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153

Halogens, dioxins/furans
• Halogen compounds in fuels and fuel/flue gases
• Chlorine-related corrosion
• HCl control in flue gases and fuel gases
• Dioxins/furans
Dioxins/furans formation and control
• Other compounds: HF, HBr,
HBr, brominated organo-halogens
organo-halogens

see: www.hut.fi/~rzevenho
www.hut.fi/~rzevenho/
/gasbook

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Organo-halogen compounds
4 6
3 7

2 8
1 9

2,3,7,8 tetrachloro dibenzo - p- dioxin

PCB
furan
PCBs polychlorinated biphenyls 2,3,7,8 tetrachlorodibenzo furan
PCDDs polychlorinated dibenzodioxins
PCDFs polychlorinated dibenzofurans
with bromine: PBBs,
PBBs, PBDDs etc.

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 HELSINKI UNIVERSITY OF TECHNOLOGY ENE-47.153

Halogens in fossil fuels (mg/kg)

(listed as F, Cl, Br)

Coal*, lignite 20 -500 / Light fuel oil -

50-2000/0.5 -90
Peat ~ 500 Heavy fuel oil - / < 20

Estonian oil shale ~2000 Orimulsion™ ~700

Petroleum coke, “petcoke” ~ 300 Natural gas -

* Iodine 0.5 - 1.5 mg/kg

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Wood 0.08 - 0.13 Munical solid waste (MSW) 0.005 - 0.025 /

Halogens (firewood)
Bark 0.02 - 0.4 Refuse derived fuel (RDF)
0.05 - 0.25
0.001 - 0.07 /
0.3 - 0.8
in biomass Straw 0.1 - 1.5 Packaging derived fuel (PDF) 0.001 - 0.012 /
1-4
and waste Landfill gas ~50 ppmw CCl44 Car tyre scrap 500 - 700

streams Textile ~ 0.25

Auto shredder residue (ASR) 0.5 - 2

Newsprint paper ~ 0.11 Computer circuit boards 0.1 - 0.5 /2 - 6

(mg/kg) Leather waste 0.7 - 3
(epoxy or phenolic resins)
Computer monitor housings ~ 0.1 / ~ 2
Electric & electronic equip- ~ 3.5 / ~ 0.9
ment (E&E) waste plastics *
Sewage sludge 0.03 - 1
(listed as F, Cl, Br) Mixed medical waste 1-4
Polyurethane foam ~ 0.7 /~ 8/~ 3
(containing CFC11)
PVC ~ 50 Black liquor solids 0.05 - 0.2
* Polymer market mix 1998

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Oxidation rate of CO in FBC in presence of HCl

CO oxidation rate (mol/m3s) 1

0.1

0.01 1100 K
1 bar

0.001 10% O2
5% CO
10% H2O
0.0001

0.00001
0.001 0.01 0.1 1 10 100 1000 10000

HCl in gas ( ppm-v)

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Emission standards for halogen compounds

Power MSW MSW Power MSW Waste

@ 11 % O22, dry plant incinerator incinerator plant incinerator incinerator
Finland Finland EU Germany Germany USA
(1990+) (1994) (2000) (1999) (1999) (1995)
HCl no standard 10 10 50 10 29.1 or
mg/m³STP
STP 99.5% red.
HF no standard 1 1 2 1 no standard
mg/m³STP
STP

PCDD/F no standard 1 0.1 no standard 0.1 9.63

ng/m³STP
STP TEQ

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Chlorine-related corrosion #1

Dewpoint of Corrosion rate by HCl and Cl2

hydrochloric acid

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Chlorine-related corrosion #2
Important for
chlorine-related
corrosion:

HCl,
HCl, Cl2
NaCl,
NaCl, KCl,
KCl,
O2, SO2, H2O

Tube metals

Temperature

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Chlorine-related corrosion #3

Corrosion rate versus chlorine in coal

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Halogen removal
in FGD
(with forced oxidation)

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Removal of HCl (& HF, HBr)

HBr) from flue gases
• Conventional, at low concentrations:
in wet scrubber for FGD, gives ~70% removal of HCl,
HCl, HF.
Disadvantages:
– dissolution of SO2 and lime/limestone are inhibited
– HF and fly ash give AlFx complexes in FGD (Inkoo,
Inkoo, Finland)
– Corrosion, deposits formation upstream

• More suitable methods:

– (cold) inject alkali and collect salt particles in filter
– (hot) injection of calcium-based sorbent in upper furnace

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Flue gas to
Flue gas from
dust separator
SO2 separator 3-stage
Pump / HCl scrubber,
3rd stage container
1st stage
Packing set stage 3 producing
Water hydrochloric
2nd stage Pump /
container
Packing
set stage 2
acid

gives 14-18 % HCl,

HCl,
Salt solution which is further
to vaporiser Water processed to
30-31%

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Sorbents for HCl, HF, HBr (i.e. HX) #1

Limestone CaCO3 Lime CaO Hydrated lime Ca(OH)2
Nahcolite NaHCO3 Soda/trona
Soda/trona NaHCO3•Na2CO3

Melting points of halogen salts

NaF:
NaF: 988 °C ; NaCl:
NaCl: 801 °C ; NaBr:
NaBr: 755 °C
CaF2: 1360 °C ; CaCl2: 772 °C ; CaBr2: 730 °C
KF: 858 °C ; KCl:
KCl: 770 °C ; KBr:
KBr: 734 °C

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Sorbents for HCl, HF, HBr (i.e. HX) #2

Potassium salts : high vapour pressures for KF, KCl,

KCl, KBr

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Removal of HCl and HF from pulverised

coal combustion flue gas (Illinois, US, 1993)
Hydrated lime injected into a coal-fired
boiler at Ca/S=1.66, 3%-wt sulphur in fuel
Chemistry :
Injected into upper furnace at ~1250°C
Ca(OH2) → CaO + H2O
CaO + 2 HCl → CaCl2 + H2O
CaO + 2 HF → CaF2 + H2O

Results :
HCl 63-86% removal,
from 660 ppmw
HF 94-99% removal
from 49 ppmw

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Halide removal (HCl, HF)

from IGCC raw fuel gas at ~400°C
Buggenum IGCC
HCl ~ 600 ppm
HF ~ 220 ppm

Texaco IGCC
HCl ~ 500 ppm
HF ~190 ppm

for coal,
0.2 % Cl,
Cl, 0.04 % F

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Removal of HCl from flue gas

with various sorbents

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Formation of dioxins / furans #1

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Formation of
dioxins / furans #2

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“De Novo” dioxins / furans formation

Depends on 5 major factors :
1. The cooling rate of the flue gas, especially around 300°C
2. The amount of fly ash
3. The presence of trace elements, especially Cu and Pb
4. The carbon and chlorine content of the fly ash
5. The presence of free oxygen

Radical reactions Cl + OH → HCl + O, OH + H → H2O

are competing with CO + OH → CO2 + H
giving apparently lower stoichiometry,
stoichiometry, giving more soot and CxHy

Deacon reaction : 2HCl + ½ O2 <=> Cl2 + H2O

catalysed by Cu, Pb,
Pb, Sn,
Sn, .... ; reaction equilibrium to Cl2 below ~500°
~500°C

Cl2 + O2 + CxHy + time @ 250-350°C → PCDDs/Fs

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Equivalence schemes for PCDD/Fs

Dioxin I- TEF Furan I - TEF
2,3,7,8-TCDD 1 2,3,7,8-TCDF 0.1
1,2,3,7,8-PCDD 0.5 1,2,3,7,8-PCDF 0.05
1,2,3,4,7,8-HxCDD 0.1 2,3,4,7,8-PCDF 0.5
1,2,3,6,7,8-HxCDD 0.1 1,2,3,4,7,8-HxCDF 0.1
1,2,3,7,8,9-HxCDD 0.1 1,2,3,6,7,8-HxCDF 0.1
1,2,3,4,7,8,9-HpCDD 0.01 2,3,4,6,7,8-HxCDF 0.1
1,2,3,4,6,7,8,9-OCDD 0.001 1,2,3,7,8,9-HxCDF 0.1
1,2,3,4,6,7,8-HpCDF 0.01
1,2,3,4,7,8,9-HpCDF 0.01
1,2,3,4,6,7,8,9-OCDF 0.001
International Toxic Equivalence Factors (I-TEF) (NATO, 1988) standardize the toxicity of the
dioxins and furans, to derive a toxic equivalence as 2,3,7,8-TCDD. The I-TEF for the dioxins
and furans without chlorine atoms at the 2, 3, 7, and 8 positions is zero.

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Rate of de novo PCDD/F formation

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Effect of calcium-based sorbents on

PCDD/F release from an FB waste combustor

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Emission control for PCDD/Fs

• Carbon injection*
• Fixed bed carbon absorption + SNCR
• SNCR + carbon injection*
• Lime / char adsorption
• SCR catalytic oxidation
• SCR catalytic oxidation + carbon injection*
* collected downstream in (a separate) dust control system

also for PCBs, brominated compounds (PBBs

(PBBs,, PBDD/Fs)

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Dioxins/furans control for waste incinerators

(MSW = municipal solid waste)

process PCDD/Fs from gas clean-up PCDD/Fs removal

furnace ng/m³STP system efficiency %
5 incinerators for RDF 43 - 2157 wet scrubber + > 95.7
or MSW fabric filter
3 incinerators for 28 - 783 SCR + wet scrubber 87.7 - 99.6
MSW + fabric filter
pilot incinerator for 87 - 2277 sorbent injection + > 99.55
MSW fabric filter
MSW incinerator 170 wet scrubber + ESP 64.3

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PCDD/F removal by a bag filter :

effect of entrance temperature

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Other halogens #1:

control of HF + HCl

Process* Temperature HF removal HCl removal

at outlet E C % %
dry sorbent injection + fabric filter 160 - 180 98 80
spray dryer absorber + ESP 140 - 160 99 > 95
spray dryer absorber + fabric filter 140 - 160 99 > 95
spray dryer absorber + dry sorbent ~ 200 99 > 95
injection + ESP or fabric filter
ESP + wet scrubber 104 - 122 99 > 95
spray dryer + west scrubber + 104 - 122 99 > 95
ESP or fabric filter
* sorbent = sodium- or calcium- based sorbent

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Other halogens #2:

formation of brominated dioxins/furans
(PBDD/Fs) from PBDE flame retardants

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