Electron Beam Flue Gas Treatment - PlasTEP

PlasTEP Summer School and Training Course
Warsaw/Szczecin 2011
Andrzej Pawelec
Electron beam flue gas treatment
Szczecin, 2 August 2011

Some history
• Early phase (Japan, 1970s)
• Pilot plants phase (Japan, USA, Germany, Poland 1980s,
1990s)
• Industrial plants phase (China, Poland, late 90s)
• Recent attempts (China, Bulgaria, Middle East)
Present operating plant:
• EBFGT at Pomorzany Power Station, Poland
• New facilities under construction

Technology basis

The idea of EBFGT
Conventional process
(wet-FGD + SCR)
EBFGT

Pollutants removed by EB method
The method has been designed for simultaneous removal of:
• SO 2
• NO x
Also there proceeds removal of other pollutants as:
• HCl, HF etc.
• Volatile Organic Hydrocarbons (VOC)
• Dioxins
• Mercury
• Others…

Electron beam effect on gas
Primary radiolysis products
4.43N eV 2
0.29N 2*
+ 0.885N( 2 D) + 0.295N( 2 P) + 1.87N( 4 S) + 2.27N 2+
+ 0.69N + +
2.96e -
100
5.377O eV 2
0.077O 2*
+ 2.25O( 1 D) + 2.8O( 3 P) + 0.18O * + 2.07O 2+
+ 1.23O + + 3.3e -
7.33H 2
O 0.51H 2
+ 0.46O( 3 P) + 4.25OH + 4.15H + 1.99 H 2
O + + 0.01H 2+
+
0.57OH 100 eV + + 0.67H + + 0.06O + + 3.3 e -
7.54CO 2
4.72CO + 5.16O( 3 P) + 2.24CO 2+
+ 0.51CO + + 0.07C + + 0.21O + + 3.03 e -
100
100
eV
1. J.C. Person, D.O. Ham: Radiat. Phys. Chem. 31 (1988) 1
2. H. Matzing: Model studies of flue gas treatment by electron beams, in: Application of isotopes and radiation in
conservation of the environment, IAEA-SM-325/186, International Atomic Energy Agency, Vienna 1995, pp.
115-124

Electron beam effect on gas
Secondary reactions
O( 1 D) + H2O 2OH *
N 2
+
+ 2H 2 O
*
H 3 O + + OH + N 2
O( 3 P) + O 2 + M O 3 + M
e - + O 2 + M
H 3 O + -
+ O 2
O - 2 * + M
HO 2 + H2 O
As a result of these primary and secondary reactions OH * ,
HO 2
*
, O * radicals,O 3 and other oxidizing species are formed,
that can oxidize NO, SO 2 and Hg

SO x / NO x removal

SO 2 removal pathways
radiothermal
SO 2
+ OH* + M HSO 3
+ M
HSO 3
+ O 2
SO 3
+ HO 2
*
SO 3
+ H 2
O H 2
SO 4
thermal
H 2
SO 4
+ 2NH 3
(NH 4
) 2
SO 4
SO 2
+ 2NH 3
(NH 3
) 2
SO 2
(NH 3
) 2
SO O 2 , H 2
O
2
(NH 4
) 2
SO 4
1. H. Namba: Materials of UNDP(IAEA)RCA Regional Training Course on Radiation Technology for
Environmental Conservation TRCE-JAERI, Takasaki, September/October 1993, 99-104
2. A.G. Chmielewski: Nukleonika 45(1) (2000) 31

NO x removal pathways
NO oxidation
NO 2 removal
NO + O( 3 P) + M NO 2
+ M
O( 3 P) + O 2
+ M O 3
+ M
NO + O 3
+ M NO 2
+ O 2
+ M
NO + HO 2
* + M NO 2
+ OH* +M
NO + OH* + M HNO 2
+M
HNO 2 + OH* NO 2
+ H 2 O
NO 2
+ OH* + M HNO 3
+ M
HNO 3
+ NH 3
NH 4
NO 3
H. Namba: Materials of UNDP(IAEA)RCA Regional Training Course on Radiation Technology for Environmental
Conservation TRCE-JAERI, Takasaki, September/October 1993, 99-104

NO x reduction in the presence of
ammonia
NO + N( 4 S) N 2
+ O
NO 2
+ N( 4 S) N 2
O + O
N( 2 D) + NH 3 NH* + NH 2 *
NO + NH 2
* N 2
+ H 2
O
NO 2
+ NH 2
* N 2
O + H 2
O
NO + NH* N 2
+ OH*
NO 2
+ NH* N 2
O + OH*
H. Namba: Materials of UNDP(IAEA)RCA Regional Training Course on Radiation Technology for Environmental
Conservation TRCE-JAERI, Takasaki, September/October 1993, 99-104

Simplified reaction mechanism
HNO 3 NH 4 NO 3
OH
OH
NO
O, OH OH
NO 2
NH 3
HNO 2
OH O 2 , OH H 2 O
SO 2 HSO 3 SO 3 H 2 SO 4
NH 3
NH 3
(NH 3 ) 2 SO 2
O 2 , H 2 O
(NH 4 ) 2 SO 4

Reaction mechanisms and sequence
of E-beam process

NO X removal factors
NO x removal depends on such parameters as:
• Dose (1 kGy = 1kJ/kg)
• NO x inlet concentration
• Ammonia concentration (stoichiometry)

SO 2 removal factors
Main process parameters influencing SO2 removal efficiency :
• Temperature
• Humidity
• Ammonia stoichiometry
• Dose
• Other parameters

Dependence of NO x and SO 2 removal
efficiencies on dose

VOC/mercury removal

The structures of PAHs emitted from coal
combustion
naphtalene acenaphtene anthracene fluoranthene
pyrene
benzo(a)pyrene
dibenzo(a,h) anthracene

PAHs’ emission at EB pilot plant
at EPS Kawęczyn [μg/Nm 3 ]
PAH name 2001 2000
naphtalene n.m. 0.001 - 0.009
acenaphtene C 12
H 10
0.005 – 0.006 0.354 – 1.027
fluorene n.m – 0.022 0.119 – 0.592
phenentrene 0.217 – 0.585 0.554 – 1.369
anthracene C 14
H 10
0.128 – 0.487 0.324 – 0.367
fluoranthene C 16
H 10
0.041 – 1.122 0.817 – 1.124
pyrene C 16
H 10
0.105 – 0.244 0.093 – 0.607
benzo(a)anthracene 0.153 – 5.750 2.804 – 4.680
chrysene 0.537 – 2.305 0.555 – 1.604
benzo(e)pyrene C 20
H 12
0.195 – 0.407 0.084 – 0.291
benzo(a)pyrene 0.254 – 0.661 0.804 – 2.467

Aromatic VOC decomposition
mechanism
Positive ions’ charge transfer reactions
Radical – neutral particles reactions
•OH radical reactions
M + + RH = M + RH +
˙OH + C 6
H 5
CH 3
= R1˙ (OH radical addition)
C 6
H 5
CH 3
+ ˙OH = R2˙ + H 2
O ( H atom abstraction)
•Organic radicals’ reactions
R. Atkinson: Chem. Rev. 85 (1985) 69
C 6
H 6
+ ˙OH = C 6
H 5
OH + H (H atom elimination)
R˙ + O 2
= RO 2˙
2 RO 2˙ = 2RO˙ + O 2
RO 2˙ + NO = RO˙ + NO 2
RO˙ + O 2
= HO 2˙ + products ( aromatic-CHO, -OH)
RO˙ aliphatic products

Removal efficiency of PAHs(%)
PAHs removal efficiency
100
90
80
70
60
without NH3
NH3
50
40
30
20
10
0
Acenaphthene
Fluorene
Phenanthrene
fluoranthene
Benzo(a)pyrene
A. Ostapczuk, A.G. Chmielewski, Y. Sun: Electron beam flue gases treatment as an integrated method of SO 2
,
NOx and volatile organic compounds (VOC) control. Fifth Inetrnational Symposium and Exhibition on
Environmental Contamination in Central and Eastern Europe. 12-14 September 2000, Prague, Czech
Republic, p. 227

Mercury oxidation
First step of removal process
Hg o oxidation removal
Hg2+ Mercury oxidation proceeds in reaction chamber
EPS Pomorzany – reaction chamber

According to:
Does it work?
Jo-Chun Kim, Ki-Hyun Kim, Al Armendariz and Mohamad Al-Sheikhly: Electron Beam Irradiation for
Mercury Oxidation and Mercury Emissions Control, J. Envir. Engrg. Volume 136, Issue 5, pp. 554-559 (May
2010)
At medium energy levels, approximately 98% of
gaseous mercury vapor was readily oxidized.
Expreriments were performed for following parameters:
Hg concentration in gas about 16 µg/m 3
applied doses of E-beam
2.5 – 10 kGy

Installation construction

The scheme of industrial installation
A.G. Chmielewski, E. Iller et al.: Modern Power Systems, 53-54 (May 2001)

History of investment :
‣ Feasibility Study 1994
‣ Basic Engineering 1996, technical design
‣ Contract with z IAEA, Sumitomo 1996
‣ Contract with Energobudowa (general contractor)
1998
‣ Begin of construction 1 IV 1999
‣ Start-up of the plant X 2000
‣ Routine operation IV2003

Main operational data
• Flue gas flow rate 100 000 - 270 000 Nm 3 /h
• Pollutants removal efficiency:
95 % SO 2
70 % NO x
• Total accelerators power: 1.04 MW
• Inlet flue gas parameters:
temperature 130 – 150°C
SO 2 concentration 1500 – 2200 mg/Nm 3
NO x concentration 400 – 600 mg/Nm 3
• Ammonia water consumption: 150 – 300 kg/h
• By-product yield: 200 – 300 kg/h

nom
nom
nom
nom
nom
Main units of the plant
AIR COMPRESSORS
AMMONIA WATER UNLOADING
AND STORAGE STATION
M
OPWP
OPWP
t =
250°
C
M
PROCESS WATER
M
M
M
M
t = 80°
C
p = 1.3
OWCW III
t = 20° C Q= 2100Nm 3
p = 0.8
SPRAY
COOLER
CISTERN
M
P2
Z3
PP
P1
M
Z1
Z2
P3.1
M
M
P3.2
Ammonia
storage
and
dosing
Flue gas
conditioning
Control
and
monitoring
AMMONIA
WATER
EVAPORATION
COLUMN
M
Z4
P7.1
M
M
P7.2
M
Reaction unit
A1
B1
BY-PRODUCT ELECTROSTATIC
PRECIPITATOR
WSW
M
Byproduct
collecting
and storage
M
REACTION CHAMBER 1
DC
DC
SUPPLY
NTA1
NTB1
SUPPLY
+ +
M
NTA2
NTB2
BY-PRODUCT STORAGE HOUSE
AND GRANULATOR
A2
B2
M
REACTION CHAMBER 2

Control, monitoring and data
management system
E-beam flue gas treatment process
Flue gas
T 0 , w 0 , s 0 , C 0SO2 , C 0NOx
water
compressed air
steam
Cooling and
humidification
waste
water
T 1 , w 1 , s 1 , C 0SO2 , C 0NOx
Ammonia
storage
ammonia
Mixing
T 1 , w 1 , s 1 , a 0 , C 0SO2 , C 0NOx
electric
energy
Reaction
T 2 , w 1 , s 2 , a 1 , C 1SO2 , C 1NOx
electric
energy
Filtration
T 2 , w 1 , s 3 , a 1 , C 1SO2 , C 1NOx
electric
energy
Transportation and storage of
by-product
electric
energy
Compression of purified
flue gas
electric
energy
Granulation or
packaging
T 2 , w 1 , s 3 , a 1 ,
C 1SO2 , C 1NOx
electric
energy
Loading and
transportation

Cooling and humidification process
1. Cooling column with dry bottom
2. Cooling column with water recirculation

Cooling and humidification process
3. Cooling in ducts

EPS Pomorzany
gas cooling tower

1. Liquid ammonia
Ammonia supply system

2. Ammonia water
Ammonia supply system

EPS Pomorzany
– ammonia
water tank

EPS Pomorzany
- accelerator

Accelerator
vs. kinescope

Reaction unit
•power suppliers
•water cooling system
•windows cooling
system
•X-radiation shielding
•ventilation system

EPS Pomorzany
– process vessel

Accelerator and reaction chamber
Zasilanie katody
Zasilacz DC
Katoda
Tuba przyspieszająca
Elektrody przyspieszające
Cewki odchylania
Skaner
Pompa próżniowa
Powietrze chłodzące
folie

Dose deposition in reactor
Arbitral units

Different reactor construction variants
Variant 1
Variant 2
Variant 3
Variant 4

Velocity field
Variant 1
Variant 4

The obtained results

Filtration
• Electrostatic precipitator
• Bag filter
• Wet gravel bed filter
• Venturi scrubber

EPS Pomorzany - ESP

By-product
storage
EPS Pomorzany
– byproduct storage building

Control and monitoring system
Control room at EPS Pomorzany

Removal [%]
The obtained results
The dependence of SO 2 and NO x removal efficiency on
dose
100
90
80
SO2
70
60
50
40
NOx
30
20
10
0
5,0 5,5 6,0 6,5 7,0 7,5 8,0 8,5 9,0 9,5 10,0
Dose [kGy]

Removal [mg/Nm 3 ]
The obtained results
The dependence of SO 2 removal on temperature
2000
1800
1600
1400
1200
1000
800
600
400
200
0
60 65 70 75 80 85 90
Temperature [°C]

Removal [mg/Nm 3 ]
The obtained results
The dependence of SO 2 and NO x removal on ammonia
stoichiometry
1800
1600
1400
1200
1000
800
600
SO2
400
NOx
200
0
30,00 40,00 50,00 60,00 70,00 80,00 90,00 100,00
Ammonia stoichiometry [%]

Removal [%]
The obtained results
The dependence of SO 2 removal efficiency on ammonia
injection mode
100
90
80
70
60
50
40
30
20
10
0
0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 0,90 1,00
Ammonia mass fraction sprayed into cooling tower

The byproduct

NPK fertilizers
made of
by-product

The by-product
by-product composition:
(NH 4 ) 2 SO 4 45-60%
NH 4 NO 3 22 - 30%
NH 4 Cl 10 - 20%
moisture 0,4 - 1%
water insoluble parts 0,5 - 2%
by-product yield:
up to 300 kg/h

By-product heavy metals concentrations
[ppm]
Metal Pb Cd Hg As
Pilot plant EPS
Kawęczyn
< 5
0.5 ÷
0.6
0.02 ÷
0.05
0.25 ÷
0.39
Max. allowable
(Polish standards)
140 140 2 50

Economy
Emission control method
Investment cost
(USD/kW e )
Annual operational cost
(USD/MW e )
Wet flue gas desulphurisation 120 3000
Selective catalytic reduction 110 4600
Wet FGD + SCR 230 7600
Electron beam FGT 160 7350
EBFGT (low NOx removal) 130 4100

Strong points of technology
• Simultaneous removal of SO 2 and NO x ,
multipollution control system
• High removal efficiency
• High flexibility of installation
• Dry process
• Wasteless process, usable byproduct
• Simple facility construction
• Easy retrofitting
• Economical competitiveness

Potential applications of EBFGT technology
• Power plants (hard coal, oil, lignite combustion) - Asia, Middle
East, developing countries…
• Refineries (oil combustion)
• Waste incinerators (VOC, dioxins)
• Ore sintering plants, (high SO 2 content)
• Chemical processes (multipollutant emission control)
• Others…

Final remarks
1. Electron Beam flue gas treatment process has been implemented in
power industry. Due to the installed beam power (over 1 MW),
plant constructed in EPS Pomorzany is the biggest radiation
processing facility ever built.
2. High efficiency of pollutants removal has been achieved.
3. The technology is competitive to conventional ones from removal
efficiency and economical points of views.
4. With the agricultural use of the by-product the method becomes
waste free and environmental friendly.
5. There are possibilities for the process application for PAH
emission control e.g. at municipal waste incineration plant.

Thank You for Your Attention