Full Wrap HDPE Recycling Final ReportV141205

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Creating markets for recycled resources
Develop a food grade HDPE recycling
process
Written by: Dr. Frank Welle
Fraunhofer Institute for Process Engineering and Packaging (IVV)
Published by:
The Waste & Resources Action Programme
The Old Academy, 21 Horse Fair, Banbury, Oxon OX16 0AH
Tel: 01295 819900 Fax: 01295 819911 www.wrap.org.uk
WRAP Business Helpline: Free phone: 0808 100 2040
Date J une 4, 2005
ISBN: 1-84405-225-7

Scope
1 Executive Summery 4
2 Glossary 6
3 I ntroduction 8
4 Aim of the Project 9
5 Project Structure 10
6 Literature study 14
6.1 Research to develop guidelines for the safe use of recycled material 14
6.2 Factors that affect contaminant migration 15
6.3 Parameters which determine the recyclability of packaging plastics 16
6.4 Measuring the cleaning efficiency of recycling processes 20
6.5 Evaluating contaminant migration 22
6.6 Sensory testing 24
6.7 Mechanical properties 24
6.8 Studies of practical market applications 25
6.9 Summary of the literature review 28
7 Sorting efficiency for UK collected HDPE bottles 29
7.1 Sorting technology used 29
7.2 Sorting efficiency of the RTT pilot plant 31
7.3 Sorting efficiency at the industrial plant of Delleve Plastics 33
8 Washing the sorted HDPE bottle fraction 36
8.1 Washing post-consumer HDPE flakes 36
8.2 Challenge test of the washing process 42
9 Supercritical CO
2
process for super-cleaning HDPE 44
9.1 Background 44
9.2 Patent review 45
9.3 Solubility data for melt phase super-critical CO2 extraction 45
9.4 Batch basis verification of the effect of CO2 pressure on extraction 49
9.5 I nitial supercritical CO2 extrusion extraction trials to decontaminate HDPE 55
9.6 Optimisation of HDPE decontamination with supercritical CO
2
60
9.7 Processing trials to optimise PP decontamination 62
9.8 Decontamination of post-consumer HDPE flakes 65
9.9 Conclusions 67
10 EREMA super-clean recycling process 68
10.1 Description of EREMA process for post-consumer HDPE Flakes 68
Development of food grade HDPE recycling process
2

10.2 Challenge test of the EREMA process 71
10.3 Specific migration of surrogates from test bottles using challenge test material 76
11 Analysis of HDPE materials 78
11.1 Analysis for post-consumer contaminants in raw materials 78
11.2 Analysis for post-consumer contaminants in milk containers made with recyclate 84
11.3 Statistical evaluation of the analytical data 87
11.4 Conclusions of the analytical work 91
12 Bottle filling trials and tests 92
12.1 Methodology 92
12.2 Results of the filling trials 92
13 Food law compliance tests 95
13.1 Migration tests 95
13.2 Sensory testing 96
14 Recyclate quality assurance 98
14.1 Quality assurance issues for post-consumer recyclate 98
14.2 Standard testing procedures 99
14.3 Correlation between migration into dairy product and choice of food simulant 99
15 Process validation (re-run) 100
16 Economic evaluation 102
17 Environmental impact assessment 104
17.1 System boundaries 104
17.2 Environmental impact assessment 107
17.3 LCA results 108
17.4 Limitations and Conclusions 111
18 Overall Project Conclusions 112
Appendix 1 Project Consortium 114
Delleve Plastics 114
RTT Systemtechnik 114
Sorema/ Previero 115
EREMA 115
RAPRA 115
Nampak 115
Dairy Crest 115
Fraunhofer IVV 115
Appendix 2 Addresses of Participants 117
Appendix 3 - Literature 118
Publications within the Project 118
Cited Literature 118
3

1 Executive Summary
This project successfully developed an industrial scale process for sorting and recycling of post-consumer HDPE
milk bottles from kerbside and bring scheme collections in the United Kingdom.
The process contains the following key steps:
Sorting of natural HDPE milk bottles
grinding and washing of the bottles by a conventional plastic bottle recycling process
super-clean decontamination by the EREMA process using high temperatures and vacuum
The ability of this recycling process to produce material suitable for use in food contact applications was checked
by means of a challenge test using artificial contaminants and by comparing the levels of contamination in the
output material from the recycling process both with the input post-consumer HDPE milk bottles and with virgin
polymer.
The analytical work demonstrated that the process is capable of producing high grade polymer suitable for use in
food contact applications from post-consumer HDPE bottles. More surprisingly it demonstrated that the level of
contaminants in bottles made from the recycled post-consumer material was lower than in bottles made from
virgin polymer.
About 600 conventional recycled flake samples, from HDPE bottles collected and sorted in the United Kingdom
were screened for post-consumer contaminants. Each sample consisted of 40 to 50 individual flakes so that the
number of individual post-consumer milk bottles analysed was in the range of 24,000 to 30,000.
The analysis showed that the main contaminants in the recycled post-use HDPE flake samples were unsaturated
oligomers. Unsaturated oligomers are short chain versions of the polymer molecule which still contain some
carbon-carbon double bonds and are therefore potentially more reactive with foodstuffs. These same compounds
were also found in the virgin HDPE pellet samples used for milk bottle production.
Compounds found in the recycled HDPE flake samples but rarely in the virgin polymer samples included:
the flavour compound limonene
a degradation product of the antioxidant additive di-tert-butylphenol
small amounts of saturated oligomers
However, the total concentration of all contaminants in the post-consumer recycled samples was similar to or
lower than found in virgin HDPE.
Contamination with other compounds that would not normally be found in virgin HDPE was rare and in most
cases related to compounds originating from normal use of HDPE bottles in non-milk applications, for example
shampoo. Non-milk containers comprised less than 2.1% of the input material to the recycling process.
Contamination from unexpected re-use of containers was extremely rare. Levels measured were very low.
Migration tests, filling trials and sensory evaluations of 4 pint milk bottles made with recyclate contents of 30%,
70% and 100% also gave satisfactory results and confirmed their suitability for use in food contact applications.
The analytical and test work concluded that HDPE milk bottles containing up to 100% recyclate
from the super-clean recycling process tested and validated during this project can be used safely
for direct food contact applications
4

The commercial potential of the super-clean recycling process was assessed.
Costs per kg recycled HDPE (excluding the cost of baled input bottles to the sorting process) were estimated as
follows:
Direct production cost 0.41/Kg
Overheads, personnel and infrastructure 0.20/Kg
Total 0.61/Kg
The overall production cost of 0.61/ Kg compares to an average price for virgin HDPE of around
1.2 per Kg
An environmental impact comparison of the full super-clean recycling process including sorting, washing and
EREMA super-clean treatment was conducted using a standard assessment methodology.
The environmental assessment demonstrated that the HDPE recycling process tested in this project
has a lower environmental impact across all impact categories than the alternative of landfill.
In conclusion, this project demonstrates that HDPE milk bottles may be recycled in closed loop on a commercially
viable and environmentally sound basis. The project demonstrates that the recycled product may be made
comparable to or even indistinguishable from virgin polymer.
The project concluded that three main quality assurance elements are essential for safe and successful recycling
of post-consumer HDPE milk bottles:
careful source control
tight production control
regular analytical checks of input and output materials
The project also tested a supercritical carbon dioxide extraction process as an alternative to the EREMA process
for the final recycling step to remove residual contaminants. Although some reduction in contaminants was
demonstrated it was concluded after a series of trials that the supercritical CO
2
extraction process is not yet
sufficiently reliable for it to be usable at industrial scale.
5

2 Glossary
Adventitious contaminants:
Any unwanted substance that deliberately or inadvertently comes into contact with the packaging material before
it is collected for recycling and that therefore may contaminate the plastic and negatively influence the quality of
the product with which a recycled packaging material is brought into contact
Challenge test:
A test of the ability of a recycling process to remove chemical contamination from packaging materials or articles.
The test involves introduction of exaggerated levels of surrogate compounds that simulate typical contaminants
and includes an evaluation of the migration of these surrogates from a model food contact packaging article into
a food or food simulant.
"Conventional" recycling processes:
A recycling procedure using process steps that include grinding, washing and surface drying of collected plastics.
The output material of conventional recycling processes are flakes customarily used for non-food or for the core
layer of multi-layer applications. Conventional recycled polymers are usually used as input material for super-
clean recycling processes.
Consumption facto (CF): r
Generally, CFs are used to correct migration test results (measured concentration in food simulant) into an
exposure value (average uptake by the consumer with the diet). The US Food and Drug Administration (FDA)
standard CFs which are relevant to this project are: CF = 0.13 for HDPE and CF = 0.35 for other polyolefins
1
.
Extraction:
Dissolution of constituents from a plastic into a solvent.
Feedstock/feed stream:
Post consumer plastics used as raw materials for recycling.
Food grade HDPE:
In Europe: HDPE plastic of a suitable standard for food applications manufactured in compliance with EU Directive
2002/72/EEC (and future amendments).
In USA: the HDPE plastic must be compliant with 21 CFR 177.1520.
Migration:
Diffusion-controlled mass transfer from a packaging material or article into food or food simulant. Classically,
migration is experimentally determined by standardised tests using food simulants. As a result of scientific
progress in this field, migration can also be mathematically modelled and predicted.
6

Migration limits:

Limits set by food regulators for maximum concentrations of migrant compounds in food simulants or foodstuffs.
For recycled food packaging material the legally prescribed overall migration limit for all compounds is of much
lower relevance than specific migration limits as defined by a threshold of no concern in the US or the specific
limits per substance laid down in EU legislation.
Post consumer HDPE:
HDPE resin that has been converted into bottles/containers, distributed and used by the consumer. Discarded
post consumer HDPE material becomes the feedstock for recycling processes.
Post-industrial HDPE:
Industrial in house plant scrap generated during the manufacturing process, which may be reused in the
production of new containers.
"Super-clean" recycling:
In most instances the process uses as a source the output material from conventional recycling, for example
washed and surface-dried flakes, and includes one or more additional cleaning steps. The output of the "super-
clean" process may be used for packaging applications in direct contact with the foodstuff, provided it meets the
appropriate regulatory guidelines or legal requirements.
Surrogates:
Organic compounds (also known as "model contaminants"). Typically they are used at exaggerated contamination
levels in tests to challenge the safety of recycled materials. They may be applied in tests individually or in
mixtures.
Threshold of no concern:
The concentration of a migrant in a foodstuff, which, from a toxicological point of view, is considered to pose no
health risk to the consumer.
Using the Threshold of Regulation concept as a basis (see US FDA 21 CFR 170.39), the US FDA has determined
that exposure to contaminants from recycled food-contact articles of the order of 0.5 ppb dietary concentration or
less generally is of negligible risk. In Europe, this concept is under discussion but a general threshold value has
not yet been adopted.
A J ECFA task force of FAO/WHO has adopted the concept of threshold of toxicological concern for the evaluation
of flavouring substances in food. The proposed no concern level is 1.5 g per person per day
[ , ] 2 3
.
7

3 Introduction
Food packaging regulations in Europe prescribe that packaging materials must not cause mass transfer
(migration) of harmful substances into food
[ ] 4
. This general requirement applies to food packaging made with
both virgin and recycled material. It is set out in more detail in Commission Directive 2002/72/EC
[ ] 5
.
Until recently, the reuse of post-consumer packaging materials for new packaging applications was impossible
due to a lack of suitable sorting and decontamination technologies and because of missing or incomplete
information about typical contamination levels of post-consumer plastics. As a result most post-consumer
packaging waste was sent to landfill or for incineration. Only uncontaminated in-house production waste was
collected, granulated, pelletised and recycled back into packaging products without further decontamination.
In the last decade, considerable progress has been made in the development of collection and sorting
technologies so that today an almost 100% single polymer stream may be supplied to the recycling process.
Most recently, decontamination processes based on sophisticated washing and thermal vacuum stripping methods
have been developed. These processes enable removal of contaminants from post-consumer materials such as
polyethylene terephthalate (PET) down to impurity levels similar to virgin materials.
Good progress has also been made in understanding and modelling the diffusion and migration of adventitious
hazardous substances from recycled plastics into foodstuffs when in direct or indirect contact with food
[ ] 6
. Today,
these migration models form the basis for compliance evaluation of food contact materials (FCM) and are being
evaluated for consumer exposure and risk assessments from FCM
[ ] 7
.
Much of the knowledge about the reuse of packaging plastics has been gained within two EU projects, AIR-CT93-
1014
[ ] 8
and FAIR-CT98-4318
[ ] 9
. One of the major conclusions of these projects was that polyethylene
terephthalate (PET), is the most promising polymer for reuse as a food packaging material due to its low
diffusivity.
As a result of this evaluation several so-called "super-clean" recycling processes were developed for bottle-to-
bottle recycling of post-consumer PET bottles. Some of these technologies are already established in the market.
Others are now moving from pilot plant to industrial scale
[ ] 10
.
The low diffusivity of PET means that in most cases the container polymer picks up only low levels of
contamination from the material it contains, even when the contact is from a non-food application. As a result it
is not always essential to remove non-food contact containers in the sorting processes that feed into super-clean
PET recycling processes. Several PET recycling processes have gained American Food and Drug Administration
(US FDA) approval for recycling PET bottles which were filled in their first use with household or body care fluids.
In some cases recycled polymers with higher diffusion and sorption characteristics, including high density
polyethylene (HDPE), have received no objection letters from the US FDA for use in certain well defined
conditions
[ ] 11
.
Increasing understanding of the level and nature of contamination in post-consumer plastics and further
innovations in recycling and decontamination technologies mean that closed-loop recycling of packaging plastics
with higher diffusivity than PET (e.g. HDPE) will soon become viable for a wider range of applications. The
translation of this progress into practical industrial solutions is still awaited. One of the reasons for the slow
progress in commercialising these processes is that the European legal requirements for food contact packaging
made with recycled content are still under discussion and are not yet clearly or uniformly defined.
8

The legislators are concerned that there is still a lack of good quality and statistically meaningful information
about the nature and amount of contaminants in recycled HDPE from post-use packaging. Data is needed for
contaminants derived from the first use of the bottles and also from misuse.
This remains an important missing link in the chain of scientific knowledge on diffusion and migration into and
out of HDPE. If the concentration of a contaminant in the recycled plastic can be correlated with the resulting
time-dependent concentration in a foodstuff it will allow legislators to set meaningful limits for contaminant levels
in recycled materials and make it easier to certify recycling processes for HDPE with confidence.
One of the aims of this project is to fill these gaps in scientific knowledge with statistically meaningful data on
contaminant levels in HDPE from post-use packaging before and after recycling.
Linking this data with existing knowledge on HDPE diffusion behaviour and measurements of the cleaning
efficiency of both conventional washing and "super-clean" recycling processes will enable scientifically convincing
conclusions to be drawn about the safety of reusing HDPE in food contact applications.
It is expected that the knowledge developed in this project will also provide the basis for development of
generally recognized standard test methods for HDPE recycling processes. These methods should be
proportionate, practical and economical whilst safe-guarding the consumer at the same time. Current protocols
are too cautious and challenging, although necessary at present as a precaution due to lack of data.
4 Aim of the Project
The overall aim of the project is to develop a cost-efficient recycling process to produce food-grade HDPE from
post-consumer recyclate for new milk bottle applications.
To achieve this aim comprehensive analysis of the post-consumer HDPE feedstock is required in order to define
the safety conditions for the process system as a basis for design of the individual process steps.
9

5 Project Structure
Table 1 provides an overview of the work packages and responsibilities of the partners within the project. The
project structure and the interactions of the individual work packages are shown in Figure 1.
Table 1: Project work packages and responsibilities
Work Packages Content Responsibility
I. Planning phase Literature study Fraunhofer IVV
II. Collection,
sorting
Provide HDPE scrap from different collection
systems in the UK
Delleve Plastics
Optimise sorting efficiency RTT Systemtechnik
Measure sorting efficiency RTT Systemtechnik
III. Granulation,
washing
Optimise label and glue removal Sorema/Previero
Optimise decontamination process Sorema/Previero
Analytical screening of flakes for post-consumer
compounds
Fraunhofer IVV
Measure cleaning efficiency of the washing and
granulation process
Fraunhofer IVV/
Sorema/Previero
IV: Super-clean
Re-extrusion and
Optimise decontamination by the EREMA
process
EREMA
decontamination
process options
Measure the cleaning efficiency of the EREMA
process
Fraunhofer IVV/EREMA
Process development and optimisation of
decontamination using the RAPRA supercritical
CO
2
extraction process
RAPRA
Measure the cleaning efficiency of the RAPRA
supercritical CO
2
extraction process
Fraunhofer IVV/RAPRA
Analytical screening of super-cleaned pellets for
post-consumer compounds
Fraunhofer IVV
V: Quality
assurance of
recyclate
Develop suitable quality assurance system Fraunhofer IVV
VI: Bottle
manufacture
Define the maximum acceptable amount of
recycled HDPE
Nampak
Measure mechanical properties Nampak
Produce test containers Nampak
10

Continuation Table 1: Overview over the work packages and responsibilities
Work Packages Content Responsibility
VI: Bottle
manufacture
(cont.)
Compliance testing and evaluation of food law
requirements of recyclate containing bottles
Fraunhofer IVV
VII. Filling of
bottles
Fill test containers Dairy Crest
Product shelf life tests including sensory tests Dairy Crest
VIII: Report and
assessment
Economic assessment of the recycling process Fraunhofer IVV
Environmental assessment of the recycling
process
Fraunhofer IVV
Final project report Fraunhofer IVV

11

Figure 1: Project structure and interdependency of work packages

providing HDPE scrap Literature study
optimisation sorting
efficiency
determination
sorting efficiency
grinding and optimisation
washing efficiency
- glues and labels
- decontamination
determination
washing efficiency
RAPRA process:
optimisation
extrusion and
decontamination
determination
cleaning efficiency
analytical
screening flakes
analytical
screening super -
clean pellets
definition maximum
amount recyclate
production of test
containers
determination of
mechanical
properties
food law
compliance testing,
migration modelling
economic and
environmental
assessment
filling test
containers
sensory tests
EREMA process:
optimisation
extrusion and
decontamination
development
quality
assurance
system (SOPs)
Literature study provide HDPE scrap
measure optimise sorting
efficiency sorting efficiency
shelf live tests
grinding and optimisation of
- washing efficiency
- glues and labels
- decontamination
measure
washing efficiency
RAPRA process:
optimisation
extrusion and
decontamination
measure
cleaning efficiency
analytical
screening of flakes
analysis
of super -
clean pellets
definition maximum
amount recyclate
production of test
EREMA process:
optimisation
extrusion and
decontamination
containers
measure
mechanical
economic and
properties
environmental
assessment
food law
compliance testing,
migration modelling
development
filling test
containers
sensory tests
quality
assurance
system (SOPs)
shelf life tests
12

Input: baled bottles
3050 kg (20% HDPE milk bottles)
Input: hand-sorted HDPE milk
bottles 9407 kg (Delleve)
Sorting PET bottles (RTT):
approx. 548 kg
Washing (SOREMA)
Migration testing (IVV):
50 bottles each
Input: red HDPE
flakes: 1500 kg
Super-cleaning (EREMA):
approx. 5000 kg (without
contamination), one-step
process
Challenge test
(SOREMA): 1500 kg
red flakes plus 100 kg
Challenge test (EREMA):
1500 kg without
contamination plus 100
kg contaminated flakes,
one-step process
Bottle
manufacturing 30%
(500 kg) recycled
HDPE (1000 kg
virgin)
Screening flakes and
pellets (IVV):
several kg each
Washing (SOREMA):
approx. 8125 kg
Bottle
manufacturing 50%
(750 kg) recycled
HDPE (750 kg
virgin)
Bottle
manufacturing
100% (1500 kg)
recycled HDPE
Bottle manufacturing
100% (1600 kg)
recycled HDPE
(contaminated)
100% (1600 kg)
recycled HDPE
(contaminated)
1500 kg without
two-step process
Filling and shelf-life tests
(Dairy Crest): 100 bottles
Challenge test
(RAPRA): 300
kg
Input: virgin
HDPE pellets
process
development
(RAPRA)
Bottle
manufacturing
100% (300 kg)
recycled HDPE
(contaminated)
Bottle
manufacturing
100% virgin
HDPE (reference)
Input: baled bottles
3050 kg (20% HDPE milk bottles)
Input: hand-sorted HDPE milk
bottles 9407 kg (Delleve)
Sorting PET bottles (RTT):
approx. 548 kg
Washing (SOREMA)
Migration testing (IVV):
50 bottles each
Input: red HDPE
flakes: 1500 kg
Super-cleaning (EREMA):
approx. 5000 kg (without
contamination), one-step
process
Challenge test
(SOREMA): 1500 kg
red flakes plus 100 kg
1500 kg without
one-step process
Bottle
manufacturing 30%
(500 kg) recycled
HDPE (1000 kg
virgin)
Screening flakes and
pellets (IVV):
several kg each
Washing (SOREMA):
approx. 8125 kg
Bottle
manufacturing 50%
(750 kg) recycled
HDPE (750 kg
virgin)
Bottle
manufacturing
100% (1500 kg)
recycled HDPE
100% (1600 kg)
recycled HDPE
(contaminated)
100% (1600 kg)
recycled HDPE
(contaminated)
1500 kg without
two-step process
Filling and shelf-life tests
(Dairy Crest): 100 bottles
Challenge test
(RAPRA): 300
kg
Input: virgin
HDPE pellets
process
development
(RAPRA)
Bottle
manufacturing
100% (300 kg)
recycled HDPE
(contaminated)
Bottle
manufacturing
100% virgin
HDPE (reference)

Figure 2: Material flows and test runs
13

6 Literature study
The project started with a literature review. Most of the literature data was already compiled by Fraunhofer IVV in
a recently published review article
[ ] 12
. The literature review focused on:
contamination levels of post-consumer plastics in general
recycling techniques with their individual decontamination efficiencies
mechanical properties and migration levels of containers made with recyclate
This section summarises the results of the literature review
6.1 Research to develop guidelines for the safe use of recycled
material
European Projects "Recycle Re-use" and "Recyclability"
In the last decade the European Commission has supported two projects dealing with the question of recyclability
and re-usability of post consumer plastics for new food packaging applications. The first project AIR2-CT93-
1014
[ ] 13
dealt with plastics packaging materials collected from packaging waste. The second project FAIR CT98-
4318
[ ] 14
focused on PET as the most favourable candidate plastic for direct food contact. Two other sections of
the project are concerned with recycled paper, board and plastics protected by functional barriers to allow reuse
in food contact applications. Both project reports provide in-depth information on analytical methods and their
validation.
Based on the results of the European Project FAIR CT98-4318
[ ] 15
proposals for future legislation were written and
filed with the European Commission. Two guidelines were published, based on contaminant migration estimates
and the results of Europe-wide analysis of post-consumer PET flakes
[ ] 16
. The first document gives detailed
recommendations for performing challenge tests and for quality assurance of recyclate containing PET articles.
The second document gives guidance on the use of functional barriers
[ ] 17
.
I
US FDA Guidelines
In 1992 and 1995 the FDA published two guidelines for industry dealing with post-consumer plastics for direct
food contact applications
[ , ] 18 19
. These guidelines provide recommendations for testing the cleaning efficiency of
recycling processes, the maximum content of post-consumer substances in packaging materials that contain
recyclate and threshold limits for migration.
Based on a review of submissions from third parties and its own research projects the FDA has recently issued an
update of its guidelines
[ ] 20
. This update takes into account new data, mainly for PET, on the contamination of
post-consumer material and the results of challenge tests. Recommendations are provided for selection of PET
feedstock material from non-food applications, which is intended to be recycled into food packaging. The FDA
also provides information on its internet homepage
[11]
about all "non objection letters" that it has issued for
recycling processes.
European ILS Document
In 1997 an expert group led by the International Life Sciences Institute Europe (ILSI) proposed specific guidelines
on the re-use of recycled plastics in food packaging
[ ] 21
. These guidelines, published in 1998, are based on the
14

results obtained from the European "Recycle Re-use" project. The intention of the document was to provide
information for industry about the European view of closed-loop recycling of post-consumer plastics. The
document gives recommendations for recycling and packaging companies, who want to use post-consumer
plastics in food contact applications.
German BfR Recommendations
The German Bundesinstitut fr Risikobewertung (BfR or formerly BgVV) published recommendations in 2000 on
the mechanical recycling of post-consumer PET for direct food contact applications
[ ] 22
. This document is the
result of a discussion of the German "Plastics Commission" on PET bottle-to-bottle recycling. The BfR document
gives recommendations for source control, challenge testing and quality assurance of post-consumer PET
intended for direct food contact.
6.2 Factors that affect contaminant migration
It is generally known that food contact packaging materials are not completely inert and can interact with the
filled product
[ ] 23
. Interactions between packaging plastics and organic chemicals are of greatest interest. Such
interactions start to occur at the point of filling and continue during the regular usage phase of a package. They
may continue even longer, in the event that a consumer reuses the empty packaging for another application by
filling it with an alternative material such as household cleaner, pesticide solution, mineral oil etc. The extent of
these interactions depends on:
the sorption properties of the polymer
the diffusion behaviour of the materials contained by the packaging
the time /temperature profile while the container and its contents are in contact.
These factors determine the potential risk of food contamination from recycled packaging plastics.
The sorption ability or inertness of the polymer is the basic parameter which affects the ease of closed-loop
recycling of packaging plastics. The inertness of common packaging polymers decreases in the following
sequence:
Poly (ethylene naphthalate) (PEN) > poly (ethylene terephthalate) (PET) >rigid poly (vinyl chloride) (PVC) >
polystyrene (PS) > high density polyethylene (HDPE), polypropylene (PP) > low density polyethylene (LDPE)
PEN, PET and rigid PVC are therefore easier to clean for reuse in packaging applications from a migration point of
view than PS and HDPE. However polymers like PS and HDPE which are more prone to absorb contaminants may
also be recycled in closed loop back into food contact packaging if the recycling process is able to remove the
higher concentrations of post-consumer substances that are likely to be present in these materials.
In order to ensure consumer safety it is important to demonstrate that the chosen recycling process can reduce
all post-consumer substances to concentrations similar to virgin materials. This requires that the recycler should
be able to measure the composition and concentration of typical substances in post-consumer plastics before and
after recycling and in the equivalent virgin polymer. .
The incoming concentration of post-consumer contaminants can be measured off-line with laboratory equipment
such as gas chromatography or HPLC or online with detecting or sniffing devices. With the help of online devices
it is possible to ensure an almost 100% check of the input materials.
If these analytical checks are performed at the feed to the recycling plant then misused bottles and those with
high concentrations of migratable substances can be rejected and the cleaning demand on the recycling process
is lower. Source control is therefore an important factor.
15

The quality of the input material to the recycling process is also affected by the number of times it has been
recycled already. The average number of cycles is a function of the blend ratio and the number of recycling steps
carried out.
At present bottle to bottle recycling levels in the UK are very low so most bottles received by recycling plants
contain a high proportion of virgin polymer. Even in parts of Europe where recycling levels are higher the average
number of cycles range from one to three
[8]
. As a result the accumulation of polymer degradation products due to
multiple recycling is in most cases of no concern.
An inherent problem in recycling, however, is the inhomogeneity of the input materials. Different polymer
manufacturers and converters use different polymer additives, lubricants, etc. in order to provide the desired
properties for their target applications. The recycled material will contain an average composition of these
additives.
6.3 Parameters which determine the recyclability of packaging
plastics
Source Control
Source control is the first and very important step in a closed loop recycling process for packaging plastics.
Efficient collecting and sorting processes are required in order to ensure a high quality feed to the recycling
process.
The feed stream material should have a minimum polymer type purity of about 99%. Other polymers, which may
affect the final product properties must be removed from the recycling stream.
The first life of the packaging material is also important. Where possible, only packages previously filled with
foodstuffs should be fed to a closed loop recycling process.
However there are exceptions. Two studies were undertaken
[ , ] 24 25
to assess whether PET materials previously
used for non-food applications could be re-used for food contact. Both studies concluded that packages from
non-food applications could be used as input material for a bottle-to-bottle recycling due to the low diffusivity of
PET.
It was shown that deposit systems and collection systems such as kerbside packaging collections with efficient
sorting processes are able to supply input materials for high value recycling. However, as mentioned above, the
higher the diffusivity of the polymer the more important is source control in order to reduce contamination with
post-consumer substances or misused packages. Modern detecting or sniffing devices are available which can
reduce the intake of undesirable post-consumer substances in the recycling stream.
Contamination Levels and Frequency o Misuse of Recollected Plastics f
Most of the published data on typical contamination of post-consumer plastics is for PET bottles and
corresponding recyclates. This section reviews several useful studies performed in this area.
Sadler et al
[ , ] 26 27
published two studies providing data on contaminants in recycled PET.
The first study identified that most compounds found in recycled PET come from the PET starting materials.
These include oligomers, flavour bases, label materials and compounds originating from base cups. Contaminants
which do not fall into one of these categories were rare.
In samples with high levels of contaminants the sum of all contaminant compounds was approximately 25 ppm.
No single contaminant appeared to be present in post-consumer PET above 1 ppm. All unusual compounds (those
not derived from the PET starting materials) in post-consumer PET were present below 0.1 ppm.
16

In the second study the identity and origin of contaminants in food grade virgin and commercially washed post-
consumer PET flakes were analysed. A total of 18 samples of post-consumer recycled PET flakes were examined.
In most cases, positive identification was possible, however, in a few cases ambiguity resulted from the
similarities in mass spectra of closely related compounds. Compounds identified were classified into categories
associated with their chemical nature or presumed origins e.g:
small and ethylene glycol related compounds (methanol, formic acid, acetaldehyde, acetic acid)
flavour compounds such as limonene
benzoic acid or related benzene dicarboxylic acid substances (benzoic and terephthalic acid and
corresponding esters, benzaldehyde, phthalates)
aliphatic hydrocarbons and acids
unexpected and miscellaneous compounds (Tinuvin, nicotine).
Bayer
[24]
has analysed samples from five different collection systems including PET containers from non-food
applications. In these samples he identified 121 substances. The total concentration of all substances found in
deposit material (returned PET food packaging where a deposit was reclaimed on the container) was 28.5 ppm.
The corresponding total concentration of contaminants in PET flakes coming from non-food applications was
found to be 39 ppm.
Key compounds identified included hexanal, benzaldehyde, limonene, methyl salicylate and 5-iso-propyl-2-
methylphenol (the flavour compound carvacrol). In conventional washed flakes a maximum concentration of
18 ppm for limonene was determined. For PET flakes from non-food applications the major compound, methyl
salicylate, was determined in a maximum concentration of 15.3 ppm.
Additionally the material was analysed after a super-clean recycling process. In this case no peak could be
detected in concentrations above the FDA threshold of regulation limit for PET of 0.215 ppm.
All three published studies found no hints of misuse of post-consumer PET bottles e.g. for storage of household
cleaners etc. This is most probably due to the fact that these studies are based on only very small flakes samples.
Statistically flakes from misused bottles should be extremely rare due to the high dilution with non-misused
containers. This is likely to be why the published studies did not detect any misuse.
Fraunhofer IVV co-ordinated a large EU project which was completed in 2002
[ , , ] 28 29 30
. 689 post-consumer PET
flake samples from commercial washing plants were collected between 1997 and 2001. The samples were taken
from conventionally recycled deposit and kerbside bottle fractions collected in twelve European countries. In
addition, 38 reprocessed pellet samples and 142 samples from super-clean recycling processes were collected.
All samples were screened for post-consumer substances and for hints of possible misuse of the PET bottles by
the consumer in order to obtain an overview of the quality of commercially recycled post-consumer PET.
For the 689 PET flake samples from conventional washing plants the average concentrations of the typical post-
consumer compounds limonene and acetaldehyde were 2.9 ppm and 18.6 ppm, respectively. Maximum
concentrations in a single sample were 20 ppm for limonene and 86 ppm for acetaldehyde. These results are in
good agreement with the earlier studies.
The impact of the collection system and the country, where the post-consumer PET bottles were collected, on the
nature and amount of contaminants was not significant. However in three bottle flakes hints of misuse of PET
bottles e.g. for storage of household chemicals or fuels were found. A statistical evaluation of these results
indicates that around 0.03 to 0.04% of the PET bottles might be misused.
Taking into account dilution of the PET flakes from misused bottles with non-misused PET bottles during washing
and grinding it would be reasonable to predict average concentrations of 1.4 to 2.7 ppm of unusual substances
17

from misused PET bottles in bulk material from commercial washing plants. These concentration estimates can be
used as the basis to set input concentrations for surrogate test compounds when designing challenge tests for
PET recycling processes.
The frequency of misuse was also detected by two further studies:
Allen and Blakistone
[ ] 31
indicate that hydrocarbon "sniffers" for refillable PET bottles rejected between 0.3%
and 1% of PET bottles as contaminated bottles. The majority of these rejections come from PET containers for
"exotic" beverages and not from harmful contaminants. Therefore the proportion of genuine misused bottles is
less than 0.3% to 1%.
Bayer et al
[ ] 32
reported the frequency of misuse of PET bottles is equivalent to one misused bottle in 10,000
uncontaminated bottles (0.01%). Both studies are in agreement with the results of the EU project led by
Fraunhofer IVV.
Huber and Franz
[ ] 33
investigated 21 reprocessed HDPE pellet samples from the bottle fraction of household
waste collections from five different sources. The aim of this study was to investigate the quality of the recycled
HDPE samples, focusing on substances which are not present in virgin polymers. This study provides important
background information for this project because it was the first published study to concentrate on HDPE rather
than PET.
The samples were recycled by conventional washing and extrusion methods without a further super-clean
recycling process. They found that the post-consumer related substances analysed in these different samples
were similar for pellets from the 5 sources. They identified 74 substances which occured in concentrations above
0.5 ppm.
The predominant species were esters of saturated fatty acids, phthalates, hydrocarbons, preservatives,
monoterpenes and sesquiterpenes including their derivatives. Most of the substances were identified as
constituents of personal hygiene products, cosmetics and cleaning agents, which were absorbed by the polymer
during storage.
The highest concentrations were found for limonene, diethylhexyl phthalate (DEHP) and the isopropyl esters of
myristic and palmitic acid. These compounds were found in concentrations between 50 ppm to 200 ppm. Many
odour compounds and preservatives were measured in concentrations of between 0.5 ppm and 10 ppm.
Huber and Franz concluded that,the nature and high concentration of contaminants found in the HDPE samples
meant that the recycled material was only suitable for non-food packaging.
In a second study Huber and Franz
[ ] 34
investigated a total of 79 samples of different polymer types (HDPE, PP,
PS and PET) from controlled collection sources. They found limonene in nearly all the polymer samples.
Concentrations were up to 100 ppm for polyolefines (HDPE and PP) and 12 ppm and 3 ppm for PS and PET,
respectively.
Limonene can be considered as a marker substance for post-consumer polymers. It is interesting to note that the
differences in the limonene concentration follow the diffusion behaviour of the polymers.
In addition to limonene Huber and Franz found phthalates, esters, alkanes, 2,6-di-tert-butyl-4-hydroxytoluene
and oligomers but no hints of misuse of the bottles for storage of toxic chemicals. They concluded that most of
the conventionally recycled polymers that they investigated should be excluded from closed-loop recycling,
because some of the contaminant substances detected are not permitted by the European positive list system for
food contact materials
35
.
18

Ezrin and Lavigne
[ , ] 36 37
investigated four samples of post-consumer dairy grade HDPE that has been recycled
by conventional processes. They assigned most of the 128 compounds that they detected to six major groups:
(i) aliphatic saturated hydrocarbons
(ii) aliphatic unsaturated hydrocarbons
(iii) aliphatic hydrocarbons with functional groups
(iv) aromatic hydrocarbons
(v) aromatic hydrocarbons with functional groups
(vi) fragrance and flavour compounds.
Most of the compounds were present at the ppb or low ppm levels in the recycled HDPE and below the levels of
typical contaminants in virgin HDPE (e.g. oligomers). Benzene, toluene, xylene and di-tert-butylhydroxytoluene
(BHT) were semi-quantified (average of four samples) at 232 ppb, 690 ppb, 388 ppb and 41 ppm, respectively.
In another study with dairy grade HDPE
[ ] 38
they compared two samples of recycled HDPE resin with two samples
of virgin HDPE resin. Average concentrations of the major contaminants were schown in Table 2.
Table 2: Average concentrations from major contaminants in HDPE from Lit
[38]
Contaminants Recycled HDPE [ppb] Virgin HDPE [ppb]
Benzene 283 57
Toluene 763 92
Xylene 529 63
di-tert-butylhydroxytoluene (BHT) 24 /

The major fragrance and flavour type compound found in the recycled HDPE samples was limonene.
Ezrin and Lavigne concluded that commercially recycled dairy grade resin does not appear to present significant
contamination problems and that the material may be suitable for some direct food contact applications.
Recycling Technology
Today a wide range of recycling technologies are available for post-consumer plastics. Most of them use a water
based washing step as their first step in order to reduce surface contamination and to separate dirt, labels and
glue.
The material is also generally granulated to flakes as one of the first steps in the recycling process.
In most cases the washing step is combined with a wet separation step where different flakes of different
polymer types such as polyolefines or PET are separated according to their density difference.
The cleaning efficiency of these washing processes can vary widely, depending on contact time, the use of hot or
cold water based washing and the choice of detergents added to the washing solution. However, typical washing
processes are only able to remove surface contaminants from the polymers
[ , ] 39 40
. They are unable to remove
organic substances, which have migrated into the polymer. Therefore the purity of washed flakes is usually
unsuitable for a closed loop recycling.
Simple remelting or re-extrusion of the washed flakes has an additional cleaning effect
[ ] 41
, however the purity is
usually insufficient for reuse in the sensitive area of food packaging.
19

The so-called super-clean processes for closed loop recycling of packaging materials use further deep cleansing
steps. Although there are many technologies commercially available, most deep cleansing processes use heat and
either, surface treatment with chemicals or vacuum to decrease the concentration of unwanted substances in the
polymers.
6.4 Measuring the cleaning efficiency of recycling processes
Challenge Test
The cleaning efficiency of recycling processes for food contact applications is usually determined by a challenge
test. Challenge tests introduce artificial contamination to the material entering the recycling process and then
measure the output results.
The aim of a challenge test is to simulate the worst possible scenario where the containers are misused for the
storage of household or garden chemicals.
The first recommendation for such a challenge test came from the American Food and Drug Administration (US
FDA)
[18,19]
in 1992. The US FDA originally suggested real contaminants such as chloroform, diazinon, gasoline,
lindane, and disodium monomethyl arsenate as surrogate compounds for use in challenge tests. However it has
been shown in the past that the stability of these surrogates during recycling is in some cases limited so that they
may degrade during the recycling process. Also the analytical methods used to detect the surrogates are often
difficult to develop and have high detection limits.
The surrogates used in a challenge test should not degrade during the recycling process. Otherwise the measured
cleaning efficiency will be better than may be achieved in reality with other compounds and consumer safety may
be compromised.
Over the past ten years alternative surrogates have been selected to ensure that challenge tests can be used to
predict the behaviour of a wider range of other compounds.
This development was supported by evidence from more recent research that in practice the range of chemicals
found in post-use plastic (especially known genotoxic carcinogens) is extremely limited.
The surrogates used today in challenge tests are selected to cover a range of physical properties such as polarity,
volatility and different chemical types. Additionally, some compounds which are aggressive towards the polymer
itself are selected. Care must be taken in selection because chemicals which are excessively aggressive may
affect the physical properties of the polymer and its diffusion behaviour, reducing the validity of the challenge
test.
Typical surrogates used in challenge tests today include volatile compounds such as toluene, chlorobenzene,
chloroform or 1,1,1-trichloroethane and non-volatile substances like phenyl cyclohexane, methyl stearate,
tetracosane, benzophenone, methyl salicylate and methyl stearate.
The aim of the challenge test is to present the recycling process with a worst-case scenario. If the recyclate that
is produced still meets the food law requirements even under such worst case conditions it will provide
confidence that the process is able to produce recyclate suitable for reuse in food contact applications under all
foreseeable circumstances.
Over the last decade there has been controversy between scientists, industry and regulatory authorities regarding
the choice of worst-case scenarios for such challenge tests. These debates have been hampered by a lack of
good quality data on the average contamination in the input materials for recycling.
20

The choice of worst-case scenario depends on:
the typical concentration of undesired substances found in misused post-consumer containers of the
selected polymer type
the frequency of misuse of plastic containers.
Appropriate safety margins can be defined for each polymer type using this data.
Cleaning Efficiency of Conventional Recycling Processes
Post-consumer plastics for re-use in food packaging applications are usually recycled by super-clean recycling
processes. However, these processes use conventional washing steps prior to the deep-cleansing steps.. The
cleaning efficiency of conventional washing processes is therefore of interest because they set the input
concentration of post-consumer substances in the feed material entering the deep-cleansing processes.
In the literature there are a few studies on the cleaning efficiency of conventional recycling processes. These
processes contain washing and surface drying steps followed in some cases by remelting of the post-consumer
material.
Komolprasert and Lawson
[39]
analysed the influence of NaOH concentration, mixer speed and temperature on
removal of the surrogate tetracosane from spiked PET in a challenge test. The study measured residual
tetracosane in PET flakes, which were washed in small-scale experiments using 13 different conditions.
Tetracosane concentration in the washed flakes was 1.4% to 3.3% of the initial spiked level. Only variations in
mixer speed and temperature had a significant effect on removal of tetracosane from the PET flake. The effect of
NaOH concentration was insignificant.
The percentage of non-volatile hydrocarbon residues in washed PET flakes varies with the initial concentration.
The study determined a removal of 89% to 97% of each hydrocarbon by washing.
In a second study Komolprasert and Lawson
[40]
analysed the effect of washing and drying on the removal of
surrogates in both spiked PET flakes and spiked PET bottles.
In the test on spiked PET bottles they concluded that the combination of washing and drying removed 97% to
99% of the organic surrogates. One of the surrogates used in this test was an organic copper compound. The
copper concentration after washing and drying was found to be 21% of the input level (note: the low cleaning
efficiency for the copper compound is probably due to the instability of this surrogate. It reacts during recycling
to produce CuO, which cannot be removed. This behaviour shows that metal organic compounds are in general
unsuitable as surrogates for challenge tests).
In the case of the spiked PET flakes, washing and drying removed more than 99% of the initial concentration of
the organic surrogates. The high cleaning efficiencies of conventional washing and drying processes compared to
washing alone are likely to be due to the high temperatures applied during the drying step and the fact that
contaminants rarely penetrate more than a few m into the polymer surface.
The initial concentrations of the surrogates in spiked bottles are much lower than in flakes, because the surface
area of flakes is higher than for bottles.
A third study by Komolprasert et al
[41]
evaluates the decontamination effect of remelting in a laboratory
extruder. This work shows that remelting can further reduce the contamination of spiked PET.
However the real reduction is difficult to evaluate, because some of the surrogates used (diazinon, malathion,
metal organic copper compound) are not stable during extrusion. In addition volatile substances such as toluene
are almost completely removed during washing, so that it is impossible to evaluate the additional cleaning effect
during remelting for this surrogate.
21

In conclusion:
conventional washing processes are able to reduce the input concentration of post-consumer substances
in polymer flakes
the washing process itself probably removes only surface contaminants
thermal drying is able to remove substances, which are absorbed into the flakes.
Remelting processes further reduce the contamination.
Due to the fact, that different conventional recycling processes use a wide range of parameters and equipment a
general conclusion and a quantification of the cleaning effects for washing, drying and remelting processes is not
possible on basis of the above mentioned literature results. Data for the cleaning efficiency of conventional
recycling processes for HDPE are not published.
Cleaning Efficiency of Super-Clean Processes
In addition to challenge testing, quality assurance of processes for post-consumer (PCR) PET is based on careful
feedstock control and regular analysis of the final product.
Three studies of the cleansing efficiency of super-clean recycling processes for PET have been published by
Franz and Welle
[ , , ] 42 43 44
. The process investigated in the first two studies
[42,43]
contains three main steps;
washing, re-extrusion and solid-state polycondensation (SSP).
The process was challenged with three different surrogate concentration levels. The cleaning efficiencies
measured for the different surrogates and contamination levels were in the range 94% to 99%
[42]
. The results
show no significant dependency on the input concentration of the surrogates going into the process.
In the first trial the process was tested without a washing process. When a conventional washing process was
included in the second trial the cleaning efficiency increased to more than 99.3%, even for benzophenone, the
most challenging substance
[43]
.
In the third study
[44]
a recycling process without solid state polycondensation was investigated. Except for
benzophenone, the recycling process reduced all surrogates by more than 95% for initial concentrations below
100 ppm and more than 90% for initial concentrations between 100 and 500 ppm. For the most challenging
substance, benzophenone, the cleaning efficiency was approximately 77% at an initial contamination level of
294 ppm.
In this third trial the measured cleaning efficiencies were lower than for the super-clean recycling process with
solid state polycondensation. However, even in this case the specific migrations of all surrogates from PET bottles
made from contaminated and recycled PET were still far below the migration limit of 10 ppb given by the US FDA
threshold of regulation concept for PET.
6.5 Evaluating contaminant migration
Migration from a food/plastic package system is influenced by both kinetic factors (diffusion in plastic and food)
and thermodynamic factors (equilibrium partitioning between plastic and food).
It is useful to base migration evaluations on a worst-case assumption that estimates total mass transfer based on
the starting concentration of each migrant in the plastic. If this calculation leads to a migration limit being
exceeded, then it is necessary to refine the evaluation to take account of partitioning and diffusion as the critical
parameters for migration. Scientific background and guidance on how to conduct such evaluations can be found
in the literature
[23]
.
22

The US FDA suggests that dietary exposures to contaminants from recycled food contact articles at a
concentration of 0.5 ppb or less generally are of negligible risk
[18,19, ] 45
.
With the help of so-called consumption factors (CF) these dietary exposures can be converted into migration
limits. According to this concept, the migration of unknown contaminants into food may be tolerated if a certain
threshold value of concentration is not exceeded.
For an average daily food consumption the threshold concentration value is 0.5 ppb, irrespective of the packaging
type and material. The application of CFs increases the actual maximum acceptable contaminant level for each
type of polymer. For general polyolefins (CF = 0.35) the CF increases the maximum acceptable contaminant level
to 1.5 ppb.
The migration limit can also be converted into a maximum bottle wall concentration for any substance occurring
in post-consumer plastics (including substances from virgin polymers). For polyolefins the maximum
concentration in the polymer which correlates with 1.5 ppb dietary intake level is 46 ppb for a typical polyolefin
container at a thickness of 0.5 mm. This calculation is based on the very conservative assumption that all HDPE
containers are contaminated and the contaminants are assumed to migrate completely from the container into
the foodstuff. The contaminant limits calculated above also assume 100% recycled resin content in the finished
article. For testing compliance with this threshold value, the US FDA recommends a challenge test, by which the
efficiency of purification during the recycling process is determined using artificially incorporated model
contaminants. For HDPE the US FDA defined a consumption factor of CF = 0.13
[ ] 46
.
It is generally accepted that in practice diffusion-controlled migration usually results in much less than complete
transfer of substances into the foodstuffs.
Migration from virgin and post-consumer PET has been investigated in numerous projects where low diffusion
and migration rates have been reported and confirmed
[43,44, ] 47
. In some cases the contamination levels measured
are below the detection limits of the analytical methods used. Diffusion models therefore
[6, , ] 48 49
provide a useful
scientific tool for more realistic correlation between the upper migration limit allowed in the packaged foodstuff
and the corresponding maximum allowable contaminant concentration in the polymer.
A generally recognised migration model which relies on estimating the diffusion coefficients of organic chemical
substances in polymers
[23]
has recently been completed within the European project SMT-CT98-7513 "Evaluation
of Migration Models in Support of Directive 90/128/EEC"
[ ] 50
. This model correlates the migration of contaminants
into food with the molecular weight of the bottle polymer and the corresponding maximum allowable
concentrations of the surrogates in the bottle wall.
Klingelhofer et al
[ ] 51
determined the diffusion coefficients of two model contaminants in recycled HDPE. Methyl
salicylate was used as a model compound for oil based household cleaners. Xylene was used as a model for the
solvents used in paint thinner or gasoline. Xylene was found in typical post consumer recycled HDPE
samples
[36,37]
.
They found that the diffusion coefficients of xylene and methyl salicylate into (or out of) HDPE were
8.6 + 0.8 x10
8
cm
2
s
-1
and 1.4 + 0.06 x10
8
cm
2
s
-1
, respectively.
Devlieghere et al
[ ] 52
investigated the migration behaviour of conventionally recycled post-consumer HDPE
material, caustic washed material (5% NaOH, 60 min, 90 C) and caustic washed/steam stripped (1 h, 1.7 kg
steam per h and kg HDPE)/air dried (2 h, 90 C) material which was re-used in HDPE bottles.
The migration characteristics of the different bottles were compared using various food simulants such as distilled
water, 3% acetic acid, 15% ethanol, 95% ethanol and iso-octane. The bottles were filled and stored for 10days
at 40 C for distilled water, 3% acetic acid, 15% ethanol and 95% ethanol or 2 days at 20 C in the case of iso-
octane.
23

From the migration tests (and also from the sensory tests, see below) the conventionally washed and the caustic
washed recycled materials were not safe for use as a food packaging. They found that a large numbers of
contaminants were able to migrate. However the steam stripped recycled material seemed to perform almost as
well as virgin polymer.
6.6 Sensory testing
Huber and Franz
[34]
investigated the sensory properties of conventionally recycled polymers (HDPE, PP, PS and
PET) by means of odour testing.
In all the samples they detected the polymer specific odour found in virgin polymers. However they also found
that all of the recycled polymers could be identified because they detected additional odour notes.
The lowest odour deviation was noticed for PET. Increasing off-odour was noted from PS to PP and HDPE. These
results are not surprising because flavour compounds such as limonene can be found in significant concentrations
in all the polymer samples. These flavour compounds absorbed from the first use of the packaging materials.
Deep cleansing of these polymers may be expected to improve the sensory properties of recycled polymers
because the analytical work described earlier in 6.1 demonstrated that super-clean recycling processes can
greatly reduce concentrations of flavour compounds in polymers.
The sensory properties of recycled polymers are a vital parameter for a closed loop recycling. They should be
investigated in case-by-case studies for packaging materials containing the final recyclate from each recycling
process . This is because the odour threshold limits of some flavour compounds are very low (in some cases
below the analytical detection limits) so that the results of a challenge test cannot be used to predict the result of
a sensory evaluation.
Devlieghere et al
[52]
noted the migration of numerous compounds which cause an easily recognized off-flavour
in bottles manufactured from conventional recycled HDPE and also in bottles made from caustic washed recycled
material (5% NaOH, 60 min, 90 C). However steam stripped/air dried recycled material (1 h, 1.7 kg steam per h
and kg HDPE followed by 2 h at 90 C) seemed to perform almost as well as virgin material. In the sensory tests
this material could not be distinguished from the equivalent virgin polymer.
6.7 Mechanical properties
Changes in the molecular structure of the polymer may occur during recycling.
Processes have been developed for polyester polymers such as PET which are able to increase the molecular
weight by solid-state polycondensation (SSP). This process can improve the mechanical properties of the
polymer.
In the case of polyolefins a decrease in molecular weight typically occurs due to oxidation and mechanical stress
during bottle manufacturing, use and recycling. The sorption of compounds into the plastics material may also
change the mechanical properties of post-consumer plastics. This is more likely in the case of polyolefins due to
their higher sorption rates.
Spinks and Ayrton
[ ] 53
investigated the effects of multiple pass extrusion on the structure and properties of
dairy-grade HDPE. In their tests they put the polymer through up to ten cycles. They found that repeated
extrusion caused thermo-oxidative degradation.
During the first two cycles a cross-linking process was dominant. During further extrusion cycles chain scission
was slightly more dominant.
24

Melt flow index and impact strength show a steady decline with multiple pass extrusion whereas the modulus
increases. The most significant practical problem however, was a strong increase in colour (yellowing) during
multiple pass extrusion.
El'darov et al
[ ] 54
also investigated multiple pass extrusion processing of HDPE. They found considerable changes
in molecular weight. In the absence of an inhibitor additive the molecular weight of polyethylene either increases
or decreases depending on the oxygen content of the processing environment.
They concluded that oxygen performs a double function. It increases the rate of radical initiation due to hydro
peroxide decomposition and also affects the competition between degradation and cross-linking in the secondary
reactions of the radicals. Peroxide radicals are incapable of attaching themselves to macromolecules, so the
relative rate of degradation increases in the presence of oxygen.
In contrast a study from Boldizar et al
[ ] 55
found that post-consumer HDPE did not degrade to any significant
degree during ten cycles of simulated recycling, where each cycle included one extrusion and one indoor aging
step equivalent to 2-3 years.
Takahashi
[ ] 56
showed that melt temperature, heat of fusion, dynamic modulus of elasticity and tensile-impact
energy of recycled HDPE material in the moulded form were within the range of variation of the equivalent virgin
polymer.
Devlieghere et al
[52]
tested virgin and recycled HDPE and observed only minor and mostly non-significant
differences for E-modulus, tensile strength and elongation.
The steam treated recycled material (1 h, 1.7 kg steam per h and kg HDPE followed by 2 h at 90 C) was found
to be an appropriate material for the production of HDPE bottles.
Pattanakul et al
[ ] 57
compared the physical properties of virgin HDPE with virgin/recycled HDPE blends
containing up to 100% recycled material. The recycled HDPE was obtained from post-consumer milk bottles.
It was found that elongation at break was the mechanical property most affected by the content of recycled
HDPE. Overall, however, the recycled HDPE from milk bottles was found to be a material with useful properties
not very different from those of virgin resin and thus could be used, at an appropriate blend ratio with virgin
HDPE.
6.8 Studies of practical market applications
Three-layer PP Cups for Dairy Products
Franz, Huber and Piringer presented a study in 1994
[ ] 58
which investigated the safety in food contact use of
symmetrically coextruded three-layer polypropylene (PP) cups with recycled post-consumer PP in the core layer
(mass fraction 50%) and virgin food grade PP in the adjacent layers.
The recycled PP contained about 95% PP and 5% PS. It was carefully source controlled and had been used for
packaging of yoghurt in its first life. The intended application for the recycled material was again packaging of
milk products such as yoghurt with short storage times under refrigerated conditions.
The strategy in this study was to compare the recycled plastic with new, food grade plastic material of the same
type in three ways:
1. Analysis of the raw materials (virgin versus recycled PP pellets),
2. Analysis of the finished food contact articles (virgin versus recycled cups)
3. Migration testing of both types of cups (virgin and recycled) under both regular and more severe test
conditions
25

Post-consumer or recycling-related potential migrants were identified and quantified in the first two groups of
tests. These compounds were then used as indicator substances to be monitored in migration measurements in
the third set of tests..
The major post-consumer related compound was limonene, a flavour compound, which can be found in many
foodstuffs and also in the non-food area.
It was found that none of the post-consumer or recycling-related substances could be detected analytically in the
food simulants (at a detection limit of 13 ppb) under standard migration test conditions. However, from the
results obtained under more severe test conditions, it could be concluded that even for limonene (the compound
with the highest migration rate) migration into a milk product will be below 1 ppb and far below 1 ppb for other
post-consumer substances.
In conclusion, based on the US FDA threshold of regulation concept
[18]
the use of co-extruded multi-layer material
for the intended application was considered to be safe.
Multi-layer PET Bottles for Soft Drink Applications
Franz et al published a further study in 1996
[ ] 59
in which they investigated the effectiveness of a virgin PET layer
in limiting chemical migration from recycled PET.
For this purpose three-layer bottles were prepared with an inner buried layer of PET, which was deliberately
contaminated. The model contaminants used were toluene, 1,1,1-trichloroethane, chlorobenzene, phenyl decane,
benzophenone, phenyl cyclohexane and copper(II) acetylacetonate.
No migration was detected through a barrier of virgin PET of 186 + 39 m thickness into 3% acetic acid using
general migration test conditions of 10 days at 40 C and also after 6 months storage at room temperature.
Migration testing with 50% and 95% ethanol as severe contact media, which are relatively aggressive to PET also
failed to produce measurable migration rates.
They used a diffusion model for limonene (a substance for which diffusion coefficients were available) to estimate
that a breakthrough of a substance with comparable molecular weight would take place after 7.5 years or
0.8 years at room temperature or 40 C, respectively for a 100 m thick PET layer.
It was concluded that an intact PET bottle layer in contact with the food represents an efficient functional barrier
against migration from any possible contaminant encapsulated in a recycled PET material under normal conditions
of use for soft drinks.
Studies on Multi-layer PET and PET Films for Food Packaging
Piringer et al
[ ] 60
concluded a study in which,the migration behaviour under different test and contact medium
conditions was systematically investigated for several co-extruded three-layer PET films.
These films were spiked in the core layer with toluene and chlorobenzene surrogates and had a PET barrier layer
thickness either side of the core layer of between 20 m to 60 m. They observed that the migration measured
through the different barrier layers was predictable and developed a diffusion model for predicting the functional
barrier properties of layered films based on Fickian diffusion.
It was also found necessary to consider the effects of diffusion from the core layer to a virgin barrier layer during
the co-extrusion process for reliable prediction of migration.
The mathematical model presented in this paper estimates the maximum allowable contaminant concentration in
the core layer for a given barrier thickness and a given threshold or specific migration limit.
Similar studies
[49]
investigated the functional barrier behaviour of high impact polystyrene (HIPS) using
symmetrical three-layer films, again spiked in the core layer with toluene and chlorobenzene.
26

The thickness of the HIPS barrier layer was greater than in the above PET example (50 m, 100 m and
200 m). The contact medium was 50% ethanol, which is a recognised contact medium for fatty food products
for this plastic. Testing was carried out at 40 C for up to 76 days.
The research concluded that HIPS was an appropriate functional barrier, provided the barrier layer is optimised
for the particular purpose. Generally, layer thicknesses from 100 m to 200 m were found to be very efficient,
even under the exaggerated test conditions used in this study to simulate fatty contact.
For aqueous food products and ambient or refrigerated applications a HIPS barrier layer will be even more
effective.
As in the PET study, this study investigated contamination of the virgin barrier layers by compounds from the
core layer during the high temperatures of the co extrusion process. It was found that, for a 50 m HIPS barrier
layer, the same contamination of the food contact surface with the surrogate toluene was achieved within
1 second at the co-extrusion temperature of 200 C as after one year of storage at room temperature.
Mono-layer PET Bottle for Sof Drink Applications t
Due to the higher cost of manufacturing multi-layer PET bottles, the bottle manufacturing and recycling
companies started to develop high performance recycling processes, which allow bottles to be made without a
functional barrier of virgin PET.
One decade later several super-clean recycling processes are now established at industrial scale
[10]
. By 2002,
recycling companies in Europe had installed total recycling capacity of about 65.000 tons of super-clean post-
consumer PET suitable for use in direct food contact applications. The cleaning efficiencies of all the industrial-
scale deep-cleansing recycling processes for PET have been investigated by challenge tests and the results are
well known.
Monolayer HDPE Bottles for Fresh Milk
In 2002 a milk bottle-recycling project was launched in Northern Ireland
[ ] 61
. Milk bottles were collected by a
deposit system and were sent to a bottle-to-bottle recycling process. As a result of the deposit collection system
the recycled HDPE was completely under source control and had been used in its prior application only for
packaging of fresh milk.
The collected material was recycled first by a conventional washing based recycling process and then further
deep-cleansed using a super-clean process. The recycled material was re-used in new milk bottles at 20% to
30% content without a functional barrier. The intended application was for fresh milk with short storage times
under refrigerated conditions.
The project had several R&D phases. Firstly post-consumer HDPE milk bottles were analysed for compounds
which could be potential migrants. Subsequently the deep-cleansing process was optimised and its cleaning
efficiency was evaluated by a challenge test. Only HDPE related compounds such as oligomers could be detected
in the recycled polymer after deep cleansing.
For quality control purposes an online sniffing device based on a so-called electronic nose was integrated into the
recycling process. This sniffing device is able to detect potential migrants such as solvents or other volatile
substances, which might be introduced into the recycling process.
Based on the challenge test results, upper limits for the concentration of volatile substances could be defined so
that any HDPE batches with higher levels could be detected and separated for reuse in non-food packaging
applications.
The sophisticated recycling techniques used in this project compensated for the greater difficulty of recycling
HDPE in closed loop compared to PET.
27

Another point to note is that the project was started in Northern Ireland. This is a relatively small market scale
which is easy to control. All of the HDPE milk bottles were provided by only two bottle manufacturers. These
manufacturers were part of the project.
By reading the bar code the collection vendors are able to separate bottles from these two manufacturing
companies and reject other milk bottles. As a result only milk bottles from bottle suppliers and filling companies
which support the project are sent to the bottle-to-bottle recycling process. The recycling company was therefore
able to influence the choice of glues, label and colours used by the bottle manufacturers. This helped to improve
the recycling process further.
6.9 Summary of the literature review
The literature study indicates that there is no technical barrier to the use of recycled plastics in food applications.
They can be applied in direct food contact applications provided super-clean recycling processes are used or they
can be protected from direct food contact by a functional barrier.
From a legal point of view, there may be limitations on the use of recycled plastics in food contact applications,
because different European countries still apply different regulations. The EU has not yet issued harmonised
rules.
Whatever happens, the use of recycled plastic materials in packaging applications must not be at the expense of
the public health, nor should it alter the quality of the food materials contained by the packaging.
28

7 Sorting efficiency for UK collected
HDPE bottles
Delleve Plastics provided HDPE scrap for this project. This material was generally representative of post-consumer
HDPE packaging material collected in the UK. This material was sourced from:
A kerbside collection in the South East of the UK
A bring scheme collection in the North West of the UK
The input material for the project was the plastic bottle fraction from these sources with plastic films and other
non-bottle material removed.
Table 3 gives an overview of the composition of the material that entered the sorting process.
Table 3: Composition of the input material (average value for 10 bales)
Bottle type Absolute amount [kg] Percentage
HDPE milk bottles 610 20%
Other HDPE bottles 610 20%
PET bottles 1525 50%
PS, PP, other plastic bottles 183 6%
Residue 122 4%
Total 3050 100%

7.1 Sorting technology used
The aim of the sorting trials was to collect natural HDPE milk bottles. The optical sorting technology of RTT
Systemtechnik GmbH was used.
29

Figure 3: Schematic diagram showing separation of bottles by positive sorting
The newest technology from RTT, UniSort P, uses near infrared detection of the polymer types. The wavelengths
of different polymer types are shown in Figure 4. Different polymer types such as PE, PP, PS, PA, PET, PVC and
ABS can be separated with this technology.

Figure 4: NI R wavelength of different polymers (UniSort P)
The UniSort P technology from RTT is unable to separate natural and coloured HDPE bottles from each other. The
HDPE fraction from the first sort was therefore sorted again using the UniSort C technology in order to separate
the coloured HDPE bottles. See Figure 5.
30

Using this technology the separation of natural HDPE bottles was successful due to the fact that the natural HDPE
milk bottles have characteristic wavelength between 1750 nm and 2100 nm in comparison to HDPE non-milk
bottles.

Figure 5: NIR wavelength of HDPE milk bottles used for sorting from other HDPE bottles (UniSort C)
Both of the Unisort processes use principal components analysis (PCA or PLS methodology) for extraction of the
characteristic wavelength for the different polymers and colours.
7.2 Sorting efficiency of the RTT pilot plant
In the first step of the project 12 tonnes of material provided by Delleve were shipped to RTT in Zittau. Part of
this material was sorted by the pilot plant at RTT. The results were used to optimise the polymer database in
order to increase the sorting efficiency. Table 3 shows the sorting results from the RTT pilot plant at Zittau.
Table 4: Results of the sorting trials from the pilot plant in Zittau (Unisort P)
Type Percentage
HDPE milk bottles 86.6%
HDPE milk bottles clumped with other bottles 10.1%
PET bottles 1.0%
Residue (mostly attached paper) 0.4%
HDPE non-milk bottles 1.9%
Total 100%

31

The following conclusions were drawn from the pilot plant sorting trials:
The particle size of the bottle fraction is suitable for automatic separation
The material contains a relatively small proportion of non-bottle materials
The relatively small proportion of HDPE bottles in the input stream(20%) means that a positive sorting
method, where HDPE items are positively identified and ejected, should give the best results
Colour sorting should be done in a second step using the mixed HDPE fraction from the initial sort
There was some clumping of HDPE bottles with PET (or other materials) which reduced the sorting
efficiency
In conclusion the material provided by Delleve should be suitable for supply to a fully automated sorting process.
The small proportion of HDPE milk bottles in the mixed scrap made it necessary to sort large amounts of baled
material in order to obtain the 8 te of natural HDPE milk bottles which were needed for the next stage of the
project. In addition clumping of HDPE bottles with other materials during the baling process reduced the sorting
efficiency. For full scale production the baling pressure of the input material should be optimised in order to
minimise clumping while maintaining an adequate bale volume.
It was interesting to note that wavelength differences of more than 1800 nm occurred in the near infra red
wavelength spectra for non-milk and milk HDPE bottles. The question arose whether these differences are a
special case for the UK market, since most of the virgin HDPE material for milk bottles in the UK originates from
one virgin supplier.
Sorting tests were therefore performed on both milk bottles and non-milk containers from the US market. It was
found that US milk containers are comparable with UK milk containers in that there is also a difference in the NIR
spectra for milk and non-milk HDPE containers of about 1800 nm. It therefore appears that the technology
applied in this study to remove non-milk containers may be viable for other regional markets as well.
32

1800 nm 1800 nm

Figure 6: NIR wavelength of HDPE milk bottles from the US market used for sorting from other
HDPE bottles (UniSort C)
7.3 Sorting efficiency at the industrial plant of Delleve Plastics
In the second stage of the trial the optimised database for bottle sorting that was generated in the pilot trials at
Zittau was installed in the optical sorters used at the sorting plant of Delleve Plastics in St. Helens. The industrial
scale plant was used to sort 3 tonnes of mixed baled bottles. A flow chart of the sorting steps and the mass flow
through the sorting process is given in Figure 7.
33

UniSort P
positive sorting
UniSort C
negative sorting
material composition:
(average value of 10 bales)
HDPE milk bottels 20 % = 610 kg
HDPE others 20 %= 610 kg
PET 50 %= 1525 kg
PS, PP, other plastic 6 %= 183 kg
Residue 4 % = 122 kg
Total 100 % = 3050 kg
Input
flow path
HDPE milk bottels 15 kg
HDPE others 515 kg
PET 1428 kg
PS, PP, others 101 kg
Residue 105 kg
Total 2164 kg
eject: PE
milk bottle
flow path
final product
two bales
HDPE-milk bottels
HDPE others 83 kg
PET 65 kg
PS,PP, others 82 kg
Residue 15 kg
Total 253 kg
eject 633 kg
Sorting Step 1
positive by resin
Sorting Step 2
positive by color
Input
HDPE milk bottels
clumped together 65 kg
with PET bottles
HDPE non milk 12 kg
PET 6 kg
Residue 2 kg
Total 85 kg
Hand
inspection
Bale 1 270 kg
Bale 2 278 kg
Total 548 kg
Shipped to Sorema, Italy
Sorting Step 3
Manual inspection
eject 886 kg
UniSort P
positive sorting
UniSort C
negative sorting
PET 50 %= 1525 kg
Total 100 % = 3050 kg
Input
PET 50 %= 1525 kg
Total 100 % = 3050 kg
Input
flow path
HDPE others 515 kg
PET 1428 kg
PS, PP, others 101 kg
Residue 105 kg
Total 2164 kg
eject: PE
milk bottle
flow path
final product
two bales
HDPE-milk bottels
HDPE others 83 kg
PET 65 kg
PS,PP, others 82 kg
Residue 15 kg
Total 253 kg
eject 633 kg
Sorting Step 1
positive by resin
Sorting Step 2
positive by color
Input
HDPE milk bottels
clumped together 65 kg
with PET bottles
HDPE non milk 12 kg
PET 6 kg
Residue 2 kg
Total 85 kg
Hand
inspection
Bale 1 270 kg
Bale 2 278 kg
Total 548 kg
Shipped to Sorema, Italy
Sorting Step 3
Manual inspection
eject 886 kg

Figure 7: Flowchart of the sorting steps at Delleve
The sorting efficiency of the process was tested for two scenarios (see Table 5):
(i) further sorting of the output stream of the RTT process by handpicking before automatic sorting
(ii) automatic sorting without further sorting.
In the first scenario the feed material was hand sorted on the conveyor belt before the automatic sorter in order
to remove impurities such as HDPE milk bottles clumped with other bottles, PET bottles and non-bottle materials.
In this scenario the output fraction contained more than 99% natural HDPE milk bottles.
For scenario (ii) no hand sorting was used on the basis that all other impurities apart from non-milk HDPE bottles
should not be critical because the sink-swim process of the washing line that follows the automatic sorter should
remove impurities such as PET. In scenario (ii) the HDPE milk bottle fraction contained about 12 kg of HDPE non-
milk bottles. These could not be removed during the further recycling steps. In this scenario the output fraction
of natural HDPE milk bottles is 97.9% (or slightly higher due to the fact that the HDPE bottles clumped with other
bottle will increase the HDPE milk bottle fraction during grinding).
34

Table 5: Results of the sorting trials with two scenarios (i) further sorted by handpicking and (ii)
without further sorting, but washing using a sink-swim step
Type Amount
[kg]
Scenario 1 Scenario 2
HDPE milk bottles 548 548 548
HDPE milk bottles clumped with other bottles
(mostly PET)
65 removed by
handpicking
removed by downstream
sink-swim process
PET bottles 6 removed by
handpicking
sink-swim process
Residue (mostly attached paper) 2 removed by
handpicking
sink-swim process
HDPE non-milk bottles 12 removed by
handpicking
12
Total 633 548 560
Purity >99% >97.9%

In both scenarios the loss of HDPE milk bottles was 10.2% (610 kg in the input stream to 548 kg in the output).
In conclusion the sorting process is able to provide a good quality input material for the further cleaning steps,
which is suitable for a closed loop recycling.
The ILSI document
[21]
recommends a minimum of 99% food grade polymer for the input material to closed loop
recycling processes. This goal was achieved using scenario (i). For scenario (ii) the goal was also probably
achieved, because most non-milk HDPE bottles are also manufactured from food grade HDPE.
However, some authorities define "food grade" polymers as a polymer which was in contact with foodstuff. The
discussion as to whether the input material should be "food grade material" or "food grade material from bottles
filled with foodstuffs" is not finalised.
The German BfR recommends a minimum fraction of 99% PET for the closed loop recycling of PET bottles
[22]
.
This is defined such that PET bottles used for non-food applications are considered as a foreign polymer type.
The conclusion of this study is that non-milk bottles should be separated by handpicking until the EU discussion is
finalised and the European Community has published its "Recycling Directive".
35

8 Washing the sorted HDPE bottle
fraction
8.1 Washing post-consumer HDPE flakes
Post-consumer pre-sorted bottles from the sorting trials at Delleve were shipped to SOREMA, Italy. The aim of
the washing trials was to remove glue, labels and other surface contaminants and to achieve some
decontamination of post-consumer compounds. Target output of the washing trials was high quality HDPE flakes,
suitable for further deep-cleansing processes.
SOREMA used the standard hot washing process that they manufacture for PET bottle-to-bottle recycling. Figure
8 below shows a flow chart of the SOREMA process.
Details of the procedure used at SOREMA are as follows:
Manual sorting
29 bales of input material with a total weight of 9407 kg were sorted manually.
Two separate fractions were processed:
First fraction: two bales from the initial pilot sorting trials at RTT with a total weight of 529 kg. 4 kg of PET, PVC,
Fe and coloured HDPE were manually separated from this fraction prior to washing.
Second fraction: 23 bales from the bulk sorting trials at Delleve with a total weight of 7646 kg. 15 kg of PET,
PVC, Fe and coloured HDPE were manually separated from this fraction prior to washing.
4 of the bales from Delleve (total weight of 1.232 kg) contained many bottles of coloured HDPE and
contamination with a total weight of 220 kg.
Granulation and aerodynamic separation.
9168 kg of bottles were granulated and passed through a screen of 12 mm round holes followed by an
aerodynamic separator. This step separated 438 kg of labels and fines.
Pre-washing
SOREMAs patented hot pre-washing system takes the worst quality baled bottles and continuously removes large
and abrasive contaminants, almost all glue, paper labels and dirt on the polymer surface. The machine used for
this step is slow moving with very few moving parts.
The bottles are mixed with a hot caustic solution in a stainless steel cylindrical vessel. 30% caustic soda is added
to the washing solution in order to give a caustic concentration in the vessel of 2% with approx. pH 12 and a
temperature of about 93C. The bottles were agitated in the solution long enough to remove any glue.
In this trial a total of 8730 kg HDPE flakes were processed. 150 kg of paper and HDPE fines were separated
(estimated dry weight). The residence time was 4 to 10 min.
36

Grinding
After pre-washing the bottles were cut into smaller pieces in the grinding section. During grinding, water was
sprayed into the cutting chamber. Any residual paper with the flakes was pulped and then separated in the
washing centrifuge.
Chemical washing and separation
The final washing process was the chemical washing, separation, rinsing, drying and aerodynamic separation
cycle. The washing temperature was approximately 93 C. SOREMA added RP14 product (Mac Dermid), diluted at
2.5%, to the process water,
A total of 8580 kg HDPE flakes were processed.
The following residues were separated: 60 kg paper and fines from the chemical washing, 26 kg plastic from
flotation and 119 kg labels from the aerodynamic separation. The residence time was 6 to 12 min.
Colour Sorting of Washed Flakes
The washed flakes still contained about 1% coloured flakes so a further colour-sorting step was necessary.
The flakes were optically sorted on an AF 0914 machine at the MikroSort testing laboratory in Wedel, Germany.
Before conducting the bulk separation the sorting process was optimised for maximum reduction of impurities
and minimum loss of material in a pre-test.
The particle size distribution of the HDPE flakes was also measured. See Table 6
Table 6: Size distribution of the HDPE flakes
Particle size Amount [%]
>8.0 1.3
6.3 8.0 27.6
5.0 6.3 9.0
4.0 5.0 24.7
3.1 4.0 14.5
2.5 3.1 11.3
<2.5 11.6

4180 kg of dried flakes from the chemical washing process were sorted in the bulk trial without separation of the
fine material (<2.5 mm). The product from the flake sorting process contained less than 100 ppm of coloured
HDPE flakes. The loss of good material with the coloured flakes was approx. 3%. It was found that the optical
sorter was able to distinguish between opaque and white flakes with an efficiency equivalent to the coloured
flakes.
The mass balance of the washing trial is summarised in Table 7.
37

Table 7: Overall mass balance of the washing trials
Step Input [kg] Output [kg] Type of waste %
Bales 29 bales 9407 100.0
Manual sorting 9407 239 Containers 2.5
Granulation and aerodynamic
separation
9168 438 Labels 4.8
Pre-washing 8730 150 Paper/fines/ contamination 1.7
Chemical washing and aerodynamic
separation
8580 205 Paper/fines/ contamination 2.4
Flake sorting 8375 250 Coloured Flakes 3.0 (estimated)
Total 9407 8125 86.4

38

Figure 8: Flow chart of the SOREMA washing process
39

Figure 9: Flow chart of the colour sorting using the MikroSort technology
input 1,0t/h
0 12 mm -
Final product
coloured: <100ppm
0,25 t/h
1. sorting step
Mikrosort 1
0,2t/h 1,05t/h
3. sorting
step
MikroSort
1/3
2. sorting step
MikroSort 2/3
0,1t/h
Online return
0,15t/h
0,95t/h
0,05t/h
Reject fraction
loss of transparent

flakes: 3%
40

Input
coloured flakes 1.4%
coloured 9% coloured<500 ppm
coloured

Figure 10: Results of the colour sorting using the MikroSort technology
coloured 30% coloured<1% coloured<1%
<100 ppm
Final product Rejected Recirculated Recirculated
625 kg 425 kg 4180 kg 250 kg
41

8.2 Challenge test of the washing process
The cleaning efficiency of the washing process was measured by a challenge test. The test was carried out by
deliberately introducing contaminated post-consumer HDPE material with the feed.
Natural HDPE flakes from the first washing trial were contaminated with surrogate contaminants. This
contaminated material was then washed together with non-contaminated red HDPE flakes using SOREMAs pilot
plant washing line. Using the pilot plant with a throughput of about 1000 kg h
-1
allowed the use of a small
quantity (50 kg) of contaminated material for the challenge test. This reduced the amount of hazardous
chemicals that had to be handled. After the washing step, samples were withdrawn and the contaminated natural
flakes separated from the non-contaminated red flakes. The natural flakes were analysed for residual
contamination levels.
The surrogates were chosen following FDA recommendations
[18,19]
and in agreement with EU-relevant
criteria
[16,21,22]
. The surrogates chosen covered a spectrum of volatility and polarity and a broad range of
migration-relevant molecular weights. They also contained a variety of functional groups inlcuding hydrocarbons,
chlorinated hydrocarbons, a ketone and an ester functional group.
The following surrogates were used: toluene, chlorobenzene, phenyl cyclohexane, methyl stearate and
benzophenone. Chloroform, a well-known very aggressive chemical to HDPE, was applied to ensure strong
interactions with the HDPE matrix and therefore better transport of the surrogates into the polymer. All
surrogates are commercially available and were used for the contamination experiments without further
purification.
Contamination of the HDPE flakes was achieved by the following procedure: 50 g of each of the liquid and solid
surrogates were mixed and stirred until a homogenous solution was obtained. This surrogate mixture was mixed
with 5 kg of recycled post-consumer HDPE flakes to give a contaminated master-batch. The master-batch was
blended with another portion of 50 kg of post-consumer HDPE material and then stored in a sealed steel
container for 7 days at 50 C with periodical agitation. During this time sorption of the chemical compounds into
the contaminated HDPE flakes was achieved. Using this contamination procedure a total of 55 kg contaminated
post-consumer HDPE flakes were produced for each contamination level.
The success of the contamination was verified by measurement of the concentration of the surrogates in the
contaminated input material. The contaminated flakes were fed into the washing process as described above.
Contaminant concentrations were measured either by headspace screening of the contaminated flakes or solvent
extraction followed by gas chromatography. The input surrogate concentrations were in the range 700 to
900 ppm.
The cleaning efficiency of the washing process was determined for each surrogate by comparison of the
concentration in the HDPE samples after treatment with the initial concentration in flakes entering the washing
process (Equation 1).
Eq. 1: 100%
mass surrogate initial
recycling after mass surrogate
1 (batch) efficiency cleaning
=
Unfortunately the analytical uncertainty was very high, especially for the non-volatile compounds. Therefore the
estimated cleaning efficiencies also have a high degree of uncertainty. For this reason two independent analytical
procedures were used for determination of the cleaning efficiencies. However, due to analytical interferences it
was still not possible to estimate the cleaning efficiency of the washing process for some compounds.
42

For example the washed material appeared to contain higher levels of methyl stearate than the input material. It
should be noted that the input contamination levels applied were extremely high in comparison to the
concentrations typically found in post-consumer HDPE flakes (see Chapter 10.3).
Table 8 summarises the results of the washing process challenge test.
Table 8: Washing process challenge test results
Toluene Chlorobenzene Phenyl
cyclohexane
Methyl
stearate
Benzophenone
Initial concentration prior to
washing and super-clean
recycling
722 + 142 917 + 294 852 + 503 739 + 566 884 + 611
Estimated cleaning efficiency
of washing process (measured
by headspace GC)
60.1% 52.1% 8.9% n.d.
[a]
26.3%
Concentration after washing
process (measured by GC after
solvent extraction)
405 + 25 583 + 34 973 + 113 1182 + 321 764 + 109
estimated cleaning efficiency 43.9% 36.4% n.d.
[a]
n.d.
[a]
13.5%
[a]
not determined due to analytical interferences (see text)

43

9 Supercritical CO
2
process for super-
cleaning HDPE
9.1 Background
Both the SOREMA washing process (see Chapter 8) and the EREMA super-clean recycling process (see Chapter 10)
are commercially available processes, which have already been optimised for recycling of HDPE milk bottles. In
contrast, the novel super-cleaning process based on supercritical CO2 that is described in this chapter is less
developed.
It was decided to try to develop a process based on supercritical CO2 extraction because this process route should in
principle offer a lower cost and more efficient method for extracting a wide range of contaminants than the EREMA
process.
CO2 is a low cost extraction material. It can be made to enter the supercritical state relatively easily under typical
extrusion conditions in standard vented extruders. Once in the supercritical state, it becomes a powerful solvent for a
wide range of materials. It can be removed from the extruder by a simple venting process without the need for
expensive vacuum extraction. It can then be recovered and separated from the contaminants that it has extracted,
simply by reducing its pressure after the vent.
The trials and other investigations conducted are summarised in Table 9.
Table 9: Work Packages for Development of the supercritical CO
2
process
Work done Feed material Investigators
Patent review / RAPRA Technology
Literature review of scCO
2
solubility data / RAPRA Technology
Phenyl cyclohexane scCO
2
solubility tests / Birmingham University
Batch contaminant extraction tests using
scCO
2
Virgin HDPE loaded with a mixture of
surrogate compounds
Birmingham University
Initial decontamination trials for HDPE
using scCO
2
extrusion extraction
Virgin HDPE (Rigidex, BP Solvay) loaded
with a mixture of surrogate compounds
RAPRA Technology
Optimisation of decontamination trials for
HDPE using scCO
2
Virgin HDPE (Stamylan HD9650, DSM)
loaded with a mixture of surrogate
compounds
RAPRA Technology
Further decontamination trials using scCO
2
extrusion extraction with PP in place of
HDPE
Virgin PP (BB125MO, Borealis) loaded
with a mixture of surrogate compounds
RAPRA Technology
Decontamination of real HDPE bottle flake
using scCO
2
Post-consumer HDPE bottle flake from
SOREMA washing trials loaded with a
mixture of surrogate compounds
RAPRA Technology

44

Unfortunately it became obvious during the trials conducted for this project that the melt phase supercritical CO2
extraction process is not yet robust enough to allow routine super-cleaning of HDPE.
The results of the trials are still reported in detail in this section because super-cleaning of HDPE using supercritical
CO2 may become a commercially viable alternative to the EREMA process with further process development work.
9.2 Patent review
A detailed review of the patent literature and intellectual property rights (IPR) relating to the use of super-critical
carbon dioxide in extrusion processes was undertaken by Rapra Technology Ltd.
9.3 Solubility data for melt phase super-critical CO2 extraction
In order to confirm the viability of super-critical CO
2
extraction in the melt and to help predict process temperature
and pressure conditions the literature was reviewed for published data on the solubility and/or extraction of different
chemicals from plastics using super-critical carbon dioxide at temperatures up to 145 C.
Data on the ILSI surrogates
[21]
was particularly useful as these cover a range of polar and non-polar chemicals with
differing volatilities and solubility parameters and can act as pointers to the likely behaviour of milk bottle
contaminants. The applied surrogates were:
1,1,1-Trichloroethane (a polar, volatile penetrant)
Benzophenone (polar, non-volatile penetrant)
Toluene and chlorobenzene (non-polar, volatile penetrants)
Phenyl cyclohexane (non-polar, non-volatile penetrant)
Methyl stearate (substitute chemical for organometallic compounds, non-volatile penetrant)
Heptane Solvent for the above
9.3.1 Literature solubility data
Literature solubility data are shown in Figure 11. The reference temperatures shown for each of the chemicals were
the recorded temperatures that were nearest to the likely maximum operating temperature of the process (approx.
145 C).
Only liquid phase data were available for benzophenone. The data presented for this compound were predicted from
the liquid phase data and should be treated with caution.
Solubility data for phenyl cyclohexane could not be found in the literature and were therefore determined
experimentally.
The literature data show that, of the ILSI surrogates, the materials with the lowest solubility in super-critical CO
2

were the polar non-volatile methyl stearate and the non- polar, non-volatile phenyl cyclohexane. A cross-over in their
respective solubilities at approx. 200 bar was suggested from the data.
45

0
0.2
0.4
0.6
0.8
1
1.2
1.4
50 70 90 110 130 150 170 190 210 230 250 270 290
Pressure (bar)
S
o
l
u
b
i
l
i
t
y

(
g

C
o
m
p
o
n
e
n
t
/
g

C
O
2
)
Heptane 121 C Heptane 204.1 C
Toluene 120.5 C Toluene 203.8 C
Methyl Stearate 70 C Trichloroethane 80 C
Benzophenone 50 C Chlorobenzene 80 C
Chlorobenzene 120 C Cyclohexylbenzene at 145 C

Figure 11: Solubility versus pressure [bar] for the compounds heptane
[62]
, toluene
[63]
, chloro-
benzene
[64]
, methyl stearate
[65]
, trichloroethane
[66]
, benzophenone
[67]
The following observations may be made from the published data:
Heptane, toluene, methyl stearate, trichloroethane, benzophenone and chlorobenzene all had some solubility
in CO
2
.
The critical mixture composition had been evaluated at the conditions reported for all the compounds with the
exception of chlorobenzene. This means that an increase in pressure above the highest reported pressure
would result in the component being totally miscible with CO
2
(i.e. the existence of a single phase mixture).
Extrapolating the data for chlorobenzene, the critical mixture pressure limit is approximately 160 bar at 80 C
and 230 bar at 120 C. The latter is closer to the likely maximum operating temperature of the process.
The data reported for methyl stearate, trichloroethane, benzophenone and chlorobenzene were at
temperatures below the desired operating temperature. An increase in temperature will lead to an increase in
the vapour pressure of the components and generally higher solubilities. However, an increase in temperature
at constant pressure leads to a decrease in CO
2
density, which would lead to a decrease in its solvent power
toward the surrogate chemicals. There is always a trade-off between vapour pressure and CO
2
density in a
system. If the pressure is maintained at a high enough level then the decrease in density as a result of
increased temperature will not be significant, and consequently, an increase in temperature will lead to
increased solubility of the surrogate chemical in CO
2
.
Methyl stearate requires the highest pressure to attain miscibility. The maximum temperature from available
literature data was 70 C. Again an increase in temperature will lead to increased solubility providing the CO
2

density is not reduced significantly (see above).
46

From the literature data, operating pressures close to or higher than 200 bar at the blow off stage of the
extruder are proposed to give sufficient CO
2
density (0.337 g cm
-3
at 145 C, 200 bar) for maximum
extraction. (This is significantly higher than the pressures used in the initial extraction trials as discussed
above).
The solubilities reported in the literature were for pure component binary mixtures (i.e. CO
2
+ component).
The apparent solubility of a component in the extrusion process will be affected by the presence of the
polymer and the other surrogate components. The solubilities shown in Figure 11 are unlikely to be attained
in practice as these are reported for systems at equilibrium. The extrusion process is dynamic and the
solubility and hence the extractability of the components will depend on the flow rate of CO
2
through the
process.
When CO
2
is introduced into the feed it plasticizes the polymer. As a result an excess of CO
2
must be used in
order to ensure that contaminant chemicals are accessible and extractable from the polymer matrix.
9.3.2 Phenyl cyclohexane solubility tests
As solubility data for phenyl cyclohexane were not available in the literature they were measured at Birmingham
University at 145 C and pressures of 100 to 300 bar.
Materials: phenyl cyclohexane (98%) was supplied from Sigma-Aldrich UK, and was used without further
purification. Liquid carbon dioxide was obtained from BOC, CP grade, and had a given purity of 99.995%.
Equipment: The apparatus used to determine the high-pressure vapour data is shown in Figure 12. The equilibrium
cell (Parr Instruments, USA) had an internal volume of 25 cm
3
and was fitted with in-line sapphire windows. It was
maintained at 145 C by a pair of thermostatically controlled band heaters. The pressure was recorded using a
transducer (Druck PTX 1400) with dedicated display to within 0.1 bar and the temperature was recorded to within
0.1 C using a Watlow 93 temperature controller and J type thermocouple.

5
Rotameter
P T
P
1
2
3
4
6

Figure 12: Cloud point apparatus
1: Pressure Generator; 2: View Cell; 3: Cold Collector; 4: Stirrer; 5: Flow Totalyser; 6: Camera+Monitor
Procedure: A known mass of phenyl cyclohexane was charged into the cell and the vessel closed.
Liquid carbon dioxide was compressed by the use of a pressure generator (HIP, model 62-6-10) and supplied to the
equilibrium cell. The temperature in the cell was increased to the desired isothermal condition and the pressure rose
until dissolution of the compound occurred and a homogeneous phase existed.
The homogeneous condition was verified by a colour camera directed at the view cell. Dissolution was aided by the
use of an impeller (Rushton turbine) coupled to an external magnetic drive.
Once the compound had been fully dissolved, the pressure was lowered to the onset of the cloud point by altering
the volume of the cell. The pressure and temperature were then recorded.
47

The sample could then be re-dissolved by increasing the pressure and the above procedure was repeated to verify
the cloud point pressure.
The pressures shown in Table 10 are the mean of up to three repeat determinations and the variance was no greater
than +0.8 bar. The volume of CO
2
present in the vessel at the cloud point was determined from the CO
2
density and
the internal volume of the cell. CO
2
densities were taken from NIST.
Table 10 and Figure 13 show the solubility data obtained between nominal pressures of 100 and 300 bar. Due to the
experimental technique used to measure the solubility, the determination of solubility at a particular pressure cannot
be guaranteed (i.e. at 100, 150 or 200 bar etc.). The pressure depended on the amount of solute initially charged in
the cell. The solubility data shown in Table 10 were therefore determined at the resulting cloud point pressures for
the masses of phenyl cyclohexane charged into the pressure cell.
Table 10: Solubility data for phenyl cyclohexane in CO
2

Pressure [bar] Solubility [g solute per g CO
2
]
102.8 0.017
171.7 0.065
223.9 0.139
240.7 0.258
280.3 0.640

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
100 150 200 250 300
P (bar)
S
o
l
u
b
i
l
t
y

g

c
o
m
p
o
n
e
n
t

/

g

C
O
2
145 C

Figure 13: Solubility data for phenyl cyclohexane in CO
2
48

9.4 Batch basis verification of the effect of CO2 pressure on
extraction
Before commencing the extrusion trials batch extraction tests were conducted at Birmingham University to confirm
the literature solubility data in the context of the HDPE extrusion process. Extruded material containing the ILSI
surrogates was extracted using super-critical CO
2
at 145 C and at pressures of approx. 100 (actual 100.4) and 300
(actual 298.6) bar.
Contaminated HDPE material (sample 4) was extruded through the RAPRA extruder without the application of the
addition of CO
2
.
Prior to extraction the HPDE sample was sheared into slivers using a plane type device. Photos of the prepared
samples used for extraction at 100 and 300 bar are shown in Figure 14.

A B
Figure 14: Photographs of prepared HDPE samples prior to extraction, A: Sample for 100 bar, 145 C,
B Sample for 300 bar, 145 C (Note the penny coin was used for scale and applies to both images).
The extraction involved passing a stream of CO
2
continuously through the polymer bed. The experimental set up did
not allow introduction of the high shear that is encountered in the extrusion process. However, the shear
encountered in extrusion will enhance CO
2
mixing and extraction of the surrogates.
Apparatus: A 100 ml stirred pressure vessel with two pairs of in-line sapphire windows (Parr Instrument Co., USA)
was used for the extraction tests. Agitation was only applied during CO
2
extraction. The windows enabled visual and
photographic observation of the HDPE at the process conditions.
The once-through continuous supercritical extraction process involves compressing liquid carbon dioxide in a solvent
delivery section to the process pressure P, which is beyond its critical pressure P
c
(73.78 bar) and then heating this
compressed liquid to the process temperature T, which is beyond its critical temperatureT
c
(31.04 C).
The carbon dioxide, now in a supercritical fluid state, enters the extraction vessel and is contacted with the sample.
After passing through the material bed, the scCO
2
stream containing any extracted compounds leaves the extraction
vessel and is reduced to ambient pressure across a throttling valve. The volatile components that were present in the
stream drop out of solution and the CO
2
is vented to atmosphere.
A schematic of the process is shown in Figure 15.
49

D rying
T u be
P - 1
L iqu id P ump
P

P

B a c k - P re s s ure
R e gu la to r
V e nt
E xtra c to r
P uls e
D a mpe ne r
T
P
T
V - 1
M a s s F lo w
M e te r
T
C O 2

H 1

T
P
H 2
V e nt

Figure 15: Extraction apparatus

Solvent delivery: The solvent delivery section (shown in the highlighted box) was designed to supply CO
2
to the
extraction section at the desired temperature and pressure.
Carbon dioxide (BOC, liquid withdrawal CP grade) was withdrawn from the cylinder at bottle pressure (approx.
50 bar) through a shut off valve, a drying tube, an in-line 15 mm filter (Nupro SS-4TF-Filter), a non-return valve and
a refrigerated heat exchanger, H1, maintained at approximately 5 C by an external refrigeration unit (Grant). This
ensured complete liquefaction of the CO
2
prior to entry into the pneumatically driven liquid compressor pump P-1
(Haskell MCP-71).
The chiller unit was kept as close as possible to the pump and the feed pipe was lagged with insulating material in
order to avoid vaporisation of the liquid CO
2
. The flow rate of CO
2
was maintained slightly above the requirements of
the system by adjusting the stroke rate of the pump and an air regulator valve (Wilkerson CB6-C4-F00).
An adjustable back pressure regulator control valve (BPR), (TESCOM 26-1720-22-099), maintained the desired
system pressure downstream and recycled the excess CO
2
through a recycle loop. This unit was accurate to within
1 bar throughout the pressure range used in these experiments.
After the pump the compressed liquid CO
2
was fed through a non-return valve to H2, a thermostatically controlled
jacket tube heat exchanger containing oil. The temperature of the liquid CO
2
stream was raised to close to the
extraction temperature, where the compressed liquid entered the super-critical fluid state.
A pressure gauge was sited at the entry to the heat exchanger and was coupled to an emergency depressurisation
valve (Whitey SS-83-KS4).
50

The back pressure regulator allowed any CO
2
leaving the pump at a higher pressure than desired to be re-circulated
back into the low pressure feed side of the pump via the re-circulation loop situated after the non-return valve
(Autoclave Engineers, TWO 4400). This valve was included to prevent high pressure CO
2
from returning to the gas
supply line. Adjustment of the back pressure regulator control valve loaded the spring closure thus allowing the
compressed liquid CO
2
into the extraction system. When the liquid pressure in the system reached the pressure limit
on the spring closure it was forced open and the excess re-entered the CO
2
feed line. This arrangement allowed the
pump outlet pressure to be kept independent of the system pressure and CO
2
flow rate.
Extraction: Prior to entering the extraction section, the CO
2
stream first passed through a check valve (Autoclave,
TWO 4400) and a mass flow meter (Rheonik RHE 08).
The stainless steel inlet tube was kept hot by a heating tape to avoid temperature fluctuations. A pair of
thermostatically controlled band heaters heated the pressure vessel. A thermocouple probe connected to a digital
readout was mounted in the solvent stream at the point of entry to the vessel. A further two thermocouples were
situated in a port near the top of the pressure vessel and in the stream exiting the vessel.
System pressure was monitored by a pressure transducer (Druck, PTX-521-00 0-700 bar) that was coupled to a
digital readout (Druck DEI 260).
Weighed quantities of the pre-treated polymer sample were charged into a glass sample holder, which was used to
retain the polymer in the vessel. The extractor was raised to the desired pressure and temperature and held for
30 min to equilibrate the system. An inlet tube directed the CO
2
stream into the polymer sample and mass transfer of
the components into the CO
2
occurred as the stream passed through the polymer bed. The stream left exited the
base of the vessel, taking with it any solubilised surrogate chemicals.
Solute/ solvent separation: Separation was achieved by pressure reduction directly to ambient conditions. This
resulted in the deposition of the surrogate chemicals from the compressed gas stream.
The solute -laden solvent stream exited the pressure vessel and passed through a heated micro-metering valve
(Hoke, 1335 G4Y). No extracted components were precipitated in the metering valve.
The CO
2
stream was then directed to an external vent. A two-stage decompression was not necessary and there was
no significant blocking of the vent valve due to the high process temperature. Any potential blockages were
prevented by the use of a heat gun (Bosch PHG).
The flow of CO
2
through the system was observed using an on-line mass flow meter. The CO
2
flow was continually
monitored and adjusted by the micro-metering valve to give a stable carbon dioxide flow rate. Further adjustments
were made in order to maintain the temperature, pressure and flow rate constant as the extraction process
proceeded for a duration of two hours. At 10 min intervals the mass flow of carbon dioxide, temperature and
pressure were recorded. When the test finished, first the pressure and then the temperature were brought back to
ambient conditions.
The mean mass flow rate was determined from the mass of carbon dioxide used and the duration of the extraction.
A mean flow of 4.7 g min
-1
was measured for the extraction at 100 bar and 3.8 g min
-1
at 300 bar.
Once conditions had returned to ambient, the extraction vessel was opened and the polymer was removed from the
sample holder, cut and placed in sample bottles.
During the extraction, photographs were taken of the polymer at the process conditions. Figure 16 A and B shows
the polymer at 145 C, 100 and 300 bar, respectively. The polymer can be seen in the top half of the window. The
base of the glass sample holder can be seen in the bottom half. The window diameter is 15 mm.
It can be seen that the polymer became translucent during the test, presumably as it was plasticized by the CO
2
.
In comparison, Figure 17 A and B shows the system at 60 bar and 145 C (at this condition the polymer has opacity)
and at 200 bar in a preliminary extraction study. In Figure 17 A it appears that the polymer was less translucent. This
was due to the modification of the CO
2
contactor, which blocked the light source. The contactor tube can be just
made out in the photograph.
51

A B
Figure 16: Photographs of HDPE extraction at process conditions, A at 100 bar, 145C; B at 300 bar,
145C
As a comparison, Figure 17 shows the system at 60 bar and 145C (at this condition the polymer was opaque) and at
200 bar in a preliminary extraction study. In Figure 17A it appears that the polymer was less translucent. This was
due to the modification of the CO
2
contactor, which blocked the light source. The contactor tube can be just made
out in the photograph.

A B
Figure 17: Photographs of HDPE at process conditions, A: at 60 bar, 145 C, B at 200 bar, 145 C
Analysis of samples: One gram portions of the samples (approx. 2 mm
3
) and non-extracted control material were
allowed to stand in sealed 22 ml headspace vials with 5 ml of dichloromethane. The vials were sealed with PTFE lined
septa and cap and stored at 40 C for 6 d (144 h).
The resulting solutions were then examined by GC-FID together with standard mixed solutions of the surrogates of
known concentration. The results are given in Table 11. The increased extraction of the non-volatile surrogates at
300 bar is in line with the theoretical predictions.
52

Table 11: Amounts of surrogate chemicals in flake samples (batch process)
Sample ID Concentration surrogates [g g
-1
] (reduction due to CO
2
)
Trichloroethane Heptane Toluene Chlorobenzene Phenyl
cyclohexane
Benzophenon
e
Methyl
stearate
Sample 4
100 bar CO
2
<5 (>84%) <1 (>99.6%) <1 (>90%) <1 (>50%) 19 (68%) 44 (10%) 82
[a]
Sample 4
300 bar CO
2
<5 (>84%) <1 (>99.6%) <1 (>90%) <1 (>50%) 0.6 (99%) 1.5 (97%) 3 (96%)
Control without
CO
2
32 238 10 2 60 49 67
[a]
The higher level of the polar methyl stearate measured in the 100 bar extract compared to the control sample is
assumed to be due to a non-uniform level of material contamination.
The molecular weight distributions of these samples, in particular the amount of residual material of molecular
weight lower than 1000, was examined by gel permeation chromatography using the same experimental protocol as
reported above.
The refractive index and differential pressure traces below (Figure 18 and Figure 19) show overlays of the computed
molecular weight distributions for duplicate runs of the three materials. The plots were all normalised with respect to
area, the y-axis being a function of weight fraction.
Note that the differential pressure chromatogram was reversed with respect to the molecular weight distribution.
High molecular weight material was observed at low retention volume so appears on the left of the chromatograms
but the right hand side of the molecular weight distributions.
Also the chromatograms were normalised with respect to maximum height. No effect on the shape of the distribution
for the bulk of the HDPE resulting from the super-critical CO
2
extraction was apparent from these traces.
An expanded "y" axis molecular weight distribution plot for duplicate runs of the three samples looking at the low
molecular weight material is shown in Figure 20.
The amount of low molecular weight material (<1000 g mol
-1
) is in the range 0.2% to 0.3%.
These results show a small loss of low molecular weight HDPE material, particularly with the 300 bar CO
2
extraction
pressure. It is likely (but not proven) that such a small loss of low molecular weight HDPE will have no significant
effect on the processing characteristics of the treated material.
53

Molecular Weight Distribution
Sample1
Sample4
100 bar
Sample4
300 bar
2.00 3.00 4.00 5.00 6.00 7.00
0.00
0.20
0.40
0.60
0.80
1.00
Log M
W
n
(
l
o
g
M
)

Rapra Technology Limited

Figure 18: Molecular weight distributions of CO2 treated samples versus untreated reference sample

Differential Pressure Chromatograms
Sample1
Sample4
100 bar
Sample4
300 bar
8.0 10.0 12.0 14.0 16.0
0
20
40
60
80
100
120
Retention Volume
R
e
l
a
t
i
v
e

R
e
s
p
o
n
s
e


Figure 19: Differential Pressure Chromatograms of CO2 treated samples versus untreated reference
sample
54

Sample 1
Sample 4
100 bar
Sample 4
300 bar
2.00 3.00 4.00 5.00 6.00 7.00
0.00
0.20
0.40
0.60
0.80
1.00
Log M
W
n
(
l
o
g
M
)

x
1
0
-
1


Figure 20: Molecular weight distributions of CO2 treated samples versus untreated reference sample
(detail from Figure 19)
9.5 Initial supercritical CO2 extrusion extraction trials to
decontaminate HDPE
Initial processing trials were undertaken using a vented, 50 mm single screw extruder at RAPRA.
The extruder screw had a L/D ratio of 34:1 and it was possible to inject super critical carbon dioxide at various barrel
points upstream of the vented section.
Extrusion conditions were manipulated to ensure that the carbon dioxide was introduced into the process in the
super-critical region (T = 31 C: P = 73 bar). Initial trials were performed on a virgin HDPE material (Rigidex; BP
Solvay) to establish appropriate conditions.
Extraction studies were performed at various scCO
2
addition levels. From the results of these studies and from a
theoretical assessment, subsequent work concentrated on refining the design of the extraction system.
It is suspected that the volatile stream exiting the extruder should to be kept at the super critical condition to
maximise the efficiency of the extraction process. Work was undertaken to understand how these modifications could
be implemented in practice.
Contaminated test material was first prepared by soaking 6 kg of virgin HDPE pellets (Rigidex BP Solvay received
from Nampak) for 1 week at 40 C with a solution of the following chemical surrogates in heptane:
2% methyl stearate
2% trichloroethane
2% benzophenone
10% toluene
2% chlorobenzene
2% phenyl cyclohexane
55

The heptane solution was then decanted and the granules dried in aluminium trays in the opening to a fume
cupboard for approximately 72 h. The resulting granules were further dried in the open laboratory and subsequently
mixed 20:1 with additional virgin material to obtain approximately 120 kg of contaminated material for trials.
Following installation, the extruder was run at various speed and temperature settings to determine those settings
that would allow the injection of CO
2
in the super critical phase. Out of these, four sets of settings were selected for
detailed analytical evaluation.
For every set, the contaminated material was first run without introduction of carbon dioxide and then with low,
moderate and high flows of supercritical CO
2
. Samples from each run (strips of extruded material 30 mm wide x
3 mm thick) were retained for analysis. Details of all zone temperatures, pressures, screw speeds, motor currents,
output rates and pump settings were recorded.
Comparative analysis of levels of residual contaminants in strips extruded with and without the super critical CO
2
was
undertaken using headspace gas chromatography and dichloromethane extraction gas chromatography. The low
volatility surrogates could not be measured using the headspace approach. The molecular weight distribution of
material extruded with and without the CO
2
extraction (Samples 2 and 4) was compared using gel permeation
chromatography. Of particular interest was the effect of the CO
2
on the amount of material of molecular weight less
than 1000.
Extraction results obtained are provided in Table 12. (Similar data was obtained for the volatile species using
headspace gas chromatography.)
Of the four settings examined in detail, three conditions generally gave significant reductions in surrogate
concentrations in excess of those losses associated with processing. Some variations in the concentration of the
absorbed surrogates in the feedstock were apparent. As expected, a greater loss of the volatile surrogates was
observed with the CO
2
.
56

Table 12: Amounts of surrogate chemicals in original granules, control samples and 2160 cm
3
h
-1
of CO
2
samples as determined by dichloromethane
extraction (four specific process conditions)
Sample ID Concentration surrogates [g g
-1
] (reduction due to CO
2
)
Trichloroethane Heptane Toluene Chlorobenzene Phenyl cyclohexane Benzophenone Methyl stearate
Sample 1 - Control without CO
2
21 265 20 8 82 60 100
Sample 1 - with CO
2
19 197 18 9 100 93 105
2
33 392 38 15 116 74 135
Sample 2 - with CO
2
18 (46%) 177 (55%) 13 (66%) 5 (67%) 88 (24%) 53 (28%) 92 (32%)
2
37 382 34 13 115 75 164
Sample 3 - with CO
2
16 (57%) 200 (48%) 18 (47%) 8 (39%) 102 (11%) 70 (7%) 113 (31%)
2
33 425 39 17 130 100 112
Sample 4 - with CO
2
16 (52%) 205 (52%) 19 (51%) 10 (41%) 106 (19%) 76 (24%) 114 (0%)
Original Granules 1
[a]
55 864 127 48 114 123 60
[b]
Original Granules 2 57 905 132 51 120 119 59
[b]
[a]
corrected for 1/19 dilution with virgin HDPE,
[b]
Extraction variables?

57

For Samples 2 and 4 molecular weight distributions were measured in addition to the contaminant analysis. The
results are presented in Table 13.
No significant changes in distribution were observed.
Table 13: Molecular weight distributions
Sample M
w
M
n
Polydispersity Peak area <1000
dalton
Sample 2 with CO
2
104,000
104,000
19,300
19,200
5.4
5.4
0.27%
0.27%
Sample 2 no CO
2
104,000
105,000
19,800
19,200
5.3
5.5
0.23%
0.25%
Sample 4 with CO
2
104,000
103,000
18,400
18,200
5.7
5.6
0.27%
0.30%
Sample 4 no CO
2
104,000
103,000
18,600
18,300
5.6
5.7
0.24%
0.25%

Figure 21 shows an overlay of the computed molecular weight distributions for duplicate runs of the four samples.
The plots are all normalised with respect to area, the y-axis being a function of weight fraction. The minor
differences in proportion of sample with molecular weights less than 1000 are not considered to be significant and
this is confirmed by the overlay plot (Figure 22).
Sample2
2160cc/hr with CO2
Sample2
No CO2
Sample4
2160cc/hr with CO2
Sample4
No CO2
2.00 3.00 4.00 5.00 6.00 7.00
0.00
0.20
0.40
0.60
0.80
1.00
Log M
W
n
(
l
o
g
M
)

Figure 21: Molecular weight distributions for duplicate runs of the four samples
Development of a Food Grade HDPE Recycling Process

58

Sample 2
2160 cc/hr CO2
Sample 2
No CO2
Sample 4
2160 cc/hr CO2
Sample 4
No CO2
2.00 3.00 4.00 5.00 6.00 7.00
0.00
0.25
0.50
0.75
1.00
Log M
-1
W
n
(
l
o
g
M
)

x
1
0
-
1

Rapra Technology

Figure 22: Molecular weight distributions for duplicate runs of the four samples (detail from Figure 21)
In conclusion, initial studies of the possible use of super-critical CO
2
for extraction of model contaminant compounds
from HDPE established that a reduction in concentration of a range of surrogate chemicals can be achieved. These
reductions are greater than those achieved by melt processing alone.
Under the conditions investigated, no detectable change was measured in the molecular weight distribution of
material extruded with super-critical CO
2
.
The maximum observed reductions in surrogate concentrations compared to material extruded without CO
2
, are
presented in Table 14.
Table 14: Average observed reductions (from Table 12) in surrogate concentrations compared to
material extruded without CO
2
and cleaning efficiencies in comparison to the input concentrations
Surrogate Input concentration
[ppm]
Reduction during
extrusion due to CO
2
Overall cleaning efficiency
Trichloroethane 56 50% 69.6%
Heptane 885 51% 78.1%
Toluene 130 54% 86.9%
Chlorobenzene 50 47% 84.0%
Phenyl cyclohexane 117 11.6% 15.4%
Benzophenone 121 20.5% 45.5%
Methyl stearate 60 n.d.
[a]
n.d.
[a]
[a]
not determined due to analytical interferences
A theoretical assessment of the solubility and extractability of a range of chemicals (the ILSI proposed contaminant
surrogates listed above) indicated that much higher levels of extraction should be possible if higher CO
2
pressures
are used and the CO
2
is kept in the super-critical state until well after venting from the extruder. Modifications were
made to the single screw extruder to investigate this.

59

9.6 Optimisation of HDPE decontamination with supercritical CO
2

Whilst the initial work used Rigidex HD6007 XA HDPE material from BP Solvay, the work in this part of the project
was undertaken on a different HDPE product, Stamylan HD9650 from DSM. These trials were also conducted at
RAPRA.
Processing the Stamylan material proved difficult, the main problem being the propensity for vent flow. The material
was prone to flow up, and freeze off in the vent port of the extruder. The Stamylan material appeared more prone to
vent flow than the Rigidex material trialled earlier.
Considerable effort was directed at solving this problem through temperature profile manipulation, but ultimately it
became necessary to run the extruder in a starve fed configuration. Feed material was metered into the throat of the
extruder via a separate volumetric feeder, in this case a Brabender Flexi Wall 33 unit.
In a vented extruder the flow across the metering zones before and after the vent must be balanced to prevent
accumulation in the vent area. The origin of the vent flow problem is unclear but it is likely that the problem is
associated with incomplete melting of the material in the compression zone of the screw. The extruder screw used
was probably incapable of dealing with high viscosity HDPE melts.
Material for these trials was contaminated according to the Fraunhofer protocol (see Chapter 8.2). The procedure
was scaled such that a 25 l steel drum could be filled with 12.1 kg of contaminated feedstock. This allowed sufficient
free space for mixing the contents during drum rolling.
Three extraction trials were run:
(i) without super-critical CO
2
,
(ii) with super-critical CO
2
and atmospheric (non-pressurised) venting
(iii) with super-critical CO
2
and pressurised venting.

The results are given in Table 15.
Even in the absence of CO
2
the level of contaminant fell when the material was processed through the vented
extruder, presumably as a result of heat and shear imparted by the process. Surprisingly, the effect was most
pronounced for the non-volatile species methyl stearate and benzophenone.
Injecting super-critical CO
2
to the extruder, with atmospheric extraction from the vent, promoted an increase in the
extraction of the toluene and chlorobenzene species. These species are the most soluble in super-critical CO
2
whilst
phenyl cyclohexane and methyl stearate are the least soluble. The latter two show the least response to super-critical
CO
2,
which may not be surprising.
The situation with pressurised extraction was more complex. The benefits anticipated were not observed. There was
a decline in extraction level for all the species with the exception of benzophenone.
The melt extrudate from the pressurised extraction trial was heavily foamed, indicating the presence of dissolved
carbon dioxide in the polymer. It is possible that the contaminants were carried through the process dissolved in the
gas and therefore remained in the product at higher levels than expected.


60

Table 15: Results of the decontamination trials with Stamylan HD9650
Sample ID Concentration surrogates [ppm] (overall cleaning efficiency due to CO
2
)
Toluene Chlorobenzene Phenyl cyclohexane Benzophenone Methyl stearate
Input Concentration 458 613 702 800 815
Extraction in absence of super-critical CO2 384
(16.2%)
522
(14.8%)
652
(7.1%)
495
(38.1%)
632
(22.5%)
Extraction in the presence of super-critical CO2 with atmospheric (non
pressurised) venting
198
(56.8%)
295
(51.9%)
571
(18.7%)
571
(28.6%)
661
(18.9%)
Extraction in the presence of super-critical CO2 with pressurised venting 280
(38.9%)
403
(34.3%)
638
(9.1%)
683
(14.6%)
638
(21.7%)

61

9.7 Processing trials to optimise PP decontamination
Initial trials (Section 9.5 and Section 9.6) concentrated on establishing the optimum conditions necessary to
process HDPE resins. The aim was to establish a set of robust processing conditions under which it was likely that
the CO
2
would maintain supercritical conditions (31 C and 73.1 bar) in the injection and mixing zones.
Because of problems with extruding HDPE on the RAPRA extruder it was subsequently decided to investigate the
extraction process on a polypropylene (PP) material, using the same contamination procedure. Polypropylene
would be easier to handle in the RAPRA extruder but should behave in a similar way to HDPE from a
contamination extraction point of view. The polypropylene extraction trials were performed using a Borealis
BB125MO copolymer resin.
The RAPRA extrusion system was modified to allow the extraction system to operate at supercritical pressures.
This required the manufacture of a robust, certified, extraction housing which would be coupled to a down
stream take-off system and which would allow pressure to be controlled and the contaminated species to be
precipitated separately from the extrusion process.
The RAPRA trial rig used a 50 mm Bone Cravens Single screw extruder. The extruder screw had an L/D ratio of
34:1. The venting zone was located some 23D from the front of the feed zone.
The screw was derived from a 120 mm Falzoni extruder system, designed primarily for the recycling of soft PP
scrap, where the vent was necessary for removal of volatiles. The overall compression ratio of the screw is 2.8:1.
To aid mixing of the super-critical CO
2
the screw design incorporated two rows of mixing pins 2D downstream of
the vent zone. The barrel of the extruder was tapped at several positions along its length to accommodate
pressure transducers and poppet valve injectors for super-critical CO
2
addition.
Gas was introduced into the process at a location 16D from the front of the feed zone, i.e. 7D upstream of the
vent port.
A three strand-pelletising die was fitted to the extruder head and the output was cooled in a water bath prior to
pelletisation.
A take-off pot was connected to the extruder vent zone by four M16 bolts. The pot was fitted with a flanged lid,
which was secured by means of a "C" clamp arrangement. The take-off pot was fitted with both a calibrated
pressure gauge and a pressure relief valve (100-150 bar range). Prior to use the apparatus was pressure tested
and certified to 200 bar.
A flow diagram of the down stream extraction process after the extruder vent port is shown in Figure 23.
The volatile stream is directed from the extruder vent port along "Swagelock" tubing, to a knock-out vessel
PV1. Valve V2 controls the flow rate in the system, whilst the regulating valve V3 allows the pressure within this
vessel to be safely lowered to below supercritical pressures, typically around 10 bar.
Under these conditions volatiles should come out of the gas phase so they can be collected in the knock out
vessel PV1.
The CO
2
stream can exit the equipment by two routes. Route one passes the CO
2
stream through a hydrocarbon
trap and then to atmosphere. The second route vents the CO
2
direct to atmosphere.
Carbon dioxide was drawn from a liquid take-off cylinder and pumped into the process via a "Williams piston
pump" (model P250V250). The inlet of the pump was sub-cooled by attaching to a manifold block through which
a refrigerant solution at ca. 4 C was circulated. Sub-cooling was necessary to prevent the CO
2
vaporising within
the pump body. Pump output was controlled by the variables of piston stroke length and the stroke speed.
A poppet valve injector, flush fitting with the extruder barrel, was used to introduce the gas into the melt.

62

The carbon dioxide flow rate was measured by a Rheonik RHM015 mass flow meter situated in-line after the
pumps. The device operates by the Coreolis principle and is capable of detecting flow rates in the range of 0.002-
0.04 kg min
-1
. The mass flow meter was calibrated prior to experimentation.
to ambient
P
RV1
V1
from extruder blow-
off port
V2 V3
V4
V5
PV1
AT
V6
drain
to ambient

Figure 23: Flow diagram of the downstream extraction process after the extruder vent port
In order to measure the cleaning efficiencyof the process the material was contaminated according to the
Fraunhofer protocol in a similar manner to the HDPE resin in the previous trials.
An experimental plan was drawn up to explore the relationship between super-critical CO
2
flow rate, extruder
output rate (screw speed) and extraction process (atmospheric pressure, vacuum and pressurised). This would
give an insight on the effect that residence time and shear rate would have on the process; both factors having
an influence on mass transfer and diffusion. The results of the decontamination trials are given in Table 16.
In the trials without super-critical CO
2
, best extraction was achieved using high screw speed and vacuum. As
expected there was a decline in extraction with decreasing species volatility. Toluene offers the best result (39%
removal) whilst benzophenone the least (14% removal). Methyl stearate did not seem to respond to any form of
extraction. Indeed in most situations the concentration recorded in the extracted species was greater than the
control.
In the trials using super-critical CO
2
two trends were evident. The volatile substances (toluene and
chlorobenzene) with greatest solubility in super-critical CO
2
achieved the best extraction response when they
were subjected to pressurised extraction (Runs 25/26; 31/32; 29/30; and 27/28).
The last run gave the best results for the more volatile species. In this case the material was simultaneously
subjected to high levels of super-critical CO
2
and a low throughput rate (long residence time). In this situation
70% of the toluene was extracted and 62% of the chlorobenzene.
For the non-volatile species (phenyl cyclohexane, benzophenone, and methyl stearate) the situation was
reversed. In this instance pressurised extraction offered, on the whole, inferior extraction, when compared to
atmospheric or vacuum venting. Phenyl cyclohexane and methyl stearate had the least solubility in CO
2
. It is
likely that the poor uptake of the species in the CO
2
limits extraction under pressure and these less volatile
species are carried through to the outlet of the extruder.

63

Table 16: Results of the decontamination on Borealis BB125MO (best trial highlighted)
Contaminating level (ppm) Sample CO2
rate
[a]

Output
rate [b]
%CO
2
Extraction
mode
Toluene Chlorobenzene Phenyl cyclohexane Benzophenone Methyl stearate
Input - - - - 158 190 174 166 131
1/2 0 Low - Atmospheric 129 3 160 2 159 1 164 1 169 2
7/8 0 Low - Vacuum 115 10 144 13 137 1 147 3 166 1
3/4 0 High - Atmospheric 126 1 158 1 147 1 152 1 164 6
5/6 0 High - Vacuum 97 4 123 4 132 4 142 3 163 3
15/16 Low Low 30.6 Atmospheric 964 124 2 131 1 134 1 150 5
23/24 Low Low 20.1 Vacuum 90 0 116 1 131 1 138 2 155 1
25/26 Low Low 22.4 Pressurised 58 2 86 2 152 10 166 12 168 4
13/14 Low High 30.1 Atmospheric 67 2 91 2 123 1 132 1 155 2
21/22 Low High 16.8 Vacuum 72 1 96 3 129 1 137 3 147 1
31/32 Low High 15.8 Pressurised 62 2 89 3 130 4 139 3 155 3
9/10 High Low 47.7 Atmospheric 75 6 95 7 99 6 112 4 141 4
17/18 High Low 37.6 Vacuum 80 1 103 2 113 3 123 4 146 2
27/28 High Low 29.2 Pressurised 48 1 73 2 146 3 161 5 167 1
11/12 High High 29.2 Atmospheric 66 5 88 6 113 2 126 4 151 3
19/20 High High 24.3 Vacuum 65 5 88 6 118 5 128 8 145 1
29/30 High High 19.8 Pressurised 57 1 83 1 145 8 160 13 159 12
[a]
high CO
2
addition rate: approx. 4.8 kg h
-1
, low approx. 2.7 kg h
-1
,
[b]
high screw speed: 60rpm (approx. 17.5 kg h
-1
), low 35 rpm (approx. 12.8 kg h
-1
)

64

9.8 Decontamination of post-consumer HDPE flakes
The flake extraction trials were performed on sorted, recycled HDPE milk bottle flakes, which had previously gone
through the SOREMA washing process.
The material was contaminated according the Fraunhofer contamination procedure (see Chapter 8.2).
The equipment arrangement was similar to that used for the polypropylene extraction (see above). The material
proved difficult to process, and as with the Stamylan virgin grade, was prone to vent flow and erratic output
rates. Because of the lack of reliability, it was decided to run the trial at a constant output rate of 50 rpm and
vary the CO
2
addition rate between two levels, in combination with the three extraction routes: atmospheric,
vacuum and pressurised.
As with the earlier Stamylan HDPE trial it is clear that the process was not optimised for HDPE extrusion. The
erratic extrusion output rate and the attendant effects on shear rate, residence time and CO
2
addition rate made
the results difficult to interpret with any degree of confidence.
There is a lot of variability in the data, particularly for pressurised extraction, which gave the least reliable
process operation.
For the trial runs without CO
2
extraction, the best extraction yields (approx. 20%) were obtained for the volatile
species (toluene and chlorobenzene). As expected the non volatile species responded less favourably.
Extracting with super-critical CO
2
improved the situation for all species but the variability of the results provided a
less clear correlation between the benefits offered by the two alternative CO
2
extraction routes.
Both the vacuum venting and pressurised extraction routes gave similar results. Approximately 60% of toluene
and chlorobenzene were extracted by runs 11/12. This was the best result, and was achieved with vacuum
venting.
The best extraction results for phenyl cyclohexane (37%), benzophenone (29%) and methyl stearate (16%) were
all achieved under conditions of pressurised extraction in runs 13/14.


65

Table 17: Results of the decontamination of post-consumer HDPE flakes (best trial highlighted)
Contaminating level [ppm] Sample CO
2
rate

Output
rate
[g min
-1
]
%CO
2
Extraction
mode
cyclohexane
Benzophenone Methyl stearate
Input - - - -
123 5 165 9 143 6 152 8 134 5
1/2
0 279 - Atmospheric. 108 5 139 7 136 3 150 1 128 6
3/4 0 275 - Vacuum 99 1 130 2 132 5 147 4 115 10
5/6 NR (80%) 218 NR Atmospheric. 68 4 94 4 132 1 148 4 127 4
11/12 68 (80%) 136 50 Vacuum 47 0 67 1 119 2 139 3 116 1
13/14 60 (80%) 191 48 Pressurised 53 13 77 14 90 8 108 10 112 13
7/8 84 (100%) 188 45 Atmospheric. 57 3 80 5 125 6 142 6 119 5
9/10 96 (100%) 205 47 Vacuum 62 5 86 6 138 6 158 8 143 10
15/16/17 95 (100%) 143 66 Pressurised 51 7 73 10 110 8 136 14 127 20


66

9.9 Conclusions
The results of this Chapter show, that the supercritical CO
2
extraction process developed during this project was
able to remove contaminants.
Whilst trials with both PP and HDPE resulted in species extraction, PP was more successful, principally because the
extrusion process was more reliable.
In the case of HDPE further work should be focused on the reproducibility of the decontamination results and
reliability of the process in general.
It is likely that provision of a better melt seal in the process would allow for greater pressures to be developed,
thus improving the extraction of the non volatile species by the pressurised route.
However as the earlier theoretical work showed, the pressures required to significantly improve the CO
2
solubility of
species such as methyl stearate are well beyond the super-critical point.
It will be difficult to establish a reliable melt seal - on either a twin or single screw extruder - without recourse to
an isolating device such as a melt pump.
Of course it is still unclear if the high pressures necessary for more complete extraction would themselves cause
issues with vent flow.
The extraction of polar components such as methyl stearate, which show limited interaction with CO
2
, could
probably be enhanced by the use of a suitable co-solvent acting as a polar modifier. Such species could include
methanol, ethanol or water and the modifier could be introduced into the process in combination with the CO
2

stream. If high pressures prove unattainable, then this may become a viable route for improving the extraction
performance of the process. However adding other co-solvents could complicate the solvent recovery part of the
process.
The interesting feature of the process is that extraction of the volatile and non-volatile species are promoted by
different regimes. The former respond to pressurised extraction with super-critical CO
2,
while the latter seemed to
be hindered by this approach. The reason probably lies in the limited solubility of the species in carbon dioxide at
the pressures encountered (30-50 bar, see Figure 11).
Another important point is the scaling up of the decontamination process. One has to bear in mind that ability to
form an effective seal will vary with output rate and as such will also have an effect on scale up and economics.
Twin-screw extrusion invariably offers better mixing than a single screw process and hence the mass transfer of
the system would be improved. If one accepts that a melt pump is necessary for a single screw process, then it can
be safely assumed that it would be required for a twin-screw process, whose pressure generating capacity is
reduced in comparison. The modular nature of a twin-screw extruder, equipped with a melt pump does potentially
offer a greater applicability to the process than a single screw extruder.
In conclusion the results show that, in principle, the removal of post-consumer contaminants from HDPE is possible
with a relatively simple, single step process and with a relatively short residence time.
However, the super-critical process investigated in this study was not sufficiently reliable for use as a commercial
recycling process. Further investigations are necessary to make the process suitable for recycling applications.
Development of food grade HDPE recycling process 67

10 EREMA super-clean recycling
process
10.1 Description of EREMA process for post-consumer HDPE Flakes
The EREMA super-clean recycling process consists of two main process steps:
pre-decontamination, where washed flakes are subjected to temperatures of about 90 C and a vacuum
of about 3-5 mbar (residence time about 30 min)
decontamination, where the flakes are heated to about 120 C with a vacuum of about 1-2 mbar
(residence time about 45 min)
The decontamination step is followed immediately in the same unit by extrusion and melt filtration, where the
material is re-extruded with degassing at 220-230 C followed by melt filtration.
Both the SOREMA washing system and the EREMA super-clean recycling process are continuous operations. If
these two processes are combined with downstream equipment for blending with virgin polymer and then
production of bottles they can, in principle, be used for inline recycling of post-consumer HDPE bottles straight back
into bottles.
In this study the EREMA super-clean process for HDPE flake was investigated at a throughput of 200-300 kg h
-1
.
The two step system described above was tested and also a single step system where the pre-decontamination
step was eliminated.
The single step process was tried as a comparison to test the importance of the pre-decontamination step. If the
pre-decontamination step could be eliminated it would reduce the capital and operating cost of the process.
Flow diagrams for the single-step and two-step systems are shown in Figure 24 and Figure 25.
The process operating conditions used in this study are given in Table 18.

Vacuum cutter
Rotating tools
Extruder
Double venting Screen changer
compactor/ drier
Extruder intake
conveyor screw
Vacuum slider

Figure 24: Process flow for the EREMA process for super-clean decontamination (one-step process)
3
Rotating tools
VACUREMA RGA T - VS

Crystallisation Drier KT
Vacuum pr e -
dryer

Rotati ng
t ools

Extruder

Screen changer

Conveying screw

Figure 25: Process flow for the EREMA process for super-clean decontamination (two-step process)

Table 18: Process parameters of the EREMA process used in this study for decontamination of post-
consumer HDPE
Machine parameter Normal operation
"one-step" (without
artificial
contamination)
Normal operation
"two-step" (without
artificial
contamination)
Challenge Test "one-
Step" (with artificial
contamination)
Challenge Test "two-
Step" (with artificial
contamination)
Temperature KT [C] / 87 / 85
Vacuum KT [mbar] / 3 - 6 / 3 - 5
Temperature reactor
[C]
130 120 120 120 125
Vacuum reactor
[mbar]
0 - 3 1 - 2 0 - 2 0 - 3
Speed extruder [rpm] 160 140 160 160
Output [kg hr
-1
] 300 280 200 - 210 200
Melt temperature [C] 255 226 251 249 252
Melt pressure [bar] 115 123 (123 151) 101 (85 130) 112 (82 128)
Screen [mesh] 150 150 150 150
Backflushing interval
[min]
/ 20 / /


10.2 Challenge test of the EREMA process
The cleaning efficiency of the EREMA recycling process was measured by a challenge test.
The tests were carried out by purposely introducing 55 kg of contaminated post-consumer HDPE flake into the
recycling process as a single slug of material.
The contamination procedure is described in Chapter 8.2. This contaminated material was introduced into the
super-clean recycling process without a washing step.
The process was challenged by introducing highly contaminated HDPE material as the full process feed over a
period of about 15 min (55 kg of contaminated material added continuously at the full plant throughput of about
200 kg h
-1
).
The contamination procedure used represents a worst-case scenario in terms of both the amount of chemicals
introduced and the contamination time. As a comparison, a single contaminated milk bottle will pass through the
process in seconds.
Note that residence time, which is one of the major factors influencing the cleaning efficiency of the process, is the
same if the process is running with contaminated material or not.
Because the process operates continuously, the cleaning efficiency had to be evaluated by taking timed samples.
Therefore samples were drawn at regular periods through each trial. These samples were analysed for their
residual contamination levels. The purification effect of the two processing steps was evaluated individually for
each surrogate.
The EREMA super-clean recycling process can be operated in two modes:
(i) the discontinuous option where the extruded pellets are filled into big bags for re-use later to make
bottles
(ii) the inline option where the recyclate is used immediately to make new HDPE bottles.
The cleaning efficiency of the super-clean recycling process in discontinuous mode was calculated using Equation 1
(Section 8.2).
The initial mass of surrogate compounds entering the recycling process was calculated using Equation 2:
Eq. 2: ion concentrat input ed contaminat mass surrogate initial = HDPE of mass total
Table 19: I nitial surrogate concentrations in the contaminated material and cleaning efficiency after
each recycling step
Concentration of surrogates in the contaminated input material and
cleaning efficiencies compared to initial concentration
cyclohexane
Methyl
stearate
Benzophenone
Initial concentration for washing and super-
clean recycling [ppm]
722 + 142 917 + 294 852 + 503 739 + 566 884 + 611
Super-clean process (1-step) 99.2% 99.1% 78.2% 33.7% 11.2%
Super-clean process (2-step) 99.8% 99.8% 94.5% 75.6% 38.1%
Washing and super-clean recycling (1-step) 99.7% 99.6% 71.0% >33.7% 34.5%
Washing and super-clean recycling (2-step) 99.9% 99.9% 95.0% >75.6% 54.3%

Cleaning efficiencies of more than 99% were measured for the highly volatile compounds such as toluene and
chlorobenzene. Cleaning efficiencies were found to decrease with increasing molecular weight of the surrogates,
due to their lower vapour pressure.
In the two-step process cleaning efficiencies of 93%, 76% and 38% were measured for phenyl cyclohexane,
methyl stearate and benzophenone, respectively.
Note that these trials were conducted without washing the HDPE flake before super-clean recycling. The initial
concentration of each surrogate in the feed material was in the range 700 ppm to 900 ppm.
In practice a washing step such as the SOREMA process described in Section 8 would normally be used to clean the
flake before the super clean recycling process. This would increase the cleaning efficiency of the overall recycling
process significantly, especially for the less volatile compounds.
The concentration/time relationships for the surrogates in Figure 26 show that the highest surrogate concentrations
in the output material from the EREMA unit were measured between 30 and 60 min after first addition of the
contaminated material.
0
10
20
30
40
50
60
70
80
90
0 50 100 150 200 250 300
time [min]
c
o
n
c
e
n
t
r
a
t
i
o
n

[
p
p
m
]
toluene
chlorobenzene
phenyl cyclohexane
benzophenone
methyl stearate

Figure 26: Concentrations in the output material from the EREMA two-step recycling process plotted
against time after contamination (analysis of solvent extracts from the HDPE material)
For the most challenging surrogates (methyl stearate and benzophenone) concentrations of about 80 ppm were
measured when 55 kg of homogeneously contaminated material at a concentration of 700 ppm to 900 ppm was
introduced into the super-clean recycling process over a period of about 14 min.
It is extremely unlikely that such high concentrations would ever be encountered in the feed to the super-clean
recycling process, especially when a hot washing process is used to clean the feed material. The scenario used in
the tests may therefore be considered as a worst-case.

The individual contamination levels of each surrogate measured during the trials of the one-step and two-step
processes are shown in Figure 27 to Figure 31.
In each case the concentration of the surrogate in output samples taken from the EREMA super-clean recycling unit
is plotted against time after the start of addition of the 55Kg sample of contaminated material.
In each case the surrogate concentration was measured by headspace gas chromatography of the HDPE output
material. Note that this analytical technique is different to the solvent extract gas chromatography method used for
the results shown in Figure 26. However both techniques show similar concentration trends.
0
500
1000
1500
2000
2500
3000
3500
4000
4500
0 50 100 150
t ime [ min]
d
e
t
e
c
t
o
r

r
e
s
p
o
n
s
e

[
m
V
]
2-step process
1-step process

Figure 27: Concentration of toluene in the output material after the one- and two-step processes

0
500
1000
1500
2000
2500
3000
3500
0 50 100 150
t ime [ min]
d
e
t
e
c
t
o
r

r
e
s
p
o
n
s
e

[
m
V
]
2-step process
1-step process

Figure 28: Concentration of chlorobenzene in the output material after the one- and two-step
processes

0
500
1000
1500
2000
2500
0 50 100 150 200 250
t ime [ min]
d
e
t
e
c
t
o
r

r
e
s
p
o
n
s
e

[
m
V
]
2-step process
1-step process

Figure 29: Concentration of phenyl cyclohexane in the output material after the one- and two-step
processes
0
50
100
150
200
250
300
350
400
450
500
0 50 100 150 200 250
time [min]
d
e
t
e
c
t
o
r

r
e
s
p
o
n
s
e

[
m
V
]
2-step process
1-step process

Figure 30: Concentration of benzophenone in the output material after the one and two-step
processes

0
10
20
30
40
50
60
70
80
90
0 50 100 150 200 250
t ime [ min]
d
e
t
e
c
t
o
r

r
e
s
p
o
n
s
e

[
m
V
]
2-step process
1-step process

Figure 31: Concentration of methyl stearate in the output material after one and two-step processes

The inline version of the super-clean recycling process allows the production of HDPE bottles that contain recyclate
directly from washed post-consumer HDPE flakes.
For the inline process, the total amount of surrogates remaining after the recycling process was estimated by an
integral equation, which takes account of time, surrogate concentration in the HDPE samples and HDPE mass flow.
The procedure used is described in detail in the literature [44].
The maximum concentrations (c
max
) of surrogate compounds measured in bottles made using the super-clean
recycling process, when operated inline with a bottle blowing unit, are related not only to the cleaning efficiency of
the recycling process but also to the dilution effect of the uncontaminated HDPE flakes which are mixed with the
recycled material in the feed stream to the bottle extrusion and blowing unit.
Dilution with uncontaminated material means that the concentration of surrogate compounds measured in the
bottles produced by the in-line process will be lower than in the product from the discontinuous super-clean
recycling process, which is not diluted.
"Reducing factors" were therefore defined as described in Equation 3 in order to estimate the cleaning efficiency of
the super clean recycling process when operated in inline mode:
Eq. 3:
100%
ion concentrat initial
ion concentrat maximum
1 (inline) factor reducing
=

Table 20 shows the estimated concentrations of the surrogates that could be achieved in HDPE bottles produced by
the in-line option of the super-clean recycling process based on the results of the trials of the discontinuous process
option.
For these estimates it was assumed that the finished bottles contained about 25% by weight of challenge test
material. This is the same ratio as in the challenge test recorded in Table 19.

Table 20: Estimated maximum concentrations of the surrogates in the bottles that could be produced
by the inline option of the super-clean recycling process and reduction factors (for initial
concentrations see Table 19)
Maximum concentration of the surrogates in the HDPE material in [ppm] and
reduction factors in comparison to the initial concentrations (Table 20)
cyclohexane
Methyl
stearate
Benzophenone
Super-clean process (1-step) 3 (99.6%) 4 (99.6%) 36 (95.8%) 78 (89.4%) 79 (91.1%)
Super-clean process (2-step) <1 (>99.9%) <1(>99.9%) 7 (99.2%) 44 (94.0%) 23 (97.4%)

10.3 Specific migration of surrogates from test bottles using
challenge test material
Two batches of 4 Pint HDPE containers were manufactured by Nampak using samples of the challenge test
material. See Section 10 for more detail. The following containers were shipped to Fraunhofer IVV for analysis:
Test bottles manufactured from 100% one step super cleaned challenge test granules (contaminated
material)
Test bottles manufactured from 100% two step super cleaned challenge test granules (contaminated
material)
The concentration of the surrogates measured in the bottle wall was below the analytical detection limit of about
0.02 ppm for the more volatile surrogate compounds and up to about 10 ppm for the less volatile surrogates.
The specific migration of the surrogate compounds into a food simulant (95% ethanol) was measured by
immersing 1 dm
2
of the bottle wall totally in 100ml of the the food simulant and storing for 10 days at 20 C. The
concentration of the surrogates in the migration solution was then measured.
The concentrations of the surrogates in the food simulant solution were found to be below 10 ppb.
Bottle manufacture and performance testing
After super-clean recycling with the EREMA process the material was used for bottle manufacturing by Nampak.
The following material was shipped to Nampak:
1890 kg super cleaned granules (non-contaminated) processed by EREMA's one step process
910 kg challenge test granules processed by EREMA's one step process
1116 kg challenge test granules processed by EREMA's two step process
Test bottles of the super-clean recycled material were blow moulded at Nampak using a Uniloy 350 eight head unit.
A 4 pint standard milk bottle (weight 42 g) was used as the test container.
In the first trial, bottles were blown from 100% super-cleaned granules without any adjustments to the operating
parameters. The head temperature was 170 C. However it was found necessary to increase the weight, as the
bottles were 1.4 g below the weight of those produced with the virgin BP HDPE.
Unfortunately the granules delivered by EREMA had a slight green tinge and there was also a characteristic burnt
odour, most probably coming from the PCR HDPE or from too high a temperature in the extruder during the super-
clean recycling process.
Each of the three samples of super-clean recycled material was used to produce three batches of bottles containing
100%, 50% and 30% recyclate.

BP Rigidex 6007 XA HDPE was used as the virgin polymer for blending with the EREMA material. It was also used
to produce a reference batch of 100% virgin bottles.
Bottles taken from the production trials were subjected to standard bottle testing procedures and successfully
checked for:
Weight
Neck and thread dimensions
Leak testing, bottles were filled and laid on their side.
Samples from each batch of bottles were analysed as described in section 11 below.

11 Analysis of HDPE materials
11.1 Analysis for post-consumer contaminants in raw materials
In order to conduct a risk assessment of closed loop recycling of HDPE milk bottles it is important to obtain good
quality data on:
the average concentration and nature of adventitious contaminants found in misused bottles
the frequency of misuse of HDPE milk bottles
An important objective of this study was therefore to obtain statistically meaningful measurements of the nature
and extent of post-consumer contaminants in post-consumer HDPE milk bottles recovered from the UK market.
In this study 600 conventionally recycled HDPE flakes from post-consumer milk bottles were screened for
contaminants.
In addition, pellet samples were taken after super-clean recycling of the conventionally recycled HDPE material and
analysed for residual contamination.
As a reference, 20 pellet samples of virgin HDPE were sampled by the bottle manufacturer over a period of several
months and were also analysed.
A fast screening method for post-consumer compounds in HDPE samples was developed for the study in order to
allow rapid analysis of the large number of samples required. The method chosen was headspace gas chromato-
graphy. This reduces the sample preparation procedure to weighing and sealing the flakes into a headspace vial.
The following headspace GC/FID method was used:
Sample preparation: 1.0 g of each HDPE sample was sealed into a 22 ml headspace vial
Gas chromatograph: Perkin Elmer AutoSystem XL with flame ionising detector (FID)
Column: DB 1 - 30 m - 0.25 mm i.d. - 0.25 m film thickness,
Temperature program: 50 C (4 min), rate 20 C min
-1
, 320 C (15 min),
Pressure: 50 kPa Helium, split: 10 ml min-1.
Headspace autosampler: Perkin Elmer HS 40 XL,
Oven temperature: 120 C, needle temperature: 130 C,
Transfer line temperature: 140 C,
Equilibration time: 1 h, pressurisation time: 3 min,
Injection time: 0.02 min,
Withdrawal time: 3 min.
It was shown in earlier work
[29,30]
that the headspace GC method is able to measure substances up to molecular
weights of approximately 350 g mol
-1
with detection limits between about 0.02 ppm for highly volatile compounds
and about 10 ppm for less volatile compounds.
The method developed for this study allows correlation of measured retention times of unknown analytes with their
approximate molecular weights (Figure 32).

0
2
4
6
8
10
12
14
16
18
0 50 100 150 200 250 300 350
molecular weight [g/mol]
r
e
t
e
n
t
i
o
n

t
i
m
e

[
m
i
n
]
polar
non-polar

Figure 32: Correlation between molecular weight and the retention of compounds using the
headspace screening method
Molecular weight is a very important factor in risk assessment of potential contaminants because the migration rate
into a food simulant depends on the initial concentration in the bottle wall and the molecular weight of the
potential migrant
[12,30]
.
105 standard substances were used for this correlation ranging from acetaldehyde as the smallest molecule
(44 g mol
-1
) up to n-docosane (310 g mol
-1
). Using this correlation the molecular weight of unknown substances
can be estimated from their retention times in the headspace screening test.
No change was made to the gas chromatographic system or the temperature program throughout the whole
project duration of approximately three years. As a result the measured retention times vary by only approximately
0.1 min. This was proved with standard substances at regular intervals during the project.
An inherent characteristic of the post-consumer HDPE flake material was the high homogeneity of the 200 g
samples taken for analysis. They may therefore be considered to be very representative of the bulk material.
Typically a 1.0 g aliquot taken from the 200g sample for analysis of post-consumer substances consists of 40 to 50
flakes. It is most unlikely that this analytical 1.0 g aliquot will contain two flakes from the same HDPE milk bottle.
Consequently, there is high inhomogeneity between individual flakes in a small sample.
The advantage of this feature is that an overview of 40 to 50 bottles can be obtained by measurement of one
analytical sample.
It is obvious that collected HDPE milk bottles are not homogeneously contaminated, therefore the amount of post-
consumer substances and their concentrations in the recycled HDPE flakes will vary from sample to sample and
from flake to flake.

The concentrations of suspicious compounds in the headspace gas chromatograms can be estimated by comparing
the detector response of the headspace gas chromatograms to the concentrations found after solvent extraction in
the same samples.
For this purpose the challenge test samples were analysed using both the headspace screening method and solvent
extraction using dichloromethane as the extraction solvent.
The solvent extraction technique can be calibrated easily using standard solutions of the surrogates in
dichloromethane.
There was a linear correlation between both sets of results.. The slope of the linear regression represents the
sensitivity of the headspace screening method for compounds in the same retention time range. The results for
phenyl cyclohexane and benzophenone are shown in Figure 33 and Figure 34.
y =55,304x
R
2
=0,8373
0
500
1000
1500
2000
2500
3000
0 10 20 30 40 50
concentrati on [ppm]
h
e
a
d
s
p
a
c
e

r
e
s
p
o
n
s
e

[
m
V
]
60

Figure 33: Correlation between the detector response of headspace analysis and the concentration of
phenyl cyclohexane in the HDPE samples when analysed by solvent extraction

y =5,5027x
R
2
=0,7804
0
100
200
300
400
500
600
0 20 40 60 80 100 120
concentrati on [ppm]
h
e
a
d
s
p
a
c
e

r
e
s
p
o
n
s
e

[
m
V
]

Figure 34: Correlation between the detector response of headspace analysis and the concentration of
benzophenone in the HDPE samples when analysed by solvent extraction
Figure 35 shows a typical headspace gas chromatogram for virgin HDPE pellets. The major compounds detected
are alkene oligomers of HDPE (e.g. decene (R
t
= 7.5 min), dodecene (R
t
= 9.6 min), tetradecene (R
t
= 12.6 min)).
The concentrations of decene and dodecene measured in the virgin samples were around 20 ppm.
Figure 36 shows a typical headspace gas chromatogram for washed post-consumer HDPE flake samples from the
first washing trial The concentrations measured are similar to the those found in the virgin reference materials.
Figure 37 shows a typical headspace gas chromatogram of for a second sample of washed post-consumer HDPE
flakes from a second washing trial that used a slightly different input material.
In this case the washed flake samples contain post-consumer compounds in a similar concentration range to the
oligomers in the virgin samples. The following compounds were determined in nearly all of the flake samples tested
from this batch: limonene (retention time R
t
= 7.9 min), dodecane (R
t
= 9.7 min), 2,4-di-tert-butylphenol (R
t
=
12.0 min) and tetradecene (R
t
= 12.7 min).
The flavour compound limonene probably comes from contamination of the material during collection of the HDPE
bottles due to contact with soft drink bottles in the bale.
The saturated alkanes and 2,4-di-tert-butylphenol are generated by degradation during the recycling process. 2,4-
di-tert-butylphenol is a degradation product of the additive Irgafos 168
(see below) which is commonly used as an

antioxidant in polyolefins. The measured concentrations of these recycling-related compounds were similar to or
lower than the oligomers found in virgin HDPE.
However additional substance peaks were found in some of the flake samples. Figure 38 and Figure 39 show
chromatograms for washed HDPE flake samples which contain additional suspicious unknown compounds.in
concentrations up to about 130 ppm.
For the HDPE flake material shown in Figure 39 the concentrations were estimated to be 130 ppm for the
substance peak with retention time (R
t
) of 7.5 min and 40 ppm for R
t
= 9.4 min. Note that these concentrations are
measured before super-clean recycling. If the cleaning efficiency of the super-clean recycling process is taken into
account (e.g. 92.7% for the surrogate phenyl cyclohexane) then 130 ppm before super-clean recycling corresponds
to about 10 ppm after super-clean recycling. 10ppm is similar to the concentration of oligomers detected in virgin
HDPE.

When the analysis was repeated using a second sample from the same batch the additional substance peaks could
not be detected. This is because the flake samples are not homogeneously contaminated. Only one or two
individual flakes within the sample contain the unknown substance peaks. The origin of these substance peaks is
likely to be either non-milk HDPE bottles or misused HDPE bottles.
Non-milk bottles collected from the handpicking process were investigated in order to investigate the origin of the
unknown substance peaks. Most of the non-milk bottles contained higher concentrations of all the contaminant
compounds and significantly higher concentrations of some individual compounds. The analyses show that in most
cases the unknown compounds are fragrances that are typically used in shampoos or household cleaners.
In conclusion the unknown substance peaks identified during the screening of conventionally recycled HDPE flakes
are most probably related to flakes from non-milk bottles.
Each sample of flakes analysed by headspace GC contains about 40 to 50 individual flakes. This means that during
this project around 24,- 30,000 post-consumer milk bottles were screened for contamination. Only a small number
of samples showed hints of additional compounds. Most of these are probably related to contamination with non-
milk bottles rather than misuse.

retention time [min]
Figure 35: Typical headspace gas chromatogram of virgin pellets (reference sample)

Figure 36: Typical headspace gas chromatogram of post-consumer washed flake samples (washing
trial 1)

Figure 37: Typical headspace gas chromatogram of post-consumer washed flake samples (washing
trial 2)

Figure 38: Example of a headspace gas chromatogram for a washed flake sample with unknown
compounds

Figure 39: Example of a headspace gas chromatogram for a washed flake sample with unknown
compounds

Figure 40: Typical headspace gas chromatogram of super-clean recycled HDPE
11.2 Analysis for post-consumer contaminants in milk containers
made with recyclate
A similar programme of analysis was conducted for the HDPE bottles containing recyclate that were produced for
this project by Nampak.
The analytical method used was the same as for the flake and pellet materials (Chapter 11.1). This means that all
gas chromatograms produced within this study are directly comparable.
Figure 41 shows a typical gas chromatogram for HDPE containers manufactured from 100% virgin material.
Figure 42 to Figure 44 show typical gas chromatograms for HDPE containers using 30%, 50% and 100% super-
clean recyclate, respectively.
The gas chromatogram fingerprints for all the test bottles are very similar. However, the concentrations of the
compounds analysed decrease with increasing amount of recyclate.
This agrees with the results of the material analysis prior to bottle making where the super-clean recycled material
was shown to contain smaller amounts of migration-relevant compounds than the virgin HDPE.
Note that the 1-step super-clean process of EREMA was used for production of the test containers.
From the results of the challenge tests it can be concluded that the amount of migration relevant compounds will
decrease further for bottles manufactured from super-clean HDPE using the 2-step process.

Figure 41: Typical headspace gas chromatogram of milk container manufactured from 100% virgin
HDPE (BP Rigidex 6000 XA)

HDPE (BP Rigidex 6000 XA) and 30% super-clean recycled HDPE (1-step process)

HDPE (BP Rigidex 6000 XA) and 50% super-clean recycled HDPE (1-step process)

Figure 44: Typical headspace gas chromatogram of milk container manufactured from 100% super-
clean recycled HDPE (1-step process)
In order to compare the additive content and non-volatile compound contamination of the recycled HDPE material
with virgin HDPE, the materials were also analysed by extraction with the solvent dichloromethane.
The extract samples were analysed by gas chromatography. The analytical method used is able to identify
compounds with molecular weights between 150 g mol
-1
and about 850 g mol
-1
.

The solvent extraction procedure is much more labour intensive than headspace screening so fewer samples could
be analysed.
Two representative gas chromatograms of the dichloromethane extracts are shown in Figure 45 and Figure 46 for
milk bottles containing 100% recyclate and milk bottles manufactured from virgin HDPE.
The signal pattern of HDPE oligomers in the solvent extracts was found to agree with the headspace screening
results.
2,4-di-tert-butylphenol, a typical compound found in recyclates but not in virgin material was also identified in the
solvent extraction samples from the recycled HDPE.
This shows that both analytical methods (headspace screening and extraction of compounds followed by GC) have
overlapping detection areas so that no compounds could be missed from detection.
The concentrations of the compounds that were detected in both the virgin and recycled HDPE samples are in
similar ranges. Two antioxidant additives were identified in the recycled HDPE samples: Tris(2,4-di-tert-
butyl)phosphite (Irgafos 168
CAS-No. 31570-04-0) and Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate

(Irganox 1076
, CAS-No. 2082-79-3). Both antioxidant additives were still present in their active form so that
readditivation of the recyclate is probably unnecessary.

Figure 45: Typical gas chromatogram of the dichloromethane extracts of milk container
manufactured from 100% super-clean recycled HDPE (1-step process)

Figure 46: Typical gas chromatogram of the dichloromethane extracts of milk container
manufactured from virgin HDPE

11.3 Statistical evaluation of the analytical data
The principal component analysis (PCA) method was used to conduct a statistical evaluation of the analytical
results.
This study used a software program that was developed at Fraunhofer IVV in cooperation with HKR
Sensorsysteme, Munich, Germany. This program uses the raw data from the headspace gas chromatograms (ASCII
output) as input for the PCA.
The quantitative information from headspace gas chromatograms is separated into 14 selected time slides on the
retention time axis. These are integrated separately. Each headspace gas chromatogram is therefore reduced to 14
data points for analysis by PCA.
The software uses the Gaussian Decision Function for discrimination of the samples[68]. The ellipses around the
different clusters are 95% borders with equal distance to the centre of the cluster (Mahalanobis Distance). As an
artificial reference sample a virtual headspace gas chromatogram with no substance peaks was used.
The following retention time windows were defined (see faint cross-hatched areas in Figure 47):
#1: 0.00 to 6.00 min, #2. 6.00 to 7.40 min, #3: 7.40 to 7.80 min, #4: 7.8 to 8.10 min, #5: 8.10 to 9.75 min, #6:
9.75 to 11.20 min, #7: 11.20 to 11.40min, #8: 11.40 to 11.80 min, #9: 11.80 to 12.20, #10: 12.20 to 12.60,
#11: 12.60 to 13.00, #12: 13.00 to 13.80, #13: 13.80 to 14.20 and #14: 14.20 to 16.00.

Figure 47: Time slices used for evaluation of the HDPE samples (PCA approach):
red: typical headspace gas chromatogram of virgin HDPE
blue: typical headspace gas chromatogram of washed post-consumer HDPE flakes
The PCA results for the recyclate and virgin pellet samples analysed in this study are shown in Figure 48.

2. Dimension

1. Dimension
Figure 48: PCA analysis of post-consumer HDPE flakes and pellets samples in comparison to virgin
HDPE:
washed post-consumer HDPE flakes (First washing trial, 96 samples of 40 to 50 individual flakes)
washed post-consumer HDPE flakes (Second washing trial, 504 samples of 40 to 50 individual flakes)
super-clean recycled samples (17 pellet samples)
virgin HDPE (40 pellet samples)
"0" virtual gas chromatogram with no substance peaks.


The study analysed the headspace GC results from 600 conventionally washed flake samples, 17 super-clean
recycled pellet samples and 20 virgin pellet samples. The washed samples came from two washing trials with two
different input materials from 20 different lots of routine milk bottle production.
The analysis in Figure 48 shows that the virgin pellet samples were very similar. The PCA plot shows these samples
clustered closely together which indicates similar concentrations of impurities within each pellet sample. The virgin
material results are more closely clustered than any of the other groups of results which indicates the greatest
homogeneity.
The super-clean recycled samples are closer to the zero point ("0" in Figure 48) than the virgin HDPE pellets. The
zero point represents a virtual gas chromatogram with no substance peaks. The closer distance to the zero point
indicates a lower concentration of polymer impurities in the super-clean pellets than in the virgin material.
The results for washed flakes are also quite closely clustered, which indicates that the washed flakes are also
relatively homogenous in terms of their content of extractable compounds.
The flake samples from the two independent washing trials separated into two clusters. The reason is most
probably not the washing efficiency itself but most likely the slightly different input quality used for both washing
trials.
These results indicate the huge potential of Principle Component Analysis (PCA) for discriminating between polymer
samples on the basis of their contamination level.
The sample, which shows the largest deviation from the cloud, is sample 34. The headspace chromatogram for this
sample is shown in Figure 39. In this sample decene was measured in a significantly higher concentration (about
130 ppm) than in other flake samples. One other unknown substance peak was also found, in a concentration of
about 40 ppm. Some of the flakes in this sample therefore possibly came from a bottle which had been misused.
The results of the PCA of the gas chromatogram results from HDPE test containers manufactured from different
amounts of super-clean recycled HDPE are shown in Figure 49 below.

2. Dimension

1. Dimension
Figure 49: PCA analysis of bottles from post-consumer recycled HDPE (super-clean material) in
comparison to HDPE pellets
For each bottle type 36 headspace gas chromatograms (from eight individual bottles each) were evaluated.
The results show that the clusters for 100% super-clean recycled pellets and the bottles manufactured from those
pellets are closest to the zero point (virtual gas chromatogram without peaks). This indicates that super-clean
recycled material contains the smallest amount of migration relevant compounds.
Results for bottles manufactured from 100% virgin pellets and the virgin pellets themselves are furthest from the
zero point.
The cluster for the test bottles manufactured from 50% recyclate lies between the clusters for 100% virgin and
100% recyclate bottles.
The PCA method could therefore be used as a recognition test for bottles containing super-clean recyclate. It could
also be used for semi-quantitative estimation of the recyclate amount used for bottle manufacturing.

11.4 Conclusions of the analytical work
600 conventionally recycled flake samples were analysed for post-consumer contamination levels within this study.
Each sample contained 40 to 50 individual flakes so that the study effectively analysed 24-30,000 individual post-
consumer milk bottles.
The most common contaminants in conventional recycled flake samples were unsaturated oligomers. These
compounds were also found in virgin HDPE samples. In addition limonene, di-tert-butylphenol and saturated
oligomers were found in the recycled material.
The concentrations of all the compounds found in the recycled material were similar to or lower than the ranges
found in virgin HDPE.
Contamination with compounds not normally found in virgin HDPE compounds was rare and was in most cases
related to non-milk bottles. Non-milk bottles were found to comprise less than 2.1% of the input material to the
recycling process.
The maximum concentration found in one flake sample was 130 ppm, which corresponds to 5200 to 6500 ppm in
the individual bottle on the assumption that the flake sample contained 40-50 flakes and that all the contamination
came from a single flake within this sample.
The recycling process investigated in this study was based on an efficient sorting process, hot washing of the
granulated bottles and in the case of the super-clean recycled samples, further deep cleaning of the flakes with
high temperature and vacuum.
Although good results were obtained for bottles made by the single step EREMA process the two-step super-clean
recycling process rather than the single step process should be used, due to its higher cleaning efficiency for less
volatile compounds.
Handpicking after automatic sorting is recommended in order to decrease the amount of non-milk bottles in the
feed to the recycling process.
The analytical results demonstrate clearly that the full super-clean recycling process including
sorting, washing and two stage deep cleaning with vacuum and high temperature is suitable for the
recycling of post-consumer HDPE bottles for direct food contact applications.
Future investigations should concentrate on migration testing of milk bottles containing up to 100% recyclate, shelf
life testing and sensorial testing of the products.

12 Bottle filling trials and tests
12.1 Methodology
Filling trials are necessary to compare the mechanical strength, microbiological standard and sensory quality of milk
bottles manufactured from the recycled polymer against bottles manufactured from virgin polymer and filled with
fresh pasteurised milk.
For the filling trials 4-pint milk bottles were manufactured using different percentages of PCR polymer by Nampak
Plastics in Newport Pagnell and supplied to Dairy Crest's Fenstanton site.
The following test bottles were used for the trials:
A: Control, test bottles manufactured from 100% virgin HDPE (BP Rigidex 6007 XA))
B: Test bottles manufactured from 30% super-cleaned granules (EREMA one-step process) / 70% virgin HDPE
(BP Rigidex 6007 XA)
C: Test bottles manufactured from 50% super-cleaned granules (EREMA one-step process) / 50% virgin HDPE
(BP Rigidex 6007 XA)
D: Test bottles manufactured from 100% super-cleaned granules (EREMA one-step process)
40 Bottles of each type, including the control samples were run through the complete system from de-bagging
through conveying to bottle inversion (to remove any loose debris), filling (Fogg 24/9) and capping (induction heat
seal). For this trial the labeller was not used because the bottles had to be left plain for the sensory analysis.
Finally the bottles were hand packed into roll containers prior to sorting for analysis.
Microbiological assessment was carried out by Devan Laboratories Ltd., Shropshire.
Devan followed the standard Dairy Crest methodology for assessing new products, packaging or equipment. The
method includes an aerobic plate count at 30 C for Bacillus cereus, Enterobacteriaceae, Listeria, Staphylococcus
aureus and Salmonella.
Testing was carried out in duplicate on day of production plus days 1, 5, 9, 10, 11, 12, 13 and 14. The milk was
stored at 8 C for the duration of the tests.
Sensory analysis was carried out by CCFRA in Chipping Campden to identify any burnt plastic characteristics in the
milk.
A panel of eight trained assessors was asked to independently describe the odour of each sample as it was opened
and when poured out and then to assess the taste of the milk. These assessments were carried out on two
occasions day 5 and day 7. The milk was stored at 2 C to 5 C. The samples were presented to the assessors
under random three-digit codes.
12.2 Results of the filling trials
To be regarded as acceptable microbiologically results must show no detected pathogens (Listeria, S.aureus,
Salmonella and B.cereus) at any time. The APC counts must be below 1.000.000 cfu per ml and Enterobacteriaceae
must be below 10 cfu per ml.
The microbiological results gave no indication that there is any detrimental effect on the quality of the milk from
the use of PCR material.

Samples labelled C did show very poor shelf life, this is most likely due to a "smash up" on the filler line, which
occurred during the trial run. Therefore the microbiological data does not indicate any deterioration in the quality of
the milk that is directly attributable to the use of PCR material.
Dairy Crest procedures require three satisfactory consecutive shelf life trials to be completed prior to accepting new
packaging for use.
The results of the sensory tests are given in Table 21. The descriptors used by the panel were collated and inserted
into Table 21, indicating the number of times each descriptor was used and the intensity found. To be regarded as
acceptable organoleptically, results must show no off flavours or taints and no extraneous odours or taints.
The following scale was used to indicate the intensity of the attributes used: very slight, slight, moderate, strong,
very strong.
Five days after packaging, the control sample was described on opening as having a moderate/strong milk and sour
milk odour, with a very slight/slight plastic taint odour. Seven days after packaging, the milk odour intensity
remained the same, the sour milk reduced to slight, and the plastic taint remained at the same intensity.
Regarding the odour in the cup, the intensity of fresh milk for the control sample decreased from strong to slight
over the duration of the study. There was no presence of sour milk or plastic taint described.
Both samples B and C had similar intensity of fresh milk, whereas sample D appeared to decrease intensity. Sour
milk was perceived as very slight in samples B and C at 5 days only; it was perceived as very slight in sample D at
both 5 and 7 days after packaging.
Plastic taint was only perceived as slight in sample D at the 7
th
day assessment.
For the flavour all samples were described as being slightly sweet at 5 and 7 days after packaging and either slight
or moderate for acid taste. Similarly, there was little change in intensity of fresh milk or sour milk flavour over the
duration of the study. There was no mention of plastic taint in any of the samples.
Despite the strong burnt odour in the bottles (which dissipated with time) the sensory panel only detected a slight
plastic taint in sample D. This suggests that test bottles made using PCR material, manufactured at correct
processing temperatures would be indistinguishable from virgin bottles. However, the results showed that the
plastic taint was detected in products during the odour assessments on opening. There was a slight increase in the
intensity of plastic taint on all samples over time on opening. Sample D was the only sample that had a plastic taint
perceived in the odour assessment in the cup at day 7. The increased concentration of plastic taint in the bottle
may suggest that the taint was mainly in the headspace as the odour dissipated significantly on opening. Also,
there were some slight changes in the intensity of the fresh milk and sour milk odour and flavour, which could be a
natural change for milk over time. In general, there was very little change in the sensory characteristics of the milk
over the duration of the study. Although these bottles had a strong distinctly burnt odour caused by reprocessing at
incorrect temperatures it was agreed to go ahead with the filling trials.
The only concern was that the higher percentage of PCR added to the bottles gave them a distinct yellowish tint.
This could affect consumer attitudes to the material. Further work would be needed to ensure there is no visible,
mechanical or quality difference between bottles made using PCR and bottle made using virgin polymer.


Table 21: Free description sensory test on bottled milk
Criteria sample A (control) Sample B 30% recyclate Sample C 50% recyclate Sample D 100% recyclate
Odour on
opening
5 d 7 d 5 d 7 d 5 d 7 d 5 d 7 d
Strength of
fresh milk
3 (moderate) 3 (moderate) 2 (very
slight/slight)
3 (slight) 2 (slight) 2 (slight) 2 (slight) 3 (moderate)
Sour milk 3 (moderate) 3 (slight) 3
(slight/moderate)
4 (moderate) 4 (very
slight/slight)
3 (moderate) 3 (moderate) 3 (strong)
Plastic 4
(very/slight/slight)
1 (slight) 2
(slight/moderate)
2 (moderate) 3 (slight) 1 (moderate) 2 (very slight) 2 (slight)
Odour in a cup
Strength of
fresh milk
3 (strong) 5 (slight) 2 (very
slight/slight)
5 (slight) 2 (slight) 5 (slight) 2 (slight) 5 (very slight)
Sour milk Nil Nil 1 (very slight) Nil 1 (very slight) Nil 1 (very slight) 1 (very slight)
Plastic Nil Nil Nil Nil Nil Nil Nil 1 (slight)
Flavour
Sweet 8 (slight) 8
(slight/moderate)
7 (very
slight/slight)
8 (slight) 8 (slight) 8 (slight) 7 (very
slight/slight)
8 (slight/
moderate)
Acid 7 (slight) 5 (slight) 5 (slight) 5 (moderate) 7 (slight) 4 (moderate) 6 (slight) 4 (moderate)
Fresh Milk 7
(moderate/strong)
6 (moderate/
strong)
7
(slight/moderate)
6 (strong) 6
(slight/moderate)
6 (strong) 7
(moderate/strong)
6
(moderate/strong)
Sour Milk 1 (slight) Nil 2 (slight) Nil 1 (very slight) Nil 1 (very slight) 1 (slight)
Fatty /Creamy 5
(slight/moderate)
8 (moderate) 7 (very
slight/slight)
7 (slight) 7
(slight/moderate)
8 (slight/
moderate)
7 (slight/
moderate)
7 (slight/
moderate)


13 Food law compliance tests
13.1 Migration tests
Food law compliance of the test bottles was evaluated by migration testing as part of this study.
Test bottles manufactured from the following materials were shipped to Fraunhofer for food law compliance
testing:
100% virgin HDPE (BP Rigidex 6007 XA)
100% super cleaned granules
50% super cleaned granules / 50% virgin HDPE (BP Rigidex 6007 XA)
30% super cleaned granules / 70% virgin HDPE (BP Rigidex 6007 XA)
Overall migration was tested on the bottles manufactured from recycled, but non-challenge test material.
The test conditions were 1 dm
2
contact area with 100 ml 95% ethanol (total immersion) for 10 days at 20 C.
The results of the overall migration tests are given in Table 22.
All containers show overall migration values far below the migration limit of 10 mg dm
-2
and are therefore
suitable for food contact.
Note that 95% ethanol was used in this study as the food stimulant. This can be considered as a worst-case food
simulant for dairy products.
Table 22: Results of the overall migration tests on the tests bottles manufactured from different
amounts of super-clean recycled HDPE
Bottle sample Overall migration into 95% ethanol
[mg dm
-2
]

Individual values Mean value
100% virgin HDPE 00, 0.3, 0.2 0.2
100% super cleaned granules 0.1, 0.3, 0.4 0.3
50% super cleaned granules / 50% virgin HDPE 0.3, 0.3, 0.2 0.3
30% super cleaned granules / 70% virgin HDPE 0.0, 0.1, 0.0 0.0

The specific migration of the additives Irgafos 168
, Irganox 1076
and the degradation product 2,4-di-tert-

butylphenol was also measured.
Test conditions were 1 dm
2
contact area with 100 ml 95% ethanol (total immersion) for 10 days at 20 C.
The test showed that specific migration into 95% ethanol for Irgafos 168
, Irganox 1076
and 2,4-di-tert-
butylphenol was below the analytical detection limit of 10 g dm
-2
in each case.
Gas chromatographic screening of the migration solutions showed no other substance peaks at concentrations
above 10 g dm
-2
.

13.2 Sensory testing
Further sensory tests were carried out at Fraunhofer IVV in addition to those reported in Section 12.
For sensory testing the different bottles were filled with tap water and stored for 10 days at 8 C.
The odour and taste of the water was evaluated by the sensory panel of the Fraunhofer IVV in comparison to the
reference water stored in glass bottles. A panel of seven trained testers conducted the tests.
The rating scale used for the intensity of the odour or taste difference ranged from I = 0 (no perceptible change
in smell or taste) to I = 4 (very noticeable change in smell or taste) as per DIN 10955.
Table 23: Results of the sensory tests (odour of water) on the test bottles manufactured from
different amounts of super-clean recycled HDPE (Test conditions: bottle filled with tap water,
10 days at 8 C)
Sample Description of odour Intensity
Bottles: 100% virgin HDPE No differences I = 0
Bottles: 100% super cleaned granules No differences I = 0
Bottles: 50% super cleaned granules / 50% virgin
HDPE
No differences I = 0
HDPE
No differences I = 0

Table 24: Results of the sensory tests (taste of water) on the test bottles manufactured from
different amounts of super-clean recycled HDPE (Test conditions: bottle filled with tap water,
10 days at 8 C)
Sample Description of taste Intensity
Bottles: 100% virgin HDPE Waxy, burnt, typical polyethylene I = 3.5
Bottles: 100% super cleaned granules Distinct polyethylene, sweet, dusty, bitter,
post-taste slight waxy and polyethylene
I = 2.5
HDPE
Slightly polyethylene, sweet, dusty I = 2.5
HDPE
Waxy, burnt, distinct polyethylene I = 3.5

The odour test results show no differences in the odour of water stored in any of the HDPE bottles when
compared to water stored in glass bottles.
The taste test results did note differences in the taste of water stored in HDPE bottles compared to water stored
in glass bottles.
The taste panel recorded similar levels of off-taste for the bottles made from 100% virgin and recycled material.
However the taste description of the bottle manufactured from 100% super-clean recycled HDPE had a more
unpleasant character.

On the other hand, the intensity of the off-taste was lower for bottles made from 100% super-clean recycled
material than for bottles made from 100% virgin polymer. This difference may correspond to the lower level of
contaminant compounds found in the super-clean recycled HDPE pellets (see Chapter 11.2).
No differences were measured between bottles manufactured from 30% super-clean recycled HDPE and bottles
made from 100% virgin polymer.
In conclusion, the HDPE bottles made from super-clean recycled polymer that were tested in this study seem to
be suitable for milk storage. The sensorial impact appeared to be similar to HDPE containers manufactured from
100% virgin HDPE material.

14 Recyclate quality assurance
14.1 Quality assurance issues for post-consumer recyclate
Industrial production of Post Consumer Recycled (PCR) HDPE for food contact applications requires a quality
assurance system in order to ensure consistent consumer safety.
Any super-clean recycling technology must be systematically checked and evaluated at least once by a challenge
test.
Provided the process parameters are kept constant or are not changed so as to reduce cleaning performance, the
same cleaning efficiency can be assumed for other equipment constructed in the same way.
A suitable analytical monitoring programme is recommended in order to ensure that the super-clean recycling
process continues to operate correctly and that the input concentrations do not significantly exceed the
contamination levels measured in the original challenge test study,.
The headspace analytical method developed in this study should be useful for such routine monitoring tests.
Other analytical methods may also be suitable.
A data analysis methodology based on principal component analysis (PCA) was demonstrated in this study to be
very useful for evaluation of the large amounts of raw data that are generated by routine analytical monitoring.
PCA allows quick online and automated quality control.
As demonstrated in this report (Chapter 11.3) the PCA method may also be used as a recognition test for
recyclates or for recyclate containing HDPE bottles.
Migration from a food/plastic package system is influenced by both kinetic (diffusion in plastic and food) and
thermodynamic (equilibrium partitioning between plastic and food) factors.
It is useful to start migration evaluations using a worst case assumption where total mass transfer is estimated
based on the concentration of a given migrant in the plastic (c
P,0
). If this calculation leads to a migration limit
being exceeded, then the evaluation can be refined to take account of partitioning and diffusion as these are the
crucial parameters for migration.
95% Ethanol seems to be a food simulant, which overestimates the migration in dairy product and can therefore
be considered as the worst-case of migration.
The recyclate-containing bottles tested for this project had a burnt odour when unfilled. This was probably due to
the high temperature conditions used during super-clean recycling. Water from stored in the bottles made from
recyclate had no discernable odour.
The taste transfer into water from the bottles made with recyclate was in a similar range to that for bottles
manufactured from 100% virgin HDPE.
To comply with food contact legislation sensory inertness of the recycle HDPE product for food contact articles
must be assured. This can only be achieved by appropriate sensory testing at regular intervals.
Proposed worst case scenario test conditions for sensory testing are storage of the article in direct contact with
an appropriate food simulant for 10 days at 20 C. Water is suggested as the food contact medium. However,
depending on the particular application, modified tests may be appropriate.

14.2 Standard testing procedures
Recycled HDPE will only be accepted for use in milk bottles if a suitable quality assurance system is in place to
ensure compliance with food safety standards. One of the aims of this project was therefore to develop refined,
optimised and simplified routine test methods.
A quality assurance system was established for post-consumer recycled HDPE based on the results from the
material screening and the challenge tests.
Fraunhofer IVV developed Standard Testing Procedures (STPs) based on the lessons learned during the analytical
work conducted for this project. These procedures are designed to be used by recycling companies, bottle
manufacturers and dairy companies to ensure the quality of post-consumer recycled HDPE packaging material.
The results published in this report were measured using the same analytical methodology and parameters. Gas
chromatographic fingerprints produced during routine testing can therefore be directly compared to the results of
this study.
A list of the established Standard Testing Procedures during this project is given in Table 25. The complete
Standard Testing Procedures are available from Fraunhofer IVV and WRAP.
Table 25: Standard Testing Procedures developed within this project (see Appendix)
STP 1.001 GC (FID) Method for Screening and Semi-quantification of Less Volatile Organic Compounds in PCR
HDPE
STP 1.002 Headspace GC (FID) Method for Screening More Volatile Organic Compounds in PCR HDPE
STP 1.003 Multiple Headspace Extraction GC (FID) Method for Semi-quantification of More Volatile Organic
Compounds in PCR HDPE
STP 2.001 Extraction of Polymer Additives or Impurities from PCR HDPE into Solvents and Sample Preparation
for Gas Chromatographic Analysis
STP 3.001 Identification of Medium Volatile Compounds in PCR HDPE by GC/MS
STP 3.002 Identification of Volatile Compounds in PCR HDPE by Headspace GC/MS

14.3 Correlation between migration into dairy product and choice
of food simulant
Current EU legislation still specifies that it is most appropriate to model milk products experimentally with water
(simulant A or B) because the outer packaging contact phase of the emulsion is water. However milk has a
heterogeneous liquid character. Large amounts of water (about 96%) are dispersed in small amounts (about 4%)
of fatty substances.
The EU-Project "FOODMIGROSURE" (EU Contract NO. QLK1-CT2002-2390) investigated the migration into milk
and milk products such as yoghurt or cream
[ ] 69
.
The results of this project indicate that the migration behaviour of 3.5% fat milk is more like olive oil.
The contact conditions used in this project (10 days at 40 C using 95% ethanol, as food simulant for fatty
foodstuff) are therefore more realistic than the water stimulant specified by the current legislation.
We understand that this issue will be considered in the next revision of the EU packaging legislation.

15 Process validation (re-run)
After the complete recycling process was developed, the full recycling process was re-run using about 2.5 tons of
collected HDPE milk bottles in order to validate the results.
Apart from the EREMA technology, which used an optimised screw of the extruder and the two-step process, the
same technology was used as for the first tests. The optimised parameters of the EREMA process are given in
Table 18 (normal operation "two-step).
Nampak manufactured 4 pint standard milk bottles (42 g) with 30%, 70% and 100% recyclate From the re-run
material.
This time there were no visual differences between bottles produced from 100% super-clean PCR HDPE when
compared with bottles produced from 100% virgin material. The "burnt odour", which occurred in the first test
run was significantly reduced and was barely detectable in any of the samples produced.
Samples from the re-run were also analysed using exactly the same headspace screening method that was used
in the first process trials.
The results for the re-run show that the typical HDPE oligomeric pattern was significantly decreased with
increasing amounts of super-clean recycled material in the product (Figure 50 to Figure 52).
These results indicate that HDPE milk bottles containing recyclate are likely to have better migration performance
than HDPE containers made from 100% virgin material. In addition, di-tert-butylphenol was measured only in
very small concentrations. These concentrations were close to the analytical detection limits.
The migration studies, sensory tests and filling trials were not repeated, because they gave successful results in
the first run and the contaminant levels measured in the second run were lower.

Figure 50: Typical headspace gas chromatogram of milk containers produced from 100% super-
clean recycled material from the validation re-run

Figure 51: Typical headspace gas chromatogram of milk containers produced from 70% super-clean
recycled material from the validation re-run

Figure 52: Typical headspace gas chromatogram of milk containers produced from 30% super-clean
recycled material from the validation re-run

16 Economic evaluation
An economic assessment was made of the full super-clean recycling process including the following steps:
sorting (RTT technology)
washing (Sorema technology)
super-cleaning (EREMA technology, two step process)
The cost categories evaluated included:
Investment costs
Direct production costs: energy, operators, fresh water, waste water, cooling water etc.
Overheads: overhead personnel costs (plant manager, secretary, analytical staff, etc), infra structure costs
(power supply, water treatment, etc.)rental of floor space, depreciation, interest rate on finance (6% p.a.
assumed)
The direct costs were calculated using the actual energy prices in UK from J anuary 2005.
The economic evaluation does not include the cost of the baled input material to the sorting process because this
cost can vary widely in response to supply and demand and external factors such as the price of oil.
The results are given in Table 26.
Costs per kg recycled HDPE were estimated as follows:
Direct production cost 0.41/Kg
Overheads, personnel and infrastructure 0.20/Kg
Total 0.61/Kg
The overall production cost of 0.61/Kg (excluding cost of baled input material) compares to an average price for
virgin milk bottle grade HDPE of around 1.2 per Kg


Table 26: Economic assessment of the full super-clean recycling process for HDPE
Type Sorting (RTT technology) Washing (Sorema technology) Super-cleaning (EREMA)
Material Nominal output [kg h
-1
] 2200 1100 1000
Working time [h d
-1
] 24 24 24
Working time [d y
-1
] 350 350 225
Efficiency [%] 85 85 90
Investment Equipment [] 1.000.000 3.000.000 2.000.000
Freight [] 10.000 10.000 15.000
Commissioning [] 50.000 50.000 50.000
Fixed Costs Depreciation time [y] 5 5 8
Depreciation/year [] 200.000 600.000 250.000
Interests cost p.a. (rate 6%) [] 63.600 183.600 123.900
Costs of floor space [] 90.000 60.000 28.800
Variable Costs Operator costs, energy etc. [ h
-1
] 62.26 166.82 38.79
Total production costs [ kg
-1
] 0.05 0.26 0.10


17 Environmental impact assessment
An environmental impact assessment of the full super-clean recycling process was conducted using Life Cycle
Assessment (LCA) methodology.
Possible environmental impacts of the system using this recycling process ("recycling system") were compared with the
impacts of a "reference system".
The reference system was defined as the deposition of the post consumer waste in a landfill site ("standard" waste
management system).
For each system an estimated LCA was conducted. The LCA took into account the principles of EN ISO 14040
[ ] 70
.
However the study did not aim to conform fully to ISO14040, because impacts were estimated, not calculated precisely
and because no critical review was conducted.
17.1 System boundaries
All relevant process steps were taken into account - from collection of post consumer waste up to the production of
recycled HDPE for re-use or final disposal respectively.
For the recycling scenario the following relevant processes were examined:
collection
sorting
washing
super clean recycling (EREMA 2-step process)
For the reference scenario "landfill disposal":
collection
final disposal
Transportation and energy supply were considered in both cases.
In the case of the reference scenario the environmental impact of producing additional virgin HDPE to replace the
material sent to landfill was taken into account (expanded reference scenario).
The processes upstream (production of virgin HDPE for first use, blow moulding of milk bottles, filling, distribution, use)
and downstream (blow moulding from recyclate in the recycling system or from virgin material in the reference system)
are identical for both scenarios.
An important fact in this context is that the high specification of the recycled HDPE material from the WRAP process
enables the production of new milk bottles from 100% recycled material with the same weight as bottles from virgin
material.
The upstream and downstream processes are excluded from the environmental impact assessment because they are the
same for both scenarios. So only a part of the whole milk bottle life cycle, namely the waste management phase, is
studied here. This is an important point, which must be taken into account when analysing and evaluating the results.

Life Cycle Inventory
For all processes including power supply and transportation detailed input/output descriptions were used including:
amount and specification of input material, products and waste
amount of electrical power, water, emission into air and water
sorting and preparation losses, etc.
Input data was collated from the following sources:
Interim WRAP Report on this project
[ ] 71

Cost sheets
[ ] 72

Charts / Data from SOREMA
[ ] 73

Charts / Data from EREMA
[ ] 74

Not all of the data from these sources was fully compatible. Additional assumptions and estimates were made in order to
complete the collection and recycling process descriptions for the purpose of the environmental impact evaluation.
The environmental impact parameters for landfill disposal, transportation, energy supply and HDPE production were
estimated from published data
[ , , , , , ] 75 76 77 78 79 80
.
The flow chart for the full super-clean bottle-to-bottle recycling process is given in Figure 53.
The reference scenario "landfill" is described in Figure 54.

Collection/
Transportation
(truck 40 km)
Super Clean Recycling
EREMA
Washing Sorema
Sorting RTT
Recycling system
5000 kg Input material (bales)
including 1000 kg milk bottles:
20% Post consumer milk bottles
20% other HDPE bottles
50% kg PET bottles
6% kg other plastic bottles
4% kg residue
500 kg recycled
HDPE for Re-use
19 kg diesel fuel
emissions
4250 kg waste
emissions
emissions
1200 MJ from gas
165 kWh electricity
2000 l water
50 kWh electricity
150 kWh electricity
500 l water
Landfill site
200 kg waste
5000 kg bales
750 kg milk bottles,
sorted
550 kg milk bottles,
washed
50 kg waste
2000 l waste water

Figure 53: Flow chart for the full super-clean HDPE recycling scenario (simplified)

Collection/
Transportation
(truck 40 km)
Landfill site
Reference system, expanded with HDPE production
emissions
emissions 24,5 kg diesel fuel
5000 kg Input material
(1000 kg milk bottles):
20% Post consumer milk bottles
20% other HDPE bottles
50% kg PET bottles
6% kg other plastic bottles
4% kg residue
HDPE Production
500 kg primary
HDPE
emissions
resources

Figure 54: Flow chart for expanded landfill disposal reference scenario (simplified)

17.2 Environmental impact assessment
17.2.1 Impact categories
The results of the LCA study are presented in the following environmental impact categories:
primary energy equivalent (in MJ /1000 kg used milk bottles)
global warming potential (in kg CO
2
-Equivalents/1000 kg used milk bottles)
acidification potential (in mol SO
2
/1000 kg used milk bottles)
eutrophication potential (in mol PO
4
/1000 kg used milk bottles)
amount of waste (in kg/1000 kg used milk bottles)
17.2.2 Classification and characterization
The environmental impacts in each category were calculated for both scenarios. The LCI results were converted into so-
called indicator results for each impact category using standard characterization factors.
17.2.3 Sensitivity analysis
As a sensitivity check the more important process parameters were identified and additional calculations were carried out
for each scenario using modified parameters in order to test the sensitivity of the results to variations in the parameters
that were assumed.
The following additional scenarios were calculated with modified parameters:

Recycling system:
Scenario "Recycling 75%"
Scenario "Recycling 75%+50 kWh": Need of electricity for sorting 100 kWh (instead of 50 kWh) per 750 kg
sorted milk bottle output
Scenario "Recycling 75%+100 km": Transport distance for recycled HDPE granulate to user: 100 km (instead of 0
km)
Scenario "Recycling 75%+200 km": Additional transport distance for collected waste: 100 km (instead of 0 km),
and transport distance for recycled HDPE granulate to user: 100 km (instead of 0 km)
Scenario "Recycling 60%": Recycling efficiency 60% (instead of 75%)
Reference system:
"Landfill+HDPE 2003"
"Landfill+HDPE 1999": Data for virgin HDPE production in the reference system according APME 1999 (instead of
APME 2003)
17.3 LCA results
17.3.1 Primary energy equivalent PE
Figure 55 compares the environmental impacts estimated for each scenario in terms of primary energy equivalent.
In all cases the primary energy consumption of the recycling scenario is 25,000-30,000 MJ /1000 kg milk less than for
the reference scenario. This difference is equivalent to approximately 300-400 kg virgin HDPE. The recycling efficiency
(the amount of recycled HDPE used in each bottle) has the greatest influence on the result.
Primary Energy Equivalent, PE [MJ/1000 kg milk bottles]
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
R
e
c
y
c
l
i
n
g

7
5
%
R
e
c
y
c
l
i
n
g

7
5
%
+
5
0
k
W
h
R
e
c
y
c
l
i
n
g

7
5
%
+
1
0
0
k
m
R
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c
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c
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i
n
g

7
5
%
+
2
0
0
k
m
L
a
n
d
f
i
l
l
+
H
D
P
E
1
9
9
9
L
a
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d
f
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+
H
D
P
E
2
0
0
3
R
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c
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c
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g

6
0
%
L
a
n
d
f
i
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+
H
D
P
E
1
9
9
9
,

6
0
%
L
a
n
d
f
i
l
l
+
H
D
P
E
2
0
0
3
,

6
0
%
P
E

[
M
J
]

Figure 55: Primary energy Equivalent PE for the waste management scenarios
17.3.2 Global Warming Potential GWP
The difference in global warming potential between the recycling and reference scenarios is about 500 kg CO
2
per 1000
kg milk bottles (Figure 56). This difference is equivalent to approximately 250-300 kg virgin HDPE.

Global Warming Potential, GWP [kg CO2/1000 kg milk
bottles]
0
500
1000
1500
2000
2500
3000
R
e
c
y
c
l
i
n
g

7
5
%
R
e
c
y
c
l
i
n
g

7
5
%
+
5
0
k
W
h
R
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c
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c
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i
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g

7
5
%
+
1
0
0
k
m
R
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g

7
5
%
+
2
0
0
k
m
L
a
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d
f
i
l
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+
H
D
P
E
1
9
9
9
L
a
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d
f
i
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+
H
D
P
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2
0
0
3
R
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c
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c
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i
n
g

6
0
%
L
a
n
d
f
i
l
l
+
H
D
P
E
1
9
9
9
,

6
0
%
L
a
n
d
f
i
l
l
+
H
D
P
E
2
0
0
3
,

6
0
%
G
W
P

[
k
g

C
O
2
]

Figure 56: Global Warming Potential GWP for the waste management scenarios
17.3.3 Eutrophication Potential EP
Transportation distances have a strong influence on the eutrophication potential environmental impact in the case of the
recycling scenarios. This is because road transport is a major cause of eutrophication (smog formation) (Figure 57). The
choice of APME data for virgin HDPE production have a strong influence on the result for the reference system.
The difference between the recycling and reference scenarios is about 1-6 mol PO
4
per 1000 kg milk bottles. A similar
impact is caused by the production of 250-400 kg virgin HDPE.
Eutrophication Potential, EP [Mol PO4/1000 kg milk
bottles]
0
1
2
3
4
5
6
7
8
9
R
e
c
y
c
l
i
n
g

7
5
%
R
e
c
y
c
l
i
n
g

7
5
%
+
5
0
k
W
h
R
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c
y
c
l
i
n
g

7
5
%
+
1
0
0
k
m
R
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c
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g

7
5
%
+
2
0
0
k
m
L
a
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d
f
i
l
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+
H
D
P
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1
9
9
9
L
a
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+
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2
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0
3
R
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6
0
%
L
a
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+
H
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P
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1
9
9
9
,

6
0
%
L
a
n
d
f
i
l
l
+
H
D
P
E
2
0
0
3
,

6
0
%
E
P

[
m
o
l

P
O
4
]

Figure 57: Eutrophication Potential EP for the waste management scenarios

17.3.4 Acidification Potential AP
For AP, too, the most important effect on the difference between recycling and reference system comes from the choice
of HDPE-data used in the reference system. The differences shown in Figure 58 (30-160 mol SO
2
/1000 kg milk bottles)
are equivalent to the impacts caused by the production of 350-450 kg virgin HDPE.
Acidification Potential, AP [Mol SO2/1000 kg milk bottles]
0
50
100
150
200
250
R
e
c
y
c
l
i
n
g

7
5
%
R
e
c
y
c
l
i
n
g

7
5
%
+
5
0
k
W
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7
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%
+
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%
+
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+
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%
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,

6
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%
L
a
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+
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D
P
E
2
0
0
3
,

6
0
%
A
P

[
m
o
l

S
O
2
]

Figure 58: Acidification Potential AP for the waste management scenarios
17.3.5 Municipal Solid Waste MSW
Dependent on recycling efficiency the amount of waste for disposal is 400-500 kg /1000 kg milk bottles less than in the
reference system (Figure 59).
Municipal Solid Waste on landfill site, MSW, landfill
[kg/1000 kg milk bottles]
4200
4300
4400
4500
4600
4700
4800
4900
5000
5100
R
e
c
y
c
l
i
n
g

7
5
%
R
e
c
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7
5
%
+
5
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+
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%
+
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6
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%
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3
,

6
0
%
M
S
W

o
n

l
a
n
d
f
i
l
l

[
k
g
]

Figure 59: Municipal Solid Waste MSW for the waste management scenarios

17.3.6 Use of Water
In addition to the impact categories listed in section 17.2.1, the use of water by the different scenarios is compared in
Figure 60 .
The two virgin HDPE production data sets used give very different figures for water consumption. The more recent APME
data indicates no significant difference in water consumption between the two groups of disposal scenarios.
Use of Water [m/1000 kg milk bottles]
0
5
10
15
20
25
30
R
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]

Figure 60: Use of water for the waste management scenarios
17.4 Limitations and Conclusions
This analysis assumes that the HDPE recyclate produced by the super-clean process can be used as a direct replacement
for virgin HDPE polymer. If the recyclate can only be used in lower grade applications then the conclusions of the LCA
will not be valid.
This analysis also assesses the environmental impact of the two scenarios in a limited range of impact categories and for
a limited range of process conditions. No LCA can assess all possible impacts on the environment or all possible process
conditions.
Taking these factors into account the following conclusions can be made:
HDPE recycling via the developed bottle to bottle recycling process causes less impact on the environment than
landfill disposal in the impact categories examined for this project.
The impacts avoided by bottle to bottle recycling of 1000 kg milk bottles rather than landfill disposal are equivalent
to the impacts caused by the production of about 300 kg virgin HDPE material.
With the exception of the eutrophication potential category, transportation distance and energy consumption for
the recycling processes are of minor importance for the results.
Higher losses in the upstream sorting and preparation processes reduce the positive effects on the environment.
For good positive a high recycling efficiency must be realized.
Within this study only the HDPE milk bottles were evaluated in comparison to the alternative scenario of "landfill
disposal". However the bales, which are the input in the recycling process, contain approximately 50% PET bottles. For
the 50% PET bottles it was assumed that these bottles are still going into landfill. If these PET bottles are also recycled
(which in practice they would be because PET is easier to recycle) then the positive effect of the LCA would significantly
increase. The reason for not taking PET bottles into account was that the LCA needs completely different boundaries.

18 Overall Project Conclusions
This project successfully developed an industrial scale process for sorting and recycling of post-consumer HDPE milk
bottles from kerbside and bring scheme collections in the United Kingdom. The process contains the following key steps:
Sorting of natural HDPE milk bottles from the feedstock material
Grinding and washing of the bottles
Super-clean decontamination
The sorting process was optimised within the project and its sorting efficiency was evaluated. A sorting efficiency of
more than 99% of natural HDPE milk bottles was demonstrated, provided natural non-milk bottles were sorted out by
hand-picking before the washing process.
If handpicking is not used the output fraction of natural HDPE milk bottles is 97.9%.
The ILSI recommended input specification (food grade polymer purity >99%) is achieved if handpicking is used.
However the discussion about "food grade material" is still in progress.
The scenario without handpicking might be viable if the definition of polymer purity is in the range of 97%. For the time
being manual post-sorting using handpicking is recommended until EU legislation is clarified.
The washing process was optimised and challenged at industrial scale using purposely contaminated HDPE flakes. The
input concentrations of the surrogates were in the range 740 ppm to 920 ppm. Such input concentrations are very high
and never reached in reality for the expected input materials. The cleaning efficiencies measured for the washing
process alone were in the range 50% to 60% for volatile solvents. For non-volatile components the cleaning efficiencies
were lower, for example, 9% and 27% for phenyl cyclohexane and benzophenone, respectively.
The EREMA super-clean recycling process, which is already used for PET decontamination, was successfully adapted to
treat HDPE milk bottle flakes. The cleaning efficiency was also measured using a challenge test. Input concentrations
were in the range 740 ppm to 920 ppm and the flakes were introduced in a worst-case scenario without step washing.
The cleaning efficiencies measured for the super-clean recycling process were better than 99% for the solvents (toluene,
chlorobenzene), approximately 95%, 76% and 38% for phenyl cyclohexane, methyl stearate and benzophenone,
respectively.
Taking the washing process into account, the cleaning efficiencies for the overall process rise to 99.9% for toluene and
chlorobenzene, 95%, 76% and 54% for phenyl cyclohexane, methyl stearate and benzophenone, respectively. As the
cleaning efficiency most probably depends on the input concentration it can be assumed that the cleaning efficiency will
be higher at real contamination levels, which will be much lower than the levels used in the challenge tests.
In order to measure actual contamination levels in post-consumer HDPE, about 600 conventional recycled flake samples,
collected and sorted in the United Kingdom were analysed for post-consumer contaminants. Each sample consists of 40
to 50 individual flakes so that the number of individual containers tested was in the range 24000 to 30000 post-
consumer milk bottles.
Predominant contaminants in hot-washed flake samples were unsaturated oligomers. These compounds were also found
in virgin HDPE pellet samples used for milk bottle production.
The flavour compound limonene, the degradation product of antioxidant additives di-tert-butylphenol and small amounts
of saturated oligomers were found in higher concentrations in the post-consumer samples than in the virgin HDPE.
However, the overall concentrations of all contaminants in post-consumer recycled samples were similar to or lower than
in virgin HDPE.

Contamination with other HDPE compounds not normally found associated with HDPE was rare and was in most cases
related to the normal first use of HDPE bottles for non-milk applications such as shampoo. These type of bottles
comprised <2.1% of the input to the recycling process.
The maximum concentration of an unknown compound found in one sample of 1 g (40-50 flakes) was estimated at
130 ppm, which corresponds to a contamination of 5200 to 6500 ppm in the individual bottle whioch contributed the
contaminated flake to the sample.
Both the output material from the recycling process and HDPE milk bottles made with up to 100% recyclate were tested
for their suitability for food contact.
Both the output material and the milk bottles made with recyclate were similar or better than virgin HDPE pellets from a
migration point of view. This is because polymerisation side products like oligomers were also removed during the
decontamination process.
In order to prove the performance of the bottles made with recyclate, migration tests, filling trials and sensory tests
were successfully performed with 4 pint milk bottles with recyclate contents of 30%, 70% and 100%. All tests showed
no significant differences between recyclate containing bottles (up to 100%) and reference bottles manufactured from
virgin HDPE.
Research work was also done during the project on super-critical CO
2
decontamination. The results show that in principle
the decontamination of post-consumer contaminants is possible with a relatively simple, single step process and with a
relatively short residence time. However the super-critical process investigated in this study was not sufficiently robust
for use at industrial scale. Further investigations are necessary to make the process suitable for recycling applications.
An economic evaluation of the super-clean recycling process was conducted.
The direct production costs of the super-clean recycling process were calculated to be 0.41 per kg recycled HDPE,
excluding the cost of the baled input bottles.
Assuming overhead personal costs (plant manager, secretary, analytical staff, etc) and infra structure costs (power
supply, water treatment, etc.) of 0.20 kg
-1
the overall production costs were calculated to be 0.61 kg
-1
excluding the
cost of baled input bottles. This compares to a typical cost for virgin milk bottle grade HDPE of around 1.2/Kg.
The environmental impact assessment for the super-clean recycling process was positive. All impact categories analysed
had a lower environmental impact than the alternative of landfill.
I n conclusion the output material from the super-clean recycling process can be reused for direct food
contact applications for HDPE milk bottles up to 100% recyclate content.
The process developed during this project has been demonstrated to work at tonnage scale and should be
economically viable. I t is a better environmental option for treatment of post-use HDPE bottles than
landfill.


Appendix 1 Project Consortium
Table 27 gives an overview of the project consortium and the role of the companies in the project. Detailed information
about the companies is given below.
Table 27: Project consortium and the role of the participants in the project
Participant Role in the Project
Delleve Plastics, Stratford upon Avon, UK Source of baled bottles from several UK
suppliers
RTT Systemtechnik, Zittau, Germany Sorting of bottles
Sorema/Previero, Alzate Brianza, Italy Granulation and washing of sorted bottles
EREMA, Linz, Austria Super-clean recycling
RAPRA Technology, Shawbury, UK
Super-clean recycling, polymer
characterisation
Nampak Plastics Limited, Milton Keynes, UK
Bottle blow moulding , mechanical properties
of the recyclate containing bottles
Dairy Crest Limited, Telford, UK Filling, product shelf life testing
Food Standards Agency, London, UK Member of the project Board providing advice
on EU and UK legislative requirements and
compliance
Fraunhofer Institute for Process Engineering
and Packaging, IVV, Freising, Germany
Analytical screening of post-consumer HDPE,
determination of process cleaning efficiency,
challenge testing and compliance testing and
evaluation

Delleve Plastics
Delleve Plastics, founded in 1964 and incorporated 1972, is UKs only large user of domestic HDPE for bottle making,
finished product, recycling and manufacturing. Source material is from a range of UK suppliers, such as local authorities
and waste management companies. Delleve Plastics is involved in development of industry standards for recycled
materials. Within the project Delleve Plastics supplied post-consumer HDPE bottles from a range of UK suppliers. Further
information: http://delleve.co.uk.
RTT Systemtechnik
RTT Systemtechnik, founded in 1990 after the German Unification, is an equipment manufacturing company, which
provides sorting solutions to the waste and recycling industry with a turnover of approx. 3.5 Mio. . RTT also provides
the European automotive industry with customised solutions in the field of special machinery and equipments. In 1995,
RTT introduced the first UniSort sorting module for post-consumer plastic bottles or other materials. Right from the
start, RTT have invested substantial resources in developing sorting technology. Based on a high selective NIR UniSort
Sensor RTT is able to detect recyclable materials with 128 wavelengths per measure point (the standard NIR technology

uses a maximum of twelve wavelengths). The UniSort was used in the project for optimising the sorting process.
Further information: http://www.unisort.com.
Sorema/Previero
Sorema/Previero merged in 1992 from the two companies, which were founded 1976 and 1922, respectively.
Sorema/Previero is the world leader in the supply of plastic washing equipment and bottle washing equipment with a
turnover of approx. 20 Mio. . Sorema/Previero has been involved in at least two PET bottle-to-bottle recycling projects
and a food grade HDPE recycling project. Sorema / Previero has a permanent pilot scale test facility on site, which was
used in the project for the optimisation of granulation and washing. Further information: http://www.sorema.it.
EREMA
EREMA, founded in 1983, is one of the world leaders in supply of plastics recycling equipment. EREMA has been involved
in several of PET bottle to bottle recycling projects and also in HDPE recycling processes. In 2000 EREMA received their
first no objection letter for their PET bottle-to-bottle recycling process from the American Food and Drug Administration
(FDA)
[ ] 81
. Currently EREMA is supplying their VacuREMA super cleaning systems to a number of industrial use
production companies in Europe and the Americas. EREMA has extensive testing facilities including their VacuREMA
super cleaning systems, which was used in the project for decontamination. Further information: http://www.erema.at
RAPRA
RAPRA Technology Limited, formally known as the Rubber and Plastics Research Association of Great Britain, is the
largest consultancy in the UK specialising in rubber and plastics materials, processes and products. It offers a
comprehensive range of services to tackle both technical and commercial problems. In 2002 RAPRA had a turnover. Of
6.7 Mio. GBP. RAPRA has developed a decontamination process based on super-critical carbon dioxide (CO
2
), which will
be further developed and optimised for the decontamination of post-consumer HDPE. Further information:
http://www.rapra.net
Nampak
Nampak is one of the world leaders in supply of extrusion blow moulded plastic liquid containers. In UK Nampak is the
leading supplier of HDPE milk containers with a turnover approx. 100 Mio. GBP (UK only). The global turnover is
approx. 1.2 billion GBP. Nampak used a production facility Uniloy 4 head machine for manufacturing recyclate
containing HDPE bottles. They also have test equipment for mechanical properties of test bottles. Further information:
http://nampak.com.
Dairy Crest
Dairy Crest Group plc is the largest broadly based dairy food company in the UK, with leading brands Clover, Cathedral
City, Davidstow, Frijj and, through a joint venture, the Yoplait brands. Dairy Crest operates in six business areas:
spreads, cheese, liquid products, fresh dairy products (a J V with Yoplait), household and ingredients. Turnover in 2002
was 1.182 Mio. GBP. The company serves both the retail grocery trade and major food manufacturers and has leading
positions in all sectors within the dairy market. Within the project Dairy Crest filled the recyclate containing bottles and
conducted shelf life and sensory tests. Further information: http://www.dairycrest.co.uk
Fraunhofer IVV
The Fraunhofer-Institute for Process Engineering and Packaging (IVV) is one of 57 institutes of the Fraunhofer
Association, which is the largest organisation for applied research and development in Europe. Fraunhofer IVV consists

of several scientific departments and groups one of them being the Product Safety and Analysis Department. Main
research topic of this department is the interaction between foodstuffs and packaging materials. Further Information:
http://www.ivv.fraunhofer.de.
The head of the migration group, Dr. Franz, is active as national or personal expert to the EU Commission (DG Sanco,
DG Research) and the German BfR (former BgVV) as well as member of CEN TC 194/SC1 (General chemical methods of
test for food contact materials) and its working groups (on overall migration, specific migration, plastics additives,
migration modelling and other) as well as the German DIN mirror committee. He is also involved in topics of the
Packaging Task Force Committee of the International Life Science Institute (ILSI). The group has successfully
participated in and coordinated several European projects within the 3
rd
, 4
th
and 5
th
Framework programs of the
European Commission.
The main areas of research and other activities, which are relevant to the project, have been for many years:
Overall and specific migration testing of food contact materials (FCM)
Development of quick predictive and alternative evaluation methods for compliance testing of FCM
Theoretical approach to the diffusion-controlled migration of packaging components into foodstuffs
Development of highly selective and sensitive analytical methods for trace components in foods and packaging
materials including post-consumer recyclates
Membership in several national working groups dealing with legislative as well as analytical aspects of FCM

Appendix 2 Addresses of Participants
Delleve Plastics Limited
Unit 6, Goldicote Business Park
Stratford upon Avon, CV37 7NB, UK
Mr. Lee Clayton (general manager)
Tel. 0044 (0) 1789 740 102
email: lee@delleve.co.uk
RTT Systemtechnik GmbH
Hirschfelder Ring 9
02763 Zittau, Germany
Mr. Ernie Beker (authorized representative)
Tel. 0049 (0) 6104 665 761
email: wrap@unisort.com
Sorema/Previro
Via dei Platani 11
22040 Alzate Brianza, Como, Italy
Mr. Dario Previero (general manager)
Tel. 0039 (0) 31 619 224
email: sales@sorema.it
EREMA GmbH
Freindorf Unterfeldstrae 3
4052 Ansfelden/Linz, Austria
Mr. Manfred Hackl (management assistent)
Tel. 0043 (0) 732 3190 144
email: m.hackl@erema.at
RAPRA Technology
Shawbury
Shrewsbury, Shropshire SY4 4NR, UK
Mr. J ohn Sidwell (principal consultant polymer analysis)
Tel 0044 (0) 193 9250 383
email: jsidwell@rapra.net
Nampak Plastic Europe Limited
Woburn Sands
Milton Keynes, Bucks, MK17 8SE, UK
Mr. J on Sweet (marketing director)
Tel. 0044 (0) 1494 870 418
email: jon.sweet@eu.nampak.com
Mr. Tony Hancock (consultant)
Tel. 0044 (0) 208 952 960 20
email: thinc007@aol.com
Dairy Crest Limited
Technical Development Centre
Crudington
Telfort, Shopshire, TF6 6HY, UK,
Ms. Lesley Moody (senior packaging technologist)
Tel. 0044 (0) 1952 653 069
email: lesley.moody@dairycrest.co.uk
Food Standards Agency
Aviation House
125 Kingsway
London WC2B 6NH
Mr. Richard Sinclair
Tel. 0044 (0) 2072 768 514
email: richard.sinclair@foodstandards.gsi.gov.uk
Fraunhofer-Institute for Process Engineering and
Packaging (IVV)
Giggenhauser Strae 35
85354 Freising, Germany
Dr. Frank Welle (business field manager Product
Safety)
Tel. 0049 (0) 8161 491 724
email: welle@ivv.fraunhofer.de
Dr. Roland Franz (head of migration group)
Tel. 0049 (0) 8161 491 746
email: franz@ivv.fraunhofer.de


Appendix 3 - Literature
Publications within the Project
F. Welle, Post-consumer contamination in HDPE milk bottles and design of a bottle to- bottle recycling process, oral
presentation on 3
rd
International Symposium on Food Packaging - Ensuring the Safety and Quality of Foods,
18. November 2004, Barcelona, Spain
F. Welle, Post-consumer contamination in HDPE milk bottles and design of a bottle-to-bottle recycling process
Food Additives and Contaminants, 2005, 22(10), 999-1011
Cited Literature

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[ ] 15
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[ ] 34
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[ ] 39
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[ ] 43
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7), 627-640
[ ] 50
O. Piringer, K. Hinrichs, Evaluation of Migration Models, Final Report of the EU-project contract SMT-CT98-7513,
Brussels 2001
[ ] 51
E. D. W. Klingelhofer, M. Ezrin, R. A. Weiss, Diffusion of hazardous contaminants in recycled high density
polyethylene, Congress Proceedings ANTEC'95, 1995, 3710-3714
[ ] 52
F. Devlieghere, B. De. Meuleanaer, J . Demyttenaere and A. Huygherbaert, Evaluation of recycled HDPE milk bottles
for food applications, Food Additives and Contaminants, 1998, 15(3), 336-345
[ ] 53
G. M. Spinks, S. Ayrton, Degradation of dairy-grade high density polyethylene during multiple pass extrusion,
Materials Forum, 1992, 16, 137-140

l
f
f
r
[ ] 54
E. G. El'darov, V. M. Gol'dberg and G. E. Zaikov, The kinetics of the chemical changes during extrusion of
polyethylene, Polymer Degradation and Stabi ity, 1986, 16, 291-296.
[ ] 55
A. Boldizar, A. J ansson, T. Gevert, K. Mller, Simulated recycling of post-consumer high density polyethylene
material, Polymer Degradation and Stability, 2000, 68, 317-319
[ ] 56
K. Takahashi, Performance of 25% recycled content HDPE blow moulded bottles, Congress Proceedings ANTEC'96,
1996, 3460-3463
[ ] 57
C. Pattanakul, S. Selke, C. Lai, J . Miltz, Properties of recycled high desity polyethylene from milk bottles, J ournal o
Applied Polymer Science, 1991, 43(11), 2147-2150
[ ] 58
R. Franz, M. Huber, O. -G. Piringer, Testing and evaluation of recycled plastics for food packaging use - possible
migration through a functional barrier, Food Additives and Contaminants, 1994, 11(4), 479-496
[ ] 59
R. Franz, M. Huber, O. -G. Piringer, A. P. Damant, S. M. J ickells, L. Castle, Study of functional barrier properties of
multilayer recycled poly (ethylene terephthalate) bottles for soft drinks, J ournal o Agricultural and Food Chemistry,
1996, 44(3), 892-897
[ ] 60
O. Piringer, M. Huber, R. Franz, T. H. Begley, T. P. McNeal, Migration from food packaging containing a functional
barrier: mathematical and experimental evaluation, J ournal of Agricultu al and Food Chemistry, 1998, 46(4), 1532-1538
[ ] 61
Personal Communication to Fraunhofer IVV from Green Cycle, Armagh, Northern Ireland, internet
http://www.greencycle.info
[ ] 62
Kalra et al., J . Chem. Eng. Data, 1978, 23(4), 317-321
[ ] 63
Ng and Robinson, J . Chem. Eng. Data 1978, 23(4), 325-327
[ ] 64
Walther and Maurer, Berichte Bunsenges. Phys. Chem. 1992, 8, 981-988
[ ] 65
Inomata et al., Fluid Phase Equilibria 1989, 46, 41-52
[66
] Fink and Hershey, Ind. Eng. Chem. Res. 1990, 29, 295-306
[ ] 67
Tarantino et al., J . Chem. Eng. Data 1994, 39, 158-160
[ ] 68
G. Niebling, Strategien der Signalverarbeitung in der Chemosensorik Konventionelle Methoden und neuronale
Netze, PhD Thesis, Technical University of Munich, 1996, page 14 ff.
[ ] 69
R. Franz, Migration modelling from food contact plastics into foodstuffs as a new tool for consumer exposure
estimation, Food Additives and Contaminants, in press
[ ] 70
DIN EN ISO 14040, 14041, 14042 and 14043
[ ] 71
Development of food grade HDPE recycling process (5. Interim Report), Fraunhofer IVV, published by WRAP
[ ] 72
Process costs HDPE recycling process, email from Fraunhofer IVV from March 23, 2005
[ ] 73
Emails from March 3 and 8, 2005 from Fraunhofer IVV and EREMA
[ ] 74
Email from March 3, 2005 from Fraunhofer IVV
[ ] 75
Actual data base for LCA calculation with the software "Heraklit"
[ ] 76
Data from GEMIS 4.2, http://www.oeko.de/service/gemis/
[ ] 77
Data from ProBas, http://www.probas.umweltbundesamt.de/php/index.php
[ ] 78
Eco-Profile of High Density Polyethylene, APME 2003
[ ] 79
WRAP: Plastic bottle recycling in the UK, March 2002
[ ] 80
Heyde, M., Kremer, M.: Recycling and Recovery of Plastics from Packaging in Domestic Waste, LCA Documents Vol.
5, ecomed publishers 1999
[ ] 81
No objection letter CTS 66652 for the EREMA process for PET bottle-to-bottle recycling with direct food contact from
17.11.2000 and amendments from 07.06.2001 and 10.02.2003

Appendix 4 - Standard Test Procedures
for food grade HDPE
This section contains copies of the standard test procedures for food grade HDPE that were developed for this project by
Fraunhofer IVV.

Frauhho!er IVV - SIahdard 1esI Procedure S1P 1.001
CC (FID) MeIhod !or Screehihg ahd Semi-quahIi!icaIioh o! Low
VolaIile Orgahic Compouhds ih PCR HDPL
Pevision Number. 0 Supersedes. !7.0!.2005 Llleclive. !7.0!.2005 Page. ! ol 3

Prepared by. Peviewed by. Approved by.

1 8asic Prihciple
Cas Chromalography (CC) wilh llame lonisalion Deleclor (llD) is lo be used as a
Slandard Tesl Procedure in screening and semi-quanlilicalion ol low volalile organic
compounds in posl-consumer recycled (PCP) HDPL.
2 Re!erehces
STP 2.00!. Lxlraclion ol polymer addilives or impurilies lrom polymers inlo
dichloromelhane and sample preparalion lor gas chromalographic analysis
3 ApplicabiliIy
Posl-consumer recycled HDPL can be used lor lhe produclion ol conlainers lor Dairy
producls e.g. lresh milk. Therelore, il is imporlanl lo have a Slandard Tesl Procedure
lhal can delermine lhe levels ol low volalile organic compounds in polymers. CC (llD) is
a reliable Slandard Tesl Procedure lor such analyses.
4 ApparaIus
CC equipmenl. Hewlell Packard HP 6890 wilh Aulosampler (or equivalenl)
5 ReagehIs ahd SIahdards
Dichloromelhane p.a.
-Oclane
95' Llhanol
8ulylhydroxyanisol (8HA) p.a.
Tinuvin 324, Ciba
6 Procedure
6.! Sample Preparalion
!.0 g ol lhe polymer sample is exlracled wilh !0.0 ml dichloromelhane lor 72 h al
40C. An aliquol ol lhe exlraclion solvenl is used lor CC analysis. 8ulylhydroxyanisol
(8HA) and Tinuvin 234 are used as inlernal slandards added lo lhe solulions belore CC
analysis.
Pevision Number. 0 Supersedes. !7.0!.2005 Llleclive. !7.0!.2005 Page. 2 ol 3


6.2 Slandard Preparalion
Slandard slock solulions ol 8HA and Tinuvin 234 in 95' elhanol al a delined
concenlralion ol approx. !000 mg l
-!
. Weigh !0 0.! mg ol each inlernal slandard inlo
a !0 ml volumelric llask and dilule lo lhe mark wilh 95' elhanol. Place slopper in llask
and mix lhoroughly. Calculale lhe exacl concenlralion ol each analyle in mg l
-!
.
Slandard solulions may be slored lor up lo 6 monlhs al 4 C in lhe dark.
6.3 Sel-up, Condilions and Program lor Apparalus
Column. J&W Scienlilic D8 ! - 20 m - 0.!8 mm i.d. - 0.!8 m lilm lhickness (or
equivalenl), lemperalure program. 50 C (2 min), rale 5 C min
-!
, 340 C (!0 min),
pressure. 50 kPa helium, splil. !0 ml min
-!
. The llD-signals in lhe gas chromalograms are
inlegraled.
Under lhese condilions, lollowing relenlion limes are lound (examples).
2,2,4,6,6-penlamelhylheplane. 4.2 min
undecane. 7.0 min
dodecane. 9.8 min
lridecane. !2.2 min
hexadecanoic acid. 26 min
ocladecanoic acid. 30 min
bulylhydroxyanisol 8HA (inlernal slandard). !6.0 min
lrgalos !68. 46.5 min
Tinuvin 234 (inlernal slandard). 48.5 min
Oxidized lorm ol lrgalos !68. 50.4 min
lrganox 245. 53.6 min
6.4 Tesling ol Sample and Slandard
lnjecl lhe samples applying lriple injeclions logelher wilh lhe blank samples under lhe
condilions in 6.3.
6.5 Calculalions
The llD is a mass seleclive deleclor and can lherelore be used lor semi-quanlilicalion ol
any organic compound by comparison ol lhe deleclor response ol known inlernal
slandards. Semi-quanlilicalion was achieved by comparison ol lhe deleclor response ol
lhe inlernal slandards (8HA lor medium volalile subslances and Tinuvin 234 lor low
volalile subslances) and lhe response lor lhe delecled (unknown) compounds. Dillerenl
response laclor belween analyle and inlernal slandard, which are usually in lhe range ol
0.8 lo !.2, are nol laken inlo accounl. Using lhis procedure lhe concenlralion ol
unknown compounds can be semi-delermined as well as compounds where slandard
solulions ol lhe analyle do nol exisl. The concenlralion ol a delecled compound can be
calculaled lrom lhe slandard concenlralion and lhe deleclor response ol lhe slandard
using lhe lollowing equalion.


c
compound
= C
slandard
/deleclor response
slandard
) x deleclor response
compound

6.6 Limils ol Deleclion
The limil ol deleclion depends on lhe subslance and lhe individual response laclors.
However using lhe above described procedure lhe deleclion limils lor (unknown)
compounds are usually in lhe range ol 0.2 ppm lo 0.5 pm.
6.7 Addilional llems lor Discussion
Due lo lhe lacl lhal lhe (semi)-quanlilicalion is achieved using an inlernal mulli-
slandard, lypical validalion dala (e.g. linearily, deleclion limils elc.) cannol be
delermined. ll should be noled lhal lhe locus ol lhis melhod is lhe screening ol polymer
exlracl due lo polymer impurilies, which are usually unknown. ln addilion neal slandard
solulions ol polymer impurilies are in mosl cases unavailable. Using lhe above-
menlioned melhod lhe concenlralion ol polymer impurilies idenlilied or unidenlilied
can be calculaled. ll a delecled subslance is ol loxicological concern a special STP lor
lhis compound should be crealed using slock solulions ol lhe neal compound. ln
addilion complele validalion dala should be delermined.
7 Speci!icaIioh HisIory
Pevision 0. Llleclive. !7.0!.2005 original lesl procedure

Headspace CC (FID) MeIhod !or Screehihg High VolaIile
Orgahic Compouhds ih PCR HDPL


1 8asic Prihciple
Headspace Cas Chromalography (CC) wilh llame lonizalion Deleclor (llD) is lo be used
as a Slandard Tesl Procedure in screening volalile organic compounds in posl-consumer
recycled (PCP) HDPL.
2 Re!erehces
STP !.003. Mulliple Headspace Lxlraclion CC (llD) Melhod lor Semi-quanlilicalion ol
High Volalile Organic Compounds in PCP HDPL
3 ApplicabiliIy
Posl-consumer recycled HDPL can be used lor lhe produclion ol conlainers lor dairy
lhal can delermine volalile organic impurilies in polymers. Headspace CC (llD) is a
reliable Slandard Tesl Procedure lor such analyses.
4 ApparaIus
CC equipmenl. Perkin Llmer AuloSyslem XL (or equivalenl)
None
6 Procedure
!.0 g ol lhe polymer malerial is cul inlo pieces ol aboul 0.3 x 0.3 mm and pul inlo a
22 ml headspace vial, which is closed wilh a seplum cap.
Column. J&W Scienlilic D8 ! - 30 m - 0.25 mm i.d. - 0.32 m lilm lhickness,
lemperalure program. 50 C (4 min), rale 20 C min
-!
, 320 C (!5 min), pressure.
50 kPa helium, splil. !0 ml min
-!
. Headspace aulosampler. Perkin Llmer HS 40 XL, oven
lemperalure. !20 C, needle lemperalure. !40 C, lransler line. !40 C, equilibralion
Headspace CC (FID) MeIhod !or Screehihg High VolaIile
Orgahic Compouhds ih PCR HDPL


lime. ! h, pressurizing lime. 3 min, injeclion lime. 0.02 min, wilhdrawal lime. 3 min.
The llD-signals in lhe gas chromalograms are inlegraled.
Under lhese condilions, lollowing relenlion limes are lound (examples).
!,3-dioxolane. 2.3 min
-hexane. 2.4 min
!,3,5-lrioxolane. 2.8 min
-heplane. 3.2 min
-oclane. 5.! min
-decane. 8.2 min
-dodecane. !0.0 min
-lelraodecane. !!.9 min
-hexaodecane. !3.3 min
-ocladecane. !4.6 min
-docosane. !6.8 min
6.3 Tesling ol Sample
Lach sample was exlracled and analysed in lriplicale.
6.4 Calculalions
None
The deleclion limils vary depending ol lhe dislribulion coellicienls belween polymer and
headspace and lhe vapour pressure ol lhe analyles and cannol generally be delermined.
Typically polymer consliluenls in lhe ppm range (g analyle per g polymer) can be
delecled up lo a molecular weighl ol approx. 300 g mol
-!
. ll should be noled, lhal lhe
screening melhod is used as a screening melhod and is nol suilable lor quanlilicalion. ll
a compound is delecled which is ol loxicological concern a special melhod lor
quanlilicalion should be eslablished.
None

MulIiple Headspace LxIracIioh CC(FID) MeIhod !or Semi-
quahIi!icaIioh o! High VolaIile Orgahic Compouhds ih PCR
HDPL


1 8asic Prihciple
Headspace Cas Chromalography (CC) wilh llame lonizalion Deleclor (llD) in lhe
"mulliple headspace exlraclion" mode is lo be used as a Slandard Tesl Procedure in
screening and semi-quanlilicalion ol volalile organic compounds in posl-consumer
2 Re!erehces
STP !.002. Headspace CC (llD) Melhod lor Screening High Volalile Organic Compounds
in PCP HDPL
3 ApplicabiliIy
lhal can delermine lhe levels ol volalile organic compounds in polymers. Headspace CC
(llD) in lhe mulliple headspace exlraclion (MHL) mode is a reliable Slandard Tesl
Procedure lor such analyses.
4 ApparaIus
CC equipmenl. Perkin Llmer AuloSyslem XL (or equivalenl)
n-Nonane
Dimelhylacleamide
6 Procedure
HDPL


Slandard solulion ol n-nonane in dimelhylacelamide al a delined concenlralion ol
approx. !000 mg l
-!
. Weigh !0 0.! mg ol n-nonane inlo a !0 ml volumelric llask and
dilule lo lhe mark wilh dimelhylacelamide. Place slopper in llask and mix lhoroughly.
Calculale lhe exacl concenlralion ol each analyle in mg l
-!
. Slandard solulions may be
slored lor up lo 6 monlhs al 4 C in lhe dark.
Column. J&W Scienlilic D8 ! - 30 m - 0.25 mm i.d. - 0.32 m lilm lhickness,
-!
, 320 C (!5 min), pressure.
50 kPa helium, splil. !0 ml min
-!
. Headspace aulosampler. Perkin Llmer HS 40 XL, oven
lemperalure. !20 C, needle lemperalure. !40 C, lransler line. !40 C, equilibralion
lime. ! h, pressurizing lime. 3 min, injeclion lime. 0.02 min, wilhdrawal lime. 3 min.
Mulliple headspace exlraclion mode wilh nine injeclions. The llD-signals in lhe gas
chromalograms are inlegraled.
Under lhese condilions, lollowing relenlion limes were lound (examples).
!,3-dioxolane. 2.3 min
n-hexane. 2.4 min
!,3,5-lrioxolane. 2.8 min
n-heplane. 3.2 min
n-oclane. 5.! min
Lach sample was exlracled and analysed in lriplicale.
6.5 Calibralion
The syslem was exlernally calibraled using lhe lolal evaporalion lechnique wilh !0 l ol
a !000 ppm slandard ol n-nonane in dimelhylacelamide.
6.6 Calculalions
lnlegrale lhe peak area ol each analyle lrom lhe CC (llD) gas chromalogram lor each
injeclion. Due lo lhe loss ol analyle during each injeclion lhe concenlralion (as well as
lhe peak area) ol lhe analyle will exponenlially decrease. lrom a linear regression ol lhe
logarilhm ol lhe peak area lhe absolule amounl ol analyle can be calculaled. lollowing
lhe procedure described below lhe sum ol lhe overall deleclor response lor each
analyle is independenl lrom lhe vapour pressure, phase ralio and parlicipalion
coellicienls belween headspace and polymer so lhal lhe analyle can be semi-quanlilied
by exlernal calibralion using a mulli-analyle slandard. The advanlage ol lhe procedure is
lhal unidenlilied compounds can be semi-quanlilied, which is impossible using
HDPL


convenlional headspace lechniques due lo lhe lack ol inlormalion aboul vapour
pressure, phase ralio and parlicipalion coellicienls.
Due lo lhe lacl lhal lhe lirsl injeclion has lhe highesl error lhe experimenlally
delermined area A
!
is calculaled lrom lhe slope q and lhe inlercepl ln A
0
lrom lhe linear
regression. The calculaled area A
!
* is used lor lhe lurlher calculalions.
Lqualion !. ln ln
*
A A q
! 0
= +
Lqualion 2. A e
A * ln
*
!
!
=
The sum ol lhe areas A
i
lor each analyle i can be calculaled lrom lhe slope q and lhe
calculaled inlercepl A
i!
*.
Lqualion 3. A
A
e
|
q
|
|
=
=
=
!
!
!

The absolule amounl W
i
ol analyle in lhe headspace vial in comparison lo lhe mulli-
analyle slandard ol lhe amounl W
Sl
can be calculaled lrom Lqualion 4.
Lqualion 4. W
A
A
W
|
|
5|
5|
=

The dillerenl headspace volumes ol lhe sample (wilh polymer) V
P
and lhe slandard
(wilhoul polymer) V
0
will be considered using lhe volume laclor l
V,
which is delined by
Lqualion 5.
Lqualion 5. |
v
v v
v
|
=
0
0

Wilh help ol lhe volume laclor l
V
lhe area ol lhe mulli-analyle slandard can be
calculaled lrom Lqualion 6.
Lqualion 6. A A |
5| 5| v
*
=

HDPL


The concenlralion c
i
ol lhe analyle i in lhe polymer P can be calculaled lorm lhe weighl
ol lhe polymer sample and lhe concenlralion ol lhe analyle i in lhe headspace vial W
i
.
Lqualion 7.
weight
W
c
i
i
=
ll should be noled lhal lhe above procedure can only applied il lhe analyle show an
exponenlial decay wilh increasing numbers ol injeclions. ll nol, lhe analyle is generaled
during analysis or is nol slable under lhe applied lhermal headspace condilions.
Therelore lhe deleclion limils vary depending on lhe perlormance ol lhe linear
regression as well as lrom lhe slope and cannol generally be delermined. Typically high
volalile polymer consliluenls in lhe ppm range (g analyle per g polymer) can be
delecled down lo a concenlralion ol approximalely ! ppm.
None
7 LiIeraIure
The mulliple headspace exlraclion procedure is described in delail in lhe lollowing
publicalions.
8. Kolb, L. S. Lllre, Theory and praclice ol mulliple headspace exlraclion,
Chroma|ohraph|a, 1991, J2, 505-5!4
8. Kolb, L.-S. Lllre, Slalic Headspace-Cas Chromalography, Theory and Praclice,
Chapler 5.5, Wiley-VCH 1997, lS8N 0-47!-!9238-4

LxIracIioh o! Polymer AddiIives or ImpuriIies !rom PCR HDPL
ihIo SolvehIs ahd Sample PreparaIioh !or Cas
ChromaIographic Ahalysis


1 8asic Prihciple
Lxlraclion ol posl-consumer recycled (PCP) HDPL wilh dichloromelhane is used as a
Slandard Tesl Procedure in lhe analyses ol polymer addilives or polymer impurilies. The
lesl samples are exlracled wilh a slalic exlraclion procedure.
2 Re!erehces
STP !.00!. CC (llD) Melhod lor Screening Low Volalile Organic Compounds in PCP
HDPL
STP 3.00!. ldenlilicalion ol Medium-volalile Compounds in PCP HDPL by CC/MS
3 ApplicabiliIy
producls e.g. lresh milk. Therelore, il is imporlanl lo have a Slandard Tesl Procedure lor
lhe exlraclion ol polymer addilives or impurilies lrom lhe polymer inlo solvenls. The
exlracls are used lor quanlilicalion and idenlilicalion ol polymer addilives and impurilies
using gas chromalographic melhods.
4 ApparaIus
Drying Chamber al 40 C
8ulylhydroxyanisol (8HA) p.a.
Tinuvin 324, Ciba
6 Procedure
6.! Lxlraclion ol Polymer
Weigh !.0 g ol each HDPL sample inlo a 20 ml vial lo an accuracy ol 0.02 g and
immerse in !0 ml dichloromelhane wilh an accuracy ol 0.05 ml. Seal lhe vial using one-
way seal caps. Aller 72 h lhe solvenl is decanled lrom lhe polymer and slored overnighl
al 4 C. ll a precipilale occurs aller slorage al 4 C lhe exlracl is decanled again.
LxIracIioh o! Polymer AddiIives or ImpuriIies !rom PCR HDPL
ihIo SolvehIs ahd Sample PreparaIioh !or Cas
ChromaIographic Ahalysis


6.2 Sample Preparalion lor CC
Aliquols ol lhe exlracls are used lor CC analysis. 8HA and Tinuvin 234 are added al a
concenlralion ol approx. 500 ppm. Subsequenlly lhe exlracls are used wilhoul lurlher
sample preparalion.
Slandard slock solulion ol 8HA and Tinuvin 234 in 95' elhanol al a delined
concenlralion ol approx. !000 mg l
-!
. Weigh !0 0.! mg ol each inlernal slandard inlo
a !0 ml volumelric llask and dilule lo lhe mark wilh 95' elhanol. Place slopper in llask
and mix lhoroughly. Calculale lhe exacl concenlralion ol each analyle in mg l
-!
.
Slandard solulions may be slored lor up lo 6 monlhs al 4 C in lhe dark.
None

IdehIi!icaIioh o! Medium VolaIile Compouhds ih PCR HDPL by
CC/MS


1 8asic Prihciple
Cas Chromalography (CC) wilh Mass Deleclor (MS) is lo be used as a Slandard Tesl
Procedure in idenlilicalion ol medium volalile organic compounds in posl-consumer
2 Re!erehces
STP 2.00!. Lxlraclion ol polymer addilives or impurilies lrom PCP HDPL inlo
dichloromelhane and sample preparalion lor gas chromalographic analysis.
3 ApplicabiliIy
lhal can idenlily medium volalile organic compounds in polymers. CC (MS) is a reliable
Slandard Tesl Procedure lor such analyses.
4 ApparaIus
CC equipmenl. ThermoQuesl CCQ wilh Aulosampler (or equivalenl)
6 Procedure
!.0 g ol lhe polymer sample is exlracled wilh !0.0 ml dichloromelhane lor 72 h al
40C. An aliquol ol lhe exlraclion solvenl is used lor CC/MS analysis. 8ulylhydroxyanisol
(8HA) and Tinuvin 234 are used as inlernal slandards added lo lhe solulions belore CC
analysis.
Column. J&W Scienlilic D8 ! MS - 30 m - 0.25 mm i.D. - 0.25 m lilm lhickness,
lemperalure program. 80 C (2 min), rale !0 C min
-!
, 340 C (30 min), lull scan,
IdehIi!icaIioh o! Medium VolaIile Compouhds ih PCR HDPL by
CC/MS


scanning range m/z 40-800. lor lhe idenlilicalion lhe mass speclra are compared wilh
commercially available MS dalabases lrom NlST.
6.3 Tesling ol Sample and Slandard
lnjecl lhe samples applying lriple injeclions logelher wilh lhe blank samples under lhe
condilions in 6.2.
6.4 Calculalions
None
The limil ol deleclion depends on lhe subslance and lhe individual mass lragmenlalion.
However, lhe deleclion limils ol medium-volalile compounds are usually in lhe range ol
! ppm.
None

IdehIi!icaIioh o! VolaIile Compouhds ih PCR HDPL by
Headspace CC/MS


1 8asic Prihciple
Headspace Cas Chromalography (CC) wilh Mass Deleclor (MS) is lo be used as a
Slandard Tesl Procedure in idenlilicalion ol volalile organic compounds in posl-
consumer recycled (PCP) HDPL.
2 Re!erehces
STP !.002. Headspace CC (llD) Melhod lor Screening High Volalile Organic Compounds
in PCP HDPL
3 ApplicabiliIy
producls e.g. lresh milk. Therelore, il is imporlanl lo have a Slandard Tesl Procedure lor
idenlilicalion ol volalile organic compounds in polymers. Headspace CC (MS) is a
reliable Slandard Tesl Procedure lor such an analyses.
4 ApparaIus
CC equipmenl. Hewlell Packard 6890 coupled wilh headspace aulosampler Perkin
Llmer HS 40 XL and Hewlell Packard Mass seleclive deleclor MSD 5973 (or
equivalenl).
None
6 Procedure
Column. Macherey-Nagel Oplima ! MS - 30 m - 0.25 mm i.d. - 0.25 m lilm lhickness,
-!
, 320 C (!5 min), Headspace aulo
sampler. Perkin Llmer HS 40 XL, oven lemperalure. !20 C, needle lemperalure.
IdehIi!icaIioh o! VolaIile Compouhds ih PCR HDPL by
Headspace CC/MS


!40 C, lransler line. !40 C, equilibralion lime. ! h, pressurizing lime. 3 min, injeclion
lime. 0.06 min, wilhdrawal lime. 3 min. Mass speclromeler. Ll, lull scan, scan range 40-
550 Dallon, scan rale 0.6 s. lor lhe idenlilicalion lhe mass speclra are compared wilh a
commercially available MS dalabases lrom NlST
Lach sample should be analysed lwice.
None

Full Wrap HDPE Recycling Final ReportV141205

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R

(see below) which is commonly used as an

CAS-No. 31570-04-0) and Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate

and the degradation product 2,4-di-tert-

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