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

R’2002 EBFRIP Thermal processes Bromine Recovery 23

For more information, visit:

TAMARA report on E&E plastics containing BFRs:

WWW.APME.ORG

All studies will be published via: