dbd discharge process for voc depollution of gases through ... · 3. fundamental knowledge on...
TRANSCRIPT
DBD discharge process for VOC depollution of
gases through radical mechanisms and
polymerization -
Industrial scale-up development .
S. Dresvin(2) , J. Amouroux(1),
And the scientific team : S. Ognier(1), L. Martin(1), E. Gasthauer (3), S. Zverev(2)
A.Vargauzun (2), A. Kruchinin (2)
Industrial development: M. Maze(3), P. Rousseau(3)
(1) LGPPTS / UPMC / ENSCP
(2) Polytechnic University of St-Petersburg
(3) Centre de Recherche Eurovia Management St-Petersburg 20012
Outline
1. General aspects of european regulations on VOC
2. Industrial processes for gas depollution and energy consumption
3. Fundamental knowledge on toluene depollution by an experimental DBD discharge
3.1. Set-up
3.2. Analytic control by GC-MS and mechanisms
3.3. Competition mechanisms between oxygen species
3.4. Competition mechanisms between carbon ring
4. Industrial scale-up and first results/ Eurovia company
[Patent n° 24/12/2004 PCT/FR 2004/ 003382]
5. Conclusion
What’s a volatile organic compound?
• Ethane (30):
• 1-butene (56):
• Isoprene (68):
• Ethylbenzene (106):
• Ethylene (28):
• trans-2-Butene (56):
• n-Hexane (86):
• o-m-p-Xylene (106):
• Acetylene (26):
• cis-2-Butene(56):
• Propene (42):
• n-Pentane (72):
• n-Octane (114):
• 1,2,3- Trimethylbenzene (120):
• n-Butane (58):
• i-Pentane (72):
• i-Octane (114):
•1,3,5- Trimethylbenzene (120):
• i-Butane (58):
• 1,2,4-Trimethylbenzene (120):
•1-Pentene (70):
• Benzene (78):
• Formaldehyde (30):
• 2-Pentene (70):
• Toluene (92):
• i-Hexane (86):
• Propane (44):
• 1,3-Butadiene (54):
• n-Heptane (100):
CH3
CH3
O
VOCs listed by the European Union (Directive 2002/3/CE)
European and French laws define a volatile organic compound as an "organic compound,
except methane, with a vapor pressure higher than 0,01 kPa at the temperature of 293,5 K or
having a same volatility in particular using conditions".
Evolution of VOC emissions in French air
Maximum emission
permitted in 2010:
1050 kt/y (directive
2001/80/CE)
ISO 14001: international norm which permit industrial plants to certify the establishment of
an amelioration program of their environmental performances.
In application of the legal norm ISO 14001
Other
Other carrying
Road carrying
Residential - Tertiary
Manufacturing industry
Energy transformation
Agriculture - sylviculture
Classical VOCs treatment process: thermal and catalytic oxidation
CnHm + (m + n/4) O2 m CO2 + n/2 H2O
source: ADEME technical form
limitations:
1- Secondary effluent
2- High energy consumption
Thermal oxydation Catalytic burn
Temperature 800 °C 300 to 350°C
Concentration 1 to 8 g/Nm³ 0 to 5 g/Nm³
Gas flow 1000 to 300 000 Nm³/h up to 70 000 Nm³/h
Power needed to heat a
gas flow of 1.000 m3/h
300 kW 150 kW
Dirty effluent
Heat exchanger Air treated Combustion chamber
Burner
Plan tubular plaque
Burner
Ventilator
Air treated
Heat
exchanger
Dirty effluent
Pre-heating zone
Reactor conception • Discharge type choice
• Interaction discharge /catalyst
point-to-plane HT
HT
wire-
cylinder
Fixed bed / discharge
HT
particles
Plasma processes for VOCs treatment
Fluidized bed
Langleron Symposium of
catalysis & plasma chem.istry,
220 th Nat. Meeting, 2000, 415
J. S. Chang, Journal of
Electrostatics, 2003, 57, 273
Francke, ISPC 14, 1999, 2655
Mok, Ind. Eng. Chem. Res. 2003, 42, 2960
Coupling plasma
and catalysis
Plasma as a tool
to enhance adsorption
VOCs CO2 + H2O
Current trend:
Our strategy:
VOCs polymerised and/or
oxidised molecules
ENERGY
COMSUMPTION
COMPARISON
Thermal oxidation (800 °C)
900 J/L
Plasma assisted catalysis
200 J/L
Catalytic oxidation (300 °C)
450 J/L
Plasma + Adsorption
10 J/L
Experimental setting
by-product
characterization by
GC-MS
System controlling the electrical discharge
(numerical oscilloscope 500 MHz)
0
5 000
10 000
15 000
20 000
25 000
30 000
35 000
40 000
45 000
50 000
0 5 10 15 20 25 30
I: 0,4 mA
U: 10 kV
10 µs
U
I
gas mixing:
O2 (10 %), H2O (0,48 %), toluene (1000 ppmv) in N2
at 100 °C and 105 Pa
Mass flowmeters
water toluene
Heat exchanger
Sampling filter and
syringe
R
E
A
C
T
O
R
N2 O2
Chromatogram of molecules cached
by sampling filter
Applied tension and discharge
puled signal
The multipoint-to-plane geometry dielectric barrier discharge reactor
Parallel Batch reactors (one for each point)
Gas entrance
Gas way out
Stainless steel electrode
13 points F 1mm, high
5mm
Dielectric F 31mm 4
mm thick
Stainless steel low field
electrode
F 25mm, 6mm thick
26 mm
120 mm
2 mm
200 mm
35 mm
Stainless steel high field
electrode
HV 10-20 kV
45 kHz
Strong
recycling
zone
The wire-to-cylinder geometry dielectric barrier discharge reactor
Gas entrance
Gas way out
44 mm
Stainless steel high
field electrode
Copper low field electrode
300 mm
gap = 2 mm
35 mm
80 mm
glass:
ceramic:
FID = 11mm
FOD = 14mm
FID = 20mm
Two layer- dielectric
battery of batch reactors HV 10-20 kV
45 kHz
Discharge hydrodynamic in a wire-to-cylinder DBD reactor
electric pulses:
adding O (3P, 1D)
discharge reactor = 35 steps of elementary batch
reactors
Sortie
35 1 n n+1
N2, O2, H2O,
toluene
Hydrodynamic deeply modified by
electrical wind due to elementary
discharges
35 mm
on one axe: 35 points computed by
35 unitary reactors
HV electrode
HV electrode
dielectric
Ground electrode
HV electrode
Impulsion
time: 100 ns
Frequency time 20 s
Residence time 200 s
Isotopic labeling as a help for the reaction mechanisms comprehension
VOC isotopic labeling:
VOC destruction mechanisms study
CH
2
H2
H2
Analytic technique interest (GC-MS):
• Retention time unchanged
• Mass spectrum different
CH2
+
CH2
+
H
H
H
C+
H
H
H
C+H
H
H
CH2
+
CH2
+
H
H
H
C+
H
H
H
C+H
H
H
D
D
D
Reactant isotopic labeling:
Validation of the O2 oxidation activity and his action
in VOC destruction
18O2 16O2
C H
H
H
+1 +2 +3
Deutérium
H2O non labeled
Labeled molecules:
Labeled molecules
acid Hydroxyacetic
C H 3
O
O H D3 23 %
Acetaldehyde O 18 C H 3 18 C H 3 between 1% and 2%
O 18
34 %
Acetone O
C H 3
D 55 %
Propyne CH 3 C CD 51 %
Isocyanomethane DN CH 20 %
Cumene C H C H 3
C H 3
D 38 %
Hydroxypropanone C H 3 C
C H 2 O H
O
D 4 %
Methylpropylbenzene C H 2 D
56 %
Diethylbiphenyl C H 2
D
between 57% and 61%
Dimethylbenzene C H 2
C H 3
D
27 %
Cymene C H 3 D
between 2 % and 7 %
Non labeled molecules
11 saturated linear molecules
12 unsaturated linear molecules
18 linear oxidized molecules
28 cyclic molecules
2 •CH3 + 6 O° CO + CO2 + 3 H2O
Labeled molecules produced by the DBD discharge
Isotopic ratio
The entire oxidation phenomena is important:
Labeled molecules Isotopic ratio
Acetone formation mechanism
0
20
40
60
80
100
120
140
160
180
200
7,9 7,95 8 8,05 8,1 8,15
61 58
0
20
40
60
80
100
120
140
160
180
200
7,9 7,95 8 8,05 8,1 8,15
61 58
CH3
CH3
O
Temps de rétention (min)
Inte
nsit
é r
ela
tive (
ua
)
CH3
O
D
0
20
40
60
80
100
120
140
160
180
200
7,9 7,95 8 8,05 8,1 8,15
61 58
0
20
40
60
80
100
120
140
160
180
200
7,9 7,95 8 8,05 8,1 8,15
61 58
CH3
CH3
O
Temps de rétention (min)
Inte
nsit
é r
ela
tive (
ua
)
CH3
O
D
CH3
CH3
O
DCH3
CH3
O
D
30 % of C H 3 C H 3
O 18
benzene ring preferential cut
CH3
CH3
O
D D no
CH3
CH3
O
and 60 % of
oxidation by a hydroxyl radical
the carbonated string is coming from ring opening
area (peak m/z=61) = 1015
area (peak m/z=58) = 2006
1 015 + 2 006
1 015 = 0,336
from toluene, there is 2 on 7
possibilities to produce a 3-
carbon chain containing the
methyl group.
7
2 = 0,286
CH C
CH3
OH
CH C
CH3
OH
CH2
CH3
O
H
CH3
18O
18O
• Ring excitation and rupture by atomic oxygen
radicals
•Benzene ring opening according to preferential
mechanisms
• Radicals coming from toluene are getting down
in energy by reorganization, oxidation by
hydroxyl radical, or hydrogenation
• Little nitrated molecule formation
• Strong oxidation phenomena between methyl
group and O2
Conclusions
•O: 1 S, 1 D and 3 P
C
C
C C
C
C
• CH 3
C
C
HAP
cycles
fonctionalized by
linear molecules
linear molecules
C 11 H 24
C H 2
Deposits
Oxidation
par O 2 , •O,
•OH
O
C O 2
O
O
O
O
O
O O H
O
N N
O
O N
NO 2
Nitration
Ring activation Ring opening
mixing pollutants
and activated radical
particles
air
and VOCs flow
fixe-bed reactor
out flow of
purified air
fixe-bed reactor
VOCs from bitumen treatment by plasma reactor coupled with fixed beds:
Saint Petersburg Polytechnic University’s pilot/ S.Dresvin
Activated oxygen
production by DBD
plasma cassettes
air air
Conception of the discharge pilot.
Electric characteristics
cassettes: 60 electrodes plighted with glass
(1’) or quartz (1&2) gap: 1 mm
P(1’) = 150W P(1,2) = 200W
Electric signal produced by the HV
generator 5 kHz
i (A)
u (kV)
200 µm
2 A
10 k
V
80 mm
150 mm
80 mm
160 mm
150 mm
150 mm
F 80 mm 200 mm
100 mm
80 mm
100 mm
F 120 mm
310 mm
Bitumen reservoir
inferior fixed-bed of stones
DBD
discharge cassette
superior fixed-bed of stones
Tbitume = 300 °C
Sampling filter
chemical analyses
156 m3/h 156 m3/h
352 m3/h
40 m3/h
Conception of the discharge pilot.
Hydrodynamic characteristics
Flow modeling with CFD software FLUENT©
Grid velocity (m/s)
20cm
40,49cm
Plaque perforée 2
1st stone bed (20 cm)
porosity = 0,4
2nd stone bed (20 cm)
porosity = 0,4
V = 10,5 m/s
D = 800 m3/h
V = 1,39 m/s
D = 200 m3/h
V = 1,39 m/s
D = 200 m3/h
V =3,84 m/s
D = 400 m3/h
Sampling filter coloration as a witness of the treatment efficiency
Paraffinic Naphthenic
non treated
fume
« oxidized »
fume and
retained on 2
fixed stone beds
« oxidized » fume
and retained on 1
fixed stone bed and
1 chalk bed
« oxidized »
fume
yellow - ocher coloration:
heavy molecules are retained
clarified filters: diminution of
the heavy molecules quantity
0,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
1,6
1,8
Ben
zaldeh
yde
M=1
06
Ben
zaldeh
yde
met
hyl M
=120
Ben
zaldeh
yde
dim
ethy
l M=1
34
Pht
halic
acid
M=1
66
Ben
zo[b
]thioph
ene,
sub
M=1
76
Pht
halic
acid
met
hyl M
=180
Phe
nant
hren
e dim
ethy
l M=2
06
Are
a o
f sp
ecie
s m
ass p
eak /
Are
a o
f in
tern
al
sta
nd
ard
mass p
eak
An
thra
cen
e d
10 M
=188
VOC from naphtenic bitumen
VOC from naphtenic bitumen treated by DBD
O
O
S
OOHOH
O
+100%
+100%
+100%
+100%
+100%
-35%
-95%
OOHOH
O
O
Modification of molecular species by Dielectric Barrier Discharge treatment
GC-MS analysis
For naphtenic bitumen
Oxidation mechanisms
Desulfurisation
Destruction of HAP by oxidation diacide
DBD effect (active oxygen)
0,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
1,6
1,8
Ben
zaldeh
yde
M=1
06
Ben
zaldeh
yde
met
hyl M
=120
Ben
zaldeh
yde
dim
ethy
l M=1
34
Pht
halic
acid
M=1
66
Ben
zo[b
]thioph
ene,
sub
M=1
76
Pht
halic
acid
met
hyl M
=180
Nap
htha
lene
M=1
28
2-M
ethy
lnap
htalen
e M
=142
Diben
zoth
ioph
ene
met
hyl M
=198
Alkan
e C21
H44
M=2
96
Are
a o
f sp
ecie
s m
ass p
eak /
Are
a o
f in
tern
al
sta
nd
ard
mass p
eak
An
thra
cen
e d
10 M
=188
VOC from naphtenic bitumen treated by DBD
VOC from naphtenic bitumen treated by DBD and aggregate
O
O
S
S
OOHOH
O
-70%
-80%
-100%
-45%
-80%
-70%
-85%
-100%
-70%
-90%
OOHOH
O
O
CnH2n+2
Modification of molecular species by Dielectric Barrier Discharge treatment
GC-MS analysis
For naphtenic bitumen
Aggregate effect
Adsorption mechanisms on Aluminosilicate
• Fume treatment by a low activated oxygen flow is acquired. In 15’, an
augmentation of 45 % of the retained fume mass and until 300%
augmentation in 30’ with paraffinic bitumen fume.
• Activated oxygen attack sulfured (sulfurs and thiols) functions,
responsible of bad odors.
RSH + O3 RO + SO2 + ½ H2O
• Minerals fixed-beds (as stone) can adsorb by-products.
• The absence of CO: treatment is not a combustion.
Conclusions
Prototype
Gevrey-Chambertin - Vialco
Additional aspiration
2500 m 3 /h Air
(100 à 1000 m 3 /h)
Emissions
(5 m 3 /h + 25 à 100 m 3 /h)
Emissions
(1200 m 3 /h)
100 m3/h
100 m3/h
DBD Discharge
Filter 1 Chimney Filter 2
Gas flow
source : Pascal Rousseau
source : Pascal Rousseau
DBD
Plasma
Air
Fumes to
be treated
cleaned
gas
Air
Chimney
Filter 1 Filter 2
Gas flow
Concentrations schématiques des composés
émis dans l’atmosphère
CO
VM
olé
cule
soxy
gén
ées
Poly
mèr
es
Rad
icau
x
CO
VM
olé
cule
soxy
gén
ées
Poly
mèr
es
Rad
icau
x
CO
V
Molé
cule
soxy
gén
ées
Poly
mèr
es
Rad
icau
x
+Plasma
+Granulat
1 2 3
Oxygène
excité
Principe
1
Concentrations schématiques des composés
émis dans l’atmosphère
CO
VM
olé
cule
soxy
gén
ées
Poly
mèr
es
Rad
icau
x
CO
VM
olé
cule
soxy
gén
ées
Poly
mèr
es
Rad
icau
x
CO
V
Molé
cule
soxy
gén
ées
Poly
mèr
es
Rad
icau
x
+Plasma
+Granulat
1 2 3
Oxygène
excité
Modifications
chimiques des
COV et odeurs
Principe
2
1
Concentrations schématiques des composés
émis dans l’atmosphère
CO
VM
olé
cule
soxy
gén
ées
Poly
mèr
es
Rad
icau
x
CO
VM
olé
cule
soxy
gén
ées
Poly
mèr
es
Rad
icau
x
CO
V
Molé
cule
soxy
gén
ées
Poly
mèr
es
Rad
icau
x
+Plasma
+Granulat
1 2 3
Oxygène
excité
Piégeage sur
matériaux
granulaires
Principe
3
Modifications
chimiques des
COV et odeurs
2
1
Depollution of gas waste by dielectric barrier
discharge (DBD)
Collaboration with University of Pierre and Mary
Curie
Vertical variant