Resources, Conservation and Recycling 55 (2011) 865–875

Contents lists available at ScienceDirect

Resources, Conservation and Recycling

journal homepage: www.elsevier.com/locate/resconrec

Review

Twenty years of PET bottle to bottle recycling—An overview

Frank Welle
Fraunhofer Institute for Process Engineering and Packaging (IVV), Giggenhauser Straße 35, 85354 Freising, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Polyethylene terephthalate (PET) has become the most favourable packaging material world-wide for
Received 5 March 2011 beverages. The reason for this development is the excellent material properties of the PET material, espe-
Received in revised form 20 April 2011 cially its unbreakability and the very low weight of the bottles compared to glass bottles of the same filling
Accepted 23 April 2011
volume. Nowadays, PET bottles are used for softdrinks, mineral water, energy drinks, ice teas as well as
for more sensitive beverages like beer, wine and juices. For a long time, however, a bottle-to-bottle recy-
Keywords:
cling of post-consumer PET packaging materials was not possible, because of the lack of knowledge about
PET bottle
contamination of packaging polymers during first use or recollection. In addition, the decontamination
Bottle-to-bottle recycling
Food packaging
efficiencies of recycling processes were in most cases unknown. During the last 20 years, PET recollection
Mechanical recycling as well as recycling processes made a huge progress. Today, sophisticated decontamination processes,
Super-clean recycling so-called super-clean recycling processes, are available for PET, which are able to decontaminate post-
consumer contaminants to concentration levels of virgin PET materials. In the 1991, the first food contact
approval of post-consumer PET in direct food contact applications has been given for post-consumer
recycled PET in the USA. Now, 20 years after the first food approval of a PET super-clean recycling pro-
cess, this article gives an overview over the world-wide progress of the bottle-to-bottle recycling of PET
beverage bottles, e.g. the recollection amount of post-consumer PET bottles and the super-clean recycling
technologies.
© 2011 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 866
2. Recollection of post-consumer PET bottles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 866
2.1. Recollection rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 866
2.2. PET bottles as input for bottle-to-bottle recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 867
2.3. End markets for PET recyclates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 868
3. PET manufacturing and recycling processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 868
3.1. Virgin PET polymerisation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 868
3.2. Depolymerisation processes to monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 869
3.3. Conventional versus super-clean PET recycling processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 869
3.4. Multi-layer packagings—functional barrier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 869
3.5. PET super-clean recycling technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 870
3.6. PET super-clean recycling processes based on pellets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 870
3.7. PET super-clean recycling processes based on flakes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 871
3.8. PET super-clean recycling processes based on depolymerisation of the flake surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 872
3.9. PET super-clean recycling processes based on partial depolymerisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 872
4. Legislative aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 873
4.1. Guidelines and regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 873
4.2. Risk assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 873
5. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 874
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 875
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 875

E-mail address: welle@ivv.fraunhofer.de

0921-3449/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.resconrec.2011.04.009
866 F. Welle / Resources, Conservation and Recycling 55 (2011) 865–875
1. Introduction
Polyethylene terephthalate (PET) has become the most
favourable packaging material world-wide for water and softdrinks
bottles. The reason for this development is the excellent material
properties of the PET material, especially its unbreakability and the
very low weight of the bottles compared to glass bottles of the same
filling volume. In comparison to other packaging polymers, PET has
also a high clarity as well as good barrier properties towards mois-
ture and oxygen. As a consequence, PET has mainly substituted
glass as packaging material, but also metal cans. Nowadays, PET
bottles are used for softdrinks, mineral water, energy drinks, ice
teas as well as for more sensitive beverages like beer, wine and
juices. The amount of PET bottles for beverages is still increasing
world-wide.
For a long time, however, the recycling post-consumer packag-
ing materials into new packaging application was possible only for
glass bottles and jars just as for metal cans. For packaging polymers
a recycling of post-consumer packaging materials into direct food
contact packaging applications was not possible, because of the
lack of knowledge about contamination of the packaging polymers
during first use or recollection. In addition, the decontamination
efficiencies of recycling processes were in most cases unknown.
Therefore the evaluation of the food law compliance status of the
post-consumer recyclates was not possible for a long time. The
main problem is that substances from the beverages as well as haz-
ardous compounds from potentially misused containers for storage
of household cleaners or garden chemicals might be absorbed into
the polymer. If these absorbed post-consumer contaminants are
not removed from the packaging polymer during recycling, they
might migrate into foodstuff from the recyclate containing pack-
aging materials. In addition, additives which are not approved for
food packaging materials might enter the food packaging stream
if non-food packaging materials of the same polymer type were
also re-collected and recycled together with the food packaging
materials. For one packaging polymer, however, the situation is
much favourable. Due to the very inert character of PET, recycling
technologies have been developed to establish a bottle-to-bottle
recycling of post-consumer PET bottles.
Ecological demands just as discussions, e.g. on littering and on
carbon footprint, gave pressure on the public community, so that
together with the increasing amount of PET bottles all over the
world, also the recollection of post-consumer PET bottles and the
recycling of them was steadily increasing. Recollected PET bottles
were therefore more and more available for recycling. In the begin-
ning PET recyclates are mainly used for the production of polyester
fibres. On the other hand, in a bottle-to-bottle recycling stream
the recollected PET bottles end up into new PET beverage bottles.
On the first glance, it seems not to be so important if the recol-
lected PET bottles were recycled into non-food applications or again
into new beverage bottles. In both cases crude oil is substituted
by post-consumer PET bottles. However, traditional PET recycling
markets like fibre applications were hardly in a position to absorb
the increasing amount of recollected and recycled PET bottles. This
situation enforces the development of bottle-to-bottle recycling
processes for PET beverage bottles. However, post-consumer con-
taminants still have to be decontaminated to concentration levels
of virgin PET materials, even if worst-case scenarios are assumed
e.g. the use of highly contaminated PET bottles as an input for
the recycling processes. This leads to the development of sophisti-
cated decontamination processes, so-called super-clean recycling
processes. But not only the increasing amounts of recollected PET
bottles available have pushed the development of bottle-to-bottle
recycling concepts. PET bottle-to-bottle recycling was also driven
by the softdrink and mineral water companies due to ecological
and marketing reasons. Together with machinery manufactures,
Fig. 1. Recollected PET bottles in Brazil, Europe, Japan and the USA [in 1000 t].
these bottle-to-bottle recycling concepts had been introduced into
the market world-wide. Today, PET bottles with up to 50% post-
consumer PET recyclates are on the market in some regions (e.g.
Europe).
In the 1991, the first recycling process for post-consumer PET
in direct food contact applications has been approved in the USA.
Twenty years later, it is time to give an overview over the world-
wide progress of PET bottle-to-bottle recycling.
2. Recollection of post-consumer PET bottles
2.1. Recollection rates
In many countries recollection systems for post-consumer PET
bottles as well as for other packaging materials (paper and board,
metal cans, glass, plastic packaging) have been established. For PET
beverage bottles, in principle, there are two major recollection sys-
tems established: (i) curbside collections and (ii) deposit systems.
In curbside collections, the PET bottles are recollected together
with other packaging materials e.g. recollection within green dot
systems. The PET bottles are sorted automatically and/or by hand-
picking out of the plastic packaging fraction. Curbside collections
provide typically an input material for the recycling processes,
which contain PET bottles from food applications together with a
certain amount of non-food PET containers. In deposit systems the
consumer brings the PET beverage bottles back into the store in
connection with redemption of the deposit. From a food law com-
pliance point of view, deposit systems have the huge advantage,
that the recollected PET bottles are usually 100% beverage bottles.
Quantitative data of recollected PET bottles over the last ten to
twenty years are available for some countries e.g. the USA (Napcor,
2011), the European countries (Petcore, 2011), Brazil (Abipet 2011)
and Japan (Japan, 2011). Fig. 1 shows the recollection amounts of
PET bottles for the above mentioned regions. For Europe, the rec-
ollection of PET bottles shows a huge increase over the last about
10 years. The growth rates are between 10 and 20% per year. In
2009, a total amount of 1.363.000 t of post-consumer PET bottles
are recollected (Petcore, 2011). A fraction of 223.000 t (17%) of
these recollected bottles were exported, mainly to China. On the
other hand, 67.000 t of collected bottles were imported to the EU,
mainly from the non-EU Eastern Europe countries. During con-
ventional recycling (grinding and washing) closures, labels, etc.
were removed from the recollected bottles, which leads to a loss
of 302.000 t (18%) of material. At the end, an amount of 905.000 t
of conventionally recycled PET flakes was available for reuse in
different PET recyclate applications (Petcore, 2011). For Europe,
 F. Welle / Resources, Conservation and Recycling 55 (2011) 865–875 867

Table 1 Table 2
Recollection amounts in 1000 t of PET bottles in 2009 in Europe, USA, Brazil and End markets for PET recyclates in Europe and in the USA (Petcore, 2011; Napcor,
Japan. 2011).

Country Amount (1000 t) Percentage Recollection Year Percentage Sheet Bottle Strapping Other
(only for Europe) rates fibre (food,
non-food)
Europe 1363 (sum) 48.4%
Germany 393 29% 93.5% 2001
Italy 175 13% 41.7% EU 62 16 7 10 5
France 155 11% 62.8% USA 62.1 5.3 17.3 11.7 3.6
Spain 102 7% 39.2% 2005
UK 102 7% 32.7% EU 57.0 16.2 15.2 7.8 3.8
other EU 436 32% USA 53.6 8.2 20.6 15.2 2.4
USA 655 28% 2009
Brazil 262 55.6% EU 40.5 27.0 22.0 7.0 3.5
Japan (2008) 445 77.9% USA 36.7 17.0 28.6 12.2 5.5

the recollection amounts are also available for different countries
(Table 1). The highest amounts of post-consumer PET bottles in
Europe were collected in Germany, Italy, France, Spain and the
United Kingdom. These fives countries collected 68% of all post-
consumer PET bottles in Europe in 2009. An interesting figure is
also the recollection rate (Table 1), which is the ratio between the
amount of sold PET beverage bottles in a certain region and the
amount of recollected PET bottles in the same region. In Europe,
the recollection rate is the highest in Germany (93.5%), which is
due to the general deposit system for one-way bottles as well as
for refillable PET bottles. The overall recollection rate in Europe is
48.4% in 2009 (Petcore, 2011). It is expected, that the recollection
rate in Europe exceeds 50% in 2010.
In the USA the situation is slightly different. Twenty years ago,
the USA started with higher amounts of recollected PET beverage
bottles compared to all other countries/regions. The growth rates,
however, are significantly lower than for example in Europe. As a
consequence, from 2002 on lower amounts of post-consumer PET
bottles were collected in the USA compared to Europe. For the USA,
a volume of 655.000 t of post-consumer PET bottles is recollected
in 2009. About 55% of the recollected PET bottles (363.000 t) were
exported, mainly to China. On the other hand, 44.000 t of baled post-
consumer bottles were imported into the USA. At the end, 254.000 t
of conventionally recycled post-consumer (PCR) PET flakes were
available for reuse in the USA. The loss due to removal of closures
and labels was about 25% of the recollected material during con-
ventional recycling. According to US reclaimers, the loss is about
17% of collected material for PET bottles from deposit systems and
about 26% from curbside collections. In 2009, the recollection rate
in the USA was 28% (Napcor, 2011).
In Brazil a total volume of 262.000 t of PET bottles were recol-
lected in 2009 and a recollection rate of 55.6% has been reported
(Abipet 2011). In Japan a total volume of 445.000 t was recollected
in 2008 and the recollection rate of PET bottles was 77.9% (Japan,
2011). The increase per year of recollected PET bottles in Brazil and
Japan is in the range of 10 and 20%.
recycling and decontamination processes for post-consumer PET
bottles.
• PET bottles can be typically separated easily from the recollected
waste stream by automatic systems or by hand picking. Therefore
high quality input of nearly pure PET fractions are available for
recycling.
• Caps and labels of PET bottles are made from non-PET materi-
als (e.g. from polyolefins). These foreign polymer impurities can
be easily removed from the recycling feedstream during conven-
tional recycling due to density separation.
• PET beverage bottles are mainly transparent (without colorants)
and if, mainly light blue, green or brown colours are used.
Coloured beverage bottles can be sorted easily by colour sorting
systems and recycled in four separate streams.
• PET does not need additives like antioxidants, plasticizers or slip
agents. A control of the additive status of the PET recyclates is
therefore not necessary. On the other hand, the polymerisation
catalysts like antimony trioxide or antimony glycolates are still
present in the recyclates in their active forms (Duh, 2002). This
is very important, because the polyester polymer chains can be
therefore rebuilt to longer chain polyester molecules during recy-
cling. As a consequence, the viscosity of the PET polymer can be
increased to levels of virgin PET during recycling with help of
solid state polycondensation (SSP) or similar reactions.
• PET bottles are (typically) not directly printed. Therefore the
contamination of the recycling stream with non-approved
or non-regulated compounds from printing inks like photo-
initiators or mineral oil components is therefore minimal.
• All PET raw materials used for food and non-food packaging
applications are food-grade PET which is in compliances with
European and US packaging law (or the national laws of several
other countries). Therefore, recollected PET fractions, which con-
tain a certain amount of non-food PET material, are not excluded
as feedstock materials for bottle-to-bottle recycling.
• PET is a very inert polymer, which results in a very low absorption
of compounds during the first life of the packaging material.

2.2. PET bottles as input for bottle-to-bottle recycling
PET bottles have been found to be nearly the ideal input material
for bottle-to-bottle recycling which is due to the following reasons:
• PET bottles are on the market world-wide in significant amounts.
In addition, recollection systems for PET bottles are established in
several countries, which guaranties recollection rates above the
recollection rates for most of other (plastic) packaging materials.
Therefore, huge amounts of post-consumer PET bottles are avail-
able for recycling all over the world. This makes PET interesting
as a target for recycling and sorting machinery manufacturers as
well as to PCR PET end users. As a consequence both, recycling
companies and machinery manufacturers, had been developed
Taking the above mentioned points into account, PET is one
of the most favourable packaging polymers for bottle-to-bottle
recycling. One critical point, however, is the amount of non-food
packaging materials in the recollection feedstream. Non-food PET
bottles might be higher contaminated than food packaging mate-
rials because of the possible exposure to aggressive chemicals
during the first life. Therefore, non-food PET containers might have
absorbed industrial chemicals like solvents or mineral oil. Within
the last decade, sorting technology made a huge step forward, but it
is still very hard to separate all of the non-food containers from the
recollection feedstream. As a consequence, the cleaning efficiencies
of the super-clean recycling processes have to be high enough to
decontaminate such impurities to non-detectable concentrations
in the super-clean recyclates. The necessary minimum cleaning
868 F. Welle / Resources, Conservation and Recycling 55 (2011) 865–875
Fig. 2. Installed super-clean PET recycling capacities in Europe in 2009 [1000 t per
year] (total 590.000 t).
efficiency depends on the amount of non-food bottles in the recy-
clate stream. Higher cleaning efficiencies of the applied super-clean
recycling process are necessary if higher amounts of non-food PET
containers are used as input material. In a feasibility study, it could
be shown that also an input fraction of 100% non-food contain-
ers will produce a “food-grade” PET recyclate if “state-of-the-art”
super-clean recycling processes are applied (Blanchard et al., 2003).
From a hygienic point of view, however, the input material for
bottle-to-bottle recycling should be only bottles or containers from
food applications in the first use.
2.3. End markets for PET recyclates
The end markets for post-consumer PET flakes are fibres, sheets,
bottles or containers and straps. The percentages of the post-
consumer recyclate for each of these applications for the years
2001, 2005 and 2009 are given in Table 2. In the USA as well as
in the EU, the percentages of PET recyclates going into fibre and
strapping applications are decreasing over the last decade, whereas
sheet and bottle applications are increasing. With other words, the
end use applications of post-consumer PET are moving more and
more towards packaging applications. About 49% of the PCR PET
was used for packaging applications in 2009 in Europe, most of
them in food applications. However, in absolute figures, also the
amount of PET recyclates reused in fibre applications was grow-
ing at least in Europe. E.g. in the EU the volume of PCR PET in
fibre applications has been more than doubled from 214.000 t in
2001 to 552.000 t in 2009. On the other hand, in the USA, about
234.000 t of PCR PET was used for fibre applications in 2001. Nearly
the same amount (244.000 t) went into for fibre applications in
2009. From these figures it can be concluded, that the growth of
recollected post-consumer PET bottles in the USA is going more or
less completely into the export to China. However, most probably
the exported PET materials to Far East are also going into fibre appli-
cations. In Brazil, about 19% of the PET recyclates were reused in
packaging applications (food and non-food PET packages) in 2009
(Abipet 2011). In conclusion PET fibres are still one of the main
end user markets for PCR PET world-wide, but PET bottle-to-bottle
recycling increasing more and more.
In the last decade huge capacities have been established in order
to recycle the recollected post-consumer PET bottles. Especially
super-clean recycling plants have been built up. For 2009, in Europe
a total capacity of 590.000 t super-clean PCR PET was installed
(Fig. 2, Source: unpublished study of the author). It is interesting
to note, that four of the countries in Europe with the highest rec-
ollection amounts of post-consumer PET bottles (Germany, Italy,
France and UK, see Table 1) have also installed the main capaci-
ties for super-clean PCR PET (Fig. 2). This indicates, that in Europe
the recollection rates influences the recycling capacities (and vice
versa) and that the export to China plays a minor role for Europe. In
2010 in the USA, 13 recycling plants for super-clean PCR PET were
operating with an overall capacity of 129.000 t (Napcor, 2011).
monomers
removal of water
and excess of polymerisation
ethylene glycol
pre-polymer
viscosity increase melt-phase
condensation
amorphous
PET pllets
viscosity increase, solid-state poly-
180-230 °C, >6 h condensation
inert gas or vacuum
crystallin
PET pellets
Fig. 3. Scheme of PET virgin polymerisation processes.
3. PET manufacturing and recycling processes
In this chapter some typical PET polymerisation and recy-
cling processes will be discussed. It should be noted here, that all
given process parameters like recycling steps, temperature profiles,
residence times or vacuum conditions should be understood as
parameter sets typically used in such processes. The given process
parameters are not linked to a certain polymerisation or recycling
process.
3.1. Virgin PET polymerisation processes
The polymerisation of virgin PET is starting from the monomers
ethylene glycol and terephthalic acid or terephthalic acid methyl
ester. In the first step the monomers react to a so-called PET pre-
polymer. The viscosity of this pre-polymer, however, is too low for
packaging, fibres or any other application. Therefore the viscosity
of the PET polymer has to be increased by a further condensation-
reaction of the PET material in the melt phase at temperatures
up to 280 ◦ C. The reaction product of the esterification (water or
methanol) and excessive monomer (ethylene glycol) are removed
under vacuum. At the end of the polymerisation reaction the melt
is extruded into PET pellets. The viscosity of these pellets is still
too low for PET packaging applications. Therefore a further con-
densation reaction follows, which is typically done in a solid state
post-condensation (SSP) reaction. The end product of this reaction
is crystalline pellets. A scheme of such a virgin PET polymerisa-
tion process is shown in Fig. 3. As polymerisation catalyst, typically
antimony trioxide (Sb2 O3 ) or the reaction products of antimony tri-
oxide with ethylene glycol is applied (Duh, 2002). In some cases,
germanium and titanium oxides are used as catalyst or co-catalyst.
The main reaction from the monomers to the repeating units of
polyester in the polymerisation reaction is shown in Fig. 4. In gen-
eral, trans-esterification reactions are reversible reactions, which
means that reaction partners the can react in both directions and at
 F. Welle / Resources, Conservation and Recycling 55 (2011) 865–875
terephthalic acid ethylene glycol
catalyst
O O
HO OH
HO OH
H2O
Fig. 4. Chemistry of the polymerisation of poly(ethylene terephthalate).
steady state an equilibrium is reached. In order to shift the equilib-
rium of this reaction from the monomer side towards the polymer
side, the reaction by-products water or methanol as well as exces-
sive ethylene glycol has to be removed from the reaction mixture.
This was typically done by high temperatures and the use of vac-
uum in the polymerisation reaction as well as in the SSP reaction.
On the other hand, due to the reversible character of the
trans-esterification reaction, polyesters can be degraded during
processing e.g. extrusion, bottle manufacturing or recycling espe-
cially in the presence of moisture. During this degradation the
polymer backbone is partly broken and residual polymer chains
with shorter chain length are generated. In principle, manufactur-
ing in the presence of moisture (or alcohols) will lead to a decrease
in the chain length and therefore in a decrease of the viscosity of
the polymer. Due to the fact that moisture cannot be completely
excluded during PET processing, the hydrolysis reaction occurs dur-
ing PET processing and recycling in any case. For bottle-to-bottle
recycling it is important, that the viscosity of the PET polymer is not
decreasing too much, otherwise it is not possible to introduce the
recyclate into the PET packaging market. Therefore special recy-
cling steps based on high temperature and vacuum treatment have
been introduced in order to increase the viscosity of the recyclate.
On the other hand, such a degradation reaction (hydrolysis, glycol-
ysis) can be also used for PET recycling (see below).
3.2. Depolymerisation processes to monomers
The reverse reaction of the PET polymerisation, the hydrol-
ysis or methanolysis, was used to depolymerise post-consumer
PET to its monomers ethylene glycol and terephthalic acid or
terephthalic acid methyl ester. The monomers were subsequently
purified e.g. by distillation or crystallisation and the purified
monomers were introduced again into the polymerisation pro-
cesses of virgin polyesters. Due to these purification steps of the
monomers, possible post-consumer compounds were efficiently
removed. Depolymerisation processes (so-called tertiary or chem-
ical recycling processes) of post-consumer PET to the monomers
terephthalic acid or terephthalic acid methyl ester and ethylene
glycol were the first approved recycling processes in the USA (FDA,
2011a). In 1991, the first “no objection letter” (NOL) of the US FDA
was sent to a chemical company, which would like to reuse the
purified monomers for the manufacturing of bottle grade PET. It
is interesting to note, that the FDA stated in their NOL, that the
agency does not consider such a process to be recycling, because
the terephthalic acid methyl ester was recovered by a chemical
process. In the meantime, the FDA has stated that depolymerisa-
tion of post-consumer plastics (in general) and the reuse of the
purified monomers for the re-polymerisation of food packaging
materials can be generally considered as safe and the FDA no longer
recommends that recyclers should submit cleaning efficiency data
for tertiary recycling processes for evaluation (FDA, 2006). The
purification processes of the monomers have such a high efficiency
to remove potential post-consumer contaminants, that these pro-
cesses do not need to be tested due to their cleaning efficiencies.
However, even if the process is considered generally as safe, nowa-
869
poly(ethylene terephthalate)
O O O O
O O O O O
days, PET recyclates produced by tertiary recycling processes are
not on the market in significant amounts.
3.3. Conventional versus super-clean PET recycling processes
All conventional PET recycling processes are using water based
washing of the post-consumer PET to reduce surface contamina-
tion and to wash up dirt, labels and glue. The post-consumer PET
bottles are also ground to flakes in one of the first steps of con-
ventional recycling process. As washing additives, typically caustic
soda in concentrations of about 2–3% as well as detergents are
used. Caustic soda is an aggressive chemical towards PET which
supports the cleaning of the PET surface. The applied temperatures
and caustic soda concentrations, however, are not high enough to
depolymerise the polyester. So washing with caustic soda is only
surface cleaning of the post-consumer PET material. In most cases
the washing step is combined with separation steps where non-PET
materials like polyolefins are removed from the PET stream due to
the different density of polyolefins and PET.
It is obvious, that the cleaning efficiencies of these washing pro-
cesses are depending on the residence time of the PET flakes in
the washing process, on hot or cold water based washing or on the
washing additives added to the process. Typical washing processes
are able to remove contaminants from the surface of the polymers.
They are not able to remove organic substances which have been
absorbed into the polymer. Post-consumer compounds like flavour
substances from softdrinks (e.g. limonene) are still detectable in
conventionally recycled PET materials (Franz et al., 2004a; Bayer,
2002). Therefore, the purity of washed PET flakes is usually not
suitable for the application of the recyclates in direct food con-
tact. A simple re-melting or re-extrusion of the washed flakes has
an additional cleaning effect, but still the purity is usually even
not sufficient for reuse in the sensitive area of food packaging.
However, conventional PET recycling processes play an important
role in bottle-to-bottle recycling, because in any case the first step
of super-clean recycling processes is a conventional PET recycling
step. Typical contamination levels of conventionally recycled post-
consumer PET were determined to be in the lower ppm (mg kg−1 )
range (Franz et al., 2004a; Bayer, 2002).
3.4. Multi-layer packagings—functional barrier
Conventional recycled PET flakes can be reused in the food pack-
aging area, if the PCR PET is covered by a layer of virgin PET. The
virgin layer acts as a functional barrier and reduces the migration
of potential post-consumer contaminants from the core layer into
the foodstuff. For this purpose, the functional barrier thickness has
to be in such a thickness range, that the migration of any individ-
ual post-consumer contaminant will be below 10 ␮g kg−1 foodstuff
(ppb). The 10 ppb criteria can be considered as the maximum tol-
erable migration of a (unknown) compound to the foodstuff (see
Chapter “Legislative Aspects” below).
The application of functional barriers is on the first glance a
good method to introduce recyclates into food packaging materi-
als, because the post-consumer recyclates have no direct contact to
870 F. Welle / Resources, Conservation and Recycling 55 (2011) 865–875
the foodstuff. Therefore, multilayer bottles or sheets are one of the
first recyclate containing packaging structures, which were intro-
duced into the market. However, a general problem of functional
barriers is, that the food contact virgin layer might be contaminated
with post-consumer contaminants from the core layer during sheet
or preform/bottle production. Due to the high temperatures above
the melting temperature of PET, the diffusion coefficients of con-
taminants are very high, so that the post-consumer contaminants
can migrate from the recyclate containing core layer into the virgin
food contact layer within a split second. Therefore, the amount of
post-consumer contaminants in the virgin layer of multi-layer PET
bottles (or sheets) influences the minimal thickness of the func-
tional barrier. A discussion of the contamination effects in making
multi-layer is given in the literature (Welle and Franz, 2007; Franz
et al., 1996, 1997). The use of functional barriers in multi-layer PET
bottles plays nowadays a minor role, because the preform manufac-
turing process is too expensive and too slow for modern production
lines. For PET sheets, however, multi-layer structures with conven-
tionally recycled PET in the core layer of the sheets are widely used,
because the surface layers of sheets must be in most cases func-
tionalised with additives like slip agents or anti-static additives.
So for PET sheets the multi-layer technology is part of the (virgin)
PET sheet production process anyway and the introduction of PCR
PET into the core layer of multi-layer sheets is not associated with
expensive equipment. In these cases the possible impurification of
the virgin food contact layer with post-consumer compounds is still
an issue. However, if it can be shown that the functional barrier is
efficient, super-clean recycling processes are superfluous in these
cases.
3.5. PET super-clean recycling technologies
So-called super-clean processes for PET bottle-to-bottle recy-
cling are using further deep-cleansing steps to clean-up conven-
tionally recycled PET flakes to contamination levels similar to virgin
PET pellets. Although there are many different technologies com-
mercially available the deep-cleansing processes use typically the
following process steps to decrease the concentration of unwanted
substances in the polymers:
• high temperature treatment,
• vacuum or inert gas treatment,
• surface treatment with non-hazardous chemicals.
As a general principle, potential post-consumer contaminants have
to be mobilised in the PET matrix, so that they are able to diffuse to
the surface of the PET pellet or flake e.g. by heating up to temper-
atures of about 200 ◦ C. When the contaminants have reached the
surface of the PET pellet or flake, they have to be removed from the
recyclate stream e.g. with vacuum treatment or inert gas stripping.
The use of chemicals (e.g. caustic soda) removes parts of the PET
surface. On the other hand, chemicals like ethylene glycol swell the
PET polymer matrix so that the diffusion of the contaminants to the
surface will be fasten up.
In the last two decades several recycling technologies have been
developed for the decontamination of post-consumer PET bottles.
The main focus of these developments was on super-clean recy-
cling with high cleaning efficiencies so that the decontaminated
post-consumer recyclates can be reused in direct food contact. The
first processes are very similar to virgin PET solid-state polymerisa-
tion processes which are based on PET pellets. Subsequently further
optimisations as well as new process options has been developed
and introduced into the market. In the following chapters the PET
super-clean recycling processes, which are established in produc-
tion plants, are described. It should be noted here, that additional
super-clean recycling technologies or process variations might be
recollected
PET bottles
grinding, washing, conventional
removal of caps and recycling
labels
PET flakes
280-290 °C,
re-extrusion
vacuum degasing
amorphous
PET pllets
decontamination, solid-state poly-
180-230 °C, >6 h condensation
inert gas or vacuum
crystallin
PET pellets
Fig. 5. Scheme of PET super-clean recycling processes based on pellets.
in development or in the pilot plant status. However, the follow-
ing descriptions should give only an overview over the established
super-clean recycling technologies in production scale.
3.6. PET super-clean recycling processes based on pellets
The PET recycling processes based on pellets are using as main
decontamination process the last step of the PET virgin processes,
the solid state polycondensation (SSP), as a decontamination step.
As input material conventionally recycled PET flakes are used. In
one of the first steps of the super-clean process, the washed PET
flakes were re-extruded to pellets. The pellets were subsequently
further deep-cleansed using the SSP technology. A scheme of PET
super-clean recycling processes based on pellets is shown in Fig. 5.
The SSP reaction is either in batch or in continuous working produc-
tion lines. The process parameters e.g. residence time, temperature,
vacuum or inert gas stream are in both cases very similar. Typi-
cally the residence time in solid state reactions are between 6 h
and up to about 20 h, dependent on the applied temperature and
the desired increase of the viscosity of the PET material. The tem-
peratures are in the range of about 180 ◦ C and 220 ◦ C. The fact that
the recycling facilities for the super-clean recycling are very similar
to virgin processes and that the same equipment could be used in
both processes was most probably one reason, why the super-clean
processes based on pellets were the first mechanical or “secondary”
recycling processes which entered the market.
Super-clean PET recycling based on pellets has some advantages.
Due to the re-extrusion step, all PET pellets have the same size and
the potential post-consumer contaminants are homogeneously dis-
tributed in the polymer. Also the PET matrix was homogenised.
Therefore the polymer properties can be controlled easily. The dis-
tances, however, which the potential contaminants must move in
order to reach the surface of the PET pellets are relatively long (see
discussion below). Therefore the residence times in these deep-
cleaning steps (in most cases SSP processes) are also relatively long.
In other words, the residence time of the PET pellets in the SSP
 F. Welle / Resources, Conservation and Recycling 55 (2011) 865–875
recollected
PET bottles
grinding, washing,
removal of caps and conventional
recycling
labels
PET flakes
decontamination,
180-230 °C, 1-2 h decontamination
inert gas or vacuum
super-clean
PET flakes
280-290 °C, re-extrusion
vacuum degasing (optional)
amorphous
PET pellets
crystallisation
(optional)
crystallin
PET pellets
Fig. 6. Scheme of super-clean recycling processes based on decontamination of PET
flakes.
reaction is dominated by the diffusion coefficients of the potential
contaminants in the PET polymer at the decontamination temper-
ature. The higher the temperature, the shorter is the minimum
residence time in the solid state process. On the other hand, mois-
ture from the core of the PET pellets was also eliminated during
the long residence times under vacuum and high temperature. The
equilibrium reaction of PET (Fig. 3) can be therefore shifted towards
higher molecular weight compounds. As a result, the viscosity of the
PET polymer typically increases during the SSP reaction. Recycling
processes based on SSP reactions are therefore used in such cases,
where an increase of the viscosity of the PCR PET is necessary. Clean-
ing efficiencies of super-clean PET recycling processes are given in
the literature (Franz et al., 1998; Franz and Welle, 1999).
3.7. PET super-clean recycling processes based on flakes
The above mentioned super-clean processes extrude in one of
the first steps the conventional recycled PET flakes to pellets. The
PET pellets are subsequently decontaminated. The re-extrusion
step and the decontamination step can also be exchanged. By doing
that, the conventionally recycled PET flakes were firstly decon-
taminated and subsequently re-extruded to pellets. A scheme of
super-clean recycling processes based on the decontamination of
PET flakes is shown in Fig. 6. It is interesting to note, that the resi-
dence times for decontamination of PET flakes are typically in the
range of only 1–2 h, which is significantly lower compared to the
residence times of PET pellets in the SSP process even if the tem-
peratures used for decontamination of PET flakes are similar to
871
1200
initial concentration: 1000 ppm
1000
concentration[mg/kg]
800
PET bottle softdrink
600
400
200
0
250 260 270 280 290 300 310 320 330 340
thickness[µm]
Fig. 7. Calculated concentration profile of a post-consumer contaminant (the
flavour compound limonene) in PET flakes (calculated with AP  = 1,  = 1577 K, initial
concentration in softdrink: 1000 ppm, K = 1, storage conditions: 365 d at 23 ◦ C, bot-
tle wall thickness: 300 ␮m). Results: Surface concentration: about 700 ppm. Mean
concentration in PET after sorption: 7.7 ppm.
the pellet recycling processes. As mentioned above, the residence
time in the decontamination process is dominated by the diffusion
coefficients of the migrants. The main reason for the significantly
shorter residence times is that potential contaminants from the first
use of the PET bottles are located near the surface of the PET flakes,
which reduces the distances for the contaminants to move to the
surface of the PET flakes significantly (see discussion below). In gen-
eral, the smaller the flake size, the shorter the residence times in the
decontamination processes. Therefore, the time to decontaminate
the PET flakes to levels found in virgin PET in a super-clean flake
process can be influenced by the flake size. However, most of the
super-clean recycling processes are using the typical flake size of
conventionally recycled PET flakes. Cleaning efficiencies of a flake
decontamination process are published in the literature (Franz and
Welle, 2002).
Experimental data for the concentration profiles of post-
consumer contaminants in PET bottles are not available in the
scientific literature. However, mathematical migration models can
be used to visualize the contamination profile of PET bottles
or post-consumer PET flakes. A calculated concentration profile
of a potential contaminant (e.g. a flavour compound) from the
first filling of the PET bottle is shown in Fig. 7. For the calcula-
tions the equations of the actual mathematical model was used
(Simoneau, 2010; Piringer and Baner, 2008). The current migra-
tion model is overestimating the migration for consumer safety
reasons. Therefore, the typically applied PET specific parameters
(AP  = 3.1,  = 1577 K) cannot be used for the calculation of the
sorption, because it will also overestimate the sorption of a com-
pound into the PET bottle wall. In order to get a more realistic
concentration profile in post-consumer PET, diffusion coefficients
derived from experimental migration kinetics were used. Due to the
reversible character of the diffusion process, diffusion coefficients
derived from migration experiments can also be used for the predic-
tion of reverse process of the migration, the sorption. The applied
parameters for the calculation of the sorption used here (AP  = 1,
 = 1577 K) were derived from experimental determinations of dif-
fusion coefficients from migration studies (Franz and Welle, 2008).
As an example the sorption of the flavour compound limonene
(molecular weight 136 g mol−1 ) after a storage time of 365 d at 23 ◦ C
872 F. Welle / Resources, Conservation and Recycling 55 (2011) 865–875

was simulated. The concentration (CP,0 ) of limonene in the con-

tact media (softdrink) was assumed to be 1000 ppm. As a result, recollected
limonene penetrates only into the first 10–15 ␮m of the PET inner PET bottles
surface. The rest of the PET bottle does not contain post-consumer
compounds. The mean value of the limonene concentration over
grinding, washing, conventional
the whole PET bottle wall is 7.7 ppm, which is in good agreement
removal of caps and recycling
with experimental data (Franz et al., 2004a; Bayer, 2002).
labels
The last step of super-clean recycling processes based on flakes,
the re-extrusion of the flakes to pellets, is from a food law compli-
ance point of view not necessary in most cases. The re-extrusion PET flakes
step has an addition cleaning effect regarding post-consumer sub-
stances, but the cleaning efficiency of the flake decontamination
step as a stand-alone process is typically high enough for food coating with NaOH, depolymerisation
law compliance approval. But on the other hand, the production >150 °C, inert gas of the surface
of recyclate containing PET preforms or sheets is in some cases dif-
ficult when PET virgin pellets have to be processed together with
super-clean PET flakes. Therefore in several cases, the super-clean super-clean
decontaminated flakes were re-extruded to pellets. The cleaning PET flakes
efficiencies of the recycling processes is in these cases slightly
higher than in the case of pure flake processes, because due to
the high temperatures during re-extrusion, potential contaminants 280-290 °C, re-extrusion
were further removed from the PET polymer. In addition a melt fil- vacuum degasing (optional)
tration step is also necessary in most cases. The latter can be done
either on the re-extrusion step to pellets or during preform or sheet amorphous
production.
PET pellets
The short decontamination times of super-clean recycling pro-
cesses based on PET flakes is an advantage in comparison to pellet
super-clean, because it safes energy which is necessary for the crystallisation
heating of the pellets over long residence times. However, a dis- (optional)
advantage is that the viscosity of the polymer cannot be increased
significantly. As shown in Fig. 3, to shift the equilibrium reaction
from the monomers or oligomers to the high molecular weight side, crystallin
it is necessary to remove water from the PET materials. Regarding PET pellets
flake processes, the water has to diffuse from the core of the flakes
to the surface and not, as in the case of potential post-consumer
Fig. 8. Scheme of super-clean recycling processes based on depolymerisation of the
contaminants, only from the surface of the flakes to the outside. PET flake surface.
Therefore the residence times typically applied in flakes decon-
tamination processes are too short for a significant increase of the
viscosity of the PET material. Only flake decontamination processes So a general value cannot be given. In contrast to the decontam-
with (i) high decontamination temperatures and (ii) long residence ination processes mentioned above, the depolymerisation reaction
times are able to increase the viscosity of super-clean PET flakes. determines the residence time and not the diffusion coefficients of
PET super-clean recycling processes based on flakes are in most potential contaminants.
cases used when a viscosity increase of the PET polymer is not nec- The cleaning efficiencies of such surface depolymerisation pro-
essary for the mechanical properties of the recyclate containing cesses are not published in the scientific literature. However, it
products. can be concluded from Fig. 7, that the cleaning efficiencies should
be similar to the other super-clean recycling processes if the first
3.8. PET super-clean recycling processes based on 10 ␮m of the flake surface is removed in minimum. Regarding the
depolymerisation of the flake surface increase of the viscosity of the PET polymer, the situation is simi-
lar to decontamination processes based on flakes. These residence
As shown in Fig. 7 potential contaminants in post-consumer PET times in the decontamination processes are too short to remove
flakes are located near to the surface of the flakes. Another efficient water molecules from the core of the PET flakes. Therefore, decon-
decontamination method is therefore a partial depolymerisation of tamination processes based on partial depolymerisation processes
the PCR PET flake surface. The partial depolymerisation of the sur- cannot increase significantly the viscosity of the PET polymer dur-
face is achieved by hydrolysing the PET polymer with caustic soda. ing super-clean recycling.
After coating of the flake surface with caustic soda and the elimina-
tion of moisture, the flakes were heated up. The PET polymer reacts 3.9. PET super-clean recycling processes based on partial
at the flake surface to the monomers ethylene glycol and sodium depolymerisation
terephthalate. The volatile reaction product ethylene glycol as well
as post-consumer contaminants were removed from the flake sur- Conventionally recycled PET flakes can be also recycled by
face by the applied high temperatures. The other reaction product, another depolymerisation process, where the PCR PET flakes are
sodium terephthalate, was removed after the reaction by rinsing of heated up together with ethylene glycol. This glycolysis reaction
the flakes with water and/or by surface neutralisation. A scheme breaks down the ester groups and a mixture of polyester oligomers
of the super-clean recycling processes based on partial depoly- is formed. The reaction is typically run in such a way, that the
merisation of the PET flake surface is given in Fig. 8. The residence oligomers formed have a similar molecular weight distribution
times of the PET flakes in such processes depend on the temper- compared to the pre-polymer in the polymerisation of (virgin) PET.
ature as well as on the thickness of the depolymerised surface. The partly depolymerised PET can subsequently be given with a
 F. Welle / Resources, Conservation and Recycling 55 (2011) 865–875
recollected monomers
PET bottles
conventional polymerisation
recycling
pre-polymer
PET flakes
partial
depolymerisation
(ethylene glycol)
amorphous
PET pllets
viscosity increase,
solid-state poly-
180-230 °C, >6 h
inert gas or vacuum
crystallin
crystallin
PET pellets
Fig. 9. Scheme of PET super-clean recycling processes based on partial depolymeri-
sation to oligomers.
by-pass extruder to the pre-polymer stream of a polymerisation
line for virgin polymers. In other words, the virgin PET processes
are fed with oligomers from PET recyclates. An advantage of these
processes is, that the production lines of virgin PET can be adapted
to post-consumer PET with only slight changes. It is interesting to
note, that using such recycling technologies the borderline between
virgin PET manufactures and recycling companies become indis-
tinct. A typical recyclate content for such processes based on partial
depolymerisation is in the range of 10–30%.
PET super-clean processes based on partial depolymerisa-
tion can be still considered as mechanical (secondary) recycling
processes, because in contrast to chemical (tertiary) recycling pro-
cesses, the purification steps like distillation or re-crystallisation
of the monomers are lacking. Potential post-consumer compounds
are still as impurities in the oligomers and have to be removed by
the re-polymerisation process. Therefore, the cleaning efficiencies
of the re-polymerisation process have to be in a position to clean-
up the recyclate containing polymer melt to an impurity level of
virgin PET. A scheme of PET super-clean recycling processes based
on the depolymerisation of the PET flakes to oligomers and the
re-polymerisation together with virgin pre-polymers is shown in
Fig. 9. The cleaning efficiencies of a super-clean recycling process
based on depolymerisation to oligomers are given in the literature
(Welle, 2008).
4. Legislative aspects
4.1. Guidelines and regulations
In the United States the US Food and Drug Administration (FDA)
discussed the use of post-consumer plastics in food applications
since the late 80s of the last century. As a result of this discus-
sion, guidelines for the approval of PCR plastics (in general) were
published in 1992 (FDA, 1992). This guideline gives recommen-
dations how to determine the cleaning efficiency of a recycling
process. A detailed description of the so-called challenge test with
recommended input concentrations of the artificial contaminants
(surrogates) are given. In addition, criteria for the evaluation of the
results are given in form of a migration threshold for post-consumer
substances. An update of the guidelines from 1992 which was based
on the work of Begley et al. (2002) was published in 2006 (FDA,
2006). A complete list of all approvals for the use of post-consumer
873
plastics in food contact applications is published in the internet
(FDA, 2011a). Most of the FDA approvals are dealing with PCR PET.
In Europe, the topic of the reuse of post-consumer PET in food
packaging applications was discussed since the early 90s. How-
ever, in contrast to the USA, recommendations or a clear legislation
were not given. It takes about 15 years till the European Com-
mission published in 2008 the Recycling Regulation (EU, 2008).
Within this Regulation, the European Commission gave the Euro-
pean Food Safety Authority (EFSA) the mandate to evaluate the
melt-phase
condensation
recycling petitions. For this purpose, the EFSA published guidelines
for the preparation of the submissions (EFSA, 2008). In contrast to
the US FDA, however, migration thresholds or recommendations
for the evaluation (pass/fail) criteria are not published by the EFSA
till now. At the moment, the Recycling Regulation is in a transition
state, which ends in 2014. Within this transition state, national law
condensation is still applicable for the evaluation of the food law compliance of
recyclates. A list of valid applications to the EFSA is published in
the internet (EU, 2011). Also similar to the USA, most of the valid
applications in Europe are dealing with PCR PET.
As a consequence of the long discussion about the evaluation of
PCR PET in Europe and the lack of a clear legislation on the Euro-
pean level, the individual European member states published some
national documents. In most cases, these documents had the sta-
tus of recommendations. However, companies which would like
to introduce the super-clean recyclates in these member states
should demonstrate that their super-clean recyclates are in com-
pliance with these national recommendations. In addition, some
documents from research groups or task forces were published. The
first document dealing with the application of recyclates (in gen-
eral) in direct food contact was published by the International Life
Science Institute ILSI (ILSI, 1998). An expert group of ILSI gave prac-
tical instructions for companies which would like to use recyclates
in food packaging applications. Similar to the US FDA a migration
limit for post-consumer compounds is recommended in this doc-
ument. In addition, the German plastics commission of the Federal
Institute of Risk Assessment (BfR) has published recommendations
for the safe recycling of post-consumer PET (BfR, 2000). In this docu-
ment, the evaluation of PET super-clean recyclates is based on three
points: (i) source control, (ii) cleaning efficiency and (iii) quality
assurance of the recyclate. In 2004, a comprehensive guide, which
was published as the conclusion of an European research project
(Franz et al., 2004b). In this document, also recommendations for
the determination of the cleaning efficiency of the PET super-clean
recycling process (challenge test) as well as on the quality assurance
of the PET recyclates are given. The last European document was
published by the French Food Safety Agency in 2006 (AFSSA, 2006).
In 2007 also the South American common market Mercosur pub-
lished a guidance document on the safe use of recycled PET for food
contact applications (Mercosur, 2007). This document gives some
guidance for the introduction of PCR PET in the South American
market.
4.2. Risk assessment
The main question of a risk assessment for PCR PET in direct
food contact is the misuse of PET bottles for storage of chemicals.
The concern is that the consumer might misuse the PET bottles
or containers e.g. for storing of household, garden and automotive
chemicals before discarding the container into the post-consumer
plastics feedstream. Because it is in principle not possible to know
which kind of chemicals the consumer might be introduced into
the containers, traditional approaches like specific migration test-
ing are not suitable for assessing the PCR PET. The FDA (FDA, 1992,
2006) gave therefore recommendations for simulating the mis-
use of the packaging materials under worst-case assumptions with
artificial (model) contaminants. Major part of the FDA guidance
874 F. Welle / Resources, Conservation and Recycling 55 (2011) 865–875
Table 3
Maximum residual concentrations CP,0 corresponding to a migration limit equal to or smaller than 10 ␮g kg−1 calculated with diffusion models (calculated with AP  = 3.1,
 = 1577 K, contact conditions: K = 1, bottle wall thickness 300 ␮m, bottle volume 1 l, bottle surface area 600 cm2 ).
Surrogate Molecular weight (g mol−1 )
Toluene 92
Chlorobenzene 113
Chloroform 119
Methyl salicylate 152
Phenyl cyclohexane 160
Benzophenone 182
Methyl stearate 298
Fictive substance 400
Fictive substance 500
Fictive substance 750
recommends to the exposure of the recycling target plastics with
a cocktail of chemical compounds (so-called surrogates) and then
processing the material to establish the capabilities of the processes
to remove post-consumer contaminants. The threshold limits for
the migration of the surrogates are given by the US FDA Thresh-
old of Regulation concept (FDA, 2011b) with a general migration
limit of 0.5 ␮g kg−1 foodstuff (ppb) per surrogate (FDA, 2006). In
general, this migration limit is increased for the different poly-
mer types according to their individual consumption factors (CF).
For example, according to the US FDA concept PET packages with
recyclate content have a market share of about 5% (CF = 0.05). This
consumption factor based on the threshold of regulation concept
(FDA, 2011b) increases the migration limit for post-consumer sub-
stances from PCR PET by a factor of 20 up to 10 ␮g kg−1 (ppb).
By following the argumentation of this concept, the migration of
any post-consumer compounds, independent if the compounds are
identified or not, should be below of 10 ␮g kg−1 in the foodstuff
packaging in PET at the end of the shelf life. The Mercosur document
(Mercosur, 2007) follows the US FDA argumentation. The maxi-
mum concentration in the PCR PET packed foodstuff have to below
10 ␮g kg−1 . The European documents (ILSI, 1998; BfR, 2000; Franz
et al., 2004b) recommend also a migration limit of 10 ␮g kg−1 in the
PET packaged foodstuff. However, in contrast to the FDA, the focus
was on an end point of demonstrating no detectable migration at
the limit of detection of analytical methodology. The French AFSSA
came to the conclusion, that an exceptional exposure of 1.5 ␮g of
contaminant from recycled PET/person/day represents a tolerable
health risk, even when the chemical structure of the contaminant
has not been identified (AFSSA, 2006).
Using the migration endpoint criteria of 10 ␮g kg−1 in the
PET packaged foodstuff (as an example), the maximum con-
centrations of the surrogates in the super-clean recyclates or
recyclate containing PET bottles can be calculated. The mathemat-
ical migration model and the polymer specific parameters for PET
polymers described in the literature were used for the calcula-
tions (Simoneau, 2010; Piringer and Baner, 2008). As mentioned
above, the applied migration models overestimate the migration
of a certain compound in a food (simulant). The maximum con-
centrations after storage of 10 d at 40 ◦ C as well as after 365 d
at 25 ◦ C are given in Table 3. For the calculation of data given
in Table 3 the currently accepted parameters for PET (AP  = 3.1,
 = 1577 K) were used. Due to the overestimative character of these
parameters, the data given in Table 3 can be considered as the
worst case of migration. The low molecular weight compounds
like solvents (e.g. toluene, chlorobenzene or chloroform) have the
highest migration potential. As a consequence, the concentrations
of these low molecular weight compounds which are correspond-
ing to a migration of 10 ␮g kg−1 foodstuff are significantly lower
than for the high molecular weight compounds. Therefore, bottle-
to-bottle recycling processes have to eliminate the low molecular
Calculated maximum residual concentration CP,0 corresponding to 10 ␮g kg−1
10 d at 40 ◦ C (mg kg−1 (ppm)) 365 d at 23 ◦ C (mg kg−1 (ppm))
18.3 9.2
21.7 10.9
22.7 11.4
28.9 14.5
30.5 15.5
35.5 17.6
68.9 34.4
113.7 56.6
176.3 87.7
380.8 189.5
weight contaminants very efficiently. Typical PET super-cleaning
recycling technologies have a high temperature decontamination
step. Within this decontamination step, low molecular weight
compounds are removed efficiently, because of their high vapour
pressure.
5. Conclusions and outlook
Within the last two decades the PET bottle to bottle recycling
has dramatically increased. Starting with the first FDA approval
on chemical recycling, nowadays huge capacities for PET bottle-
to-bottle recycling processes have been established all over the
world. And this trend seems to be still ongoing. Especially in Europe
a growing PET recycling business has been established since the
European Commission has been published the Recycling Regula-
tion (EU, 2008). However, the development is not only driven by the
now clear legislation. In addition, today, PET super-clean recyclates
are on the market to more or less similar prices than virgin PET poly-
mers. Therefore, the use of PCR PET into new packaging applications
is not leading to a significant cost reduction of the PET bottles man-
ufacturing process. Cost reduction is therefore not a main driving
force for PET bottle-to-bottle recycling. The positive development
is also driven by the business sector’s embracing of the sustainabil-
ity ethic and by the public’s concern about the environment. Both
result in higher post-consumer PET bottle recollection rates. And
at the end higher recollection rates lead more or less automatically
to higher recycling capacities, because PET is a high value polymer.
But, one of the main factors of the successful development was the
material itself. PET is a very inert material, which simplifies the
food law compliance evaluation of post-consumer polymers in the
sensitive area of food packaging materials significantly. Nowadays,
enormous knowledge has been established about the migration
behaviour of PET, which brings the authorities in a position to assess
the risk of using post-consumer recycled PET for food packaging
materials in all kinds of applications including long-term storage
or hot-fill or microwave applications.
But there are also some critical points. Due to the light-
weighting of the PET bottles, the yield of PET flakes from the
recollected bottle fraction is reduced, because the relative amount
of caps and labels are increasing. This gives economic pressure to
the recycling companies. In addition, additives like the acetalde-
hyde scavenging substance anthranilamide or other functional
additives like oxygen scavengers, which are also more and more
introduced into PET bottles, might have a negative influence on
the optical properties of the PCR recyclates. These additives might
result in a partial degradation during recycling and the clear PET
bottle flakes will become slight brown. So the concentration of
additives should be kept at low concentration. This example shows
that for a successful PET bottle-to-bottle recycling all partners in
the value added chain have to be in closed contact: The additives
 F. Welle / Resources, Conservation and Recycling 55 (2011) 865–875
manufacturers, the PET virgin polymer suppliers, the preform and
bottle manufacturers, the filling companies as well as the recycling
companies.
In the future most probably the use of ethanol from renew-
able resources might be increasingly used for the production of
the monomer ethylene glycol. The PET polymer will then be man-
ufactured from a certain amount of ethylene glycol, which is based
on renewable resources and not from crude oil. This might give
the PET packaging materials an additional ecological advantage.
However, at the end, PET manufactured partly from renewable
resources is still a non-biodegradable polymer which is in princi-
ple indistinguishable from mineral oil based PET. The combination
of a bottle-to-bottle recycling and monomers from renewable
resources, however, might be the key factors for sustainable PET
packaging polymers in the future.
Acknowledgements
Special thanks are due to Dr. Roland Franz (Fraunhofer IVV) for
very fruitful discussions over the last 15 years. Thanks are also Mrs.
Melissa da Costa Teixeira (Global PET, Brasil) for information about
the South American PET recycling market.
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Glossary
Bottle-to-bottle PET recycling: A production system in which the recollected post-
consumer PET bottles are used in the production of new PET beverage bottles
by use of so-called super-clean recycling processes.
Conventional PET recycling: A recycling procedure using the process steps grinding,
washing and surface-drying of re-collected PET bottles. The output mate-
rial of conventional recycling processes are PET materials customary used for
non-food or for the core layer of multi-layer applications or for fibres. Con-
ventional recycled PET is used as input material for super-clean recycling
processes.
Super-clean PET recycling: The process uses as a source the output material from
conventional recycling, for example washed and surface-dried PET material,
and includes one or more additional cleaning steps. The output material of
super-clean processes can be used for packaging applications in direct contact
to foodstuff.