Beruflich Dokumente
Kultur Dokumente
A
NOVEL
SYNERGY
OF
TWO
TECHNIQUES
IN
THE
REMOVAL
OF
CHLORINATED
AROMATIC
COMPOUNDS
and
A RECENTLY RECOGNISED ISSUE: ULTRAFINE PARTICLES
BY
NAUMAN MITHANI (#301016320)
CHEM 372
2008‐3‐7
SECTION
1: SYNERGY
OF
COMBINING
SONOLYSIS
AND
PHOTOLYSIS
IN THE DEGRADATION AND MINERALISATION OF CHLO
RINATED AROMATIC COMPOUNDS [ref. 1]
PRELUDE:
__________________________________________________________________________________________
During the past few years , advanced oxidation processes (AOP's) have received
much attention in the relatively nascent quest of environmental remediation [ref. 1.1 ‐ .4]. In
such processes, which may feature other processes and mechanisms, the strong hydroxyl
radical is the prime, common oxidant. An AOP, with certain compounds, may however bring
about the formation of toxic or overall undesirable chemical intermediates; such a process
could
also
fail
to
fully
mineralise
the
organic
compounds.
INTRODUCING
THE
SOLUTION:
__________________________________________________________________________________________
Background: It has been known that the AOP of high‐frequency ultrasound is efai‐
cient at breaking down non‐polar substances such as hydrocarbons and aromatic organic
compounds [ref. 1.5 ‐ .7]. The sonolysis processes include oxidation via •OH radical, pyrolitic
degradation and in some cases, H2O2 and HO2•―‐mediated oxidation. However, the effective‐
ness of the ultrasonic environment is reduced as the compounds become more polar by the
oxidation processes; and so, complete mineralisation is not achieved [ref. 1.5, .8 ‐ .11].
The other AOP is TiO2 assisted photocatalysis/photolysis, also the subject of extensive
research. In addition of its ability to effectively remediate organic compounds, it succeeds
where sonolysis fails, degradation during the latter stages when the compounds have been
rendered more polar (rapid breakdown to CO2 and H2O). The •OH radical bears a role in this,
but direct hole induced oxidation on the surface of the catalyst opens up a new avenue for
the degradation mechanism [ref. 1.13 ‐ .16]. However, neither is this process all‐successful
in the break down all organic compound contaminants.
The bright idea: The effects of the two aforementioned AOP's on organic com‐
pounds are not at odds with each other, and so a technique combining both would seem
worthwhile.
A
combination
and
sequential
test
were
run
simultaneously
on
the
naphthol
blue
dye
as
the
model
compound
[ref.
1.9].
Not
only
was
the
rate
of
degradation
enhanced
but degradation reached (near) completion in the sonolysis‐photolysis combination test.
Similar combinations of photolysis + ozonolysis [ref. 1.18] and + hydrogen peroxide [ref. 1.19,
.20] have also been investigated.
Apart from the rate and degree of completion, the combinative approaches also re‐
solve
the
matter
of
accumulation
of
toxic
intermediates
during
the
degradation
process(es).
EXPERIMENTAL
OVERVIEW:
__________________________________________________________________________________________
Four chlorinated aromatic compounds were selected for the experiment(s) as the
model
compounds:
O
O
2,4‐dichlorophenoxyacetic 2,4‐D
OH
acid
Cl Cl
(common
herbicide)
O
2‐(2,4‐dichlorophe‐ 2,4‐DP
OH
noxy)propionic
acid
Cl Cl
(common
herbicide)
2,4‐dichlorophenol OH
(oxidation product of the two 2,4‐DCP
above) Cl Cl
Cl
OH
2,4,6‐trichlorophenol 2,4,6‐TCP
(drinking
water
contaminant)
Cl Cl
Many
experiments
have
seen
the
formation
of
the
long‐lasting
2,4‐DCP
from
2,4‐D
under advanced oxidation systems [ref. 1], which is more toxic than the starting material
[ref. 1.5, .27 ‐ .32]. The sonolysis + photolysis technique resolves such an issue of stable,
prevalent intermediates of greater toxicity in addition to higher rates and degree of comple‐
tion
of
the
overall
degradation
process.
EXPERIMENTAL
MAIN:
__________________________________________________________________________________________
FIGURE 2. Structure
experiment. 2,4-D and
is also classified as a
in the breakdown of
cept that a Hanovia quartz, mercury‐vapour immersion lamp, jacketed in a glass cylinder
was set beside the reaction vessel. This allowed for the water‐cooled copper (II) sulphate to
circulate uniformly and remove (by absorption) all light of wavelength less than 315 nm.
Also, the ice‐water bath was covered with foil so as to maximise light exposure.
Combination setup: the only change was the inclusion of ultrasonic waves; the lamp
and the transducer were both turned on.
Reagents and data: 100 mL solutions of 2,4‐D and 2,4‐DCP of concentrations rang‐
ing from 1×10‐4 to 7×10‐4 mol/L, along with 0.2 g of TiO2. The TiO2 was removed by centrifu‐
gation, the concentrations were determined by HPLC. The equilibrium concentrations were
measured and plotted vs. no. of moles of compound adsorbed per gram of TiO2; the equilib‐
rium adsorption coefaicient was determined from the gradients of the graphs.
Detection: compounds and intermediates present (thereby the extent of degrada‐
tion) were detected by HPLC. Samples were drawn at different intervals during the oxida‐
tion processes (the TiO2 was removed by centrifugation if it was present).
TOC: total organic carbon. Mineralised carbon was detected with an error margin of
±
5%.
92% water, and 2% of the acetic acid solution. By 18 min, the
or sonolysis, photolysis, mixture was 70% methanol, 27% water, and 3% acetic acid
nts. The transducer and solution, and it returned back to the original composition at
he individual experiment. the 30 min mark. A Photodiode Array detector monitored
the 200-400 nm range. Intermediates were identified by
ducer (Figure 1). This comparison to the retention times and spectra of authentic
of the transducer from samples.
put as determined by TOC. Mineralized carbon was measured using a Shimadzu
ely 50 W. The cell was
RESULTS
AND
PERFORMANCE
se, which held it in a
Total Organic Carbon: Analyzer, model TOC-5050 equipped
with an ASI-500A autosampler. All experiments were carried
xperiments, the trans- out at least in duplicate. The reported values are within the
remained submerged experimental error of (5%.
__________________________________________________________________________________________
e temperature inside
lutions were sparged Results and Discussion
riments.
Sonolytic Degradation of 2,4-D and Other Model Com-
otocatalysis and pho-
pounds. The herbicide 2,4-D undergoes quick degradation
n the same vessel as
when subjected to sonolysis in Ar or O2 saturated solutions.
s. A Hanovia (medium
SONOLYTIC
Hydroxyl
rsion lamp distributed
: generated during the cavitation process
radicals
DEGRADATION
are the primary oxidants responsible for 2,4-D degradation,
e reaction vessel. The
reactions 1 and 2. By comparing the products with those
ylinder. This allowed The
herbicide,
2,4‐D
readily
degraded
under
sonolysis
(in
argon
or
oxygen
saturated
obtained from selective radiolytic degradation we were able
pper sulfate solution,
to demonstrate the role of •OH radicals in sonolytic degrada-
ngths lower than 315
tion of aromatic •compounds
solutions,
oxidised
by
the
(5).
OH
radical
as
illustrated
below:
the one described in
ed in Figure 1. During
ysis experiments, the H2O ⊃⊃⊃f •OH + H• (1)
to maximize the light
•
iments, the solutions OH + 2,4-D f products (2)
hout the experiments.
lysis. The setup for the In addition to 2,4-D, three other model compounds were
as that used in the The
three
other
model
compounds
were
also
tested,
with
similar
results.
Since
2,4‐
also tested in the present study (2,4-DP, 2,4-DCP, and 2,4,6-
addition of ultrasonic TCP) to compare the effectiveness of sonolysis and photo-
DCP
is
a
main
intermediate
of
the
degradation
of
2,4‐D
and
2,4‐DP,
its
breakdown
is
crucial
were turned on during catalysis in overall degradation. The structures of these
compounds are shown in Figure 2. 2,4-DCP is the major
of 2,4-D and 2,4-DCP chemical intermediate formed during the initial oxidation of
in
the
evaluation
of
the
performance
of
the
techniques.
The
break‐down
of
the
herbicides
M of 100.0 mL volumes 2,4-D and one of the major intermediates in the breakdown
olutions were covered of 2,4-DP. Hence, the accumulation/degradation of 2,4-DCP
followed
a
quasi‐airst
order
decay
with
lifetimes
of
12
an
11
min.
for
2,4‐D
and
2,4‐DP
xposure and were set during the breakdown of 2,4-D/2,4-DP is crucial in deci-
TiO2 was removed by phering the overall rate of degradation and mineralization.
ntrations were respectively.
deter- In the sonolysis of O2-saturated 2,4-D and 2,4-DP solu-
concentrations were tions, we observed quick degradation of the herbicides. The
f compound adsorbed decay of the herbicides follows a pseudo-first-order decay
used to calculate the with degradation lifetimes of 12 and 11 min for 2,4-D and
2,4-DP, respectively. Figure 3 shows the decrease of 2,4-D
taken out at different upon exposure to high frequency ultrasound, and the small
experiments. For the amount of 2,4-DCP that is detected and subsequently
s were removed by degraded. A key observation in the degradation of 2,4-D is
und degradation and that no real build-up of the main intermediate, 2,4-DCP,
d using a Waters HPLC occurs, revealing the main strength of the sonolytic degrada-
7 plus Autosampler, tion process. The sonolytic degradation of 2,4-DCP in solution
with an Alltech Econo- indicated a degradation rate that is similar (lifetime ) 11
m). A solvent gradient min) to 2,4-D. Thus, in the high frequency (660 MHz)
r containing 1% acetic ultrasonic degradation of 2,4-D, effective oxidation takes place
TiO2(h) or
FIGURE 4. (A) Change in total organic carbon content (TOC, ppm) of model compound solutions when subjected to 660 kHz ultrasonic
FIGURE
waves in4.O -sparged
(A) Change
2 system over a in total(B) Change
4 h period. organic carbon
in TOC (ppm) of modelcontent (TOC,
compound solutions usingppm) of model
TiO photocatalysis compound solu
(500 mg/L
2
solution and CuSO filter solution). (a) 2,4-D; (b) 2,4-DP; (c) 2,4-DCP; and (d) 2,4,6-TCP.
waves in O2-sparged system over a 4 h period. (B) Change in TOC (ppm) of model compound s
4
solution
1928
and CuSO4 filter solution). (a) 2,4-D; (b) 2,4-DP; (c) 2,4-DCP; and (d) 2,4,6-TCP.
9 E N VIR O N M E N T A L S CIE N C E & T E C H N O L O G Y / V O L. 37, N O . 9, 2003
min.
FIGURE 7. Ox
FIGURE 5. Photocatalysis of 0.24 mM 2,4-D solution with O2-sparged (9), (b) sono
system. The breakdown of (a) 2,4-D (9) leads to the longer-lasting sonolysis, PS
(b) 2,4-DCP (b), with a lifetime (20 min) more than twice that of for the comb
2,4-D (8 min).
Combin
TOC:
Photolysis
redeems
itself
by
performing
far
better
than
sonolysis
as
far
as
TOC
mental resu
is
concerned.
The
results
would
suggest
that
it
is
a
powerful,
rapid
technique
for
degradation
(Figures 3-5
mineralisation. of the indivi
are establis
experiment
(chlorinated
degradation
these defici
FIGURE 6. Adsorption of (a) 2,4-D and (b) 2,4-DCP (moles × 10-6) processes.
in the dark for 24 h per gram of TiO2 plotted against the equilibrium approach w
concentration (µm). the degrada
We have
radicals. The type of chemistry that ensues may also be to establish
high frequency ultrasound for 5 h, only about 50% reduction certain organic compounds, which show a higher degree of
ght. Photoinduced Towasachieve
in the total organic carbon effective
seen. As indicated in our oxidation
resistance in the tend
to TiO photocatalysis, photocatalysis
to accumulate in 2
5
previous study, low molecular weight organic acids (e.g.,
charge transfer at experiments, it is necessary
oxalic acid) accumulate in solution during sonolysis, and for substrates to interact with
solutions. Such longer survival of chemical intermediates in
a water treatment process can be problematic if they turn
oth valencetheir
band the TiO2 surface. Such surface
degradation occurs with an extremely slow rate. Being
polar in nature, these carboxylic acids are repelled from the
interactions
out to be more lead
toxic than the parent to a faster
compounds.
Whereas TiO photocatalysis is slow in its ability to 2
ontribute toprobability
hydrophobic oxidation
the of interaction
cavitation bubble by the photogenerated
surface, which decreases the
with OH radicals. Their resistance
holes
efficiently break and surface
down chlorinated phenols, hydroxyl
it is quite
powerful in its ability to induce complete mineralization in
to sonolytic oxidation makes the overall process of miner- a short period of time. As soon as 2,4-DCP is oxidized to
alization of organic compounds very slow. more polar compounds, further oxidation to the point of
Photocatalytic Degradation. The photocatalytic degra- mineralization is fairly rapid. The change in total organic
dations of 2,4-D and other model compounds were carried carbon in the photocatalytic breakdown of the model
out in the same cell that was employed for sonolysis. The compounds, illustrated in Figure 4B, supports this argument.
illumination was done externally by placing the mercury lamp All four compounds transformed by TiO2 photocatalysis were
close to the solution cell that was used for sonolysis. completely mineralized in 2-3 h, compared to the incomplete
Compared to sonolysis, a different pattern of reactivity mineralization (less than 50% during the same period) noted
emerged for the chlorinated aromatic compounds in the in the sonolysis experiments.
photocatalytic studies using TiO2 and UV light. Photoinduced To achieve effective oxidation in the photocatalysis
charge separation in TiO2 is followed by charge transfer at experiments, it is necessary for substrates to interact with
the interface, depicted in reactions 3-5. Both valence band the TiO2 surface. Such surface interactions lead to a faster
holes and surface hydroxyl radicals contribute to the oxidation by the photogenerated holes and surface hydroxyl
FIGURE 4. (A) Change in total organic carbon content (TOC, ppm) of model compound solutions when subjected to 660 kHz ultrasonic
n content (TOC,wavesppm) of model
in O -sparged system overcompound
2 solutions
a 4 h period. (B) Change in TOC (ppm) when subjected
of model compound to 660
solutions using kHz ultrasonic
TiO photocatalysis (500 mg/L 2
solution and CuSO filter solution). (a) 2,4-D; (b) 2,4-DP; (c) 2,4-DCP; and (d) 2,4,6-TCP.
(B) Change in TOC (ppm) of model compound solutions using TiO2 photocatalysis (500 mg/L
4
b) 2,4-DP; (c)1928
2,4-DCP; and (d) 2,4,6-TCP.
E N VIR O N M E N T A L S CIE N C E & T E C H N O L O G Y / V O L. 37, N O . 9, 2003
9
Mineralisation
(removal
of
TOC)
was
complete
by
~3
hours
compared
with
only
/ V O L. 37, N O . 9, 2003
50%
by
~5
hours
under
sonolysis.
Mechanism: the substrates must interact with TiO2 surface for efaicient oxidation, as
photogenerated holes and surface hyrdoxyl radicals bring about quick oxidation. The type of
chemistry that ensues may also be dependant on the extent of adsorption [ref. 1.14].
2,4D and 2,4DCP compared further: Since their reactivities (lifetimes) we starkly
different,
this
was
explored
further.
The
adsoprtion
results
are
as
follows:
FIGURE
FIGURE 5. Photocatalysis of 0.24 mM 2,4-D solution with O2-sparged (9), (b
system. The breakdown of (a) 2,4-D (9) leads to the longer-lasting sonoly
(b) 2,4-DCP (b), with a lifetime (20 min) more than twice that of for the
2,4-D (8 min). FIGURE 7. Oxidative d
FIGURE 5. Photocatalysis of 0.24 mM 2,4-D solution with O2-sparged (9), (b) sonolysis (2)
system. The breakdown of (a) 2,4-D (9) leads to the longer-lasting sonolysis, PS (b). Co
TiO2
(b) 2,4-DCP (b), with a lifetime (20 min) more than twice that of mentas
for the combination
2,4-D (8 min).
degrad
Combined Sono
mental results(Figur
obtain
degradation ofthe
of 2,4i
(Figures 3-5)are
demon es
of the individual pro
experi
are established in
(chlor
experiments exhibi
(chlorinateddegrad
pheno
degradation. The o
thesebd
these deficiencies
FIGURE FIGURE
6. Adsorption of of(a)(a)2,4-D and(b)(b) 2,4-DCP -6)
6. Adsorption 2,4-D and 2,4-DCP (moles(moles
× 10-6) × 10
processes. proces
The me
in the dark for 24 h per gram of TiO22 plotted against the equilibrium
in the dark for 24 h per gram of TiO plotted against the equilibrium approach were
approdem
concentration (µm). the degradation of
concentration (µm). the de
We have employe
radicals. The type of chemistry that ensues may also be
As
per
the
isotherm
shown
above,
the
equilibrium
constant
value,
K,
is
360
L/mol
to establish the We ben
radicals. dependent
The type uponof thechemistry
extent of adsorption (14).
that ensues may alsooxidation
be processes
to esta
for
2,4‐D
and
110
L/mol
for
2,4‐DCP,
one‐third
that
of
its
precursor.
In
light
of
the
mecha‐
Earlier studies aromatic compound
dependent upon thehave
extent employed Langmuir-Hinshelwood
of adsorption (14). oxidat
oxidative degradat
analyses to follow the degradation of chlorinated phenols in
nism
cited,
this
can
be
explained
by
the
greater
afainity
of
2,4‐D
for
the
surface
of
TiO
Earlier studies slurries
UV-irradiated have (employed
14, 33, 34). Such Langmuir-Hinshelwood
analyses point to the 2.
photocatalysisaroma
and s
fact The degradation
oxidat lif
analyses tothat the adsorption
follow the degradationof molecules oftochlorinated
the TiO2 surface is
phenolsas in
compared to th
the limiting factor in dictating the overall rate of degradation.
UV-irradiated slurries (14,that 33, 34 photo
Other studies indicate no ).strong
Suchcorrelation
analyses existspoint toindividual
the photocat
fact that the adsorption ofadsorption
molecules and to thethe TiO Table 1 The
summa d
between the strength of initial 2 surface
rate of is
chlorinatedas com
aromat
the limiting factor(35,
degradation in36 ). Since thethe
dictating reactivities
overallofrate 2,4-Dofand 2,4-
degradation.
catalysis, and combi
DCP in the photocatalysis experiments proved to be blatantly
Other studies indicate individ
different, we probed thethat no strong
adsorption behaviorscorrelation
of these two exists
lifetimes for the chlo
between the strength
compounds. Variousofconcentrations
adsorption inand 100 the
mL initial
sample rate in the
of combination Tab
degradationvolumes(35, of 2,4-D
36).and Since 2,4-DCP
the were stirred with
reactivities of200 mg ofand either
2,4-D 2,4-
the chlori
photoca
example, 2,4-DCP,
breakdown,catalys
TiO2 in the dark for 24 h. After removal of the TiO2 by
DCP in centrifugation,
the photocatalysis experiments
the equilibrium proved
concentrations todeter-
were be blatantly has a lif
different, minedweand probed
graphed the adsorption
against the number behaviors
of moles of of these system
solute two lifetimt
compared
sonolysis and in phot
the
compounds. adsorbedVarious
per gram ofconcentrations
TiO2. The adsorption results in 100 are shown
mL sample enhancement of 2,
volumes
in Figure 6. The adsorption isotherm for 2,4-DCP yielded an
of 2,4-D and 2,4-DCP were stirred with 200 mg either
of degradatio
observed
equilibrium constant value, K, of 110 L/mol, while the K value
TiO2 inforthe 2,4-Ddark for 24ath.
was calculated 360After removal
L/mol. While of the TiO2rate
both compounds
examp
byenhancement o
are considered to be weakly adsorbing species (36),were the deter- breakd
centrifugation, the equilibrium concentrations ko
herbicide 2,4-D exhibits a three times greater adsorption system
mined ability
and graphed against
than the 2,4-DCP. Thethe number
greater adsorption of ofmoles
2,4-D toof solute
sonoly
adsorbed the per gram
catalyst of TiO
surface, though 2. The adsorption
moderate, providesresults
an explana-are shown
where the k values
tion6.for the higher degradation rate observed for 2,4-D inyielded
the determined enhan
from the
in Figure The adsorption isotherm for 2,4-DCP an
photocatalytic experiments. degradationobserv
proces
equilibrium constant value, K, of 110 L/mol, while the K value
rate en
SONOLYSIS
+
PHOTOLYSIS
COMBINED:
Summary: the rate of oxidative degradation was signiaicantly enhanced when the
both techniques were carried out simultaneously; the degradation lifetimes measured were
lesser than those measured under one technique only. Table 1 summarises the degradation
lifetime magnitudes under sonolysis, photolysis and under the combination:
dividual rates [ref. 1] as per the following equation:
kobsd = ksono + kphotocat
where the kvalues are quasi‐airst order rate constants,
calculated from the reciprocal lifetimes of the corresponding degradation processes [ref. 1]
TOC factor: the reduction in TOC was also improved upon; the addition of ultrasonic
waves reinforce the rate of mineralisation under photolysis, already adept at reducing TOC.
Overall, an improvement is obvious.
the effectiv
phenyltriflu
observe syn
frequency
the effectiveness of remediat s
tion approa
phenyltrifluoromethyl ketone
observe synergy using simultan
frequency (
frequency sonolysis of TiO2 su
tion approachozonolysis,
was only effec
frequency (30improving
kHz). By comb t
ozonolysis, Hoffman and c
orange solu
improving the mineralization r
of from
orange solutions ozone.20% to m
of ozone.
The resu
The results described in th
the advantage the advant
of combinin
FIGURE 8.FIGURE
Mineralization ofof2,4-D
8. Mineralization solutions
2,4-D solutions usingusing photocatalysis
photocatalysis
frequency
frequency sonolysis for the s m
(9), sonolysis (b), and
(9), sonolysis thethecombination
(b), and system
combination system (2) as(2) as inchange
change in compounds. It is we
aromatic
total organic carbon in ppm. aromatic co
total organic carbon in ppm. high-frequency ultrasound is
high-freque
nonpolar compounds (5, 7, 39
TABLE 2. Effect of TiO2 Loading on the Degradation Rate of nonpolar
chlorinated aromatic compoun co
2,4-Dichlorophenol
TABLE 2. Effect of TiO2 Loading on the Degradation Rate datively of
strengthens our argument th
chlorinated
transformed at the
2,4-Dichlorophenol degradation lifetime, ((1) min
strengthens
Chlorinated aromatics all hav
combined sonolysis bubble surface, which provide
TiO2, g/L degradation lifetime,
photocatalysis ((1) min
and photocatalysis datively tra
The hydroxyl radicals produ
0.5 20 7.7
Chlorinated
bubble interface initiate the o
0.25 combined
7.4 sonolysis bubble surfa
more polar compounds. Since
TiO2, g/L 0.125 photocatalysis
21.5 and7.4photocatalysis
becomes less effective in furth
The hydrox
0.064 25.6 8.1 we do not observe complete m
0.5 0.034 20 49.0 8.2 7.7 bubble
oxidized compounds intein
formed
0.020 8.8
0.25 0.010 >60 8.8 7.4 morecavitation
for the hydrophobic polar
mations take place. Hence, son
0.125 0 21.5 only 9% degradation 11.0 7.4 becomes
for the complete mineralizatioles
after 90 min
ozonolysis, Hoffm
improving the min
orange solutions fr
of ozone.
The results des
the advantage of
FIGURE 8. Mineralization of 2,4-D solutions using photocatalysis
TiO2
control:
the
variation
of
degradation
lifetimes
as
affected
by
different
TiO frequency
2
sonolys
(9), sonolysis (b), and the combination system (2) as change in
aromatic compou
total organic carbon in ppm.
loadings
is
shown
here: high-frequency ul
nonpolar compou
TABLE 2. Effect of TiO2 Loading on the Degradation Rate of chlorinated aroma
2,4-Dichlorophenol strengthens our a
degradation lifetime, ((1) min datively transform
Chlorinated arom
combined sonolysis bubble surface, wh
TiO2, g/L photocatalysis and photocatalysis The hydroxyl rad
0.5 20 7.7 bubble interface in
0.25 7.4 more polar compo
0.125 21.5 7.4 becomes less effec
0.064 25.6 8.1 we do not observe
0.034 49.0 8.2 oxidized compoun
0.020 8.8 for the hydrophob
0.010 >60 8.8
mations take place
0 only 9% degradation 11.0
after 90 min for the complete m
complimentary n
apparent, since it
An interesting observation in these experiments is the
The
amount
of
catalyst
is
systematically
halved
at
regular
intervals.
When
the
cata‐ the point of comp
fact that the decrease in total organic carbon was expedited
in the combination experiments. Although photocatalysis is
lyst
loading
is
small,
an
all
too
signiaicant
difference
is
seen
between
the
sole
and
combined
Suggestions hav
quite effective in mineralizing organic compounds, the prevents the catal
techniques.
The
combination
techniques
remains
efaicient
even
at
low
loadings,
whereas
addition of ultrasonic waves augments the speed of min- transfer of molecu
eralization. Figure 8 shows the decrease in organic carbon While this argume
the
sole
photolysis
technique
utterly
fails.
of aqueous solutions of 2,4-D during the individual and alone cannot expla
combined systems. A significant benefit in mineralization tion experiments.
rate is noted when the combined system is compared to the
The
results
concur
with
the
hypothesis
that
higher
degration
rates
at
higher
TiO facilitates the bre
2
high-frequency ultrasound results. suspensions. For t
We also independently assessed the role of direct UV-
loadings
is
due
to
an
additive
effect
of
two
techniques.
Other
factors
such
as
better
mass
was performed usi
irradiation in the combined experiment. The degradation the TiO2 suspens
transfer
are
of
lesser
importance
under
standard
conditions,
but
may
be
a
factor
at
lower
lifetimes of the four model compounds were determined frequency ultrasou
using sonolysis under ultraviolet irradiation, without any flowing to finely d
TiO2
loadings.added TiO2 catalyst. No difference was realized by the turned off, solute
presence of UV light during the sonolysis experiments. The catalysis experimen
absorption
TOC
under
TiO band of these compounds lies in the range of of 2,4-DCP in th
2
control:
with
low
catalyst
loadings,
there
is
still
efaicient
minerali‐
281-287 nm and tails off around 310. Since the light filtering degradation lifetim
sation
under
the
combination.
Mineralisation
of
2,4‐DCP,
complete
at
~3
hours,
is
unaffect‐
solution used in the photolysis experiments cuts off wave- without sonolysis
lengths below 315 nm, the tested compounds should not be treatment of the ca
ed
by
catalyst
loadings
of
≥10
mg/L;
affected directly by the therate
UVof depletion of carbon is, however, lower.effects but canno
light. 2,4,6-Trichlorophenol
showed a slight decrease in lifetime of the compound. This observed in the co
small difference, noted in Table 1, is within the experimental ment. Similar fin
error of ( 1 min. These control experiments confirm that the loadings.
additive effect seen in the combination experiment arises We further eva
from the photocatalytic activity of the TiO2 nanoparticles photocatalysis and
and not the UV light. loadings. These re
tocatalysis s
of toxic inter
in thesimultan
tocatalysis comb
of toxic intermediat
in theAcknowledg
combination
We thank Dr
Acknowledgments
the Departm
We thank Dr. K. Vin
for providin
the Department of C
The work d
for providing the fac
the Basic
The work En
described
the Basic Energy Sc
This is contr
This isLaboratory.
contribution
Laboratory.
Literature
Literature Cited C
FIGURE 9. Change
FIGURE 9. Changein in
thethetotal
totalorganic carbonofof2,4-DCP
organic carbon 2,4-DCP solutions
solutions (1) D.Ollis, D.
(1) Ollis, F.; Al-Ek
in photocatalysis or the
in photocatalysis combined
or the combined photocatalysis/sonolysis experi-
photocatalysis/sonolysis experi- ment om fW enatterofa
ments using various loadings of TiO : (a) photocatalysis,
ments using various loadings of TiO22: (a) photocatalysis, 10 mg/L; 10 mg/L; (2) Jeworski, M.;
(2) Jeworski He
(b) photocatalysis,6464mg/L;
(b) photocatalysis, mg/L; (c)
(c) photocatalysis,
photocatalysis, 500500mg/L; (d) (d)
mg/L; 196. 196.
photocatalysis + sonolysis, 10 mg/L; (e) photocatalysis + sonolysis, (3) Hoigne, J. Chem
photocatalysis + sonolysis, 10 mg/L; (e) photocatalysis + sonolysis,
250 mg/L; (f) photocatalysis + sonolysis, 500 mg/L.
(3) Hoigne,
Pollutants by Oz
250 mg/L; (f) photocatalysis + sonolysis, 500 mg/L. The HaPollutan
ndbook o
of the two processes, as described above. Additional factors, T he H an
Springer-Verlag:
Under
sole
photolysis,
if
the
TiO
of thesuch
twoasprocesses,
improved 2
loading
is
less
then
10
mg/L,
the
change
in
TOC
is
severe.
as described
mass transfer, are above. Additional
less important factors,
under
(4) Springer
Andreozzi, R.; C
1999, 53 ,
(4) Andreoz51.
suchstandard
as improved conditionsmassbut transfer,
may play are aless important
larger
Quantitatively,
after
~3
hours,
only
less
than
40%
of
TOC
is
resolved.
role in theunder (5) Peller, 1999,
J.; Wiest, 53
degradation at lower TiO loadings.
standard conditions but 2may play a larger role in the 3176.
The degradation results for 0.2 mM solutions of 2,4-DCP (5) Peller,
(6) Hart, E. J.; Fische J.
degradation at lower TiO2 loadings. 284. 3176.
with varying TiO2 loading are summarized in Table 2. In
The
thesedegradation
experiments,results
the amountfor 0.2 mM solutions
of catalyst of 2,4-DCP (7) Serpone,
was systematically
(6) Hart, E.
N.; Terz
with decreased
varying TiO 2 loading
in half, are summarized
over several cycles. With small in Table 2. In
catalyst
1994, 284.
98 , 2634.
(8) Destaillats,
(7) SerponeH.; C
theseloading,
experiments,
a major the amount
difference of catalyst
is prevalent was systematically
between the inde- Phys. C1994,
hem. A98 2
pendentinphotocatalysis
decreased half, over severaland the cycles.
combinationWithprocess.
small TiOcatalyst
2 (9) Stock, N. L.; Pelle
e(8)
chnoDestailla
loadings
loading, as small
a major as 10 mg/L is
difference of TiO 2 are sufficient
prevalent between the inde- (10) TColarusso,
to maintain l. 2000, 3
PhysP.; . CSeh
an effective degradation rate in the combination experiment.
pendent photocatalysis and the combination process. TiO2 (11) Vinodgopal, (9) Stock,K.;NP
Conversely, in the photocatalysis experiments, (no sonolysis)
loadings as smallofas2,4-DCP
10 mg/L of TiO2at are sufficient to maintain 1998, 32 Te, c3646.
hnol.
the lifetimes lengthen TiO 2 loadings smaller (12) Kamat, P. V. C he
an effective (10) Colaruss
than 125degradation
mg/L. With a rate loading in the
of 34combination experiment. (13) Liu,
mg/L, the performance G.; Li, X.; Z
(11) Vinodgo
Conversely, in thefor
is maintained photocatalysis
the combination experiments, (no sonolysis)
process (lifetime ) 8.2 Technol. 2000, 3
1998, 32
min) and of
the lifetimes diminishes
2,4-DCP substantially
lengthen atinTiO the2 loadings smaller (14) Li,
photocatalysis X.; Cubbage,
C(12)
hem. Kamat,
2001, 143P
thanexperiment With a )
125 mg/L.(lifetime 49 ( 2 min).
loading of 34Thus,
mg/L, it is
theclear that the
performance (13) C.;
(15) Nasr, Liu, G.;
Vinodg
combination approach remains very effective for degradation
is maintained for the combination process (lifetime
of 2,4-DCP even at very low levels of TiO2, a trend not present
) 8.2 padhyay, TecA.hnK.; olK.
(16) Hoffman, M.
(14) Li, X.; Cu R.;
min)inand diminishesphotocatalysis.
the independent substantially in the photocatalysis Chem. Rev. 1995
experiment (lifetime )process
The combination 49 ( 2also min). Thus,
offers clear that the (17) Malato,CS.;
it is mineraliza-
effective
h em . 2
Blan
combination
tion ratesapproach remains
with low catalyst very At
levels. effective for degradation
TiO2 loadings of 10 Environ. 2002,C.3
(15) Nasr,
padhyay
(18) Naffrechous, E.;
eralization. Figure 8 shows the decrease in organic carbon While this argument is certainly valid in a general sense, it
of aqueous solutions of 2,4-D during the individual and alone cannot explain the synergetic effects seen in combina-
combined systems. A significant benefit in mineralization tion experiments. We tested the hypothesis that sonolysis
rate is noted when the combined system is compared to the facilitates the break-up of TiO2 aggregates in aqueous
high-frequency ultrasound results. suspensions. For this purpose, a photocatalysis experiment
We also independently assessed the role of direct UV- was performed using sonolytically treated TiO2 catalyst. First,
irradiation in the combined experiment. The degradation the TiO2 suspension (no solute) was subjected to high
lifetimes of the four model compounds were determined frequency ultrasound waves for 30 min with the oxygen gas
using sonolysis under ultraviolet irradiation, without any flowing to finely disperse the TiO2. The ultrasound was then
turned off, solute was added, and the independent photo-
Opresence
SUMMARY
of UV :‐
added TiO2 catalyst. No difference was realized by the
VERALL light during the sonolysis experiments. The catalysis experiment was completed. The degradation lifetime
absorption band of these compounds lies in the range of of 2,4-DCP in this case was 18 min as compared to a
281-287 nm and tails off around 310. Since the light filtering degradation lifetime of 20 min (Table 2) using the catalyst
without sonolysis treatment. These results show that pre-
_________________________________________________________________________________________________________
solution used in the photolysis experiments cuts off wave-
treatment of the catalyst with sonolysis has limited beneficial
lengths below 315 nm, the tested compounds should not be
affected directly by the UV light. 2,4,6-Trichlorophenol effects but cannot account fully for the enhancement
showed a slight decrease in lifetime of the compound. This observed in the combined photocatalysis/sonolysis experi-
small difference, noted in Table 1, is within the experimental ment. Similar findings were also noted at different TiO2
error of ( 1 min. These control experiments confirm that the loadings.
additive effect seen in the combination experiment arises We further evaluated the synergy effects by carrying out
from theThe
following
table
compiles
a
summary
of
the
main
characteristics
of
the
two
tech‐
photocatalytic activity of the TiO2 nanoparticles photocatalysis and combination experiments at different TiO2
and not the UV light. loadings. These results are consistent with the hypothesis
Earlier efforts have been made to combine sonolysis with that the main explanation for the enhancement in rate of
niques
and
their
synergy.
either ozonolysis (8, 37) or photocatalysis (38) to improve degradation at the higher TiO2 loadings is the additive effect
about under simultaneous sonolysis + photolysis. The lack of long‐lived accumulation of
more
toxic
intermediates
is
also
a
major
achievement.
SECTION
2: ON‐LINE
ANALYSIS
OF
THE
SIZE
DISTRIBUTION
OF
FINE
AND ULTRAFINE AEROSOL PARTICLES IN FLUE AND
STACK GAS OF A (GERMAN) MUNICIPAL WASTE INCINER
ATION PLANT: EFFECT OF DYNAMIC PROCESS CONTROL
MEASURES AND EMISSION REDUCTION DEVICES [ref. 2]
PRELUDE:
__________________________________________________________________________________________
There has been intensive research in the past decade that citing the adverse health
effects of particulate emissions. Fine particles (d < 2.5 μm) and ultraVine particles (d < 0.1
μm) can penetrate the lungs upto the alveolar region if inhaled, thus are of great concern to
human health. Particulate emission control legislations, effectively, do not factor ultraVine
particles; and total particle mass is an incomplete measure of lung‐penetrating power since
the bulk is made of particles of >2.5 μm diameter, which precipitate in the nose or throat if
inhaled.
An
appropriate
measure
would
be
fraction
of
particles
in
the
size
range
of
PM2.5
and PM1.0 (particulate matter with diameters less than 2.5 μm and 1.0 μm respectively). To
this end, such emissions of a German municipal waste incineration plant are investigated.
__________________________________________________________________________________________
Combustion of aerosols in model systems e.g. laboratory burners [ref. 2.6 ‐ .8] has
been much studied, whereas little or no detailed data is available on the properties of com
bustion aerosols in the state of formation from industrial incineration plants [ref. 2]. Aerosols
formed of industrial combustion exhibit residence times in the tens of seconds before being
emitted. This allows for the gas and the particle phases to interact strongly. Therefore, a dif‐
ferent behaviour as compared to that in the lab settings in expected.
The purpose of the study were as follows:
(1) Investigate the effect of process control measures on the particle‐size distribution in
the range of 0.017 μm ‐ 10 μm.
(2) Reinforce and encourage the presence of scrubbers
(3) The
consequence
of
alue‐gas
cleaning
methods/devices.
EXPERIMENTAL
INTRO:
__________________________________________________________________________________________
The equipment setup is comprised of an aerodynamic particle sizer (APS) for parti‐
cles with diameters of 0.5 ‐ 30 μm, a scanning mobility particle sizer (SMPS) for diameters
of 0.017 ‐ 0.6 μm, a condensation particle counter, a homemade sampling system [ref. 2]
and
heavy‐duty
statistics
in
the
processing
of
data.
{A
diagram
is
shown
below.}
FIGURE 3. C
FIGURE 2. Particle sampling and measuring system: (a) scheme averaging dh a
of the on-line particle sampling and analysis system; (b) photograph size distribut
of the sampling and dilution system (1/10 000); and (c) photograph and after the
of the particle measurement unit in mobile rack. statistics, the
below 600 nm
sampling and analysis scheme as well as photographs of the drops drama
sampling system and the measurement cabinet are depicted
in Figure 2. 3b). In prac
The SMPS measures the mobility of charged aerosol by two instr
particles in a high voltage electric field. The mobility is in backup f
inversely proportional to the volume-equivalent diameter d
The
APS
measures
the
volume
equivalent
diamater,
d,
whereas
the
SMPS
measures
the aerodynamic diameter, dae, a slight difference, which is compensated for by the applica‐
tion of heavy‐duty statistics. An overall particle‐size distribution graph is shown here:
FIGURE FIGURE
3. Combination
3. Combination ofofAPS
APS and SMPS
and SMPS data.
data. (a) Algorithm
(a) Algorithm for for
system: (a) scheme
ng and measuring system: (a) scheme averaging dh anddhdhand
averaging ae from idealized
dhae from SMPS
idealized SMPS and
and APSAPS
data.data. (b) Particle-
(b) Particle-
ystem; (b) photograph
ing and analysis system; (b) photograph
size distribution
size distributionfromfrom real measurements
real of SMPS
measurements of SMPS and APSandbefore
APS before
n system (1/10 000); and (c) photograph and after the combination of both spectra. Due to poor particle
); and (c) photograph
nt unit in mobile rack. and after the combination of both spectra. Due to poor particle
statistics, the SMPS measurements stopped at 650 nm. APS channels
ack. statistics, the
below 600 SMPS measurements
nm were rejected because stopped
the APSat 650 nm.
counting APS channels
efficiency
heme as well as photographs ofbelow the 600
drops nmdramatically
were rejected at thesebecause the APS counting efficiency
particle sizes.
measurement cabinet
photographs of theare depicted
drops dramatically at these particle sizes.
abinet are depicted 3b). In practice, one individual particle cannot be analyzed
the mobility ofThe
y‐axis
represents
number
of
particles
per
size
intervals.
Since
the
no.
of
particles
count
charged aerosol by two instruments simultaneously as particles are trapped
age electric field. The mobility 3b).
is In in
practice,
backup filters, one and individual
the densityparticle
cannot be cannot
calculated be for
analyzed
ofthecharged
volume-equivalent
aerosol diameter d
ed
by
the
instrument
is
done
so
in
discrete
size
bins
with
varying
intervals
(logarithmically
in
e APS measures the particle velocity
by two all sizes as the simultaneously
instruments overlapping range isassmall. Thus, are
particles some trapped
d. The mobility is
tream, which is a function ofin
assumptions have to be made about the particle population
thebackup filters, and the density cannot be calculated for
to achieve a solution for eq 1:
uivalent diameter dvelocimetry
creasing
with
diameter),
the
no.
per
size
bin
is
normalised
to
a
bin
width
(size
interval)
of
1
dae, by laser-scattering all sizes (1) as Thetheshape overlapping range is small. Thus, some
factor κ is assumed to be constant and
he particle velocity assumptions
close to 1have for allto be made
particles. The about the is
shape factor particle
defined as population
the
ata were combined according to a
μm
[ref.
author].
a function of the
d (15) into one single distribution to achieve a solution for eq 1:
ratio of the drag force on the particle and the drag force on
tering velocimetry
le density in the overlapping size an ideal sphere with identical properties. κ is 1 for water
ts and by calculating the geometric(1) The droplets shape
and close factor is assumed
κ atmospheric
to 1 for to be
particles constant
which have and
nnels.according to a
ned close to 1 for all particles. The shape factor is defined as the
undergone condensation processes. It deviates from 1 for
nm ofaggregates fibers (17).
ze range between 500 and 1000ratio
single distribution the dragand force on the particle and the drag force on
re the same particle population and (2) It is assumed that both instruments sample an identical
eenumber
overlapping an ideal
size However,
concentration. sphere with identical properties. κ is 1 for water
particle population, and therefore the measurement results
e plotted
ating thewithin droplets
the same diagram,
geometric in and close to
an identical 1 for atmospheric
concentration particles
in the overlapping which
range. In have
ping particle population appears undergonepractice, condensation
this assumption processes. It deviates
is met by carefully minimizingfrom the 1 for
erent diameters) due to the different sampling errors of both instruments and correction of the
nFrom
500the and 1000
shift nm
of the aggregates and fibers (17).
overlapping resulting data for transmission losses in the sampling lines
cle population
anges (see Figure 3a) andthe particle(2) Itand
is assumed
coincidence that both
errors instruments
using standard methodssample fromanlit-identical
ed as both diameters are related by
ntration. However, erature (18 ).
particle population, and therefore the measurement results
dthe
) ) same
F0dae2C(diagram,
dae)
(3) The number concentration graphs of both instruments
in(1)an identical concentration in the overlapping range. In
have to be monotonic. If data show peaks in the overlapping
opulation appears practice, this assumption is met by carefully minimizing the
It
should
be
noted
that
aluctuations
in
the
combustion
conditions
gave
rise
to
aluctu‐
ations in the measurements of the particle concentration in the alue‐gas duct (std. dev. of
30%).
Apart from the particle‐size distribution, the chemical composition of the alue‐gas
was also analysed (concentration of volatile and semi‐volatile organic compounds or VOC's
and
SVOC's)
[ref.
2.20,
.21
for
further
details].
EXPERIMENTAL
MAIN:
__________________________________________________________________________________________
Typical particle‐size distribution is shown here, data was collected from the 700 ...
(2)
(2)
(3)
N (3)
mum of SMPS)
mum of of
minimum APS).
SMPS)
m eq 1 for
maximum the
of APS).
.from
Assuming Fj tothe
eq 1 for
hAPS
d ae. Assuming
size range, Fj to
the APS size
channels andrange,
a
(Figure 3b). For a
PS channels and
edSMPS
he (Figure 3b). For
system
of the SMPS system
ize-distribution
e size-distribution
tition frequency
epetition
recorded frequency
every
um recorded every
SMPS data, nine
nd SMPS data, nine
btain the same
o obtain the same
S.
datedby bymeansmeans of of
ied particle-size
rtified particle-size
eres, DuSkceiSecniteinfitcific
s, D u k e
lngeern rarto(Model
aeto r (Model FIGURE
FIGURE4.4. Change
Changeof of particle-size distributionupon
particle-size distribution uponthe
thetravel
travel
of of
biasbias
ent of the
of thetwo two thetheflue
fluegas
gasthrough
through thethe boiler section ofof the
boiler section theincinerator
incineratorplant.
plant.
w
elow 10%.10%. Due Dueto to Particle-size distribution measured in the flue gas (a) at 700 °C°C
Particle-size distribution measured in the flue gas (a) at 700
enduring
during normal
normal (above)
(above)andand(b) 300 °C
(b)atat300 °C (below).
(below).
entration in in
ncentration thethe
dard deviation
d deviation 30- 30- wasperformed
was performed via via external
external calibration.
calibration. The TheVOCsVOCswere were
oughly
hly an an order
order of of analyzed by th e r m al d e so r pt io n
analyzed by thermal desorption gas chromatography-m ga s ch r o m ato gr a ph y - m assass
spsepcetcrtormetertyry(TD-GC/MS,
om (TD-GC/MS, Perkin-Elmer
Perkin-Elmer ATD ATD400 400thermal
thermal
to desorption unit coupled to a HP 5890 series II-GC with a SSQ
hethe particle-size
particle-size desorption unit coupled to a HP 5890 series II-GC with a SSQ
position (aromatic 7000/Varian 3400/ITS 40 tracker as mass-selective
7000/Varian 3400/ITS 40 tracker as mass-selective detector). detector).
ition (aromatic
pling points along
ng points along
Forfurther
For furtherdetails
details of of the
the analytical
analytical procedures
proceduressee refs2020
seerefs
g of volatile organic and 21. All flue-gas concentrations are given with respect to
volatile organic and 21. All flue-gas concentrations are given with respect to
normalized conditions (dry flue gas, 273 K, 1013 hPa, and 11
...
and
300
oC
points
in
the
alue‐stack.
A
broad
maximum
at
0.08
μm
can
be
seen
in
aigure
4a,
the max. at 0.04 μm was unstable and is to be excluded. The max. in aigure 4b (300 oC, end
of boiler) is larger, it is at 0.14 μm. The enlargement of particles further in the bolier sug‐
gests a reactive relation of gas phase species and coagulation processes [ref. 2].
Chemical composition: The concentration of major gas‐phase chemical species de‐
creases further up the alue‐gas duct (800 ‐ 300 oC) due to condensation and chemical bond‐
ing [ref. 2.24 ‐ .27]. This can shed much light on the dynamics of particle growth in the
alue‐gas chamber.
Figure 5 depicts the concentrations of some detected aromatic compounds as they
vary with temperature. At 1100 oC, the concentration seem to be commonly low; this may
be explained by thermal decomposition (high rate) and oxidation by the residual oxygen. At
lower temperatures, formation reactions overtake the rate of decomposition and so the
concentration rises. Evaluation of the 600 ‐ 200 oC range is quite complex [ref. 2]; more im‐
portantly, ultra‐trace compounds of the highly toxic poly‐chlorinated dibenzo‐p‐dioxins / ‐
furans
(PCDD/F)
is
detected.
trations of several aromatic flue-gas constituents along the flue-gas duct. The highest concentrations
FIGURE 5. Course of the concentrations of several aromatic flue-gas constituents along the flue-gas duct. The highest concentrations
FIGURE 5. Course of the concentrations of several aromatic flue-gas constituents along the flue-gas duct. The highest concentrations
are observedareforobserved
800 orfor
600800°C.
or 600 °C.
changes in the composition of the alue‐gas [ref. 2.38 ‐ .40]. The impact of using the back‐up
oil burners and cleaning of the grate with pressurised air is cited here. Reasons: the oil
burners are expected to affect soot and organic compound particles (very small particles)
and residual mineral particles (larger particles) by the cleaning.
The effects of Viring up the back‐up oil burners are presented here:
FIGURE 6. FIGURE
Influence of6. Influence
the back-up of the
oil burners at theback-up oil burners
flue-gas measuring point at 700at
°C:the flue-gasdistribution
(a) particle-size measuring at 700 °C: (a) particle
pointswitched
with burners
on (above)on
and (above) and(b)off
off (below) and (below)
3D plot and course
of the temporal (b) 3Dof the
plot of the distribution.
particle-size temporal course of the particle-size distributi
compounds in this temperature range is observed. This conditions (38-40). As gas-phase species represent the
includes compounds in
highly toxic polychlorinatedthis temperature
dibenzo- p-dioxins/- range
feedstockis observed.
for particle formationThis effects (38-40). A
conditions
and growth, transient
furans (PCDD/F or dioxins). However, as carbonaceous are assumed to have a major impact on the particle-size
includes
particulate highly
matter has been toxic
identified polychlorinated
to play a major role dibenzo-
spectrum p-dioxins/-
too. In this work two types of transientfeedstock
processes for particle for
furans (PCDD/F or dioxins). However,
in the PCDD/F formation pathways (de novo-synthesis
30)), primary measures for particle reduction in the flue gas
( 29, were as carbonaceous
investigated, the influence of the oil are assumed
burner
particle-size spectrum of the flue gas and the effects of the
on the to have a
particulate matter has been
may also be motivated by their potential impact on PCDD/F identified to play a major role spectrum
grate cleaning with pressurized air. These two cases were too. In this w
abatement.in the PCDD/F formation pathwaysfractions (de novo-synthesis
selected because they are (29,
suspected of were investigated, the
influencing
of the aerosol. While the oil burner is likely
different
A deeper understanding of the chemical processes oc-
curring on30the)), primary
particles measures
will require a chemicalfor particle reduction
characteriza- influencing the insootthe flueand
particles gasorganic gas-phase
particle-size
con- spectrum
may also be motivated by their potential
tion of the particle ensemble on a single-particle basis. Up impact on PCDD/F
stituents (i.e. the very small particles) the grate cleaning with pre
cleaning
grate should predominantly increase the amount of resus-
of the
to now, such information is only accessible by on-line aerosol
abatement.
laser mass spectrometry, which enables a simultaneous size selected because they a
pended mineral particles (i.e. the larger particles).
The
burners
are
used
during
the
starup
and
shutdown
of
the
waste
incineration
process,
and during instabilities in combustion conditions (e.g. temperature drop below 850 oC). A
new stable max. at 0.04 μm can be clearly seen, this was not seen before. The particles are
most likely soot; even though, most of the particles shall coagulate during their travel fur‐
ther through the chamber, this whole scenario is of concern since the formation of PCDD/
F's is inaluenced by carbonaceous particles [ref. 2].
Figure 7 shows the result of pneumatic cleaning of the grate on the particle‐size
distribution.
multiple orders of magnitude. The graph on the right shows the live changes as the cleaning
is paused and resumed.
Wet ESP in the stack chamber: beneait of a wet electro‐static dust precipitator. A
signiaicant reduction in particulate matter is seen, though it in not uniform: two orders of
magnitude
lesser
around
the
0.1
μm
diameter
and
one
from
0.017
to
0.07
μm.
shift of the size-dist
The high efficiency
of fine particles can
of the wet-ESP (swi
electrode). In Figur
typically measured
ESP is shown. It ca
precipitates fine an
approximately 0.05
magnitude is visib
particle diameter o
slightly weaker. In F
on the wet-ESP on
plot of a 48 min
measurement sequ
was deactivated tw
some 10 s. The graph
gained by the APS.
It
can
be
seen
that
the
w‐ESP
is
quite
effective
down
to
0.05
μm,
causing
a
reduction
of
one
In Figure 9a, two
order
of
magnitude;
it
effectiveness
drops
off
below
0.05
μm. the stack gas with ac
(i.e. over 80% of the
one depicted in the
ized by a broad ma
drastically altered
casionally. In these
creased concentrati
present. The typica
ranges from several
size distribution du
upper graph of Figu
ultrafine particle re
magnitude.
At the lower si
equipment (17 nm
particlediameter
particle diameteroo
slightlyweaker.
slightly weaker.In InF
on the wet-ESP
on the wet-ESP on on
plot of
plot of aa 4848 min
min
measurementsequ
measurement sequ
was deactivated
was deactivated tw tw
some 10 s. The
some 10 s. The graph grap
gained by
gained by the
the APS.
APS
InFigure
In Figure9a, 9a,two
tw
thestack
the stackgas
gaswith
withac a
(i.e.over
(i.e. over80%
80%of ofthe
the
one depicted
one depicted in the in the
ized by
ized by aa broad
broad ma ma
drastically altered
drastically altered
casionally. In
casionally. In these
thes
creased concentrat
creased concentrat
present. The
present. The typica
typic
rangesfrom
ranges fromseveral
severa
size distribution
size distribution du du
upper graph
upper graph of Figuof Fig
ultrafine particle
ultrafine particle re r
magnitude.
magnitude.
At the
At the lower
lower ss
equipment (17
equipment (17 nm
nm
FIGURE8.8. Effects
Effectsofofshutting
shuttingdown
downthe thewet
wetelectrostatic
electrostaticprecipitator
precipitator concentration
concentration withwith
FIGURE
(ESP) onon particle-size
particle-size distribution:
distribution: (a)(a) particle-size
particle-size distribution
distribution inin small particles
small particles in
in gg
(ESP)
the stack gas (80 °C) with ESP operating (b, green) and ESP shut gas- to
gas- to particle-pha
particle-ph
the stack gas (80 °C) with ESP operating (b, green) and ESP shut
off ([,
off ([, red)
red) and
and (b)
(b) 3D
3D plot
plot of
of the
the temporal
temporal course
course ofof the
the particle-
particle- centrations of
centrations of ultra
ultra
size distribution
size distribution in
in the
the APS
APS range.
range. with new formation
with new formation
As before, the real‐time stark contrast between ESP‐on and ESP‐off can be seen.
Inadvertently promoting ultraMine particles (UFP): Fine particles serve as nucle‐
ation sites, which are removed by the w‐ESP, and so in the absence of potential coagulation
partners,
the
consequence
is
an
increased
lifetime
of
the
newly
generated
UFP
[ref.
2,
.42].
IN
THE
END:
__________________________________________________________________________________________
The study proves the sensitivity of particle concentration and size proaile to process
control measures, combustion conditions and so on. And so, process‐integrated and alue‐
gas cleaning methods need reainement in order to periodically exacerbate UFP.
_________________________________________________________________________________________________________
_________________________________________________________________________________________________________
[ref. 1]: Peller, Wiest, and Kamat, Environ. Sci. Technol. 2003, 37, pg 1926
[ref. 2]: Maguhn, Karg, Kettrup and Zimmermann, Environ. Sci. Technol. 2003, 37, pg 4761