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July 3, 2006
POSTECH
POSTECH Plasma Sheath Laboratory
Typical plasma sources at atm pressure 3
Air
POSTECH
POSTECH Plasma Sheath Laboratory
Diagnostics of atmospheric plasma parameters 4
6
10
Line of Tgas ~ Te
0C) (°C)
5
10
Gas Temperature (rise
4
ne ~ 1018cm-3
10
Arc
MW Torch ne ~ 1015cm-3
3
10
DBD ne ~ 1012cm-3
&
2 RF
10 Jet
DBD & Pulsed Corona ne ~ 1012cm-3
1
10
0 5 10 15 20
Electron Temperature (eV)
POSTECH
POSTECH Plasma Sheath Laboratory
Non-thermal plasma processes have; 6
¾Advantages
Atmospheric pressure and room temperature
Higher reaction energy is available (attractive for chemical reactions)
Simultaneous treatment of gas and particulate materials
Simple reactor configuration is possible – Low initial cost, hybrid system
Easy operational control – Switch ON/OFF & power up/down, electrically
POSTECH
POSTECH Plasma Sheath Laboratory
Plasma chemistry in non-thermal plasma 7
10-15 sec 10-10 sec 10-8 sec 10-6 sec 10-4 sec 10-2 sec 10-0 sec
Dissociation
e + AB → A + B + e Plasma Zone
POSTECH
POSTECH Plasma Sheath Laboratory
Pollutants removal mechanism using plasma 8
Non-thermal State
Neutralization and
Formation of Salts
Chemical Reactions of
H2SO4 + 2NH3 → (NH4)2SO4 Pollutants with CAS
HNO3 + NH3 → NH4NO3
SO2 → SO3 → H2SO4
CAS CAS
POSTECH
POSTECH Plasma Sheath Laboratory
Energy Dissipation for Electric Field 9
POSTECH
POSTECH Plasma Sheath Laboratory
Historical milestone of Non-Thermal Plasma technology 10
De-NOx/SOx
Ozonizer DBD Ozone Generator VOCs Removal
(Siemens)
Water Plant (Netherlands, 1893)
Silent Discharge
(Warburg, 1904)
1857 1900 1950 1970 1980 1990 2000 year
Water Treatment
DC Corona
De-NOx/Sox
Negative HVDC-corona VOCs Removal
+Pulse Corona
1st ESP Installation
(Cottrell, 1905) Pilot-Plant Middle-
(ENEL) Scale Plant
POSTECH
POSTECH Plasma Sheath Laboratory
Pulsed plasma treatment of flue gas R&D in Korea 11
POSTECH
POSTECH Plasma Sheath Laboratory
Large-scale NTP tech. efforts for flue-gas cleaning 12
Masuda Dioxin
DC-bias Propane
Research Inc., 2001 Wire-cylinder 6,700 Dust ~6 ~92.4 %
pulse (100)
Jp. ( <5mg/Nm3 )
Wire-plate Pulse NOx (73) 60%
RIST, Ko. 2001 5,000 C3H6 (48) 4
(Plasma+ESP) (MPC) SO2 (150) 90%
Doosan-Heavy Pulse 1,700 NOx (300) NH3 9 70%
2003 Retrofitted ESP
Industry, Ko. (MPC) 100,000 SO2 (300) C2H4 (600) X 95%
Takuma
Co.,Jp. Surface corona
2003 AC (16kW) 51,000 Odor - 0.2 99%
with catalyst
(WWTP)
POSTECH, Pulse NOx (120) NH3 (370) 70%
2003 Wire-plate 42,000 1.4
Ko. (MPC) SO2 (150) C3H6 (55) 99%
POSTECH
POSTECH Plasma Sheath Laboratory
Field test (100 tons/day Incinerator at K-Iron mill) 13
MPC-120K for
simultaneous
DeSOx & DeNOx
Corona Discharge
POSTECH
POSTECH Plasma Sheath Laboratory
Layout of plasma system for flue gas treatment 14
MPC
MPC MPS
MPS
① ②
System
System System
System ③
DAMPER ⑤
GAS
ANALYZER
④
DAMPER
+PULSE
CORONA
REACTOR
ESP
ESP
CORONA
REACTOR
1. AMMONIA INJECTION
2. ADDITIVE INJECTION
⑥
3. ID FAN Gas flow rate(Nm3/hr) 50,000
4. DUST SAMPLING PORT
Gas velocity(m/sec) 1.2-1.4
5. GAS SAMPLING PORT
6. HOPPER Gas temperature(oC) 193
GP(Gas Passage) number 11
Main parameters of GP size, W x H x L(m) 3.2x6.2x4.5
Pulsed corona reactor. Total wire length(m) 480
Wire diameter(mm) 10
Distance between plates(cm) 300
POSTECH
POSTECH Plasma Sheath Laboratory
Non-thermal plasma & Electrostatic precipitator process 15
Collecting electrode
Ground electrode
Discharge
electrode
+ SO 2, NO x O 2, H 2O
Discharge
O, OH electrode
H2SO4 , HNO3
Dust
POSTECH
POSTECH Plasma Sheath Laboratory
Key Parameters of MPC Modulators 16
built by Postech-Poscon
POSTECH
POSTECH Plasma Sheath Laboratory
Circuit of MPC modulator 17
W1 R1
PS1 PSB1 PSB2
W2 R2 HVP
PS2 LB1 CB1 LB2 CB2
MS1 MS2
W4 R4
PS4
L2
L3
TP1 C2 C3 CL RL
Plasma
R6
D1 T1 Reactor
R5
D2
POSTECH
POSTECH Plasma Sheath Laboratory
MPC-120K System 18
POSTECH
POSTECH Plasma Sheath Laboratory
MPC Operation: V & I Waveforms 19
1 CVD3 [kV]
Voltage [kV]
100
2
V2 50
V1 0
Vc
ΔT ΔT -50
0 2 4 6 8 10 12 14 16 18 20
6 Time [us]
0 CT4 Reactor c u r r e nt
Time 5
Current
Δ T : Statistical time lag CT2 [kA]
4
(20 ~ 80 ns) CT3
CT3 [kA]
CT4 [kA]
uurent [kA]
(~30kV/cm) 2
C
CT2
V1 : Corona onset 1
CT5 tai l
voltage of curve 1
0
V2 : Corona onset
voltage of curve 2 -1
0 5 10 15 20
POSTECH
POSTECH Time [us] Plasma Sheath Laboratory
DeSOx Performance with MPC-120K 20
350
Ammonia (20 Nm3/hr)
300 injection
Concentration (ppm)
Plasma
250 Plasma on
off
200 Plasma on
150
100
50
0
8:52 10:04 11:16 12:28 13:40 14:52 16:04
Time
Inlet SOx Outlet SOx
POSTECH
POSTECH Plasma Sheath Laboratory
DeNOx Performance with MPC-120K 21
120
(20 Nm3/hr)
100 NH3 Plasma off
injection NH3 off
(3 Nm3/hr) Plasma on
C3H6 C3H6 off
Concentration (ppm)
Injection
80 (160 kV, 260pps)
Plasma on
60
40
20
0
8:52 10:04 11:16 12:28 13:40 14:52 16:04
Time
Inlet NO Outlet NO
Max. P/Q = 1.4 Wh/Nm3 with 55 ppm Propylene , 370 ppm NH3 Addition
: NOx removal > 70% (70~75 ppm Æ 20 ppm); ~ 22 eV/NO-molecule
POSTECH
POSTECH Plasma Sheath Laboratory
1-day TMS Data sample from Incinerator
22
(Y)Dust : 5 ~ 70 mg/m3
(P)Gas temp ~ 60°C
(P)NOx : 10~40°C
Stable dust
emission
POSTECH
POSTECH Plasma Sheath Laboratory
MPC-120K Performance Result at Incinerator 23
Best results
P/Q = 1.4 Wh/Nm3 with
55 ppm Propylene & 370
ppm NH3 addition
Yearly operation require;
~100 ton/yr Ammonia
~ 40 ton/yr Propylene
& ~150 kW electricity
Average performance
DeSOx Î > 99%
DeNOx Î ~ 70%
POSTECH
POSTECH Plasma Sheath Laboratory
Pulsed corona process results - summary 24
100
Initial NO=99ppm DCHV=32.4kV
With C3H6 ethylene Initial NO=157ppm
8 eV/NO Incinerator (MPC)
NO Removal Efficiency [%]
60
40 ENEL Data
Initial NO=150ppm Coke plant (MPC) Initial NO=350ppm
With C3H6 ethylene Initial NO=150ppm No Ammonia
With C3H6 ethylene
20 36 eV/NO
Sintering plant (MPC)
Initial NO=150ppm Initial NO=150ppm
NO ethylene 48 eV/NO
With C3H6 & NH3
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
POSTECH
POSTECH Plasma Sheath Laboratory
Primary source of NOx in cities 25
Industrial/
Industiral/
Commercial/
Commercial/
Residential
Residential Utilities
Utilities
19
19%
% 27
27% %
All
Other
Source
5%
Motor
MotorVehicles
Vehicle
49
49 %
% Sales trend of diesel passenger cars in Europe.
POSTECH
POSTECH Plasma Sheath Laboratory
Diesel Engine Test (De-NOx Process) 26
2. Plasma Reactor
operating temp.: up to 400 oC
Plasma reactor operating hours: 6 months
Advantage:
1. Low Temp. Operation : 100 oC
2. Reduce SCR catalyst volume: 1/3
3. Helpful to soot removal process
POSTECH
POSTECH Plasma Sheath Laboratory
Plasma/SCR DeNOx Result (SV: 4,000 hr -1 , 300 HP) 27
100 100
200 ppm NOx at inlet
90 90
80 80
NOx Reduction Rates [%]
70 70
60 Plasma + SCR 60
SCR
50 50
40 40
30 30
20 20
10 10
0 0
100 125 150 175 200
Temperature [oC]
Unit : kton/yr
7 84 3 76 157
Seoul
(1.4%) (8.9%) (3.8%) (7.2%) (19.5%)
22 40 2 42 44
In-cheon
(4.4%) (4.3%) (2.6%) (4.0%) (5.5%)
POSTECH
POSTECH Plasma Sheath Laboratory
Lab scale test setup for VOC removal 29
100:1
1000:1
Capacitor
I μF
HEPA Vent
Plasma Reactor
Filter
Benzene
Catalyst
Heating
Tape GR
+
MFC
FTIR
(ABB Bomem MB series)
Mixing
Box
17.5 cm
Glass/TiO2
Mass Flow
O2 N2 N2
Controller
Temperature
Controller Alumina/TiO2
POSTECH
POSTECH Plasma Sheath Laboratory
VOC decomposition using plasma+catalyst 30
200
Benzene concentration (ppm)
150
w/o packing
glass
Pulsed-corona
100 MS 5A
Pt/ Al2O3 (Noise)
Al2O3 (Noise)
50
DBD
DBD+catalyst
0
0 200 400 600 800
Specific input energy (J/L)
POSTECH
POSTECH Plasma Sheath Laboratory
Industrial application of plasma odor removal 31
120
20
100
Inlet concentraion (ppm)
Removal efficiency(%)
15 Ammonia (NH3)
80
Hydrogen sulfide (H2S)
계열3 60
10
계열4
40
5
20
0 0
10
12
14
08
14
17
14
16
20
22
26
3.
3.
3.
4.
4.
4.
5.
5.
5.
5.
5.
Days
POSTECH
POSTECH Plasma Sheath Laboratory
Microwave plasma torch treatment of exhaust gases 33
Incinerator
Microwave Plasma Torch (Dioxin, Soot,
NOx, Fly ash, etc)
POSTECH
POSTECH Plasma Sheath Laboratory
Toxic gas removal test setup using plasma torch 34
Needle
Heated line valve Exhaust
MFC
FT-IR
Wet
Gas mixing scrubber
NF3 vessel Plasma
SF6
Flow
N2
CF4
Quartz tube
O2
2.45 GHz Magnetron
Air Microwave source
Cavity
POSTECH
POSTECH Plasma Sheath Laboratory
CF4 and SF6 removal using plasma torch (~ 1kW) 36
1500
Plasma
Concentration (ppm)
1250 off
1000
750
0
60 120 180 240
Time (sec)
POSTECH
POSTECH Plasma Sheath Laboratory
Mercury(Hg) Emission Sources 37
Trash
Industry Iron & Steel
Asia Incinerator Cement Incinerator
Source : Presentation by J. Pacyna and J. Munthe Source : Environment Canada, Ontario Region (2004)
at mercury workshop in Brussels, March 29-30, 2004
Activated carbon
injection method
Photo-oxidation method
using 253.7nm,
Photocatalysis (TiO2)
Plasma method
(corona, DBD)
Mechanism of Mercury Removal using Plasma
N2 N2
O2 HgO, O2, O3,
O2
N2, NO2
Hg Plasma process Wet Scrubber
Hg0 + O3 → HgO + O2 HgO → High Solubility in water
Hg0 + O → HgO
POSTECH
POSTECH Plasma Sheath Laboratory
Elementary Mercury Oxidation Using Plasma 39
MFC
MFC
N2 Neon Transformer
Mercury Bath Variac
(Temp. Controlled)
OVEN
Tube Furnace
Mercury Hood
Analyzer Vent
Activated Carbon
POSTECH
POSTECH Plasma Sheath Laboratory
Elementary Mercury Oxidation Using Plasma 40
40
33.3 J/L
60
Plasma Off
30 15.6 J/L
20 40
21 oC 306 μg/m3
10 90 oC 273 μg/m3
0
20 150 oC 283 μg/m3
0 Plasma On
0 5 10 15 20 25 30 0 20 40 60 80 100 120
POSTECH
POSTECH Plasma Sheath Laboratory
ECO (Electro-catalytic Oxidation) Pilot Unit by Powerspan Corp. , U. S. A 41
A wet ESP
DBD reactor
~ 4000 m3/hr
Outlet Elementary Hg
10
DBD Off DBD Off DBD Off
9
Hg0 Concentration [ug/m3]
7
6
5
DRE : 56% DRE : 65%
4
3
DBD On (31.8 J/L) DBD On
2
(42.4J/L) DRE : 79%
1
DBD On (53J/L)
0
12:00 13:05 13:40 14:25 15:00 15:35 16:20 16:40 17:25 18:00 18:25
Time Flow rate → 4000 m3/hr
POSTECH
POSTECH Plasma Sheath Laboratory
Pollutants removal efficiency by plasma sources 44
Odor Odor
100 H2S,NH3
~10 ppm C7H8/ 110 ppm
SOx/ 110 ppm
90
Removal efficiency (%)
20
(1,000 Nm3/hr) DBD
DBD + Catalyst
NO/ 152 ppm
10 Torch
NOx / SOx VOCs & Hg
0
1 10 100 1000
Specific Input Energy (J/L)
POSTECH
POSTECH Plasma Sheath Laboratory
Cost Comparison (approximate estimation) 45
Plasma
Item FGD + SCR E-Beam
process
Construction
50 M$ 80 72
Cost/Unit
Depreciation
4 M$/unit-year 8.1 6.5
Expenses
First year
57.5 M$/Year 94.6 81.2
annual cost
Installation
Area 3,600 m2 8,000+300 m2 6,400 m2
Requirement
* Note; US 1$ = 1,000 Won
* Ref; S. Masuda, Non-Thermal Plasma Techniques for Pollution Control: Part B, p. 131, 1993)
POSTECH
POSTECH Plasma Sheath Laboratory
Comments-1: Plasma power supply system 46
POSTECH
POSTECH Plasma Sheath Laboratory
Comments-2 47
POSTECH
POSTECH Plasma Sheath Laboratory
48
POSTECH
POSTECH Plasma Sheath Laboratory