Bromine industry

1. Global Bromine Industry
And
Its Outlook
- Production by Country, Production Process,
Application and Forecast.
By Y. Hirayama, ICL
By Y. Hirayama, ICL-
-IP JAPAN
IP JAPAN
5. 9. 2008
5. 9. 2008

2. 2 Focused Synergistic Responsible
Content
1. Bromine Production by Country
2. Concentration by Source
3. Bromine Production Capacity by Region
4. Bromine Production Flow
5. Bromine Compounds Market by Major
Application
6. Bromine Flame Retardants
7. Bromine Outlook

3. 3 Focused Synergistic Responsible
Brief description: bromine is the only liquid nonmetallic
element. It is a member of the halogen group. It is a heavy,
volatile, mobile, dangerous reddish-brown liquid. The red
vapor has a strong unpleasant odor and the vapor irritates the
eyes and throat. It is a bleaching. When spilled on the skin it
produces painful sores. It is a serious health hazard, and
maximum safety precautions should be taken when handling it.
Table: basic information about and classifications of bromine.
Name: Bromine
Symbol: Br
Atomic number: 35
Atomic weight: 79.904 (1)
Standard state: liquid at 298K
CAS Registry ID: 7726-95-6
Bromine: the essentials

4. 4 Focused Synergistic Responsible
Isolation
¾ Isolation
¾ Isolation: bromine is available commercially so it is not normally
necessary to make it in the laboratory. Bromine also occurs in seawater
as the sodium salt but in much smaller quantities than chloride. It is
recovered commercially through the treatment of seawater with
chlorine gas and flushing through with air. In this treatment, bromide is
oxidized to bromine by the chlorine gas. The principle of oxidation of
bromide to bromine is shown by the addition of a little chlorine water to
aqueous solutions of bromide. These become brown as elemental
bromine forms.
¾ 2Br- + Cl2 → 2Cl- + Br2
¾ Small amounts of bromine can also be made through the reaction of
solid sodium bromide, NaBr, with concentrated sulphuric acid, H2SO4.
The first stage is formation of HBr, which is a gas, but under the
reaction conditions some of the HBr is oxidized by further H2SO4 to
form bromine and sulphur dioxide. This reaction does not work with the
corresponding chlorides and fluorides.
¾ NaBr (s) + H2SO4 (l) → HBr (g) + NaHSO4 (s)
¾ 2HBr (g) + H2SO4 (l) → Br2 (g) + SO2 (g) + 2H2O (l)

5. 5 Focused Synergistic Responsible

6. The Dead
Sea

7. Dead Sea
Solar
evaporation
ponds

8. 8 Focused Synergistic Responsible
Raw material harvester

9. 9 Focused Synergistic Responsible

10. 10 Focused Synergistic Responsible

11. 11 Focused Synergistic Responsible
Where Has the Market Share Gone? To China…
Aerial photo of Bromine
production area in Shandong
Chinese Bromine production
and packing facility

12. 12 Focused Synergistic Responsible
India
-
Bromine Production
Indian plant
Indian evaporation pond

13. 13 Focused Synergistic Responsible
Emerging Ukraine ???
Satellite photo of relevant
Ukrainian regions
Ukrainian bromine plant

14. 14 Focused Synergistic Responsible
Bromine Concentration by Source
10-12 g/l
2-6 g/l
3-4 g/l
0.6-1 g/l
0.2-0.3 g/l
0.05 g/l
Dead Sea Brine
Brine Wells
(USA)
Lake (India)
Shallow Sea
(Ukraine)
Underground Wells
(China)
Sea Water
(China, Japan)
Source: ICL estimates

15. 15 Focused Synergistic Responsible
Global Bromine Production Capacity- by Region
(700 KMT)
USA, 215, 31%
China, 150, 21%
Others, 50, 7%
Dead Sea, 285,
41%

16. 16 Focused Synergistic Responsible
Bromine Production (by Region - % of total production)
37%
39%
10%
14%
35%
37%
13%
14%
35%
38%
14%
12%
38%
38%
15%
10%
42%
38%
15%
6%
42%
37%
15%
6%
38%
34%
21%
7%
33%
34%
26%
7%
0%
20%
40%
60%
80%
100%
ROW 14% 14% 12% 10% 6% 6% 7% 7%
China 10% 13% 14% 15% 15% 15% 21% 26%
USA 39% 37% 38% 38% 38% 37% 34% 34%
Dead Sea 37% 35% 35% 38% 42% 42% 38% 33%
2000 2001 2002 2003 2004 2005 2006 2007

17. 17 Focused Synergistic Responsible
Production Flow in ICL-IP

18. 18 Focused Synergistic Responsible
L E G E N D : B r o m i d e
L E G E N D : B r o m i d e -
-
enriched Dead Sea brine
enriched Dead Sea brine
(1), heated by
(1), heated by preheaters
preheaters
(A) and heat
(A) and heat-
-exchanger
exchanger
(B), flows into a reaction
(B), flows into a reaction
column (C) in which the
column (C) in which the
introduced chlorine (2)
introduced chlorine (2)
l i b e r a t e d e l e m e n t a l
l i b e r a t e d e l e m e n t a l
bromine. Steam (3) is
bromine. Steam (3) is
used to strip the bromine
used to strip the bromine
out of the reaction column
out of the reaction column
and into a condenser (D).
and into a condenser (D).
from which the bromine
from which the bromine
f l o w s i n t o a p h a s e
f l o w s i n t o a p h a s e
s e p a r a t o r ( E ) . T h e
s e p a r a t o r ( E ) . T h e
bromine
bromine-
-saturated water
saturated water
(4) is returned to the
(4) is returned to the
reaction column, while the
reaction column, while the
bromine (5) passes, first,
bromine (5) passes, first,
to a distillation column (F).
to a distillation column (F).
After cooling, the purified
After cooling, the purified
liquid bromine flows to
liquid bromine flows to
s t o r a g e ( 6 ) ,
s t o r a g e ( 6 ) ,
PRODUCTION FLOW CHART
PRODUCTION FLOW CHART

19. 19 Focused Synergistic Responsible
Global Bromine Compounds Market- by Major
Application (Total in 2007- $2.5 BN)
CBF, 230, 9%
FR, 1400, 56%
Water
Trearment,
210, 8%
Industrial,
250, 10%
Agro
(Fumigants),
130, 5%
Organic
Interm., 300,
12%

20. 20 Focused Synergistic Responsible
Bromine Compounds Consumption – By
Region ($2.5 BN - 2007)
Rest of Asia,
480, 18% ROW, 200, 8%
China, 450,
18% Europe, 450,
18%
USA, 660,
25%
Japan, 320,
13%

21. 21 Focused Synergistic Responsible
Demand by Application (In terms of Bromine
– 575 KMT in 2007)
49%
5%
12%
11%
18%
4%
63
Organic Interm
67
CBF
32
Water Treatment
283
FR
105
Industrial
25
Agro-Fumigants
Bromine

22. 22 Focused Synergistic Responsible
Use of Bromine Compounds
¾ Flame retardants
¾ Agrochemicals
¾ Water treatment chemicals
¾ Pharmaceuticals and cosmetics
¾ Lead scavenger in anti-knock fuels
¾ Oilfield completion fluids
¾ Photographic chemicals
¾ Desiccants for cooling systems
¾ Bleaching and oxidizing chemicals
¾ Dyestuffs
¾ Monomers for specialty polymers
¾ Precision cleaning

23. 23 Focused Synergistic Responsible
Electrical and electronic continues to improve
the quality of our lives

24. 24 Focused Synergistic Responsible
Flame Retardants Worldwide Market
2,700
2,700 MM$ in 2005
MM$ in 2005 –
– Bromine 38%
Bromine 38%
Miscellaneous include : inorganic phosphates,
Miscellaneous include : inorganic phosphates,
melamine, MG(OH)2, boron and Molybdenum compounds
melamine, MG(OH)2, boron and Molybdenum compounds
ATH
ATH
Miscellaneous
Miscellaneous
Ｃｌ
Ｃｌ
P
P
Br
Br

25. 25 Focused Synergistic Responsible
February 14th 2005
100m high Windsor Tower in Madrid catching fire and
completely destroyed.
ICLFR.com

26. 26 Focused Synergistic Responsible
Every day in Europe :
12 fire victims and 120 severely injured
75 % of victims are in their homes
Economic damage : +/- 25 billion Euro’s
per year
In the UK since 1988 furniture regulation:
3200 lives saved 1988-2000
29000 less non-fatal injuries
Flame retardants and other
technologies are a critical part
of the fire safety solution.
The Background to VECAP Why use Flame Retardants?
The fire on an old (1980’s)
European TV self-extinguishes,
while the fire in a non fire-safe
TV, recently sold in Europe,
keeps burning and growing

27. 27 Focused Synergistic Responsible
German Dioxin Ordinance , 16.7.1999
2, 3, 7, 8, - TBDD
1, 2, 3, 7, 8, - PeBDD
2, 3, 7, 8, - TBDF
2, 3, 4, 7, 8, - PeBDF 4 together : 1 ppb max.
Above 4 plus below 4 = Total 8 : 5 ppb max.
1, 2, 3, 4, 7, 8, - HxBDD
1, 2, 3, 7, 8, 9, - HxBDD
1, 2, 3, 6, 7, 8, - HxBDD
1, 2, 3, 7, 8, - PeBDD

28. 28 Focused Synergistic Responsible
RESIN Br-FR
ABS Deca,TBBA,Br-PC Olygomer,
TAIC-6B,BEO,Br-PS,
Ethylene-Bis(Tetrabromphtalimide)
Decabromodiphenylethane,
Tris(TBNPA)phosphate
Br-Aromatic Triazine
EPS TBBA-Bis(Allylether),HBCD
TBP-Allylether,Tetrabromethane
HIPS Deca,TBBA,HBCD,
Ethylene-Bis(Tetrabromphtalimede)
BEO,Tris(TBNPA)phosphate
Decabromodiphenylethane
Br-Aromatic Triazine
TBBA-Bis(2,3Dibrompropylether)
Br-FR by RESIN APPLICATION IN JAPAN

29. 29 Focused Synergistic Responsible
PP TBBA-Bis(2,3Dibrompropylether)
Deca,TBBS,HBCD
TBBS-Bis(2,3Dibrompropylether)
Decabromdiphenylethane
Tris(TBNPA)phosphate
Br-Aromatic Triazine
PE Deca,
Decabromdiphenylethane
TBBS,TAIC-6B
TBBS-Bis(2,3Dibrompropylether)
PC TBBA, Br-PC Olygomer,BEO
PMMA Tris(TBNPA)phosphate
PBB-MA,PBB-PA
TAIC-6B, BEO
TPB-EO-Acrylate

30. 30 Focused Synergistic Responsible
PBT Deca,TBBA-2EO,TBBA-4EO
Br-PC Olygomer,PBB-PA
BEO
Ethylene-bis(Tetrabromphtalimide)
Decabromodiphenylethane
PET Deca,Br-PC Olygomer,BEO
Br-PS,TAIC-6B
Ethylene-Bis(Tetrabromphtalimide)
Decabromdiphenylethane
NYLON Deca,Poly-Dibromphenyleneoxide
Br-PS,BEO,Br-PC
Decabromdiphenylethane
Ethlene-Bis(Tetrabromphtalimide)
PVC Deca
EPDM Deca,Decabromdiphenylethane

31. 31 Focused Synergistic Responsible
EPOXY ( laminate,BEO,)
Deca,HBB,TBBA,TBP,BEO,
Br Aromatic Triazine
Dibromcrezylglycidylether
Dibromphenylglycidylether
Phenol TBBA,TBP,BEO
URETHANE FOAM
DBNPG,TBNPA,TBBA-2EO
URETHANE ELASTOMER
Deca,BEO
UPET TBBA-2EO,DBNPG,TBNPA BEO
DCPD Deca,Br-PS
Silicone (Rubber)
Deca,Decabromdiphenlyethane

32. 32 Focused Synergistic Responsible
TEXTILE (Acrylic,SBR,PP,Polyester,Cotton)
Deca,HBCD,Pentabromtoluene
TBBA-2EO
Tris(TBNPA)phosphate
Adhesive,Adhesive Tape,Paper,Paint,Ink
Plywood
Deca,TBBA-2EO,HBCD
Ammoniumbromide
Tris(TBNPA)phosphate
Decabromdiphenylethane

33. 33 Focused Synergistic Responsible
Outlook
The demand for bromine based products will grow at an
average rate of 2-2.5% per year (2% in the first 3 years and
later 2.7%)
¾ Major drivers and growth areas:
• Adoption of fire safety regulation.
• New applications (Mercury reduction, ….)
• Organic growth in the various applications, following
growth of the global economy.
¾ Offset by:
• Continued phased-out of MBr
• Decline of Deca and HBCD
• Emergence of non-halogen substitutes for BFR’s.

34. 34 Focused Synergistic Responsible
Reference
1. ICL-IP Slides, Estimated by ICL-IP
2. ICL-IP HP
3. ICL-IP Catalogue
4. VECAP Eco-Design Presentation, Hirayama
www.BSEF.com
www.BSEF.com
ip.com
ip.com
-
-
http://www.icl
http://www.icl
The information herein is given in good faith; but no warranty,
The information herein is given in good faith; but no warranty, expressed or
expressed or
implied; is made with respect to slides described.
implied; is made with respect to slides described.

35. Focused Synergistic Responsible
Thank You