Transcript Waste Management Solutions for WEE plastics containing

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
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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
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Management of E&E Plastics Waste
Total Collected in W. Europe (1999)
Landfill
–
764,000 tonnes
96%
Mechanical Recycling 3%
Energy Recovery 1%
Source: TN Sofres for APME
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Use of flame retarded plastics in
E&E equipment – 2000 data
Non Flame Retarded
Plastics - 70%
(1,030,000 tonnes)
Plastics with non -halogenated
flame retardants
– 59%
(264,000 tonnes)
Flame Retarded
Plastics - 30%
(450,000 tonnes)
Plastics with halogenated
All E&E plastics
flame retardants
– 41%
(186,000 tonnes)
FR E&E plastics
Source: TN SOFRES Consulting for APME
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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
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Bromine Recovery from
Plastics containing BFRs
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
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Analysis Input Pilot Trials from
Plastics WEEE with BFRs
Input
pilot trial
WEEE Mix
(wt%)
average
C
TV-Back
plates mix
(wt%)
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
LHV
25.4 MJ/Kg
Ratio Br/Cl
0.31
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1.24
38.00
1.83
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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
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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
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Recovery of HBr out of flue gasses from
Pilot plant Tamara
Scrubber 1
(20l/h)
Ref. RDF
Sample 1
Sample 2
Sample 3
Sample 4
Scrubber 2
(10l/h)
Ref. RDF
Sample 1
Sample 2
Sample 3
Sample 4
F (g/l)
Cl (g/l)
Br (g/l)
0.13
0.35
0.43
0.15
0.15
F (g/l)
26.28
42.10
30.06
30.60
26.38
Cl (g/l)
0.00
3.66
2.50
6.36
7.27
Br (g/l)
0.17
0.71
0.64
0.31
0.17
0.97
2.38
1.54
1.42
0.86
0.00
7.71
3.24
14.27
11.29
Scrubber with caustic (produce NaBr)
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Recovery HBr in flue gasses from
Pilot Trials at ECN Pyromate
Scrubber
Sample 1
Sample 2
Cl (g/l)
8.89
8.71
Br (g/l)
3.23
14.06
•Pilot trial with a 1,5 kg/h
•Plastics coming from Tamara trial
•Pure plastics stream
•More concentrated flue gas stream
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[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
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Working up methods for recovered Br-products
Bromine recovery from WEEE
Thermal processes:
- Incineration (MSWI)/- Co-combustion
- Pyrolysis / gasification
- Other thermal processes
HBr/HCl
NaBr/NaCl
Distillation
Electrolysis
membrane/
diafragma
electrolysis
HCl 30-35%
HBr 40-45%
Industry
application
Industry
application
BFRs
Chlorination
process
Direct
application /or
additional
process step
Bromine
Bromine
NaBr/NaCl
Biocide:
NaCl/NaBr
solution
Oildrilling
Additive
NaCl/NaBr
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De-icing
NaCl/NaBr
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Status: Bromine Recovery from WEEE
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
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Bromine Recycling in MSWI
 MSWI
 An
needs to have wet scrubbing systems
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
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MSWC or other thermal process
Income 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
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MSWCs capacity in W. Europe
Country
WEEE
MSWC
Ratio Capacity/
FR Plastics
Capacity
WEEE
(‘000 t/year)
(‘000 t/year)
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
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Bromine Recycling Economics
Steam Sales 49%
Gate Fees 28%
Br Sales 7%
Electricity Sales 16%
Individual info MSWI operators
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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
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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? YES
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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
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For more information, visit:
TAMARA report on E&E plastics containing BFRs:
WWW.APME.ORG
All studies will be published via:
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