Guidance on best available techniques and best environmental practices for the recycling and disposal of wastes containing polybrominated diphenyl ethers (pbdes) listed under the Stockholm Convention on Persistent Organic Pollutants

Disclaimer The designations employed and the presentations in this publication are possible options, based on expert judgment, for the purpose of assisting countries in their actions to reduce or eliminate releases of polybrominated diphenyl ethers (PBDEs) listed in the Stockholm Convention. UNEP or contributory organizations cannot be liable for misuse of the information contained in this publication.

1.Introduction 11

1.1.Purpose 11

1.2.Structure of the guidance document 11

1.3.Relationship to the Basel Convention 13

1.4.Relationship to other environmental concerns 13

2.Background information on POP-PBDEs 15

2.1.POP-PBDEs listed in the Convention 15

2.2.Production of commercial PBDE mixtures 16

2.3.Former uses of POP-PBDEs 16

2.3.1.Former uses of c-PentaBDE 17

2.3.2.Former uses of c-OctaBDE 17

2.4.Risks associated with POP-PBDEs 18

2.5.POP-PBDEs in waste flows 18

2.5.1.C-PentaBDE in reuse, recycling and waste flows 19

2.5.2.C-OctaBDE in reuse, recycling and waste flows 22

2.6.Separation of POP-PBDEs-containing materials 23

3.General principles and cross-cutting considerations for the recycling and disposal of wastes containing POP-PBDEs 24

3.1.General BAT/BEP considerations 24

3.1.1.Environmental management systems (EMS) 24

3.2.Waste management 25

3.2.1.General considerations 25

3.2.2.Material/Waste management in facilities and processes 26

3.2.3.Producer responsibility 31

3.3.Life cycle management 31

3.3.1.Life cycle considerations for the polymer fraction from vehicles 31

3.3.2.Life cycle considerations for recycling of WEEE and WEEE plastic 32

3.3.3.Life cycle considerations for the management of PUR foam 32

3.3.4.Life cycle considerations for bromine recovery 32

3.4.Alternatives to POP-PBDEs 35

3.5.Monitoring of POP-PBDEs/bromine in polymers 36

4.Specific BAT/BEP: POP-PBDE/BFR-containing plastic in WEEE 37

4.1.Reuse of EEE 37

4.2.Material recycling considerations for plastics containing POP-PBDEs 37

4.2.1.Labelling of POP-PBDE-containing plastic fractions and articles 38

4.2.2.Processing technologies for plastics to minimise exposure 39

4.2.3.Types and composition of POP-PBDE-containing plastics 39

4.3.Technologies to separate POP-PBDE-containing polymers 41

4.3.1.Manual dismantling approaches 44

4.3.2.Individual screening technologies to separate possibly POP-PBDE- containing bulk and shredded plastics 45

4.3.3.Combinations of technologies for producing marketable products 48

4.3.4.Comparison of technologies to separate polymer streams 50

4.3.5.Full-scale plants to separate WEEE and POP-PBDE-containing plastics 50

4.4.Energy recovery and waste management of POP-PBDE plastics 51

5.Specific BAT/BEP: POP-PBDE/BFR materials in the transport sector 52

5.1.Reuse of vehicles containing POP-PBDEs 53

5.2.Treatment and recycling of end-of-life vehicles 53

5.2.1.Dismantling and depollution of the vehicle 54

5.2.2.Shredder plants 55

5.2.3.Recycling by improved depollution and post-shredding techniques 56

5.3.Energy recovery and disposal of ASR and other ELV residues 57

5.3.1.Energy recovery 57

5.3.2.Disposal of ASR 58

5.4.Developing country considerations 58

6.Specific BAT/BEP: POP-PBDEs-containing PUR foam 59

6.1.Reuse of furniture and mattresses possibly impacted by POP-PBDEs 59

6.2.Recycling/recovery of PUR foam 60

6.2.1.Rebond: Recycling PUR foam with phase-out of c-PentaBDE 61

6.2.2.Material recovery from mattresses 61

6.2.3.Regrinding 62

6.2.4.Chemical recovery (glycolysis) 62

6.3.Labelling of articles produced from recycled PUR foams 62

6.4.Other materials possibly impacted by POP-PBDEs 62

7.Energy/material recovery from POP-PBDEs containing material through thermal destruction 64

7.1.General remarks on thermal treatment of POP-PBDE-containing materials 64

7.1.1.Calorific value and halogen content of POP-PBDE-containing materials 64

7.1.2.Monitoring of PBDD/PBDF and PXDD/PXDF release 65

7.1.3.Considerations on corrosion caused by bromine/HBr 65

7.1.4.Considerations for removal of HBr and bromine in flue gas treatments 65

7.2.Energy recovery of POP-PBDE-containing materials in incinerators 66

7.2.1.Co-incineration of plastics from WEEE 67

7.2.2.Co-incineration of ASR in municipal solid waste incinerators 67

7.2.3.Recovery of metals 68

7.2.4.Developing country considerations 68

7.3.Cement kilns 68

7.3.1.General considerations- use 68

7.3.2.Monitoring considerations 70

7.3.3.Case studies 71

7.3.4.Developing country considerations 71

7.4.Metal industries 71

7.4.1.Copper smelters and integrated smelters-refineries 72

7.4.2.Material recovery and energy recovery in electric arc furnaces 74

7.4.3.Feedstock recycling of POP-PBDE polymers in primary steel industry 75

7.4.4.POP-PBDE-containing materials in secondary aluminium industries 76

7.4.5.Antimony smelters recycling WEEE plastics 77

7.4.6.Developing country considerations 77

8.Disposal of POP-PBDE-containing wastes to landfills 78

8.1.Drawbacks of landfilling of POP-PBDE-containing wastes 78

8.2.Sanitary landfill for disposal POP-PBDE-containing wastes 79

8.3.Long-term aftercare considerations for sanitary landfills 79

References 80

Annex 1: General BAT/BEP considerations for specific sectors 95

Crushing, shredding, sieving and washing operations 95

General BAT/BEP considerations in respect to air and water releases 95

Prevention of soil contamination 96

Annex 2: Generic BAT/BEP for processing technologies of plastic 98

Techniques to reduce VOC/SVOC emission in process design 98

Techniques to reduce VOC/SVOC emission in plant design 99

Annex 3: Disposal of POP-PBDE-containing wastes to landfills 100

Landfilling of POP-PBDE-containing materials 100

Types of wastes containing POP-PBDEs that are landfilled 101

Categories of landfills to receive POP-PBDE-containing wastes 102

Delivery of wastes to landfills 103

Operation and maintenance of landfills containing POP-PBDEs 107

PBDE releases from landfills 108

Release of POP-PBDEs from landfill fires 110

BAT measures to prevent short- and long-term release of POP-PBDEs from landfills 111

BAT/BEP of landfill after care 113

Landfill mining and impact of POP-PBDEs 114

Summary, conclusions and outlook about landfilling of POP-PBDE-containing materials with regard to BAT/BEP 114

Annex 4: Emerging technologies 116

A.Destruction/thermal recovery of PBDE containing wastes 116

Melting system 116

Pyrolysis and gasification 116

Developing country considerations 117

B.Recovery of bromine from POP-PBDE/BFR containing materials 117

Thermal recovery of Bromine 119

Technologies for separating POP-PBDEs/BFRs from the polymer matrix 120

Annex 5: Determination of POP-PBDEs in articles 122

Identification of POP-PBDEs by standard PBDE analysis 122

Rapid GC-MS analysis techniques for POP-PBDEs 122

In situ monitoring of PBDEs by Raman spectroscopy 123

In situ measurement of bromine in articles 123

Sliding spark spectroscopy 123

X-ray fluorescence (XRF) 123

X-ray transmission (XRT) 124

Figure 1‑1: Structure of the guidance and mass flow for the relevant production and application of c-PentaBDE and c-OctaBDE and the reuse, recycling and disposal of wastes containing these substances 12

Figure 2‑2: Structure of polybrominated diphenyl ethers (PBDEs) 15

Figure 2-3: Schematic diagram of the life cycle of c-PentaBDE 21

Figure 2-4: Schematic diagram of the life cycle of c-OctaBDE and potential for emissions 23

Figure 3‑5: Waste management hierarchy 26

Table 3‑6: Main use areas of c-PentaBDE and c-OctaBDE and some alternative flame retardants 35

Figure 4‑7: Composition of the polymer rich mixture after metal recovery from e-Waste shredding 40

Figure 4‑8: Polymer types identified in small WEEE polymer samples (%, w/w). 41

Figure 4‑9: Stepwise separation of polymers from waste of electrical and electronic equipment and their transformation into valuable plastic-for-recycling. 43

Table 4-10: Full-scale WEEE/WEEE-plastic treatment plants and their potential to separate POP-PBDE-containing plastics. 50

Figure 5‑11: Schematic of the processing of an end-of-life vehicle 53

Figure 5‑12: Overview of the shredder process 55

Figure 5‑13: Composition of shredder waste 56

Figure A‑14: Potential options for the bromine recovery process and closing the bromine cycle (Tange and Drohmann 2002). 118

Table 2‑1: Typical PBDE homologue distribution in commercial PBDE products 15

Table 2‑2: Estimated total production of PBDE commercial mixtures, 1970-2005 16

Table 3‑3: Comparative emissions and impacts of recycling and recovery technologies 34

Table 4‑4: Combinations of separation techniques, input materials, products, status of development and remarks on related economy 50

Table 5‑5: Parts that can be recycled from ELVs 54

Table 5‑6: Overview of post-shredder technologies 57

Table 7‑7: Redox potential of halogens and boiling/melting point of potassium and sodium halogenides 66

Table 7‑8: European Smelter Capacity 74

Table A‑9: Types of landfills, and corresponding constraints for disposing of wastes containing POP-PBDEs. The table serves as an example based on existing classifications in Europe (European Commission 1999), and may vary in different countries 104