plastics (80%) is synthesized from raw materials
which derive from fossil fuels via the petrochemical industry. Thus, their
waste represents a loss of precious non-renewable resource of materials.
 Polymer recycling: model from other materials
Global paper production is based 50% on recycling while glass
production is based 75% in Europe and 70% in the US.

In all cases, these figures were not just reached by politics or public
pressure, but also by research. The fact that polymer recycling is not
growing rapidly is at least partly due to a lack of research efforts in the
field.
The cost of products incorporating waste plastic can be appreciably
higher than that of products obtained from virgin plastic, due to the
additional costs of recycling.
In addition, the quality of recycled plastic may not be comparable with
that of virgin plastic, due to the heavy recycling processes.
Finally, in some applications, plastics can be contaminated by other
materials: thus, they cannot be recycled due to the potential hazards
and harmful liquid-gases released in the environment.
 Polymer recycling: model from other materials

Progress happens, nevertheless, largely driven by industrial research,

since Academic research on recycling is rather repetitive and unrealistic
in scope.
An example is the use of tire regrind for toughening thermoplastics:
this works well if done correctly, but the simple issue of the sulphur
smell of such compounds which will prevent their application in more
than 90% of the cases is never addressed.
More efforts must be devoted to issues like compatibilization,
purification, emission reduction and long-term stability.
 Polymer recycling
Increasing costs and decreasing space of landfills are forcing
considerations of alternative options for plastic waste disposal.
But: the efficient treatment of waste polymers is still a difficult
challenge. Thus, landfilling is still the 1st option in many EU countries.
Year 2016 was fixed as the deadline for the landfill ban.
The new environmental, economic and petroleum considerations have
induced the scientific communities to increasingly deal with polymer
recycling. The recycling process is the best way to manage the waste
polymers.
Recycling of plastics can have several benefits, such as: reducing
consumption of energy; reducing the amount of the solid waste which
goes to landfill and reducing the emissions of CO2, NO and SO2 and
recycled plastic can partially replace virgin plastics produced from
refined fossil fuels.
 Polymer recycling
The traditional methods to manage waste polymers, such as combustion
or burying underground, show a negative effect on the environment like
formation of dust, fumes and toxic gases in the air, and the pollution of
underground water and other resources.
At the present time, there are different industrial techniques for
recycling of waste polymers: primary (re-extrusion), secondary
(mechanical), tertiary (chemical or feedstock recycling ) and
quaternary (energy recovery). The selection depends on the type of
polymer, on the source, on the processing, etc..
The treatment methods can be divided in chemical and mechanical.
Chemical methods are based on converting polymers into simple chain
chemicals for reuse. Cracking, gasification, hydrogenation and pyrolysis
methods could be considered as chemical recycling.
Mechanical recycling involves physical treatment.
Hand sorting, gravity (density) separation can be considered as
mechanical separation.
 Polymer recycling
The recycling rate significantly varies for different types of plastic.
However, there are some main problems for polymer recycling such as
separation. For example, PVC bottles are difficultly identified from
PET ones, but even a single PVC bottle in a melt of 10000 PET bottles
can damage the whole batch.
If PET is contaminated with PVC, in fact, PVC (amorphous, Tg80C)
will degrade at the high processing temperature used for PET (>260C),
thus producing char.
When PET and PVC are present in mixture, they are difficult to separate
due to slight differences in their density: PET density changes from 1.33
to 1.37 g/cm3 and PVC density is between 1.32 and 1.37 g/cm3.
Density sorting methods are not applicable when plastics are very close
in density (HDPE = 0.941 g/c3, LDPE = 0.9150.925 g/c3, LLDPE =
0.910.94 g/c3, PP = 0.96 g/c3).
The recycling of polymers is, therefore, more limited by separation
efficiency than by the demand for polymer waste.
 Polymer recycling

For ease of separation,

most manufacturers
determine the type of
plastics by the numerical
coding system created by
Society of Plastics
Industry (SPI) in 1980s.
The identification codes
can be found at the
bottom of most plastic
packaging.
 Polymer recycling
However, plastic tarps (teloni di plastica), pipes, toys, household
coverage and a multitude of other products do not fit into the
numbering system. So, they are not usually collected as well as the
thousands of different items realized with different polymers.
Furthermore, most polymer separation methods are expensive to
perform in large-scale application and are thus ineffective. In some cases,
separation is practically impossible to perform (for instance: chips
packaging is composed by PP and a metallic film, to keep fresh the item
stored in it).
Up to now, only gravity separation and skin flotation techniques have
been used on the industrial scale to separate the polymers.
Floating: different types of plastic flakes are separated in a floating tank
according to their density.
 Polymer recycling: Separation methods
The amount of polymer recycling is severely affected by difficulties in
separation processes: sorting is the most important step in recycling.
Many promising technologies are being investigated for separating mixed
thermoplastics, but they are still uneconomical and unreliable.
Depending on their surface characteristics, these plastics can be
separated from each other by flotation method which is useful mineral
processing technique with its low cost and simplicity.
The selective froth (schiuma) flotation technique is widely applied at
mineral processing and used for separating the materials based on their
surface character (hydrophobichydrophilic), which cannot be separated
easily by gravity or other methods. The hydrophilic surface remains in
the flotation solution while air bubbles attach to the hydrophobic one.
Selective flotation for separation of mixed polymers is controlled not
only by surface chemistry based on the different wettability (affinity)
characteristics of polymers, but also by shape and size of polymers in
waste.
 Polymer recycling: Separation methods
The hydrophobicity of the plastics is ordered as: PS > acrylonitrile
butadiene styrene (ABS) > PC > PET > PMMA > PVC >
polyoxymethylene (POM).
Both PET and PVC surfaces are hydrophobic in natural conditions.
Therefore, as the surface features of PET and PVC are so similar, it is
required to use reagents to change their surface characteristics and, thus,
to render one surface more hydrophilic, while the others are still in a
hydrophobic state.
There are many reagents in the literature used for changing the surface
character of polymers. For instance, flame treatment method are able to
change surface properties of plastics. The effect of the treatment is to
produce hydrophilic species on the surface of the plastic making it water-
wettable.
PVC particles were found to be less susceptible to surface modification
than PET, allowing the separation of PET and PVC by flotation method.
However, this is a costly process and can lead to contamination of the
recovered plastic.
 Polymer recycling: Primary recycling
Primary recycling, better known as re-extrusion, is the re-introduction of
scrap, industrial or single-polymer plastic edges and parts to the
extrusion cycle in order to produce products of the similar material.
(thermoplastic polymeric materials only)
This process utilizes scrap plastics that have similar features to the
original products. It is commonly applied in the processing line itself.
Primary recycling is only feasible with semi-clean scrap, therefore making
it an unpopular choice with recyclers.
A valid example of primary recycling is the injection molding of out of
specification LDPE crates (casse per imballaggio). Crates that do not
meet the specifications are palletized and reintroduced into the recycling
loop or the final stages of the manufacturing.
Primary recycling can also involve the re-extrusion of post-consumer
plastics. Generally, households are the main source of such waste stream.
However, recycling household waste requires selective and segregated
collection (raccolta differenziata) (involving significant operating costs).
 Polymer recycling: Mechanical recycling
In mechanical recycling, plastic waste (thermoplastic polymeric materials
only) is reused in manufacturing (plastics are re-granulated and re-
processed).
The various waste products are generally reduced in size to a more
desirable shape and form, such as pellets, flakes or powders, depending
on the source, shape and usability.
While mechanical recycling process of single thermoplastic polymeric
materials (for instance PP, PS, HDPE and LDPE) has developed to a
reasonable level, recycling of mixed thermoplastic polymers (i.e.
ABS/PC) has not progressed and remained somewhat unattractive.
Mixed recycled polymers exhibit weak mechanical properties and show
unpredictable rheological properties which preclude their usage in high
value applications.
 Polymer recycling: Mechanical recycling

The poor compatibility of the different polymers present in plastic

waste, together with the contamination by non-polymeric materials
(above all: paper), results in products with poor mechanical properties.
Therefore: separation, washing and preparation of polymer waste are all
essential steps to produce high quality, clear, clean and homogenous end-
products.
Polymer recycling: Mechanical recycling
 Polymer recycling: Mechanical recycling
One of the main drawbacks of mechanical recycles is the degradation of
polymer waste: after several processing cycles, the structure of an even
single polymer is degraded, achieving scarce mechanical properties
compared to those of a virgin one.
Energy or heat supply can cause photo-oxidation and/or mechanical
stresses with consequent breakage or branching of polymer. The quality
is the main issue when dealing with mechanically recycled products!
A number of products found in our daily lives come from mechanical
recycling processes, such as grocery bags, pipes, gutters (grondaie),
window and door profiles, shutters (serrande) and blinds (persiane), etc.
The industrial polymer waste generated in manufacturing, processing
and distribution of plastic products is well suited for the use as a raw
material for mechanical recycling due to the clear separation of different
types of polymers, the low level of dirt and impurities present and their
availability in large quantities.
 Polymer recycling: Mechanical recycling
Furthermore, in order to make recycled material suitable for high value
applications, two strategies could be employed.
In the first strategy, additives such as impact modifiers are added to
recycled resin in order to improve mechanical properties.
The second strategy is to mix appropriate quantity of recycled material
with the virgin material in order to obtain a blend that exhibits a good
balance between mechanical properties and processability characteristics
which allows its reuse: upgrading is absolutely necessary in a recycled
material.
Blending techniques are an interesting solution to obtain synergetic
properties but they are limited by compatibility considerations.
For instance: experimental studies of rheological and mechanical
properties of recycled PC and ABS of various purity levels showed that
impurity level has a very strong effect on impact strength and elongation
at break.
 Polymer recycling: Mechanical recycling
Mechanical recycling processes utilizing scrap and reclaimed (di
recupero) materials (namely blended with single virgin polymers).
 Polymer recycling: Feedstock recycling
Tertiary treatments, i.e. thermo-chemical treatment methods, cover a
wide range of technology processes which convert plastic materials into
smaller molecules, usually liquids or gases, which are suitable for use as a
feedstock (row materials) for the production of new petrochemicals and
plastics.
Products of chemical recycling have also proven to be useful as fuel.
The technology behind its success is the de-polymerization processes
that can result in a very profitable and sustainable industrial scheme,
providing a high product yield and minimum waste.
Under the category of chemical recycling, advanced process (similar to
those employed in the petrochemical industry) are: pyrolysis, gasification,
liquidgas hydrogenation, steam or catalytic cracking and the use of
polymer waste as a reducing agent in blast furnaces.
 Polymer recycling: Feedstock recycling
The main advantage of chemical recycling is the possibility of treating
heterogeneous and contaminated polymers with limited use of pre-
treatment. If a recycler is considering a recycling scheme with 40%
target or more, one should deal with materials that are very expensive to
separate and treat. Thus, chemical recycling becomes a viable solution

Feedstock recycling may be categorized into two processes, namely:

thermal degradation and catalytic degradation.
 Polymer recycling: Feedstock recycling
The thermal degradation process produces a broad product range and
requires high operating temperatures, typically more than 500C, even up
to 900C.
Catalytic degradation might offer a better solution by controlling the
product distribution as well as reducing the reaction temperature.
Drawbacks in the use of catalysis:
the activity of the catalysts can
decay due to the presence of
residual oils contain heavy metal
contaminants (such as: nickel,
vanadium and iron) which cause
severe damage and deactivate the
catalysts.
Example of Polymers that can be
treated with this process: High-
density polyethylene (HDPE).
 Polymer recycling: Feedstock recycling
Nowadays, much attention has been paid to chemical recycling (mainly
non-catalytic thermal cracking (thermolysis), catalytic cracking and steam
degradation) as a method of producing various valuable fuel fractions
from polymer waste.
By their nature, a number of polymers are advantageous for such
treatment.
PET and certain polyamides (nylon 6 and nylon 66) can be efficiently
de-polymerized.
PE has been identified as a potential feedstock for fuel (gasoline)
producing technologies. PE thermally cracks into gases, liquids, waxes,
aromatics and char.
There is also a growing interest in developing value added products such
as synthetic lubricants via PE thermal degradation. The development of
value added recycling technologies is highly desirable as it would increase
the economic incentive to recycle polymers.
 Polymer recycling: Pyrolysis
Pyrolysis (thermal cracking of polymers in inert atmosphere) is a
thermo-chemical decomposition reaction that completes the
endothermic reaction in a reducing (oxygen-free) atmosphere.
It takes place under controlled temperatures without catalysts.
Thermal degradation processes allow to obtain a number of constituting
molecules, combustible gases and/or energy, with the reduction of
landfilling as an added advantage.
The primary output of polymer pyrolysis is carbide (solid) and synthesis
gas (gaseous).
The pyrolysis (clean) gas generated by waste polymers has a high
calorific value and can be used as fuel.
Gases with higher calorific values are produced when the waste contains
significant quantities of synthetic materials such as rubber and plastics.
The remaining carbide in solid fossil fuels also has a high heat value.
In addition to fuel, waste polymers can be used as pitch (pece) and
activated carbon.
 Polymer recycling: Pyrolysis
Pyrolysis provides a number of advantages, such as: operational
advantages, environmental advantages and financial benefits.
Operational advantages could be described by the utilization of residual
output of char used as a fuel or as a feedstock for other petrochemical
processes. An additional operational benefit is that pyrolysis requires no
clean up of flue gas (gas di scarico), since the produced gas is mostly
treated prior to utilization.
Environmentally, pyrolysis provides an alternative solution to landfilling
and reduces greenhouse gas and CO2 emissions.
Financially, pyrolysis produces a high calorific value fuel that could be
easily marketed and used in gas engines to produce electricity and heat.
Several obstacles and disadvantages do exist for pyrolysis, mainly the
handling of char produced and treatment of the final fuel produced if
specific products are desired. In addition, there is not a sufficient
understanding of the underlying reaction pathways, which has prevented
a quantitative prediction of the full product distribution.
 Polymer recycling: Energy recycling
Energy recovery implies burning waste to produce energy in the form of
heat, steam and electricity. This is considered a very sensible way of
waste treatment when material recovery processes fail due to economical
constrains.
Plastic materials possess a very high calorific value (when burned),
considering that they are derived from crude oil. Since the heating value
of plastics is high, they make a convenient energy source.
The Table illustrates the calorific value of a number of single-polymer
plastics, compared to oil and MSW (Municipal Solid Waste).
 Polymer recycling: Energy recycling
Due to separation difficulties and the scarce performance achieved by
the re-processed polymers, energy recovery is sometime recommended.
Energy recovery involves complete or partial oxidation of the material,
producing heat, power and/or gaseous fuels, oils and chars besides by-
products that must be disposed.
A number of environmental concerns are associated with incinerating
plastic waste, mainly emission of certain air pollutants such as CO2,
NOx and SOx.
The combustion of plastic waste is also known to generate volatile
organic compounds (VOCs), smoke (particulate matter), particulate-
bound heavy metals, polycyclic aromatic hydrocarbons (PAHs),
polychlorinated dibenzofurans (PCDFs) and dioxins.
Carcinogenic substances (PAHs, nitro-PAHs, dioxins, etc.) have been
identified in airborne particles from incineration or combustion of
synthetic polymers such as PVC, PET, PS and PE
properly designed plants.
 Case studies

Worldwide, several innovative technologies and processes for the recycling

of polymers are under investigations in international research centers.

They must demonstrated to be: convenient (comprising each step), sound

(realistic), scalable (from laboratory to industrial plant), with no
production of toxic emissions and no severe drawbacks.

Some of them have already been adopted at industrial level.

 Case study: Polyolefins
(made up of only carbon and hydrogen atoms)

Thermoplastics contribute to the total plastic consumption by roughly

80%, and are used for typical plastics applications such as packaging but
also in other applications such as textile fibers and coatings.
Containers and packaging plastics (bags, sacks and wraps, other packaging,
other containers and soft drink, milk and water containers) represent the
highest tonnage.
The plastic industry has successfully identified workable technologies
for recovering treating and recycling of waste from discarded products.
As an example, in 2002, 388k tons of polyethylene (PE) were used to
produce various parts of textiles, of which 378k (97%) tons were made
from PE discarded articles.
 Case study: PET
About three-quarter of recycled PET in the UK and USA is used to
manufacture fibers for carpets, textile and bottles.
Two approaches have been widely promoted, mechanical recycling and
methanolysis (chemical recycling).
Once the PET has been collected and sorted, it represents a feedstock
for reclamation processing lines.
Reclamation involves washing the materials (mainly bottles) and
conditioning the plastics to be processed as semi-virgin resin or
masterbatch.
In doing so, a clear grade of PET can be produced of high quality to
compete with the virgin polymer.
Case study: PET
Case study: PET
 Case study: Packaging
Compared with other sectors, the packaging sector remains the largest
consumer of plastics. In Europe, packaging applications are the largest
segment for the plastics industry and represent 39.6% of the total
plastics demand, i.e. 46.3 million tons (year 2013, Source:
PlasticsEurope).
Containers and packaging plastics (bags, sacks and wraps, other
packaging, other containers and soft drink, milk and water containers)
represent the highest tonnage. Plastics versatility enables an almost
infinite variety of thick, thin, rigid or flexible packaging solutions,
allowing for maximum protection of goods with minimum economic
material.
Polyethylene (PE) dominates the packaging market, accounting for 56%
by weight of all produced packaging, followed by other plastics
polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS),
polyvinyl chloride (PVC) and expanded polystyrene (EPS) covering
most of the remaining 44% (Source: Packforsk Report no. 194, 2000).
 Case study: Packaging

The availability of several recovery methods provides a flexibility of

options which, combined with continuous improvements in waste
collection methods and separation techniques, has meant that
approximately 40% of plastics packaging waste is being recovered in
Western Europe. This means, however, that 60% of plastic waste is still
lost in landfill!
The exponential growth in plastic waste from packaging incited a search
for alternative means of recycling.

Why not to re-use the PET bottles in an apparently quite far area,
such as construction industry?
 Case study: Packaging
Total annual production of concrete is approximately 15 billion tons. If
PET bottle scraps could be industrially and systematic employed as raw
materials for the production of concrete this would benefit the
environment in many different ways.
It has been proven, in fact, that PET bottle (dispersed small) particles
can satisfactorily replace the fine aggregates, enhancing somehow the
final properties of concrete.
This solution will be also able to reduce the waste of natural resources,
such as mineral aggregates.
Furthermore, plastic wastes often have less weight per unit volume than
concrete aggregates. Therefore, if they replace concrete aggregates, the
unit mass of concrete structures will decrease.
 Case study: Packaging
Nowadays, research is very active in this field, lots of experimental
studies are present in literature, not always concordantly each other. As
few examples, some authors report that the PET-concretes are very
resistant in both compression and flexure compared to conventional
Portland cement concrete, others report that the compressive strength
and elasticity modulus of concrete are reduced after the direct inclusion
of plastic; the tensile strength has been found generally increased, due to
the bridging action of fibers in concrete; referring to workability of
fresh concrete, some literature reported an increase in workability with
the addition of small percentages of waste PET while others reported
an opposite influence, probably due to the different shape, size,
mechanical properties and origin of waste plastics.
It is generally recognized, however, that if a proper mix design is
identified, improvements of mechanical and physical properties
can be achieved in PET-modified concrete.
 Case study: Packaging

The cost of producing polymer concrete from waste plastics, however, is

still high!
Nevertheless, from an ecological point of view, economic and energy-
conserving benefits would be possible from the incorporation of waste
PET in concrete without any particular treatment. The main advantage
of recycling PET in concrete is, in fact, that this plastic material does not
have to be purified, nor the removal of colors is required, like in other
PET recycling applications.
 Case study: PVC
Due to its structure and composition, PVC can easily be mechanically
recycled in order to obtain good quality recycling material.
Careful and proper sorting is of crucial importance for the optimal
recycling of PVC. After an initial visual check, the collected PVC
materials are shredded into pieces of 10-15 cm. The metals and non-
ferrous metals are mechanically eliminated afterwards.
The company classifies the post-consumer plastics into rigid and flexible
material (accounting for the plasticizing content).
Rigid PVC recycled material is mainly used as an inner reinforcement
layer in pipes and profiles production, garden furniture or rigid films
manufacture.
Flexible PVC waste is recycled into powder and is used as filler in the
production, for instance, of floor coverings.
Other applications are traffic cones, fences (staccionate), flexible pipes
and tubes, footwear, bags, clothing, etc.
 Case study: nanocomposite
One of the alternative methods proposed to recycle the waste
(thermoplastic) plastics is development of blends and composites.
For instance: addition of nanofillers in the recycling process of
polymers, composites and blends
 Case study: nanocomposite
Compatibilizing, functionalizing and surface modification procedures
must be developed in order to obtain improvement in interfacial
adhesion.
The addition of functional nanofiller or a combination of nanofillers
can provide further progress and new opportunities in these materials.
The development of different preparation techniques and also,
optimization of melt mixing process could have important effect on the
final properties.
In such a way, the products prepared through the addition of
nanoparticles to the recycled polymers can offer unexpected
combinations of improved properties, low-weight, ease of processing
and low cost which can be not easily and concurrently found in other
manufactured goods.
 Case study: automotive
The automotive industry is considered a pillar industry in most countries
because of its significant economic contributions. Despite the limitations
imposed by fuel resources and environmental protection, as well as the
emergence of energy saving and new energy technologies in the
automotive industry, conventional cars continue to dominate the market
in general.
Automotive production and sales are more dominant in developed
countries than in developing countries. On the other hand, 2010
automotive production and sales has significantly improved in
developing countries, particularly in China, India and other emerging
economies whose growth rates and volumes of production and sales are
among the highest in the world.
The increase in automotive production and sales will also increase the
number of end-of-life vehicles (ELVs). In China, the annual number of
ELVs is expected to reach 13 million by 2020, whereas the global
number of ELVs will easily exceed 100 million.
 Case study: automotive
Extended producer responsibility (EPR): oblige producers to be
responsible for the life cycle of their products.
The main goals of EPR include waste prevention and reduction,
reduction of natural resource consumption and promotion of the use of
recycled materials.
The EPR policy is based on the polluter-pay principle and encourages
carmakers to include the costs of treatment and disposal into the price
of the vehicle to reflect the environmental impacts.
A number of countries have been using the EPR policy to manage end-
of-life products. The Netherlands has been the first European country
to legislate a recovery system that relies on a national system of
collection points.
 Case study: automotive 1.
A dashboard (cruscotto) is one of the most important components of
a vehicular interior. The design quality of dashboards directly affects the
quality of the vehicle interior. Given its unique spatial location,
dashboards are increasingly equipped with various functional features
(controls for airflow, sound, air conditioning and lighting).
The dashboard is located in front of the driver and typically contains the
speedometer, engine tachometer, fuel gauge and signal indicator.
 Case study: automotive 1.
The composition of the external part of the dashboard is mainly PVC.
The foam is solely composed of PU as the intermediate layer.
The framework (ossatura) consists of PC, acrylonitrile butadiene
styrene-copolymers (ABS) and PP.
PE and PA are also contained in some of the components.
The major physical characteristics of polymers are listed in the following
Table. The values of the main parameters, such as density, are
contiguous, thus causing difficulties in separation.

S-C Tm>250C S-C Tm>105C S-C Tm>130C A Tg=145C A Tg=80C A Tg=105C

 Case study: automotive 1.
After the automotive interior trim (guarnizioni) materials are crushed,
dismantling enterprises often use the flotation, winnowing (vagliatura)
or electrostatic approach to separate different materials.
In plastic separation, the foam can be easily separated from the other
materials by using the flotation approach (i.e. the density gap is huge).
However, this method cannot separate the other polymers effectively
because their densities are relatively contiguous. These polymers become
automobile shredder residues (ASR) and are disposed in a landfill.
Incineration is the earliest method of disposing ASR. The burning value
of ASR, in fact, is close to coal.
 Case study: automotive 1.
However, incineration poses numerous problems to the environment,
such as bottom ash and fly ash, which contain heavy metal impurities
(e.g. chromium, cadmium, lead and copper).
The chlorine component of ASR corrodes the incineration apparatus,
whereas the decomposition of polychlorinated biphenyls (PCBs derived
from vehicle electronic components) requires a high temperature, which
improve the processing costs and equipment maintenance costs. These
factors are considered significant obstacles to this solution.
Thus, incineration is not a suitable method for handling ASR.
Landfill disposal is also gradually being abandoned because of chemical
pollution and scarcity in land resources.
 Case study: automotive 1.
Possible solution (at design stage): the designers can adopt the single
polymer principle, which has the following advantages:
1) the use of a single polymer can significantly reduce manufacturing,
labor (e.g. manual sorting) and equipment costs (e.g., sorting equipment
and sorting reagents) when the polymer is dismantled;
2) the use of a few types of polymers corresponds to low environment
pollution and promote the improvement of recycling technology;
BUT: a single polymer possess unique physical properties and it is not
easily adaptable to any specific functional requirement!
 Case study: automotive 2.
It is estimated that 1.5 billion tyres are produced worldwide each year
which will eventually end-up as waste tyres (2011).
In terms of tonnages, waste tyres represent a significant proportion of
the total solid waste stream.
For example, approximately 3.3 million tons of waste tyres were
generated annually within Europe in 2010. More than 17 million tons are
produced worldwide each year.
The management of waste tyres in the European Union has been
regulated under the End of Life Vehicle Directive which stipulates the
separate collection of tyres from vehicle dismantlers and encourages
their recycling. In addition, the EU Waste Landfill Directive has banned
the landfilling of tyres.
These Directives have dramatically changed the tyre waste treatment
routes in the EU over the last 15 years.
For example in 1996 approximately 50% of waste tyres were sent to
landfill, however, currently the figure is only 4%.
 Case study: automotive 2.
The widely differing chemical compositions and the cross-linked
structures of rubber in tyres are the main reason why they are highly
resistant to biodegradation, photochemical decomposition, chemicals
and high temperatures.
The increasing numbers of used tyres therefore constitute a serious
threat to the natural environment. The landfill sites where the tyres are
useless stockpiled are a serious concern for both the natural
environment and human health because of the risk of fire and their
being used as a suitable habitat by rodents, snakes and mosquitoes.
The development of studies into their more efficient recovery and
recycling, and the European Unions restrictive legal regulations
regarding the management of used tyres, have led to solutions enabling
this substantial stream of rubber wastes to be converted into energy or
raw materials (both chemical processes).
 Case study: automotive 2.
A conventional tyre is a product with a complex structure and
composition, which can be made using various variants of high-quality
synthetic rubbers, mainly butyl rubber (IIR) or styrene-butadiene
rubber (SBR) and natural rubber (NR), along with a host of other
compounds added to obtain the final utilitarian form or the high
mechanical strength of the tyre.
The elastomers, which make up the rubber component of the tyre, are
strengthened with carbon black filler material.
Apart from the rubber, which makes up around 7080% of the tyre
mass, there are also steel belts and textile overlays, which give the tyre its
ultimate form and functional properties.
The construction of the tyre, therefore, involves a composite of several
layers of the rubber, textile material and steel belt and cord.
 Case study: automotive 2.
The typical compositions of passenger and truck tyres, respectively, are
shown in the following Table:

The following Table shows the basic raw material composition of tyres,
together with the percentage content of the various components used in
the manufacture of passenger and truck tyres in USA and Europe.
 Case study: automotive 2.
The presence of steel belts and textile overlays is a serious problem since
they must be separated from the rubber during tyre recycling.
Hence, in order to obtain a new product derived from automobile tyre
recycling that would satisfy high quality norms, the use of
technologically highly complex processes is required (used tyres are a
category of waste whose recycling is exceedingly difficult).
Their recycling requires high time and energy costs and is based on the
mechanical, thermal or chemical destruction of the rubber product; the
complete recovery of the raw materials used to produce them is quite
impossible.
 Case study: automotive 2.
The main options used for treating waste tyres are through the use of
tyres as fuel in cement furnaces which accounts for more than 1.15
million tons of the total 3.3 million tons of waste tyres generated each
year in the EU.
Other energy recovery options for tyres include use in power plants and
co-incineration with other wastes which use approximately 0.1 million
tons per year of tyres.
About 1.1 million tons of tyres are used in material recovery options
through the production of rubberized flooring in sports fields and
playgrounds, paving blocks, roofing materials, etc.
A significant proportion of the waste tyres are used in civil engineering
applications such as road and rail foundations (0.24 million tons) each
year.
Waste tyres can also represent as a source for alternative fuels.
 Case study: automotive 2.
Alternative treatment processes: pyrolysis technology.
Pyrolysis is the thermal degradation of the organic components of the
tyres, at typical pyrolysis temperatures of 500C to produce an oil, gas
and char product in addition to the recovery of the steel.
The oil may be used directly as a fuel, added to petroleum refinery
stocks, upgraded using catalysts to a premium grade fuel or used as a
chemical feedstock.
The gases from tyre pyrolysis are typically composed of C1C4
hydrocarbons and hydrogen with a high calorific value, of sufficient
energy content to act as fuel to provide the heat for the pyrolysis
process.
The solid char consists of the carbon black filler and also char produced
during the pyrolysis of the rubber.
It may be used as a solid fuel, as carbon black, or upgraded to produce
an activated carbon.
 Case study: automotive 2.
Pyrolysis outputs from the treatment of waste tyres:
 Case study: electrical and electronic devices
Waste electrical and electronic equipment (WEEE) contains about 10
30% of plastics; it is imperative, therefore, to include the plastic content
in economic recovery or material recycling systems.
Recycling of WEEE plastics is a big challenge, mainly due to:
1) The plastics waste fraction of WEEE consists of more than 15
different polymer types. Polymers represent approximately 20% of the
total weight of EEE and are based on different types of engineering
polymers, including acrylonitrilebutadienestyrene co-polymer (ABS),
high-impact polystyrene (HIPS), PP, PS, etc. (problems for separation).
2) A large part of WEEE plastics contain brominated flame retardants
(BFRs), including polybrominated biphenyls (PBB) and polybrominated
diphenyl ether (PBDE) (concerns for toxicity).
 Case study: electrical and electronic devices
BFRs flame retardants are substances used in plastics, textiles, electronic
circuitry and other materials to prevent them from fire.
BFRs are incorporated into plastics either through reaction or addition.
Reactive combination produces plastics with covalently bonded flame
retardants, these flame retardants are less likely to leave the product.
In contrast, additive flame retardants are simply mixed with the polymer
resin and so continually leach out of the final product.
The thermal treatment of such chemicals is likely to produce extremely
toxic halogenated dibenzodioxins and dibenzofurans. (Their use, in fact,
is somehow restricted or limited in all new electric and electronic devices
by the European directive on the restriction of hazardous substances
(RoHS).)
The energy recovery from such waste materials must be performed in
appropriate industrial plants.
 Case study: FRP
The world-wide demand for carbon fibers (CFs) reached approximately
35000 tons in 2008; this number is expected to apprecialby increase with
a growth rate of over 12% per year.
CFRP is now used in a widening range of applications, and in growing
content in most of them.
The aircraft industry is an impressive example, with Boeing 787 and
Airbus A350 having up to 50% of their weight in CFRP. Military aircraft
shows a similar trend. (Helicopters!)
The increasing use of carbon fiber reinforced polymers (CFRPs) has
raised an environmental and economic awareness for the need to recycle
the CFRP waste.
Common sources of waste include out-of-date pre-pregs, manufacturing
cut-offs, testing materials, production tools and end-of-life (EoL)
components.
 Case study: FRP
CFRP waste
(a) Out-of-date pre-preg rolls. (b) Manufacturing cut-offs. (c) Mold.
(d) EoL-aircraft wings.
 Case study: FRP
The first aircraft with structural CFRP components will soon be
decommissioned. Within few years, the same will happen to the new
composite-generation aircraft (8500 commercial planes will be retired by
2025), with each vehicle representing more than 20 tons of CFRP waste.
Within a similar time frame, the wind industry will be another great
source of CFRP waste.
 Case study: FRP
Recycling composites is inherently difficult because of:
1) their complex composition (fibres, matrix and fillers);
2) the cross-linked nature of thermoset resins (which cannot be re-
molded); and
3) the combination with other materials (metal fixings, honeycombs,
hybrid composites, etc.).
Presently, most of the CFRP waste is landfilled. The airframe of EoL
vehicles is usually disposed in desert graveyards, airports or by
landfilling.
However, these are unsatisfactory solutions for several reasons:
 Case study: FRP
environmental impact: the increasing amount of CFRP produced raises
concerns on waste disposal and consumption of non-renewable
resources;
legislation: recent European legislation is enforcing a strict control of
composite disposal; the responsibility of disposing EoL composites is
now on the components manufacturer, legal landfilling of CFRP is
limited, and for instance it is required that automotive vehicles disposed
after 2015 are 85% recyclable;
production cost: Carbon Fibers are expensive products, both in terms of
energy consumed during manufacturing (up to 165 kWh/kg) and
material price (up to 40 /kg);
management of resources: demand of virgin Carbon Fibers usually
surpasses supply-capacity; so recycled could be re-introduced in the
market for non-critical applications; and
economic opportunity: disposing of CFRP by landfilling can cost
approximately 0.20 /kg; recycling would convert an expensive waste
disposal into a profitable reusable material.
 Case study: FRP
Two technology families have been proposed to recycle CFRPs:
mechanical recycling (a) and fiber reclamation (b).
Case study: FRP
 Case study: FRP
Mechanical recycling involves breaking-down the composite by
shredding, crushing, milling or other similar mechanical process.
The resulting scrap pieces can then be separated by sieving (setacciatura)
into powdered products (rich in resin) and fibrous products (rich in
fibers).
Typical applications for mechanically-recycled composites include their
re-incorporation in new composites (as filler or reinforcement) and use
in construction industry (e.g. as fillers for artificial woods or asphalt, or
as mineral-sources for cement).
However, these products represent low-value applications; mechanical
recycling is therefore mostly used for glass fiber reinforced polymers
(GFRPs), although applications to thermoplastic and thermoset CFRPs
can be found as well.
 Case study: FRP
Fiber reclamation consists on recovering the fibers from the CFRP, by
employing an aggressive thermal or chemical process to break-down the
matrix (typically a thermoset).
The fibers are released and collected, and either energy or molecules can
be recovered from the matrix.
Fiber reclamation may be preceded by preliminary operations, e.g.
cleaning and mechanical size-reduction of the waste.
Fiber reclamation processes are particularly suitable to CFRPs: carbon
fibers have high thermal and chemical stability, so usually their excellent
mechanical properties are not significantly degraded (especially regarding
stiffness). Nevertheless, some surface defects (pitting, residual matrix
and char) and strength degradation (especially at longer gauge lengths)
have also been reported.
After reclamation, the recycled fibers are usually re-impregnated with
new resin to manufacture recycled CFRPs.
 Case study: FRP
Scanning-electron microscopy of recycled (through pyrolysis) carbon fibers.
(a) Clean recycled fibers. (b) Recycled fibers with char residue
 Case study: FRP
Pyrolysis, the thermal decomposition of organic molecules in an inert
atmosphere (e.g. N2), is one of the most widespread recycling processes for
CFRP. During pyrolysis, the CFRP is heated up to 450C to 700C in the
(nearly) absence of oxygen; the polymeric matrix is volatilized into lower-
weight molecules, while the CFs remain inert and are eventually recovered.
Oxidation is another thermal process for CFRP recycling; it consists in
combusting the polymeric matrix in a hot and oxygen-rich flow (e.g. air at
450C to 550C). This method has been used by a few researchers, being
the fluidized bed process (FBP) the most well-known implementation.
In fluidized bed process (FBP) recycling, CFRP scrap (reduced to
fragments approximately 25 mm large) is fed into a bed of silica on a
metallic mesh. As the hot air stream passes through the bed and
decomposes the resin, both the oxidised molecules and the fiber filaments
are carried up within the air stream, while heavier metallic components sink
in the bed; this natural segregation makes the FBP particularly suitable for
contaminated EoL components. The fibers are separated from the air
stream in a cyclone and the resin is fully-oxidised in an afterburner. Energy-
recovery to feed the process is feasible.
 Case study: FRP
Chemical methods for CFRP recycling are based on a reactive medium
(e.g. catalytic solutions, benzyl alcohol and supercritical fluids) under low
temperature (typically <350C). The polymeric resin is decomposed into
relatively large (and therefore of high value) oligomers, while the CFs
remain inert and are subsequently collected.
Supercritical fluids (SCFs) are fluids at temperatures and pressures
(typically just) above the critical point; at this stage, the fluid presents
itself in one single supercritical phase, while having combined
characteristics: liquid-like density and solvent power and gas-like
viscosity and diffusivity. SCFs can, therefore, penetrate porous solids and
dissolve organic materials, while still being relatively innocuous under
atmospheric conditions. Several types of SCF (usually coupled with
alkali catalysts) have been used for CF recycling, such as water,
methanol, ethanol, acetone and propanol. Chemical recycling with SCFs
is recognized for producing recycled CFs with virtually no mechanical
degradation (especially when using propanol) and for allowing
recovering of useful chemicals from the matrix.
 The Life Cycle of Thermoset Glass Fiber Composite Wind Turbine
Blades
 The Life Cycle of Thermoplastic Glass Fiber Composite Wind Turbine
Blades