dissemination and fostering of plasma based environmental ... · dissemination and fostering of...
TRANSCRIPT
Dissemination and fostering of plasma based environmental technological innovation
Plasma based destruction of VOCs – PlasTEP results
R. Brandenburg1, D. Cameron2, A.G. Chmielewski3, H. Grosch1, A. Haljaste4, T. Hoder1, M. Hołub5, T. Ivanova2, I. Jõgi4, M.-L. Kääriäinen2, M. Schmidt1, Y. Sun3, V. Valinčius6
1 INP Greifswald (Germany) 2 Lappeenranta University of Technology (Finland) 3 Institute of Nuclear Chemistry and Technology, Warsaw (Poland) 4 University of Tartu, (Estonia) 5 West Pomeranian University of Technology (Poland) 6 Lithuanian Energy Institute, Lithuania
PlasTEP WP5 results 1
WP 5 partners and contributors
05.12.2012
M. Holub M. Balcerak
D. Cameron M.-L. Kääriäinen
T. Ivanova
I, Jõgi M. Laan,
A. Haljaste
V. Valincius R. Kėzelis
T. Hoder M. Schmidt H. Grosch, W. Reich
A.G. Chmielewski A. Pawelec
Y. Sun
H. Barankova L. Bardos
E. Stamate M. Dors J. Mizeraczyk
S. Vasarevicius
PlasTEP WP5 results 2
Content
Standartization and dissimiation
● “The PlasTEP-standard”
● State-of-the-art of plasma based air cleaning
Implementation
● Reactor concepts
● Plasmas offer synergies!: Catalyst/Adsorber/Scrubbing
● Results of field tests
Outlook
●Open questions and future prospects
06.12.2012
PlasTEP WP5 results 3
The “PlasTEP-standard”
Sense (or Nonsense?)
● Comparison of different concepts between partners
06.12.2012
Energy yield EY
[g/kWh]
Selectivity SCO2
(by-products)
WP 4
WP 5
SED [J/l] = Plasma Power/Gas Flow (Specific Energy Density)
aquv. Dose= Energy /Mass of Gas
Total Power > Plasma Power
PlasTEP WP5 results 4
Comparison with other technologies
●Diversity of technologies difficult to compare, empirical approach
● Stakeholders must know investment cost and operational cost and be able to compare it with each other, e.g. power consumption, warranty intervals, consumption of additives, investment cost always specific!
06.12.2012
R. Rafflenbeul;
Example for waste air purification in flavour processing (50,000 Nm3/h; < 100 mg VOC/m3)
PlasTEP WP5 results 5
State-of-the-art: plasma deodorization
06.12.2012
R. Rafflenbeul; Rafflenbeul Anlagenbau GmbH
Plasma
Kat Pro-
cess
Injection method
• Gasflows up to 100,000 Nm3/h • Removal efficiency: 75 … 99 % • Investment cost about
10,000 € per 1,000 Nm3/h • Running cost less than 10 €/h
(@ 50,000 Nm3/h)
PlasTEP WP5 results 6
Dielectric Barrier Discharge Stack Reactor (PlasTEP)
06.12.2012
Electrode
Isolator plate
S. Müller, R.-J. Zahn; Contributions to Plasma Physics 47 (2007) 520-529
PlasTEP WP5 results 7
Example: toluene
Electron beam with catalyst (INCT)
06.12.2012
1 J/L ≈ 0.8 kGy @ 20 °C, dry conditions
Barrier discharge stack reactor (INP)
≈ 15 ppm
EY= 5.5 g/kWh
EY= 2.95 … 5.2 g/kWh
PlasTEP WP5 results 8
Toluene removal with EBFGT
Electron beam with catalyst (INCT)
06.12.2012
Pulse mode influence on toluene removal at 43.45 kGy
PlasTEP WP5 results 9
Implementation of catalyst (ASTRaL)
Activity of TiO2 catalysts, pure porous filters and plasma during (2500 ppm of toluene at 336 J/L)
● 1000 ALD layers of TiO2 catalyst on glass filters (Atomic Layer Deposition)
● Amount of removed toluene depends on applied catalyst and porosity of glass filters
● Improved selectivity of COX by catalyst application
06.12.2012
PlasTEP WP5 results 10
Implementation of catalyst (LEI)
Plasma spraying of catalytic fibers/coatings
● Two types of plasma torches
● Fiber material introduced as powder in jet of a carrier gas
● Motion and interaction of melted domains in high temperature air jet mainly depend on precursor composition, plasma jet parameters, exposure time and plasma torch construction
● Mean temperature along plasma axis: 3000 – 4000 K (flow velocity 400 – 500 m/s)
06.12.2012
Aluminium oxide (left) and zeolite (right) fibers
deposited at 2150 K flow temperature
PlasTEP WP5 results
Examples: Ethyl Acetate, Propylene (Tartu)
11 06.12.2012 PlasTEP WP5 results
Ethyl Acetate (UT) Propylene (UT)
DBD only
DBD + TiO2
DBD only DBD + TiO2
PlasTEP WP5 results
Synergy between plasma and adsorber (I)
N2
N2
O2
T-, Rh- sensor
gas
su
pp
ly
frequency
converter
oscilloscope
bypass
transformer
HV probe
resistor
FTIR
spectrometer
T-, Rh- sensor
ethanol bubbler
ac filter
element
plasma electrodes
inlet
outlet
gas distribution
plate
N2
N2
O2
T-, Rh- sensor
gas
su
pp
ly
frequency
converter
oscilloscope
bypass
transformer
HV probe
resistor
FTIR
spectrometer
T-, Rh- sensor
ethanol bubbler
ac filter
element
plasma electrodes
inlet
outlet
gas distribution
plate
Ethanol as model VOC (1000 ppm)
Surface barrier discharge (SED= 3. 6 – 47 J/L)
1.65 g activated carbon
undersized! analysis of slippage
12 06.12.2012
PlasTEP WP5 results
time [ min ] time [ min ]
rela
tive e
thano
lconcentr
ation
a) b)
c) d)
time [ min ] time [ min ]
rela
tive e
thano
lconcentr
ation
a) b)
c) d)
time [ min ] time [ min ]
rela
tive e
thano
lconcentr
atio
n
a) b)
c) d)
time [ min ] time [ min ]
rela
tive e
thano
lconcentr
atio
n
a) b)
c) d)
time [ min ] time [ min ]
rela
tive e
thano
lconcentr
atio
n
a) b)
c) d)
time [ min ] time [ min ]
rela
tive e
thano
lconcentr
atio
n
a) b)
c) d)
time [ min ] time [ min ]
rela
tive e
thano
lconcentr
atio
n
a) b)
c) d)
time [ min ] time [ min ]
rela
tive e
thano
lconcentr
atio
n
a) b)
c) d)
Ethanol slippage curves
Empty reactor
Active carbon Plasma
Plasma & AC
13 06.12.2012
time [min]
PlasTEP WP5 results
time [ min ]
time [ min ]
rela
tive e
thano
lconcentr
ation
d)
b) c)
time [ min ]
time [ min ]
rela
tive e
thano
lconcentr
ation
d)
b) c)
Ethanol slippage curves and removed VOC-mass
Active carbon Plasma
Plasma & AC
Area as a measure for
removed ethanol mass
● Physisorption of C2H5OH ● Decomposition of C2H5OH
to CO2, H2O, C2H4O ● Adsorption and Decomposition
of C2H5OH
14 06.12.2012
PlasTEP WP5 results
Result of mass balance
R. Basner, et al., Surf. Coat. Technol. (2012), http://dx.doi.org/10.1016/j.surfcoat.2012.11.028
15 06.12.2012
PlasTEP WP5 results
16
Plasma supported adsorption (qualitative)
06.12.2012
Cont. air Plasma
stage
Adsorber
sample
Reduction of resorbed ethanols with plasma treatment before AC
= reduction of the absorptive & oxidation of adsorbate
Physisorption
(Filtering)
Oxidation
(Removal)
Removal of pollutant & Regeneration of adsorbent
Gasphase
Adsorbent
Adsorbate Adsorptive
16 06.12.2012
PlasTEP WP5 results 17
Synergy between plasma and adsorber (II)
06.12.2012
● Zeolite adsorber (w/o plasma) and undecane C11H26 as model gas
● Removal of undecane by plasma; by-products: CO2 and formic acid HCOOH
● Longer time until break through of adsorber with plasma on
● Synergy effects: Activation of adsorbent Removal of adsorbed VOCs (“in-situ regeneration”) Load reduction by NTP- removal Removal of plasma-byproducts
More than
3 hours
PlasTEP WP5 results 18
Falling water reactor
06.12.2012
Water flows up through vertical hollow cylindrical electrode (inner electrode of a concentric barrier discharge) and flows down making thin water film over inner electrode treatment of water (dye removal) demonstrated treatment of gas phase?
V. Kovacevic, M. Kuraica et al.; Belgrade University
Water film
Discharge gap
High voltage electrode
PlasTEP WP5 results 19
Plasma assisted scrubbing
06.12.2012
w/o water
With water
● C11H26 reduced by plasma more effective without water film by-product: Formic acid HCOOH
● C11H26 non-soluble in water
●HCOOH soluble in water
PlasTEP WP5 results 20
Water plant field test sites
Poznań – Aquanet water plant Two objects: preliminary sedimantation tank and thermal sludge dryer
06.12.2012
Biofilter behind thermal dryer
PlasTEP WP5 results 21
Water plant field tests
Installation at thermal sludge dryer (in combination with scrubber and catalyst)
06.12.2012
PlasTEP WP5 results 22
Water plant field test results
06.12.2012
• Odor reduction from about 72,000 ou to 14,000 ou • H2S reduction up to 100% • Reduction of sulphur contaning
compounds • H2S and DMDS are the main odors • Removal of COS by plasma treatment • CS2 and SO2 as
by-products H2S-scrubber (NaOH) before plasma
PlasTEP WP5 results 23
Poultry farm field tests
06.12.2012
Exhaust air of henhouse
● Test of plasma treatment (mobile device) combinable with adsorbing agents or catalyst in the exhaust of poultry farm/henhouse
● For plasma power of 50 W (180 J/L) no detectable henhouse odors sensed
●Hexadecanoic (palmitic) acid CH3(CH2)14CO2H as most important odorous hydrocarbon is reduced from 213 µg/m3 to 65 µg/m3 in the plasma
●Most important by-product (beside CO2 and O3) Aceton C3H6O (up to 125 µg/m3 = 50 ppb, far below MAK and odor threshold!)
PlasTEP WP5 results PlasTEP WP5 results 24
Oil-shale industry field test
05.12.2012
● Test of plasma treatment (mobile device) in exhausts of oil-shale industry oil production process
● Various aliphatic and organic VOC-s treated
●No results yet available (analysis running)
PlasTEP WP5 results 25
Outlook
Plasma used mainly for deodorization issues
● Role of oxidation stage synergy with adsorption, catalysis and scrubbing … but be aware of by-products and energy consumption
● Poor understanding of the basics (role of adsorbents, role of ions …)
●Offers compact systems with a direct (instantaneous) control (electrical parameters)
Potential to expanded use of plasmas
● To understand more the physical and chemical processes of combined action, e.g., quantitative description of plasma-supported adsorption, interplay discharge physics and plasma chemistry
● To explore other fields of application (plasmas as “electrochemical transistors”*)
06.12.2012
* G. Pemen and Team, TU Eindhoven