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8th APCPST at Cairns, Australia

July 3, 2006

Environmental Applications of Plasmas

M.H. Cho, K. B. Ko, Y. C. Byun


Department of Physics & ESE-Program, POSTECH, Pohang, Korea

D.N. Shin, D. J. Koh


Air Protection Team, RIST , Pohang, Korea

* Work supported by MOST and NFRC


Contents 2

1. Introduction of plasma sources for environmental applications


2. Overview on environmental applications of plasmas
1) Non-thermal plasma technology for flue gas cleaning
2) Abatement of vehicle exhaust gases
3) VOCs and odor removal
4) Microwave plasma torch for toxic gas treatment
5) Elementary mercury removal/oxidation
3. Summary
¾ R&D results
¾ Technical & economic issues

POSTECH
POSTECH Plasma Sheath Laboratory
Typical plasma sources at atm pressure 3

Pulsed Corona(+) DBD Microwave Plasma

wire cylinder rod barrier cylinder

Air

POSTECH
POSTECH Plasma Sheath Laboratory
Diagnostics of atmospheric plasma parameters 4

Plasma Method Parameter Result Reference


Source
DBD Optical Electron Temp. 9 ~ 10 eV Kim (Seoul National Uni.) 1)
Numerical Electron Temp. 5 ~ 10 eV
Electron Density 1011 ~ 1012 cm-3 B. Eliasson 2)
F. Massines (Paul Sabatier Uni.) 3)
Optical Ion Density 1011 ~ 1012 cm-3 F. Massines (Paul Sabatier Uni.) 3)
Gas Temp. 300 ~ 600K J. Luque (Lam Research Corp.)4)
(+) Pulsed Numerical, Electron Temp. 10 ~ 12 eV Kim (Seoul National Uni.) 1)
Corona & Optical Gas Temp. rise < 50K
Micro- Optical Gas Temp. 1500K Moon(Kaist) 5)
wave Excitation Temp. 5000 ~ 7000K Karyn (M.I.T) 6)
Plasma 5500 ~ 6000K Moon(Kaist) 5)
Torch Moon(Kaist) 5)
Electron Density 1014 ~ 1015 cm-3 J. Torres (Uni. de Cordoba) 7)
1014 ~ 1015 cm-3
RF Optical Gas Temp. 393K Park (LANL) 8)
Plasma N2 Vibrational Temp. 3000K Moon(Kaist) 9)
Torch Fe Excitation Temp. 3000 ~4500K M.M. Rahman 10)
Park (LANL) 11)
Electron Temp. 1.5 eV M. Moravej 12)
1.5 ~ 2.5 eV M. Moravej 12)
Electron Density 1011 ~ 1012 cm-3
Arc Enthalpy Gas Temp. 3500 ~ 7500K Choi (Seoul National Uni.) 13)
Probe
POSTECH
POSTECH Plasma Sheath Laboratory
Comparison of the gas and electron temperatures 5

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
ƒ Atmospheric pressure and room temperature
ƒ Higher reaction energy is available (attractive for chemical reactions)
ƒ Simultaneous treatment of gas and particulate materials
ƒ Simple reactor configuration is possible – Low initial cost, hybrid system
ƒ Easy operational control – Switch ON/OFF & power up/down, electrically

¾ Things needed for improvement/industrialization


ƒ Reduction of energy consumption
: Improvement of power supply system & power delivery for plasma generation
: Additives, removal process mechanism (Chemical aspect)
ƒ Toxic by-products issues
ƒ Process stability issues

POSTECH
POSTECH Plasma Sheath Laboratory
Plasma chemistry in non-thermal plasma 7

Plasma zone Plasma, after glow zone After glow zone


Recombination
Gas-solid reactions
Ionization Ion-molecule Ion-ion Radical - radical
e + A → A+ + 2e reaction Radical - neutral Gas-gas reactions

Excitation De-exitation Radical, ion, metastable reactions


e + A → A* + e → A + hν Primary radicals Secondary radicals
(O, N, OH) (O3, HO2, H2O2)

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

Streamer propagation After Glow Zone


(~ 108 cm/sec)

POSTECH
POSTECH Plasma Sheath Laboratory
Pollutants removal mechanism using plasma 8

Plasma Discharge Produces Formation of Chemically


Energeic Electrons Reactive Species (CAS)
& UV lights (O, OH, RO2, O3)

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

Reduction by catalysts NO → NO2 → HNO3


CAS CAS

NO, NO2 + NH3 → N2, H2O


VOCs → CO2, CO,
CAS

Removal of VOCs and its byproduct


H2O, by-products

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 Flue Gas Treatment


E-beam
Pilot-Plant Test Full-Scale Plant

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

1. Lab scale test; unversities, national labs


2. Research on large-scale pilot plant;
(a) 1,700 Nm3/hr Diesel Boiler (~250 KW) : KIMM Æ ~ 1.5 W-hr/m3
(b) 2,000 Nm3/hr Coal Boiler : KEPRI Æ (test completed, 2000)
(c) 5,000 Nm3/hr Iron Ore Sinter Plant : RIST Æ ~ 3 W-hr/m3
(d) 100,000 Nm3/hr Coal Boiler : DHI Æ (test run start; 2001) Æ X
(e) 33,000 Nm3/hr POSCO Sinter Plant : RIST Æ (test run start; 2002)

3. Important R&D issues


(a) Chemical additive Î economic & non-toxic, improved energy efficiency.
(b) Optimum reactor design Î economic and reliable system.
(c) Pulse modulator research Î reliability, high efficiency, economic system.
(d) System engineering for large scale plants
(e) Miscellaneous;
- Recovery of reaction product Î Electrostatic precipitator or bag-filter

- Understading of the DeNOx & DeSOx process mechanism.

POSTECH
POSTECH Plasma Sheath Laboratory
Large-scale NTP tech. efforts for flue-gas cleaning 12

Power Flow rate Target gases Additives SIE


Institution Year Reactor DRE
supply (Nm3/h) (ppm) (ppm) (Wh/Nm3)
NOx
Wire-plate NH3 60%
ENEL, It. 1990 Pulse 1,000 (430~550) ~ 15
(plasma+ESP) CaOH2 80%
SO2 (360~500)

Pulse NOx 50%


Korea Cottrell 1998 Wire-plate 10,000 NH3 X
(RSG) SO2 89%

Dalian Univ. Pulse


1998 Wire-plate 1,400 SO2 (2000) NH3 3.9 80%
Ch. (RSG)

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

(construction:2001 ~ 2003, R&D ongoing)


MPS for dust collection
ESP + Plasma Reactor

MPC-120K for
simultaneous
DeSOx & DeNOx

Corona Discharge

POSTECH
POSTECH Plasma Sheath Laboratory
Layout of plasma system for flue gas treatment 14

FLUE GAS FROM CLEAN AIR


+ +DCHV
DCHV - -DCHV
DCHV
INCINERATOR to STACK

MPC
MPC MPS
MPS
① ②
System
System System
System ③

DAMPER ⑤
GAS
ANALYZER


DAMPER

+PULSE
CORONA
REACTOR
ESP
ESP
CORONA
REACTOR

1. AMMONIA INJECTION
2. ADDITIVE INJECTION

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

• Principle of NOx & SOx removal • Principle of ESP

Collecting electrode
Ground electrode
Discharge
electrode

+ SO 2, NO x O 2, H 2O
Discharge
O, OH electrode
H2SO4 , HNO3

Dust

• SOx + NH3 Î (NH4) 2SO4È • Dust charging by corona


• NOx + NH3 Î NH4NO3 È • Dust collection by E-field

• HCl + NH3 Î NH4Cl È

POSTECH
POSTECH Plasma Sheath Laboratory
Key Parameters of MPC Modulators 16

built by Postech-Poscon

Model : MPC-30K MPC-40KB MPC-120K


Average Power : 30 kW 40 kW 120 kW
Peak power : 260 MW 450 MW 1,500 MW
Output voltage (peak) : 130 kV 150 kV 150 kV
Peak Current : ~ 2 kA ~ 3 kA 10 kA
Pulse Length (FWHM) : 500 ns 500 ns 500 ns
Pulse Energy, max : 100 J 130 J 400 J
Rise Time (10 ~ 90%) : < 200 ns < 200 ns < 250 ns
Max. Repetition Rate : 300 Hz 300 Hz 300 Hz
Efficiency : > 65 % > 65 % > 65 %
DC Bias option : N/A ± 30 kV/10mA N/A
Output capacitance : 8 nF 10 nF 30 nF
Reactor capacitance : ~ 3 nF ~ 4 nF ~ 12 nF
Maintenance Interval : > 6 months (> 3 x 109 pulses) > 12 months
System tested by : KIMM RIST RIST
(1997) (1998) (2001)

POSTECH
POSTECH Plasma Sheath Laboratory
Circuit of MPC modulator 17

Thyrister primary switch


(20 kV – 15 kA, 5μs)
MPC secondary switch
(200 kV – 7 kA, 0.5 μs)

W1 R1
PS1 PSB1 PSB2

W2 R2 HVP
PS2 LB1 CB1 LB2 CB2

C1 L1 CVD-1 CVD-2 CVD-3 W5 LL


W3 R3
PS3

MS1 MS2
W4 R4
PS4
L2
L3

TP1 C2 C3 CL RL
Plasma
R6
D1 T1 Reactor
R5
D2

CT1 CT2 CT3 CT6 CT4 CT5

High voltage Oil Tank


primary switch

POSTECH
POSTECH Plasma Sheath Laboratory
MPC-120K System 18

Resistor panel for Main HV-Tank Cooling System for HV-


Assembly
Charging, Spark, Tail Tank & Resistor Panel
of MPC System

POSTECH
POSTECH Plasma Sheath Laboratory
MPC Operation: V & I Waveforms 19

 Pulse risetime & corona 200

onset voltage relationship. Voltage CV D2 CV D3


CVD1 [kV]
150
CV D1
Volt. CVD2 [kV]

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]

CT5 tail [kA]


Vc : Critical voltage 3
reactor current [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

SOx removal better than 99% (100~200 ppm Æ ~0 ppm) !

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

Stack gas flow rate Unstable dust


(R) Oxygen ~ 12.5%
emission

(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

2005 Emission: Avg (max) Achieved


Item
Regulation Yr-2000
Before Goal MPC-120K
SOx 30 ppm 38 (82) 10 (20) < 1 (99%)
NOx 80 ppm 64 (125) 20 (45) 25 (75%)
HCl 30 ppm 3 (9) 5 (10) < 1 (99%)

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 [%]

With C3H6 ethylene


80 Initial NO=75ppm
22 eV/NO With C3H6 ethylene

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

Delivered Energy Density [ Wh/Nm3 Æ 3.6 J/L]

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

SCR reactor Features:


1. Space Velocity:
Plasma Reactor : < 1 × 106 hr-1
SCR Reactor : 5,000 hr-1

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

300 HP Marine Engine &


Plasma + SCR reactor
Ref: Korea Institute of Machinery & Materials

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]

Ref: Y.H. Song, Korea Institute of Machinery & Materials


POSTECH
POSTECH Plasma Sheath Laboratory
Air pollutants emissions in Korea (2000) 28

Unit : kton/yr

Pollutants SO2 NOx PM10 VOC CO

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%)

45 168 10 118 142


Kyung-ki
(9.0%) (17.9%) (12.8%) (11.2%) (17.6%)

74 292 15 236 343


Sub total
(14.8%) (31.0%) (19.2%) (22.4%) (42.6%)

501 943 78 1,054 806


Whole country
(100%) (100%) (100%) (100%) (100%)

POSTECH
POSTECH Plasma Sheath Laboratory
Lab scale test setup for VOC removal 29

Power meter Oscilloscope


(WT210, Yokogawa)

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

Photocatalyst in the reactor

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)

Comparison of different NTP reactor FTIR spectrums of the byproducts


for 200 ppm benzene decompostion

Ref: Plasma Process. Polym. Vol.1 (2004) p 91-110

POSTECH
POSTECH Plasma Sheath Laboratory
Industrial application of plasma odor removal 31

DBD Reactor + Power Supply Wet Scrubber + Catalysts

• Flow Rate : 500 Nm3/hr


• Power : ~1kW
• Treated Chemicals
• NH3
• H2S
• Acetaldehyde

• Removal effi.: >99 %


• 6 months operation

DBD plasma reactor

Combined Process (Plasma + Wet Scrubber + Catalysts) installed


at Waste Treatment Facility for Odor Control

Ref: Korea Institute of Machinery & Materials


POSTECH
POSTECH Plasma Sheath Laboratory
Industrial application of plasma odor removal 32

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

Transport systems Chemical & Biological


(PM, Unburned HC, Warfare Agents
NOx, SOx, etc) (Sarin, VX, Anthrax,…)

Incinerator
Microwave Plasma Torch (Dioxin, Soot,
NOx, Fly ash, etc)

Chemical Industries Semiconductor


(H2S, NH3, VOCs, …) Industries
(PFC, HFC, C2F6, 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

Tapered Water drain


Waveguide

O2
2.45 GHz Magnetron
Air Microwave source

Ref: Energy physics research laboratory at AJOU University


POSTECH
POSTECH Plasma Sheath Laboratory
Microwave plasma torch system 35

• Waveguide-based microwave torch • Air (20 lpm)


• PRF = 500 W
Waveguide torch
2.45 GHz
Magnetron

• Cavity-based microwave torch

Cavity

POSTECH
POSTECH Plasma Sheath Laboratory
CF4 and SF6 removal using plasma torch (~ 1kW) 36

Input gas: 46 sccm CF4 + 5 lpm N2 + O2 swirl gas


For 10 lpm O2
For 15 lpm O2 Air: 30 slm, N2: 10 slm, SF6: 0.1 slm

1500
Plasma

Concentration (ppm)
1250 off

1000

750

500 DRE 82%


0.8 kW DRE 96.5 %
250 1.2 kW

0
60 120 180 240
Time (sec)

FTIR spectrum shows the SF6 removal efficiency using


variation of CF4 concentration MW plasma torch

Ref: H. Uhm, Energy physics research laboratory at AJOU University

POSTECH
POSTECH Plasma Sheath Laboratory
Mercury(Hg) Emission Sources 37

Africa Australia Etc Coal Power Plant


South America North America
Europe 18% 6% 25% 23%
4% 9%
11% 13% 18%
53% 12% 9%

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

Region Total Hg emissions (tons / year)


Washington (state) 0.22
Oregon 0.24
California 2.6
North America 202
Europe 239
Asia 1204
China 604
Source: Atmospheric Environment Vol.39 (2005) p3029–3038
POSTECH
POSTECH Plasma Sheath Laboratory
Mercury Removal Technology 38

Lab. Scale Field Scale

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

Air Teflon line (Temp. Controlled)

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

Elementary Mercury Elementary Mercury Oxidation Efficiency


Oxidation Efficiency According to Temperature
70 100
Hg0 Oxidation Efficiency [%]

Hg Oxidation Efficiency [%]


60 83.8 J/L 104.8 J/L
55.4J/L 80
50

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

Time [min] Specific Energy Density [J/L]

Inlet Hg0 Concentration 278μg/m3


Temperature 1500C

POSTECH
POSTECH Plasma Sheath Laboratory
ECO (Electro-catalytic Oxidation) Pilot Unit by Powerspan Corp. , U. S. A 41

Removal of Hg and ash


from the liquid co-product stream

Absorber : removes SO2 and NO2

A wet ESP
DBD reactor

~ 4000 m3/hr

ECO Pilot DBD Reactor


POSTECH
POSTECH Plasma Sheath Laboratory
ECO Elemental Hg Conversion Result 42

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

Technocal Report by Powerspan corp. , U.S.A


POSTECH
POSTECH Plasma Sheath Laboratory
43

Summary & Comments

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 (%)

(50,000 Nm3/hr) CF4/ 60 lpm


NO/ 200 ppm
80 C6H6/ 200 ppm
SF6/ 40 lpm
NO/ 157 ppm Hg/ 25 ppb
70 (1,700 Nm3/hr) NOx/ 75 ppm (150 oC)
(50,000 Nm3/hr) Hard to
60 C7H8/ 150 ppm C6H6/ 200 ppm break
NO/ 150 ppm pollutants
50 (2,000 Nm3/hr)
Hg/ 25 ppb
(90 oC)
40 NO/ 150 ppm
(5,000 Nm3/hr)
Corona
30 Corona + Additive
NO/ 350 ppm

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

for DeNOx Plant


500 MWe Coal burning power plant

Plasma
Item FGD + SCR E-Beam
process
Construction
50 M$ 80 72
Cost/Unit

Operation Cost 3.5 M$/unit-Yr 6.5 2.7

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

A. Pulse modulator for Positive pulsed corona


z For high efficiency Æ High frequency inverter system
z Short pulse high power switching;
Æ Magnetic pulse compression circuit
Æ Semiconductor primary swich is commercially available
z Power/unit is limited by
Æ the MPC switch economy ~ 120 kW
Æ Energy delivery is limited by reactor C & working voltage
Æ Moisture in gas is limiting condition for the peak voltage

B. DBD power supply


z Delivered energy depends on peak voltage & frequency
z Maximum practical frequency is 100 kHz
z Pratical peak voltage & power at 100 kHz is ~ 10 kV & ~10 kW

POSTECH
POSTECH Plasma Sheath Laboratory
Comments-2 47

ƒ Atmospheric plasma technologies looks very attrative for


various environmental applications for gas treatment!
z The specific input energy for flue gas (NOx & SOx) cleaning has been
improved down to ~2 Wh/Nm3 (~7 J/l) Æ ~2% operation efficiency
z [plasma + catalyst] hybrid system has better energy efficiency.
z DBD plasma is very effective for the removal of odor substances with <0.5 J/l.
z MW-plasma torch system has great potential for toxic gas neutralization.
z Preliminary test result of plasma oxidation of Hg looks very promissing.

ƒ Issues requiring further explorations


z Large scale real plant engineering
z Improvemet of energy efficiency, system reliability, process control s/w, etc
z Detailed mechanisms of pollutants removal process.
z Harmful by-product problem

POSTECH
POSTECH Plasma Sheath Laboratory
48

Thank you for your attention!

Please feel free ro send any questions.


To Prof. Moohyun Cho
E-mail: mhcho@postech.ac.kr

POSTECH
POSTECH Plasma Sheath Laboratory