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R’2002 EBFRIP Thermal processes Bromine Recovery 1
Bromine Recovery from Plastics containing
brominated flame retardants
option for Sustainable bromine production?
Lein Tange, Dead Sea Bromine Group, Eurobrom B.V.
Dieter Drohmann, Great Lakes Chemical Corporation
R’2002 - Geneva
R’2002 EBFRIP Thermal processes Bromine Recovery 2
Introduction End-of-life management
EBFRIP/BSEF objectives for WEEE with BFRs: Provide waste recovery solutions in addition to
mechanical recycling
Evaluate incineration and pyrolysis/gasification
processes including corrosion
Develop recovery options for HBr and optional Bromine
Review the feasibility and economics
R’2002 EBFRIP Thermal processes Bromine Recovery 3
Total Collected in W. Europe (1999) – 764,000 tonnes
Landfill 96%
Mechanical Recycling 3%
Energy Recovery 1%
Source: TN Sofres for APME
Landfill 96%
Mechanical Recycling 3%
Energy Recovery 1%
Source: TN Sofres for APME
Landfill 96%
Mechanical Recycling 3%
Energy Recovery 1%
Source: TN Sofres for APME
Management of E&E Plastics Waste
R’2002 EBFRIP Thermal processes Bromine Recovery 4
Use of flame retarded plastics in E&E equipment – 2000 data
Non Flame Retarded
Plastics - 70%
(1,030,000 tonnes)
Flame Retarded
Plastics - 30%
(450,000 tonnes)
Source: TN SOFRES Consulting for APME
Plastics with non -halogenated
flame retardants – 59%
(264,000 tonnes)
Plastics with halogenated
flame retardants – 41%
(186,000 tonnes)All E&E plastics
FR E&E plastics
Non Flame Retarded
Plastics - 70%
(1,030,000 tonnes)
Flame Retarded
Plastics - 30%
(450,000 tonnes)
Source: TN SOFRES Consulting for APME
Plastics with non -halogenated
flame retardants – 59%
(264,000 tonnes)
Plastics with halogenated
flame retardants – 41%
(186,000 tonnes)All E&E plastics
FR E&E plastics
R’2002 EBFRIP Thermal processes Bromine Recovery 5
Plastics from WEEE with BFRs today (186.000 tons/year)
Current situation for WEEE plastics:
– Largest volume goes to landfill
– 10% to incineration for energy recovery
– After dismantling, still 60% to landfill
– No feedstock recycling or re-use is taking place
R’2002 EBFRIP Thermal processes Bromine Recovery 7
Process:
– Co-combustion in MSWI and Feedstock Recycling
– Volumes: ca. 11,000 tonnes of bromine/year
– BFRs are converted into HBr and optional in Bromine
Distillation
Neutralisation
Peroxide route
Bromine Recovery from Plastics containing BFRs
R’2002 EBFRIP Thermal processes Bromine Recovery 8
Analysis Input Pilot Trials from Plastics WEEE with BFRs
Input
pilot trial
average
WEEE Mix
(wt%)
TV-Back
plates mix
(wt%)
C 56.60 83.78
H 5.97 7.35
N 2.81 1.01
S 0.10 0.03
Cl 5.64 1.94
Br 1.74 3.56
O 8.24 1.09
ash 18.90 1.24
LHV 25.4 MJ/Kg 38.00
Ratio Br/Cl 0.31 1.83
R’2002 EBFRIP Thermal processes Bromine Recovery 9
Bromine Recycling from BFR-containing plastics
Two pilot trials for technical-economical feasability:– TAMARA pilot plant: co-combustion with municipal solid waste
– ECN Holland: to simulate pyrolysis/gasification process
Results of economic study: – Feasible to recover 11,000 tons of bromine per year in EU.
– A bromine recovery unit will become economical with a capacity
above 500 mtons/year, depending on the local situation!
Environmental advantages:– Resources can be saved as the Bromine loop can be closed
R’2002 EBFRIP Thermal processes Bromine Recovery 10
German Pilot Plant FZK Tamara Co-combustion trial
A pilot plant as copy of a modern MSW incinerator
Trial in cooperation with APME and FZK
Capacity 250 kg/h containing 50 kg WEEE plastics
Bromine content up to 10 g/kg MSW
After combustion the HBr is transferred into the flue gas
The HBr is absorbed in a scrubber with water or NaOH
Samples were collected & tested by Bromine producers
R’2002 EBFRIP Thermal processes Bromine Recovery 11
Scrubber 1(20l/h)
F (g/l) Cl (g/l) Br (g/l)
Ref. RDF 0.13 26.28 0.00
Sample 1 0.35 42.10 3.66
Sample 2 0.43 30.06 2.50
Sample 3 0.15 30.60 6.36
Sample 4 0.15 26.38 7.27
Scrubber 2(10l/h)
F (g/l) Cl (g/l) Br (g/l)
Ref. RDF 0.17 0.97 0.00
Sample 1 0.71 2.38 7.71
Sample 2 0.64 1.54 3.24
Sample 3 0.31 1.42 14.27
Sample 4 0.17 0.86 11.29
Recovery of HBr out of flue gasses from Pilot plant Tamara
Scrubber with caustic (produce NaBr)
R’2002 EBFRIP Thermal processes Bromine Recovery 12
Recovery HBr in flue gasses from Pilot Trials at ECN Pyromate
Scrubber Cl (g/l) Br (g/l)
Sample 1 8.89 3.23
Sample 2 8.71 14.06
•Pilot trial with a 1,5 kg/h•Plastics coming from Tamara trial•Pure plastics stream•More concentrated flue gas stream
R’2002 EBFRIP Thermal processes Bromine Recovery 13
[Cl] and [Br] recovered from Pilot trial compared to natural sources
• Levels in co-combustion for Bromine will vary between 2 and 15 g/l
• For Chlorine this is 20-45 g/l
• Seawater contains ca. 65 ppm Bromine
• Dead Sea in Israel contains 10-20 g Bromine/l
• The Chlorine content is 35 g/l in seawater
R’2002 EBFRIP Thermal processes Bromine Recovery 14
NaBr/NaCl
Bromine recovery from WEEEThermal processes:
- Incineration (MSWI)/- Co-combustion- Pyrolysis / gasification- Other thermal processes
HCl 30-35% HBr 40-45%
HBr/HCl
Distillation Electrolysis membrane/ diafragma electrolysis
Direct application /or additional process step
Chlorination process
Bromine Bromine
Biocide:NaCl/NaBr
solution
Oildrilling Additive
NaCl/NaBr
De-icing NaCl/NaBr
BFRs
NaBr/NaCl
Industry application
Industry application
Working up methods for recovered Br-products
R’2002 EBFRIP Thermal processes Bromine Recovery 15
Basic process study HBr recovery
Evaluation to install an additional distillation
column to a MSWI (or Therm. Process) for HBr
The bromine recovery was tested with chlorine
Alternative option using peroxide to produce
bromine out of HBr-stream
Additional corrosion study by TNO Holland
Status: Bromine Recovery from WEEE
R’2002 EBFRIP Thermal processes Bromine Recovery 16
Bromine Recycling in MSWI
MSWI needs to have wet scrubbing systems
An eco-efficiency for Br recycling operation in MSWC
facility will be based on several factors:
Availability and composition of suitable E&E waste streams (F)
Market conditions for: Br2, HBr or NaBr
Availability of Chlorine on the site
Commercial and technical decision will be influenced by
economics of the recycling operation plus the context of
implementation of the proposed EU Directive on WEEE
R’2002 EBFRIP Thermal processes Bromine Recovery 17
MSWC or other thermal processIncome streams
Example of a dedicated or multipurpose facility:
• (Co-)feed 4 tonnes per hour of WEEE plastics
• A potential of recycling 83 kg/h of Br
• 660 tonnes of Br or 1250 ton/y of HBr 47%
The investment for HBr recovery will be between 2-3
Million Euro depending on the local situation
R’2002 EBFRIP Thermal processes Bromine Recovery 18
MSWCs capacity in W. Europe
Country
WEEE
FR Plastics
(‘000 t/year)
MSWC
Capacity
(‘000 t/year)
Ratio Capacity/
WEEE
FR Plastics
Germany 37 13 300 360
France 26 10 800 420
UK 26 21 000 815
Italy 19 2 150 114
Spain 12 1 200 100
Others 8 13 800 1 700
R’2002 EBFRIP Thermal processes Bromine Recovery 19
Bromine Recycling Economics
Gate Fees 28%
Br Sales 7%
Electricity Sales 16%
Steam Sales 49%
Individual info MSWI operators
Gate Fees 28%
Br Sales 7%
Electricity Sales 16%
Steam Sales 49%
R’2002 EBFRIP Thermal processes Bromine Recovery 20
Overall conclusion (1)
Br recovery from WEEE plastics with BFRs is
technically, economically and ecologically feasible
Halogens in plastics are transformed mainly into
HCl or HBr and can be recovered
The investment for an additional unit will be 2-3
Million Euro depending the local situation
R’2002 EBFRIP Thermal processes Bromine Recovery 21
Overall conclusions (2)
Energy recovery and feedstock recycling can play
an important role in a waste management
concept for plastics containing BFRs
EBFRIP continues to further technical
understanding of BFRs containing of waste
management processes via full scale trials and
corrosion study in thermal processes
Option for Sustainable bromine production? YESOption for Sustainable bromine production? YES
R’2002 EBFRIP Thermal processes Bromine Recovery 22
Acknowledgements
The authors wish to thank FZK, Tamara pilot plant: practical experiments to produce Br
products - J.Vehlow and his group
European Plastics Council, APME: co-sponsored of
TAMARA trial - F.Mark and H.Fish
Energy Research Centre of the Netherlands (ECN):
pyromaat pilot trial - A.Oudhuis and H.Boerrigter
BSEF as co-sponsor of the practical experiments on bromine
recovery