SCRUBBERS

:

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

2,4‐dichlorophenoxyacetic acid (common
herbicide)

2,4‐D

O OH

Cl

Cl O

2‐(2,4‐dichlorophe‐ noxy)propionic
acid (common
herbicide) 2,4‐dichlorophenol (oxidation
product
of
the
two above)

2,4‐DP

O OH

Cl

Cl

OH

2,4‐DCP
Cl
Cl

Cl

2,4,6‐trichlorophenol (drinking
water
contaminant)

2,4,6‐TCP

OH

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

acid was utilized. Th 92% water, and 2% FIGURE 1. Experimental setup employed for sonolysis, photolysis, mixture was 70% m photocatalysis, and combination experiments. The transducer and solution, and it retu lamp were turned on as needed to conduct the individual experiment. the 30 min mark. A the 200-400 nm r mounted about 4 cm above the transducer (Figure 1). This comparison to the configuration allows for the separation of the transducer from samples. the reaction mixture. The power output as determined by TO Setup:
Sonolysis
experiments
employed
an
ultrasound
of
frequency
of
660
kHz.
The
 C. Mineralize the calorimetric method is approximately 50 W. The cell was Total Organic Carb set horizontally on a fitted plastic base, which held it in a with an sonication
cell's
volume
was
700
mL, actual sample volumes were 475 to 500 mL. The pow‐ ASI-500A au consistent position. Throughout the experiments, the transout at least in dupli ducer and the lower portion of the cell remained submerged o experimental error er
output
was
50
W,
the
temperature
was
maintained
at
308
K
(35
 C)
by
the
ice‐water
bath in an ice-water bath, to maintain the temperature inside the glass vessel around 308 K. The solutions were sparged Results and Discus and
oxygen
was
used
to
sparge
the
the
solutions.
The
transducer
was
used
in
sonolysis. with oxygen gas throughout the experiments. Sonolytic Degrada Photocatalysis and Photolysis. Photocatalysis and phopounds. The herbic tolysis experiments were performed in the same vessel as when subjected to described in the sonolysis experiments. A Hanovia (medium Hydroxyl radicals g pressure) quartz, mercury-vapor immersion lamp distributed are the primary oxi by Ace Glass, Inc. was placed next to the reaction vessel. The reactions 1 and 2. lamp was set inside a jacketed glass cylinder. This allowed obtained from selec for the circulation of water-cooled copper sulfate solution, to demonstrate the

Photolysis
and
photocatalysis
were
performed
in
the
same
vessel
and
conditions,
ex‐ 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 mixture was 70% methanol, 27% water, and 3% acetic acid solution, and it returned back to the original composition at 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 TotalPERFORMANCE: Analyzer, model TOC-5050 equipped RESULTS
AND
 Organic Carbon se, which held it in a with an ASI-500A autosampler. All experiments were carried xperiments, the transout 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 Comotocatalysis and phopounds. 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 Hydroxyl radicals SONOLYTIC
DEGRADATION: generated during the cavitation process rsion lamp distributed 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 degradangths lower than 315 tion of aromatic OH
radical
as
illustrated
below: solutions,
oxidised
by
the
•compounds (5). the one described in ed in Figure 1. During H2O ⊃⊃⊃f •OH + H• (1) ysis experiments, the to maximize the light • OH + 2,4-D f products (2) iments, the solutions 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 2,4,6addition of ultrasonic TCP) to compare the effectiveness of sonolysis and photowere turned on during catalysis in overall degradation. The structures of these DCP
is
a
main
intermediate
of
the
degradation
of
2,4‐D
and
2,4‐DP,
its
breakdown
is
crucial
 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 deciTiO2 was removed by phering the overall rate of degradation and mineralization. ntrations were respectively. In the sonolysis of O2-saturated 2,4-D and 2,4-DP soludeterconcentrations 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 degrada7 plus Autosampler, tion process. The sonolytic degradation of 2,4-DCP in solution with an Alltech Econoindicated 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
V O L. 37, N O . 9, 2003 / 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
9

or sonolysis, photolysis, nts. The transducer and he individual experiment.

1927

degradation

TiO2(h) or
FIGURE 3. Sonolysis of 0.22 mM 2,4-D solution using O2 as the sparging gas. The breakdown of (a) 2,4-D (9) and (b) formation/ degradation of the intermediate 2,4-DCP (b).

The herb ucts during was relative Figure
3
shows
that
the
intermediate
2,4‐DCP,
is
almost
instantaneously
degraded,
 one observe to form 2,4-DCP. This, in turn, is quickly oxidized to various so
it
can
be
seen
that
sonolysis
is
advantageous,
in
terms
of
time
as
well.
2,4‐DCP
and
2,4,6‐ lifetime for other intermediate compounds. The additional compound difference i under study, 2,4,6-TCP, reacted in the same manner under TCP
had
decay
lifetimes
of
11
and
12
min.
respectively
when
their
samples
were
tested. be seen in t sonolytic conditions, with a lifetime of 12 min. DCP, which Whereas the sonolytic degradation lifetimes for the four and 2,4-DP chlorinated aromatic compounds are very similar and period of tim relatively short, the decrease in total organic carbon occurs the photoc at a remarkably slow rate. The decrease in TOC in the photocataly sonolysis experiments is depicted in Figure 4A. Even though which is mo the parent compounds were short-lived, mineralization was The 2,4,6-tr typically less than 50% after 4-5 h of high frequency is also less ultrasound. After subjecting a 0.20 mM 2,4-D solution to herbicides. high frequency ultrasound for 5 h, only about 50% reduction certain orga in the total organic carbon was seen. As indicated in our resistance t 5 low molecular weight organic acids (e.g., previous study, solutions. S oxalic acid) accumulate in solution during sonolysis, and a water trea their degradation occurs with an extremely slow rate. Being out to be m polar in nature, these carboxylic acids are repelled from the Whereas hydrophobic cavitation bubble surface, which decreases the efficiently probability of interaction with OH radicals. Their resistance powerful in to sonolytic oxidation makes the overall process of minera short per alization of organic compounds very slow. more polar mineralizat Photocatalytic Degradation. The photocatalytic degra-

under of 2,4,6-TCP, reacted in the same manner under carbon dationsstudy, 2,4-D and other model compounds formationcarried intermediate 2,4- in the ph be seen in the were of the chemical sonolytic conditions, with a lifetime of 12 min. DCP, which accumulates during the photocatalysis of 2,4-D out in the the sonolytic degradation lifetimes for the four and 2,4-DP solutions and remains in solution forcompounds, illustra Whereas same cell that was employed for sonolysis. The a substantial chlorinated aromatic compounds are very similar and period of time. The formation/breakdown of 2,4-DCP during All 5. The illumination the decrease in total organic carbonby placing the mercury lamp in Figure four compounds relatively short, was done externally occurs the photocatalysis of 2,4-D is shown at a remarkably slow rate. The decrease in TOC in the photocatalytic degradation lifetime of 2,4-DCP is 20 min, completely minerali close to experiments is depicted in Figure 4A.that was which is more than twice the degradation lifetime of 2,4-D. the solution cell Even though used for sonolysis. sonolysis the parent compounds were short-lived, mineralization was mineralization (less Compared than 50% after 4-5 h of high frequency pattern of reactivity a lifetime of 18 min, to sonolysis, a different The 2,4,6-trichlorophenol molecule, with typically less is also less prone to photocatalytic degradation than the ultrasound. After subjecting a 0.20 mM 2,4-D aromatic compounds in clearly in the emerged for the chlorinated solution to herbicides. These experimentsthe demonstrate thatsonolysis ex TOC:
One
downside
to
sonolysis
is
the
length
of
time
required
to
reduce
the
amounts high frequency ultrasound for 5 h, only about 50% reduction certain organic compounds, which show a higher degree of To photocatalytic studies seen. As indicated and UV light.to TiO photocatalysis, tend to accumulate in achieve effe in the total organic carbon was using TiO2 in our resistance Photoinduced previous study, low molecular weight organic acids (e.g., solutions. Such longer survival of chemical intermediates in of
total
organic
carbon.
Though
the
lifetimes
of
the
source
compounds
were
short
(11
and
 experiments, it is n charge acid) accumulate in in TiO2 issonolysis, and by charge transfer at oxalic separation solution during followed a water treatment process can be problematic if they turn their degradation occurs with an extremely slow rate. Being out to be more the the12
min.),
mineralisation
had
reached
only
50
%
in
4
‐
5
hours
Figure
4A
{below}
shows
a
to 2 surface. S interface, depicted in reactions 3-5. Whereas TiOtoxic than the parentslow in its ability Both valence band compounds. TiO polar in nature, these carboxylic acids are repelled from the photocatalysis is hydrophobic cavitation bubble surface, which decreases the it is quite holes and interaction with OH radicals. Their resistance efficientlyinbreak down induce complete mineralization in by the ph surface hydroxyl radicals contribute chlorinated phenols,oxidation to the probability of powerful its ability to
5 2 2

other intermediate compounds. The additional compound

difference in comparison with the sonolysis experiment can

plot to sonolytic oxidation makes the overall process of miner-

alization of organic compounds very slow. Photocatalytic Degradation. The photocatalytic degradations of 2,4-D and other model compounds were carried out in the same cell that was employed for sonolysis. The illumination was done externally by placing the mercury lamp close to the solution cell that was used for sonolysis. Compared to sonolysis, a different pattern of reactivity emerged for the chlorinated aromatic compounds in the photocatalytic studies using TiO2 and UV light. Photoinduced charge separation in TiO2 is followed by charge transfer at the interface, depicted in reactions 3-5. Both valence band holes and surface hydroxyl radicals contribute to the

a short period of time. As soon as 2,4-DCP is oxidized to more polar compounds, further oxidation to the point of mineralization is fairly rapid. The change in total organic carbon in the photocatalytic breakdown of the model compounds, illustrated in Figure 4B, supports this argument. All four compounds transformed by TiO2 photocatalysis were completely mineralized in 2-3 h, compared to the incomplete mineralization (less than 50% during the same period) noted in the sonolysis experiments. To achieve effective oxidation in the photocatalysis experiments, it is necessary for substrates to interact with the TiO2 surface. Such surface interactions lead to a faster oxidation by the photogenerated holes and surface hydroxyl

FIGURE in O -spargedChangea in period. (B) Change in TOC (ppm) of modelcontent (TOC, ppm) of modelmg/L waves 4. (A) system over 4 h total organic carbon compound solutions using TiO photocatalysis (500 compound solu 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 1928 solution and CuSO4 filter solution). (a) 2,4-D; (b) 2,4-DP; (c) 2,4-DCP; and (d) 2,4,6-TCP.
2 2 4
9

FIGURE 4. (A) Change in total organic carbon content (TOC, ppm) of model compound solutions when subjected to 660 kHz ultrasonic

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

1928

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

TABLE 1. Degradation Lifetimes of Chlorinated Aromatic Compounds
PHOTOLYTIC
DEGRADATION:

de compound sonolysis 11 12

sonolysis UV photoly 11 11 10 10

The
degradation
lifetimes
of
2,4‐D
and
2,4‐DP
were
observed
to
be
8
and
6
minutes,
 2,4-dichlorophenoxyacetic acid (2,4-D) 12 ~50
%
faster
than
under
sonolysis.
However,
the
effect
was
opposite
on
the
intermediates,
 2,4-dichlorophenoxypropionic acid (2,4-DP) 11

2,4-dichlorophenol (2,4-DCP)

2,4‐DCP
and
2,4,6‐TCP;
their
lifetimes
were
observed
to
be
as
high
as
~20
min.
and
~18
 a Degradation lifetim es (τ ) 1/ k) w ere obtained fro m the first-order kinetic fit of the 2 min.

2,4,6-trichlorophenol (2,4,6-TCP)

FIGURE 5. Photocatalysis of 0.24 mM 2,4-D solution with O2-sparged system. The breakdown of (a) 2,4-D (9) leads to the longer-lasting (b) 2,4-DCP (b), with a lifetime (20 min) more than twice that of 2,4-D (8 min).
TOC:
Photolysis
redeems
itself

by
performing
far
better
than
sonolysis
as
far
as
TOC
 is
concerned.
The
results
would
suggest
that
it
is
a
powerful,
rapid
technique
for
 mineralisation.

FIGURE 7. Ox (9), (b) sono sonolysis, PS for the comb

FIGURE 6. Adsorption of (a) 2,4-D and (b) 2,4-DCP (moles × 10-6) in the dark for 24 h per gram of TiO2 plotted against the equilibrium concentration (µm). radicals. The type of chemistry that ensues may also be

Combin mental resu degradation (Figures 3-5 of the indivi are establis experiment (chlorinated degradation these defici processes. approach w the degrada We have to establish

To seen. As indicated in our oxidation in the photocatalysis ght. Photoinduced organic carbon wasachieve effectiveresistance to TiO photocatalysis, tend to accumulate in in the total previous study, low molecular weight organic acids (e.g., solutions. Such longer survival of chemical intermediates in experiments, sonolysis, and a water treatment process can be problematic if they with charge transfer acid) accumulate in solution during it is necessary for substrates to interact turn oxalic at to be more compounds. the TiOextremely slow rate. Being outWhereas TiOtoxic than the parentslow its a faster surface. Such oth valencetheir degradation occurs with anacids are repelled from the surface interactionsisleadinto ability to band polar in nature, these carboxylic 2 photocatalysis hydrophobic surface, which decreases the oxidation by Their resistance efficiently break down and surface it is quite ontribute to the ofcavitation bubbleOH radicals.the photogenerated holes chlorinated phenols, hydroxyl probability interaction with
5 2 2

high frequency ultrasound for 5 h, only about 50% reduction

certain organic compounds, which show a higher degree of

to sonolytic oxidation makes the overall process of mineralization of organic compounds very slow. Photocatalytic Degradation. The photocatalytic degradations of 2,4-D and other model compounds were carried out in the same cell that was employed for sonolysis. The illumination was done externally by placing the mercury lamp close to the solution cell that was used for sonolysis. Compared to sonolysis, a different pattern of reactivity emerged for the chlorinated aromatic compounds in the photocatalytic studies using TiO2 and UV light. Photoinduced charge separation in TiO2 is followed by charge transfer at the interface, depicted in reactions 3-5. Both valence band holes and surface hydroxyl radicals contribute to the

powerful in its ability to induce complete mineralization in a short period of time. As soon as 2,4-DCP is oxidized to more polar compounds, further oxidation to the point of mineralization is fairly rapid. The change in total organic carbon in the photocatalytic breakdown of the model compounds, illustrated in Figure 4B, supports this argument. All four compounds transformed by TiO2 photocatalysis were completely mineralized in 2-3 h, compared to the incomplete mineralization (less than 50% during the same period) noted in the sonolysis experiments. To achieve effective oxidation in the photocatalysis experiments, it is necessary for substrates to interact with the TiO2 surface. Such surface interactions lead to a faster oxidation by the photogenerated holes and surface hydroxyl

n content (TOC, ppm) of model compound solutions whencompound solutions using 660 kHz ultrasonic waves in O -sparged system over a 4 h period. (B) Change in TOC (ppm) of model subjected to TiO photocatalysis (500 mg/L 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 b) 2,4-DP; (c)1928 2,4-DCP; and (d) 2,4,6-TCP.
2 2 4
9

FIGURE 4. (A) Change in total organic carbon content (TOC, ppm) of model compound solutions when subjected to 660 kHz ultrasonic

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

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 5. Photocatalysis of 0.24 mM 2,4-D solution with O2-sparged system. The breakdown of (a) 2,4-D (9) leads to the longer-lasting (b) 2,4-DCP (b), with a lifetime (20 min) more than twice that of 2,4-D (8 min). FIGURE 7.
FIGURE 5. Photocatalysis of 0.24 mM 2,4-D solution with O2-sparged system. The breakdown of (a) 2,4-D (9) leads to the longer-lasting (b) 2,4-DCP (b), with a lifetime (20 min) more than twice that of 2,4-D (8 min).

FIGURE (9), (b sonoly for the

Oxidative d (9), (b) sonolysis (2) sonolysis, PS (b). Co2 TiO for the combination s menta

Combined Sono (Figur mental results obtain of the i degradation of 2,4 (Figures 3-5) demon are es of the individual pro experi are established in (chlor experiments exhibi (chlorinated pheno degrad degradation. The o these these deficiencies bd FIGURE FIGURE 6. Adsorption of (a)2,4-Dand (b)(b) 2,4-DCP (moles × 10-6) 6. Adsorption of (a) 2,4-D and 2,4-DCP (moles × 10-6) processes. proces The me in the dark for 24 h per gram of TiO2plotted against the equilibrium TiO2 plotted against the equilibrium approach were dem in the dark for 24 h per gram of appro concentration (µm). the degradation of concentration (µm). the de We have employe radicals. The type of chemistry that ensues may also be to establish the We ben As
per
the
isotherm
shown
above,
the
equilibrium
constant
value,
K,
is
360
L/mol
 dependent upon the extent of adsorption (14). oxidation to esta radicals. The type of chemistry that ensues may also be processes aromatic compound 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 extent of adsorption (14). dependent upon thehave employed Langmuir-Hinshelwood oxidat oxidative degradat analyses to follow the degradation of chlorinated phenols in aroma nism
cited,
this
can
be
explained
by
the
greater
afainity
of
2,4‐D
for
the
surface
of
TiO2. photocatalysis and s UV-irradiated have employed Langmuir-Hinshelwood Earlier studies slurries (14, 33, 34). Such analyses point to the The degradation lif oxidat fact that the adsorption of molecules to the TiO2 surface is analyses to follow the degradation of chlorinated phenols in as compared to th the limiting factor in dictating the overall rate of degradation. photo UV-irradiated slurries (14,that 34). Suchcorrelation exists to the Other studies indicate 33, no strong analyses point individual photocat summa between the strength of molecules the initial rate of fact that the adsorption of adsorption and to the TiO2 surface Table 1 The d is chlorinatedas com aromat degradation ( in dictating the overall 2,4-D and 2,4the limiting factor35, 36). Since the reactivities ofrate of degradation. and combi catalysis, DCP in the photocatalysis experiments proved to be blatantly lifetimes the chlo Other studies we probed the adsorptionstrong correlation exists forindivid different, indicate that no behaviors of these two Tab in of compounds. Various adsorption and mL sample between the strength ofconcentrations in 100 the initial rate the combination photoca volumes of 2,4-D Since the reactivities of 2,4-D and either the chlori degradation (35, 36).and 2,4-DCP were stirred with 200 mg of 2,4example, 2,4-DCP, TiO2 in the dark for 24 h. After removal of the TiO2 by breakdown,catalys has a lif DCP in centrifugation, the equilibrium concentrations were deterthe photocatalysis experiments proved to be blatantly lifetim mined probed the adsorption behaviors solute different, weand graphed against the number of moles of of these system compared t two sonolysis and phot in the adsorbed per gram TiO2. The adsorption in 100 mL compounds. Variousofconcentrations results are shown sample enhancement of 2, in Figure 6. The adsorption isotherm for 2,4-DCP yielded an observed either volumes of 2,4-D and 2,4-DCP 110 L/mol, while the K value mg of degradatio equilibrium constant value, K, of were stirred with 200 examp rate enhancement o for 2,4-D was calculated 360 L/mol. removal of the TiO2 in the dark for 24ath. After While both compoundsTiO2 by breakd are considered to be weakly adsorbing species (36 were centrifugation, the equilibrium concentrations ), the deterko herbicide 2,4-D exhibits a three times greater adsorption system mined abilitygraphed against the number of of 2,4-D to solute and than the 2,4-DCP. The greater adsorption moles of sonoly the catalyst surface, though moderate, provides an explanaadsorbed per gram of TiO2. The adsorption results are shown the k values where tion for the adsorption isotherm for for 2,4-D in the determined enhan from the in Figure 6. The higher degradation rate observed2,4-DCP yielded an photocatalytic experiments. degradation proces observ

degrad

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:
TABLE 1. Degradation Lifetimes of Chlorinated Aromatic Compounds
degradation lifetime, ((1) mina compound sonolysis sonolysis + UV photolysis TiO2 photocatalysis combined sonolysis and photocatalysis 6.6 7.7 5.9 8.2

ted Aromatic Compounds

Degradation lifetim es (τ the first-order kinetic s of Chlorinated Aromatic Compounds ) 1/k) w ere obtained fro mphotocatalysis fit of the 2,4-decay.photocatalysis sonolysis UV photolysis and
a

2,4-dichlorophenoxyacetic acid (2,4-D) 12 2,4-dichlorophenol (2,4-DCP) 11 degradation lifetime, ((1) 2,4-dichlorophenoxypropionic acid (2,4-DP) 11 2,4,6-trichlorophenol (2,4,6-TCP) 12 sonolysis + TiO

mina

2

11 11 10 10

8.0 20.0 6.2 18 combined sonolysis

-DP)

acid (2,4-D) P) ed fro m(2,4-DP) nic acid the first-order graph: TCP)

degradation lifetime, ((1) min 12 11 8.0 6.6 sonolysis + TiO2 combined sonolysis 2,4‐DCP,
the
toxic
intermediate
has
a
lifetime
of
only
7.7
min.
under
the
combination,
con‐ 11 11 20.0 7.7 UV photocatalysis and photocatalysis 11 sonolysis 10 photolysis 6.2 5.9 12 10 11 18 8.0 siderably
lesser
than
under
any
one
technique
only.
This
is
exempliaied
by
the
following
 12 6.68.2 11 11 kinetic fit of the 2,4-decay. 11 10 12 10 20.0 6.2 18 7.7 5.9 8.2

a

w ere obtained fro m the first-order kinetic fit of the 2,4-decay.
FIGURE 5. Photocatalysis of 0.24 mM 2,4-D solution with O2-sparged system. The breakdown of (a) 2,4-D (9) leads to the longer-lasting (b) 2,4-DCP (b), with a lifetime (20 min) more than twice that of 2,4-D (8 min). FIGURE 7. Oxidative degradation of 2,4-DCP using (a) photocatalysis (9), (b) sonolysis (2), and (c) the combined photocatalysis and sonolysis, PS (b). TiO2 loading was 125 mg/L for photocatalysis and for the combination system.

Combined Sonolysis and Photocatalysis. The experimental results obtained from the sonolytic and photocatalytic degradation of 2,4-D, 2,4-DP, and chlorinated phenols (Figures 3-5) demonstrate both the strengths and weaknesses of the individual processes. Whereas slow mineralization rates are established in sonolysis experiments, photocatalysis experiments exhibit a build-up of a toxic intermediate (chlorinated phenol) during the course of 2,4-D and 2,4-DP degradation. The obvious strategy would be to overcome these deficiencies by combining the two advanced oxidation processes. The merits of such an advanced oxidation FIGURE 6. Adsorption of (a) 2,4-D and (b) 2,4-DCP (moles × 10-6) in the dark for 24FIGURE 7.TiO2 plotted against the equilibrium of 2,4-DCP were demonstrated in our preliminary study on h per gram of Oxidative degradation approach using FIGURE 7. Oxidative degradation of 2,4-DCP using (a)(a) photocatalysis photocatalysis concentration (µm). azo dye, Naphthol Blue tion with O2-sparged-sparged (b) sonolysis (2), and (c) the the degradationphotocatalysis and Black (9). mM 2,4-D solution with O2 (9), (9), (b) sonolysis (2), and (c) the combined of ansimultaneous sonolysis/photocatalysis combined photocatalysis and We have employed -D (9) longer-lasting longer-lasting to theleads to theradicals. The type of chemistry that ensues loading bewas125 mg/L for photocatalysis and and two advanced sonolysis, PS TiO2 may also was to establish for benefits of combining these 125 mg/L the photocatalysis sonolysis, PS (b). (b). TiO2 loading (20 min) more than twice upon the extent of combination).system. of e than twice that of that for thefor the adsorption (system. dependent 14 oxidation processes in the degradation of the four chlorinated combination aromatic compounds. In the case of all four compounds, the Earlier studies have employed Langmuir-Hinshelwood oxidative degradation was significantly enhanced when analyses to follow the degradation of chlorinated phenols in Combined Sonolysis and Photocatalysis. The experi- out simultaneously. photocatalysis and sonolysis were carried UV-irradiated slurries (14, 33, 34). Such analyses point to the Combined Sonolysis from Photocatalysis. The experimental results obtained and sonolytic and photocatalytic fact that the adsorption of molecules to the TiO2 surface is theThe degradation lifetimes of all the compounds decreased compared to the lifetimes obtained mental results obtained from the as and chlorinated phenols sonolytic and photocatalyticin either of the the limiting factor in dictating the overall rate of degradation. degradation of 2,4-D, 2,4-DP,individual photocatalysis or sonolysis Other studies indicate(Figuresstrongdemonstrate both the strengths and weaknesses experiments. that no 3-5) correlation exists degradation of 2,4-D, 2,4-DP, and 1chlorinated degradation lifetimes of the Table summarizes the phenols between the strength of adsorption and the initial rate of of the individual processes. Whereas slow mineralization rates the sonolysis, photochlorinated aromatic compounds in (Figures 3-5) demonstrate 2,4degradation (35, 36). Since the reactivities of 2,4-D andboth the strengths and weaknesses catalysis, and combined oxidation processes. The degradation DCP in the photocatalysis experiments proved inbe blatantly of the are established toof sonolysis experiments,chlorinated phenolsrates individual processes. two lifetimes for the photocatalysisare significantly shorter Whereas slow mineralization different, we probed the adsorption behaviors thesebuild-up of a toxic intermediate experiments exhibit a compounds. Variousestablished inin sonolysis experiments, experiments than the ones observed in are concentrations phenol) during thein the combination photocatalysis (chlorinated 100 mL sample course photocatalysis or sonolysis experiments. For either the of 2,4-D and 2,4-DP volumes of 2,4-D and 2,4-DCP were stirred with 200 mg of

The
observed
degradation
rate
follows
approximately
an
additive
rate
enhancement
of
the
in­ 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 s the effectiveness of remediat tion approa phenyltrifluoromethyl ketone observe synergy using simultan frequency ( frequency sonolysis of TiO2 su ozonolysis, tion approach was only effec frequency (30improving t kHz). By comb ozonolysis, Hoffman and c orange solu improving the mineralization r of ozone. orange solutions from 20% to m of ozone. The resu The results described in th the the advantage of advant FIGURE 8. Mineralization ofof2,4-Dsolutions usingusing photocatalysis sonolysiscombininm FIGURE 8. Mineralization 2,4-D solutions photocatalysis frequency for the frequency s (9), sonolysis (b), the combination system change change in (9), sonolysis (b), and and the combination system (2) as(2) as in aromatic compounds. It is we total organic carbon in ppm. aromatic co high-frequency ultrasound is total organic carbon in ppm. high-freque nonpolar compounds (5, 7, 39 TABLE 2. Effect of TiO2 Loading on the Degradation Rate of chlorinated aromatic compoun nonpolar co 2,4-Dichlorophenol strengthens our argument th TABLE 2. Effect of TiO2 Loading on the Degradation Rate datively transformed at the of chlorinated degradation lifetime, ((1) min 2,4-Dichlorophenol strengthens Chlorinated aromatics all hav combined sonolysis bubble surface, which provide datively tra TiO2, g/L photocatalysis and photocatalysis degradation lifetime, ((1) min The hydroxyl radicals produ Chlorinated bubble interface initiate the o 0.5 20 7.7 combined sonolysis polar compounds.surfa more 0.25 7.4 bubble Since 21.5 7.4 TiO2, g/L 0.125 photocatalysis and photocatalysis becomes less effective in furth The hydrox 0.064 25.6 8.1 we do not observe complete m 0.034 20 49.0 8.2 bubble inte oxidized compounds formed in 0.5 7.7 0.020 8.8 for the hydrophobic cavitation more polar 0.25 7.4 0.010 >60 8.8 mations take place. Hence, son 11.0 0.125 0 21.5 only 9% degradation 7.4 becomes les for the complete mineralizatio
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
TiOfrequency sonolys 2
 (9), sonolysis (b), and the combination system (2) as change in aromatic compou total organic carbon in ppm. high-frequency ul loadings
is
shown
here: nonpolar compou TABLE 2. Effect of TiO2 Loading on the Degradation Rate of chlorinated aroma 2,4-Dichlorophenol strengthens our a datively transform degradation lifetime, ((1) min Chlorinated arom combined sonolysis bubble surface, wh TiO2, g/L photocatalysis and photocatalysis The hydroxyl rad bubble interface in 0.5 20 7.7 more polar compo 0.25 7.4 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 for the complete m after 90 min 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‐ point of comp the fact that the decrease in total organic carbon was expedited Suggestions hav in the combination experiments. Although photocatalysis is lyst
loading
is
small,
an
all
too
signiaicant
difference
is
seen
between
the
sole
and
combined
 prevents the catal quite effective in mineralizing organic compounds, the transfer of molecu techniques.
The
combination
techniques
remains
efaicient
even
at
low
loadings,
whereas
 addition of ultrasonic waves augments the speed of minWhile this argume eralization. Figure 8 shows the decrease in organic carbon alone cannot expla the
sole
photolysis
technique
utterly
fails. 2,4-D during the individual and of aqueous solutions of tion experiments. combined systems. A significant benefit in mineralization facilitates the bre rate is noted when the combined system is compared to the The
results
concur
with
the
hypothesis
that
higher
degration
rates
at
higher
TiO2
 suspensions. For t high-frequency ultrasound results. was We also independently assessed the role of direct UVloadings
is
due
to
an
additive
effect
of
two
techniques.
Other
factors
such
as
better
mass
 performed usi the TiO2 suspens irradiation in the combined experiment. The degradation frequency ultrasou transfer
are
of
lesser
importance
under
standard
conditions,
but
may
be
a
factor
at
lower
 lifetimes of the four model compounds were determined flowing to finely d using sonolysis under ultraviolet irradiation, without any turned off, solute TiO2
loadings. added TiO2 catalyst. No difference was realized by the catalysis experimen presence of UV light during the sonolysis experiments. The of 2,4-DCP in th absorption band of these compounds lies in the range of TOC
under
TiO2
control:
with
low
catalyst
loadings,
there
is
still
efaicient
minerali‐ degradation lifetim 281-287 nm and tails off around 310. Since the light filtering without sonolysis sation
under
the
combination.
Mineralisation
of
2,4‐DCP,
complete
at
~3
hours,
is
unaffect‐ solution used in the photolysis experiments cuts off wavetreatment of the ca lengths below 315 nm, the tested compounds should not be effects but canno ed
by
catalyst
loadings
of
≥10
mg/L; the rate of depletion of carbon is, however, lower. affected directly by the UV light. 2,4,6-Trichlorophenol observed in the co showed a slight decrease in lifetime of the compound. This ment. Similar fin small difference, noted in Table 1, is within the experimental loadings. error of ( 1 min. These control experiments confirm that the We further eva additive effect seen in the combination experiment arises photocatalysis and from the photocatalytic activity of the TiO2 nanoparticles loadings. These re and not the UV light.

tocatalysis s of toxic inter in the comb tocatalysis simultan

of toxic intermediat in the combination Acknowledg

We thank Dr Acknowledgments

We thank Dr. K. Vin for providin the Department of C The work d for providing the fac The workBasic En the described the Basic Energy Sc This is contr This is contribution Laboratory. Laboratory.

the Departm

(1) Ollis, D. (1) Ollis, D. F.; Al-Ek ment omenter f f Wa t o a (2) Jeworski, M.; He (2) Jeworski 196. 196. (3) Hoigne, J. Chem (3) Hoigne, Pollutants by Oz Pollutan The Handbook o The H an Springer-Verlag: of the two processes, as described above. Additional factors, (4) Under
sole
photolysis,
if
the
TiO2
loading
is
less
then
10
mg/L,
the
change
in
TOC
is
severe.
Andreozzi, R.; C Springer of the two processes, mass transfer, are less important under such as improved as described above. Additional factors, 1999, 53, 51. (4) Andreoz suchstandard conditions but may play aless important the as improved mass transfer, are larger role in under (5) Peller, 1999, 53 J.; Wiest, Quantitatively,
after
~3
hours,
only
less
than
40%
of
TOC
is
resolved. degradation at lower TiO2may play a larger role in the loadings. 3176. standard conditions but (5) Peller, J. (6) Hart, E. J.; Fische The degradation results for 0.2 mM solutions of 2,4-DCP degradation at lower TiO2 loadings. 284. 3176. with varying TiO2 loading are summarized in Table 2. In (6) Hart, E. The degradation results for 0.2 mM solutions of 2,4-DCP (7) Serpone, N.; Terz these experiments, the amount of catalyst was systematically 1994, 98, 2634. 284. with decreased TiO2 loading are summarized in Table 2. In varying in half, over several cycles. With small catalyst (8) Destaillats, H.; C (7) Serpone these experiments, the amount prevalent between the indeloading, a major difference is of catalyst was systematically Phys. Chem. A98 1994, 2 pendent photocatalysis and the combination process. catalyst (9) Stock, N. L.; Pelle decreased in half, over several cycles. With small TiO2 Te(8) oDestailla chn l. 2000, 3 loadings as small as 10 mg/L of prevalent between the indeloading, a major difference is TiO2 are sufficient to maintain PhyP.; Se (10) Colarusso, s. Ch an effective degradation rate in the combination pendent photocatalysis and the combinationexperiment. 2 (11) Vinodgopal, K.; P process. TiO (9) Stock, N Conversely, in the photocatalysis experiments, (no sonolysis) 1998, 32echnol. T , 3646. loadingslifetimes of 2,4-DCP lengthen2at TiO2 loadings smaller the as small as 10 mg/L of TiO are sufficient to maintain (12) Kamat, P. V. Che (10) an effective degradation rate in the combination experiment. (13) Liu, G.;Colaruss than 125 mg/L. With a loading of 34 mg/L, the performance Li, X.; Z (11) Vinodgo Conversely, in thefor the combination process (lifetime ) 8.2 Technol. 2000, 3 is maintained photocatalysis experiments, (no sonolysis) 1998, 32 min) and diminishes lengthen at TiO2 photocatalysis the lifetimes of 2,4-DCP substantially in the loadings smaller (14) Li, X.; Cubbage, P (12) 2001, 143 Chem. Kamat, thanexperiment (lifetime ) 49 ( 2 min). Thus, it is clear that the 125 mg/L. With a loading of 34 mg/L, the performance (15) Nasr, C.; Vinodg (13) Liu, G.; combination approach remains very effective for degradation padhyay, chnolK Te A. K.; . is maintained even the combination process (lifetime ) 8.2 for at very low levels of TiO , a trend not present of 2,4-DCP 2 (16) Hoffman, M. R.; (14) Li, X.; Cu min)inand independent photocatalysis. in the photocatalysis the diminishes substantially Chem. Rev. 1995 Che experiment (lifetime )process also offers effective mineraliza- the (17) Malato, S.; m. 2 Blan The combination 49 ( 2 min). Thus, it is clear that (15)on. 2002, 3 Nasr, C. Envir tion rates with low remains very effective for degradation combination approachcatalyst levels. At TiO2 loadings of 10 padhyay (18) Naffrechous, E.;

FIGURE 9. Change in in the totalorganic carbon ofof 2,4-DCP solutions FIGURE 9. Change the total organic carbon 2,4-DCP solutions in photocatalysis or the combined photocatalysis/sonolysis experiin photocatalysis or the combined photocatalysis/sonolysis experiments using various loadingsof TiO2:: (a) photocatalysis, 10 mg/L; ments using various loadings of TiO2 (a) photocatalysis, 10 mg/L; (b) photocatalysis, mg/L; (c) photocatalysis, 500 mg/L; (d) (b) photocatalysis, 6464mg/L; (c) photocatalysis, 500 mg/L; (d) photocatalysis + sonolysis, 10 mg/L; (e) photocatalysis + sonolysis, photocatalysis +photocatalysis + sonolysis, 500 mg/L. sonolysis, 10 mg/L; (e) photocatalysis + sonolysis, 250 mg/L; (f) 250 mg/L; (f) photocatalysis + sonolysis, 500 mg/L.

Literature Literature Cited C

While this argument is certainly valid in a general sense, it eralization. Figure 8 shows the decrease in organic carbon alone cannot explain the synergetic effects seen in combinaof aqueous solutions of 2,4-D during the individual and tion experiments. We tested the hypothesis that sonolysis combined systems. A significant benefit in mineralization facilitates the break-up of TiO2 aggregates in aqueous rate is noted when the combined system is compared to the suspensions. For this purpose, a photocatalysis experiment high-frequency ultrasound results. was performed using sonolytically treated TiO2 catalyst. First, We also independently assessed the role of direct UVthe TiO2 suspension (no solute) was subjected to high irradiation in the combined experiment. The degradation frequency ultrasound waves for 30 min with the oxygen gas lifetimes of the four model compounds were determined flowing to finely disperse the TiO2. The ultrasound was then using sonolysis under ultraviolet irradiation, without any turned off, solute was added, and the independent photoadded TiO2 catalyst. No difference was realized by the catalysis experiment was completed. The degradation lifetime VERALL SUMMARY presence of UV light during the sonolysis experiments. The of 2,4-DCP in this case was 18 min as compared to a absorption band of these compounds lies in the range of degradation lifetime of 20 min (Table 2) using the catalyst 281-287 nm and tails off around 310. Since the light filtering without sonolysis treatment. These results show that presolution 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 effects but cannot account fully for the enhancement affected directly by the UV light. 2,4,6-Trichlorophenol observed in the combined photocatalysis/sonolysis experishowed a slight decrease in lifetime of the compound. This ment. Similar findings were also noted at different TiO2 small difference, noted in Table 1, is within the experimental loadings. error of ( 1 min. These control experiments confirm that the We further evaluated the synergy effects by carrying out additive effect seen in the combination experiment arises photocatalysis and combination experiments at different TiO from the photocatalytic activity of the TiO2 nanoparticles The
following
table
compiles
a
summary
of
the
main
characteristics
of
the
two
tech‐ 2 loadings. These results are consistent with the hypothesis and not the UV light. that the main explanation for the enhancement in rate of Earlier efforts have been made to combine sonolysis with degradation at the higher TiO2 loadings is the additive effect either ozonolysis (8, 37) or photocatalysis (38) to improve niques
and
their
synergy.

O

:‐

TABLE 3. Comparison of Salient Features of Different Advanced Oxidation Processes
feature degradation of nonpolar co m pounds degradation of polar co m pounds mineralization avoidance of toxic interm ediate need for a catalyst
1930
9

sonolysis good poor poor good no

photocatalysis variable good good poor yes

combined sonolysis and photocatalysis very good very good very good very good yes, in sm aller quantity

Rapid
decay
and
mineralisation
of
the
chlorinated
aromatic
organic
compounds
is
brought
 about
under
simultaneous
sonolysis
+
photolysis.
The
lack
of
long‐lived
accumulation
of
 more
toxic
intermediates
is
also
a
major
achievement.

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

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.

1. Scheme of the 23 MW waste-incineration plant. The measuring points are indicated.

FIGURE 1. Scheme of the 23 MW waste-incineration plant. The measuring points are indicated.

ne particle formation and emission of a German The main objectives considered within this stu ultrafine particle formation and emission of a German The main objectives considered within th pal waste incineration plant was investigated.was investigated. follows: municipal waste incineration plant follows: ste incineration represents a favorable technique for technique The investigation of the impact impact of p (i) for Waste incineration represents a favorable (i) The investigation of the of proces ng the volume of waste the volume of waste streams its recovering its onmeasures on the particle-size distribution i streams and recovering and measures the particle-size distribution in the reducing energy content for generation electricity and district µm in the raw in thegas: flue gas: To develop content for generation of electricity andofdistrict 0.017-10 µm flue raw To develop new 0.017-10 heating. However, in the past, municipal waste incinerators and flue-gas cleaning cleaning measures f g. However, in the past, municipal waste incinerators integrated integrated and flue-gas measures for red (MWI) had a to the emission of toxic bad reputation due to the emission of toxic particle emissions from combustion a bett had a bad reputation due particle emissions from combustion plants plants a combustion byproducts (including polychlorinated dibenzoedge of generation mechanisms of particles d stion byproducts (including polychlorinated dibenzoedge of generation mechanisms of particles during p-dioxins/-furans, PCDD/F and polycyclic aromatic hydrocombustion processes is required. ns/-furans, PCDD/F and polycyclic aromatic hydro- as mercury and combustion processes is required. carbons, PAH as well as heavy metals, such (ii) The study of the course and the va s, PAH as well ascadmium), whichsuch as a serious hazardous potential. study of the course and the variabil heavy metals, exhibit mercury and (ii) The emitted particle-size distribution: This info um), which exhibit a the past decade numerous efforts have been under-particle-sizebasis, e.g., for evaluationinformat Within serious hazardous potential. quired as distribution: This of the amo emitted emissions the past decade taken by several European countries under- toxicquired as basis, e.g., for evaluation of the amount o numerous efforts have been to reduce inhalable particles. from MWI in to reduce toxic emissions y several European countriesorder to achieve the very tight emission levels particles. (iii) The observation of the impact of flu inhalable set by the national tight emission levels MWI in order to achieve the very environmental protection authorities. For devices on the emitted particle-size distribu example, the emission limit of PCDD/F (measured as (iii) The The recent flue-gas cleaning technology needs he national environmental protection authorities. Forto 0.1 ng/m3 in observation of the impact of flue-gas international toxicity equivalent) was set devices on with respect particle-size distribution s le, the emission limit of). PCDD/F (measured as incineration in the emitted to fine and ultrafine particle pre Germany (5 Due to these efforts, waste The recent potential new formation of inhalable to be ational toxicity equivalent) was set to 0.1 ng/m3 in clean process, flue-gas cleaning technology needs partic Germany nowadays represents a relatively with respect to fine and ultrafine particle precipit equipped with waste incineration in ny (5). Due to these efforts,some of the most recent emission-reduction Experimental Section devices, such relatively clean process, absorbers, ny nowadays represents a as wet scrubbers, fabric dust filters, potential new formation of inhalable particles. ed with some of or electrostatic dust precipitators (ESP). the most recent emission-reduction (A) Measurement of the Particle-Size Dis However, thedust filters, absorbers, precipitation fine and ultrafine particle Experimentalcombustion aerosol in the waste gas of the inc Section s, such as wet scrubbers, fabric characteristics of most of the flue-gas cleaning devices are a scheme of which is shown in Figure 1, trostatic dust precipitators (ESP). (A) Measurement ofits particle-size distribution using o not yet characterized. Furthermore, the formation of particles regarding the Particle-Size Distribu wever, the fine and ultrafine particle precipitation is not yet well in industrial scale combustion processes itself combustion aerosol in the wasteaerosol measurement s sizing techniques. The gas of the incinerat

INTRODUCTION:
__________________________________________________________________________________________
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) (3) Reinforce
and
encourage
the
presence
of
scrubbers 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 2. Particle sampling and measuring system: (a) scheme of the on-line particle sampling and analysis system; (b) photograph of the sampling and dilution system (1/10 000); and (c) photograph of the particle measurement unit in mobile rack. sampling and analysis scheme as well as photographs of the sampling system and the measurement cabinet are depicted in Figure 2. The SMPS measures the mobility of charged aerosol particles in a high voltage electric field. The mobility is inversely proportional to the volume-equivalent diameter d

FIGURE 3. C averaging d a h size distribut and after the statistics, the below 600 nm drops drama

3b). In prac by two instr in backup f

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 of APS andSMPS data. (a) Algorithm for 3. Combination of APS and SMPS data. (a) Algorithm for system: (a) scheme (a) scheme ng and measuring system: averaging d anddhandfrom idealized SMPS and APS data.data. (b) Particleh d h averaging h ae dae from idealized SMPS and APS (b) Particleing and (b) photograph size distribution from real measurements of of SMPS and APS ystem;analysis system; (b) photograph distribution from real measurements SMPS and APS before before size n system (1/10 000); and (c) photograph and after the combination of both Due to poor ); and (c) photograph and after the combination of both spectra. 650 nm. APS channelsparticle spectra. Due to particle poor nt unit in mobile rack. statistics, the SMPS measurements stopped at ack. statistics, the600 nm were rejected because the APSat 650 nm. APS channels SMPS measurements stopped counting efficiency below heme as well as photographs of the drops dramatically at these particle sizes. below 600 nm were rejected because the APS counting efficiency measurement cabinet are photographs of the depicted dramatically at these particle sizes. drops 3b). In practice, one individual particle cannot be analyzed abinet are depicted aerosol the mobility of charged The
y‐axis
represents
number
of
particles
per
size
intervals.
Since
the
no.
of
particles
count­ by two instruments simultaneously as particles are trapped age electric field. The mobility is In in backup filters, and the density cannot be calculated for 3b). practice, one individual particle cannot be analyzed the volume-equivalent of charged aerosoldiameter dtwo all sizes as the simultaneously is small. Thus, are trapped ed
by
the
instrument
is
done
so
in
discrete
size
bins
with
varying
intervals
(logarithmically
in­ by instruments overlapping range as particles some e APS measures the particle velocity assumptions be the particle population d. The mobility is ofin backup filters,have tothemade aboutcannot be calculated for and density tream, which is a function the to achieve a solution for eq 1: uivalent diameter d creasing
with
diameter),
the
no.
per
size
bin
is
normalised
to
a
bin
width
(size
interval)
of
1
 dae, by laser-scattering velocimetry sizes as the overlapping range is small. Thus, some all (1) The shape factor κ is assumed to be constant and he particle velocity assumptions 1 for allto be made about the is defined as the close to have particles. The shape factor particle population ata were combined according to a μm
[ref.
author]. ratio of the drag force on the1: a function of the to achieve a solution for eq particle and the drag force on d (15) into one single distribution an ideal sphere with identical properties. κ is 1 for water tering velocimetry le density in the overlapping size (1) The shape factor for atmospheric particles which have and droplets and close to 1 κ is assumed to be constant ts and by calculating the geometric undergone particles. The shape deviates defined close to 1 for all condensation processes. Itfactor isfrom 1 for as the nnels. ned according to a ze range between 500 and 1000ratio ofaggregates and fibers (17). particle and the drag force on nm the drag force on the single distribution re the same particle population and (2) It is assumed that both instruments sample an identical an 1 for e overlapping size e number concentration. However,ideal sphere with identical properties. κ is results water particle population, and therefore the measurement droplets and close to 1 for atmospheric particles which have e plotted within the same in an identical concentration in the overlapping range. In ating the geometric diagram, ping particle population appears practice, this assumption is met by carefully minimizing the undergone condensation processes. It deviates from 1 for erent diameters) due to the different sampling errors of (17 instruments and correction of the aggregates and fibers both). n 500the shift of the overlapping From and 1000 nm resulting data for transmission losses in the sampling lines anges (see Figure 3a) the particle(2) It is assumed that both instruments sample anlitcle population and and coincidence errors using standard methods from identical ed as both diameters are related by erature (18). ntration. However, particle population, and therefore the measurement results (3) The the F d 2Cdiagram, in an identicalnumber concentration graphsoverlapping range. In concentration in the of both instruments d) ) same (dae) (1) 0 ae 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)
(3)

N

mum of SMPS) mum of APS). minimum of SMPS) m eq 1 of the maximum for APS). .from eq 1 forto Assuming F the j dae. Assuming F to h j APS size range, the APS size range, channels and a PS channels and (Figure 3b). For a ed (Figure 3b). For he SMPS system of the SMPS system ize-distribution e size-distribution tition frequency epetition frequency recorded every um recorded every SMPS data, nine nd SMPS data, nine btain the same

o obtain the same S. d by by means of ated means of ied particle-size rtified particle-size s, DuDe SciScitinicfic eres, k uke en e f ti eratr r (Model lngeneoator (Model bias of of the two ent bias the two w 10%. Due to to elow 10%. Due en during normal during normal ncentration the entration in in the dard deviation 30d deviation 30oughly an order of hly an order of

FIGURE 4.4. Change of particle-size distribution upon the travel of of FIGURE Change of particle-size distribution upon the travel the flue gas through the boiler section of the incinerator plant. the flue gas through the boiler section of the incinerator plant. Particle-size distribution measured in the flue gas (a) atat 700 °C Particle-size distribution measured in the flue gas (a) 700 °C (above) and (b) at 300 °C (below). (above) and (b) at 300 °C (below).
was performed via external calibration. The VOCs were was performed via external calibration. The VOCs were analyzed by t ermal desorption ga hromat tg graphymass analyzed by thhermal desorption gass cchromaooraphy--mass p tro ometr (TD-GC/MS, Perkin-Elmer ATD 400 thermal spsecectrmetryy(TD-GC/MS, Perkin-ElmerATD 400 thermal desorption unit coupled to a HP 5890 series II-GC with a SSQ desorption unit coupled to a HP 5890 series II-GC with a SSQ 7000/Varian 3400/ITS 40 tracker as mass-selective detector). 7000/Varian 3400/ITS 40 tracker as mass-selective detector). For further details of the analytical procedures see refs For further details of the analytical procedures see refs 2020 and 21. All flue-gas concentrations are given with respect to and 21. All flue-gas concentrations are given with respect to normalized conditions (dry flue gas, 273 K, 1013 hPa, and 11

to the particle-size he particle-size position (aromatic ition (aromatic pling points along ng points along g of volatile organic

volatile organic

...
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

s the coagulation, however, is e small particles are consumed diffusion coefficient. and coagulation effects have based flame experiments (see, In case of laboratory flames, of flame and waste-gas connd time scale and so does the ticles, whereas the cooling of mperatures down to ambient line of the waste incineration seconds. the concentration of the major the raw gas tends to decrease ue-gas duct (800-300 °C) (24sumption of gas-phase species to condensation and chemical se concentration of organic meter for understanding the n the flue-gas channel. Therecle-size distribution the connt aromatic species along the igated too. Larger aliphatic y a significant role because of emperatures, while the small ndensed on particles at these aken at five different positions ampling temperatures of 1100 zzles), 800 °C (first draw of (second draw of combustion /economizer), and 200 °C (inlet e 5, the spatial course of the matic species in the flue-gas epresent the average of three a at 1100 °C which result from

TABLE 1: Concentrations [ng/Nm3] of Several Aromatic Flue-Gas Constituents along the Flue-Gas Ducta
sampling temperature compound benzene toluene o -xylene naphthalene biphenyl dibenzofuran diobenzo- p -dioxin phenanthrene pyrene chrysene benzo[ b ]fluoranthene benzo[ a ]pyrene benzo[ g,h,i]perylene 1100 °C 800 °C 1952 242 57 355 31 1 1 93 10 2 5 9 3 600 °C 400 °C 200 °C 2388 269 4 1965 18 22 5 1240 634 123 59 23 48 71230 30532 27454 2832 5541 2233 1607 2854 376 23009 57384 22642 131 212 21 799 1440 32 85 314 9 11474 2438 6991 7662 3550 4336 37 1223 792 43 1358 559 33 1165 18 57 1954 453

a Sa m pling te m peratures w ere 1100 °C, 800 °C, 600 °C, 400 °C, and 200 °C.

nic gas-phase species is relatemperature supports thermal ell as oxidation by the residual as. Although the formation of takes place at very high tem-

peratures, e.g. in the flame zone (28), the very high decomposition rates are limiting the surviving concentration of complex organic molecules. However, when approaching lower temperatures, the concentration of all investigated compounds increases considerably reaching maximum concentrations at 800 or 600 °C. In this temperature range, the formation reactions dominate over decomposition reactions. The results given in Table 1 and depicted in Figure 5 show that the concentrations of gas-phase species are decreasing again with further decreasing temperatures. This is in line with results from preceding investigations (24-27) and the conclusions drawn from the particle-size changes during the travel of the flue gas through the duct. An increased reactive gas- to particle-phase transfer rate is expected in this temperature range, and larger PAH structures as well as inorganic compounds begin to condense onto particles with decreasing temperature. The chemical processes taking place on the particles between 600 and 200 °C are of particular complexity. For example, an increase of certain chlorinated ultratrace
V O L. 37, N O . 20, 2003 / 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
9

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 observed for 800 orfor 800°C. 600 °C. are observed 600 or
and coagulation processes. As the coagulation, however, is and coagulation processes. As the coagulation, however, is a diffusion-driven process, the particles are consumed a diffusion-driven process, the smallsmall particles are consumed first because of their first because of their higher higher diffusion coefficient. diffusion coefficient. Comparable condensation and coagulation effects have Comparable observed in laboratory-based flame experiments have condensation and coagulation effects (see, been been observed in laboratory-basedIn case of laboratory flames, for example, refs 8 and 23). flame experiments (see, however, and 23 cooling of of laboratory flames, for example, refs 8significant). In case flame and waste-gas constituents occurs on a subsecond time scale and so does the however, significant cooling of flame and waste-gas concorrelated growth of soot particles, whereas the cooling of

TABLE 1: Concentrations [ng/Nm3] [ng/Nm3] Aromatic TABLE 1: Concentrations of Several of Several Aromatic Flue-Gas Constituents along the Flue-Gas Ducta Flue-Gas Constituents along the Flue-Gas Ducta
sampling temperature compound benzene toluene benzene o -xylene

compound

1100 °C 800 °C 1952 242 57

1100 °C 800 °C 242

600 °C

sampling temperature
400 °C 200 °C

toluene

71230 30532 27454 2388 2832 1952 5541 2233 269 71230 30532 1607 2854 376 4

600 °C

400 °C 200 °C 27454 2233 2388 269

2832

5541

Process
control:
Changes
in
combustion
conditions
can
cause
drastic,
dynamic
 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 6. back-up oil burnersthe back-up oil burners at theparticle-size distribution with burners switched °C: (a) particle Influence of the Influence of at the flue-gas measuring point at 700 °C: (a) flue-gas measuring point at 700 on (above)on (above) and (b)off plot of the temporal course of the particle-size distribution. course of the particle-size distributi and off (below) and 3D (below) and (b) 3D plot of the temporal

compounds in this temperature range is observed. This conditions (38-40). As gas-phase species represent the includes compounds in this temperature range is particle formation and growth, transient effects (38-40). A highly toxic polychlorinated dibenzo-p-dioxins/feedstock for observed. This conditions furans (PCDD/F or dioxins). However, as carbonaceous are assumed to have a major impact on the particle-size includes highly toxic polychlorinated dibenzo-p-dioxins/- of transient processes for particle for feedstock particulate matter has been identified to play a major role spectrum too. In this work two types in the PCDD/F formation pathways (de novo-synthesis (29, were investigated, the influence of the oil are assumed to have a burner furans (PCDD/F or dioxins). However, asspectrum of the flue gas and the effectson the carbonaceous 30)), primary measures for particle reduction in the flue gas particle-size of the particulate matter has been identified cleaning with pressurized air. These two cases were too. In this w spectrum may also be motivated by their potential impact on PCDD/F grate to play a major role abatement. the PCDD/F formation pathwaysselected because they are suspected of influencing different in (de novo-synthesis (29, were investigated, the fractions of the aerosol. While the oil burner is likely A deeper understanding of the chemical processes oc30)), primary measures characteriza- influencing the soot particles gas particle-size spectrum curring on the particles will require a chemicalfor particle reduction in the flueand organic gas-phase constituents (i.e. the very small particles) the cleaning of the tion of the particle ensemble on a single-particle basis. Up may also be motivated by their potential impact on PCDD/F the amount of resusgrate cleaning with pre grate should predominantly increase to now, such information is only accessible by on-line aerosol abatement. enables a simultaneous size pended mineral particles (i.e. the larger particles). selected because they a laser mass spectrometry, which

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.

FIGURE 7. Effect of cleaning-flap operation to remove the the ashes fromthe grate on particle-size distribution (APS) at (APS) at the flue-gas measuring FIGURE 7. Effect of cleaning-flap operation to remove ashes from the grate on particle-size distribution the flue-gas measuring point at 300 °C: (a)atAPS°C: (a) APS spectra at normal operation (b, green) andduringflap operation ([, red) and (b)andplot of the temporal course point 300 spectra at normal operation (b, green) and during flap operation ([, red) 3D (b) 3D plot of the temporal course of the distribution. of the particle-size particle-size distribution. of fine dust particles which may be predominantly composed of inorganic material. They are periodically reintroduced into of inorganic material. They are periodically reintroduced into the combustion chamber by opening the cleaning flaps and blowing pressurized air through them from the ash-bin side the combustion chamber by opening the cleaning flaps and of the grating (see Figure 1). from the ash-bin side blowing pressurized air through them This cleaning procedure is performed every 30 min for a time span of approximately 20 of the gratingThe increased air1). This cleaning procedure is (see Figure flow induced by the cleaning procedure s. performed every alsomin for a additional particles from the fuel bed. may 30 discharge time span of approximately 20 During this cleaning procedure, a cleaning procedure s. The increased air flow induced by the very different particle-size distribution was observed. The reintroduced fuel bed. may also discharge additional particles from the particles are much larger than newly formed soot particles as demonDuring this cleaning procedure, ais consistent withparticle-size very different the assumption strated in Figure 7. This distribution that predominantly agedreintroduced particles are was observed. The mineral particles are additionally much larger released. Because of the very short cleaning procedure only than newly formed soot particles as demonAPS spectra (size distribution above 1 µm) could be obtained, strated in Figure 7. This is consistent with the assumption since one SMPS scan lasts 90 s. that predominantly aged obtained by theFigure 7a shows the particlemineral particles arenormal operation additionally size distribution APS during released. Becausewellthe very the cleaning procedure ([). During the of as during short cleaning procedure only (b) as
of fine dust particles which may be predominantly composed

Precipitator) and Possible Regeneration of Ultrafine Particles in the Stack. In the previous section, the effect of ticles in the Stack. In the previous section, the effect of primary process control measures on the particle-size distribution of the flue gas was considered. on the particle-size primary process control measures The particle emission of industrial flue gas plants, however, also distribution of the combustion was considered. The particle depends on the so-called secondary flue-gas cleaning emission ofas wet scrubbers, fabric filters, or electrostatic industrial combustion plants, however, also measures such depends on the so-called the health relevance of cleaning dust precipitators. With respect to secondary flue-gas inhalable particulate matter it is particularly filters, or electrostatic measures such as wet scrubbers, fabricimportant to evaluate flue-gas cleaning measures regarding the efficiency dust precipitators. With respect to the health relevance of of fine and inhalable ultrafine particulate matter precipitation. The particulate matter it is particularly important to actual design of flue-gas cleaning devices is optimized for evaluate flue-gas cleaning measures regarding an efficiency the precipitation of particulate mass which is not the appropriate measure for the efficiency of fine and precipitation. The of fine and ultrafine particulate matter ultrafine particle design of flue-gas cleaning devices of optimized for actual removal. Within this study the particular case is the wet the electrostatic dust precipitator is considered.MWI entire is not an precipitation of particulate massThe plant which flue-gas cleaning system of the investigated appropriate measure forunit (slurry of active carbon/ ultrafine the efficiency of fine and consists of a spray absorbing

Precipitator) and Possible Regeneration of Ultrafine Par-

The
aine
dust
particle,
which
comprise
the
large
amounts
of
ash
loosed,
causes
a
rise
in
 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.

It
can
be
seen
that
the
w‐ESP
is
quite
effective
down
to
0.05
μm,
causing
a
reduction
of
one
 order
of
magnitude;
it
effectiveness
drops
off
below
0.05
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.

In Figure 9a, two 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

particle diameter o particle diameter o slightly weaker. In slightly weaker. In F on the wet-ESP on on the wet-ESP on plot of a 48 min plot of a 48 min measurement sequ measurement sequ was deactivated tw was deactivated tw some 10 s. The grap some 10 s. The graph gained by the APS gained by the APS. In Figure 9a, tw In Figure 9a, two the stack gas with a the stack gas with ac (i.e. over 80% of the (i.e. over 80% of the one depicted in the one depicted in the ized by a broad ma ized by a broad ma drastically altered drastically altered casionally. In thes casionally. In these creased concentrat creased concentrat present. The typic present. The typica ranges from severa ranges from several size distribution du size distribution du upper graph of Fig upper graph of Figu ultrafine particle r ultrafine particle re magnitude. magnitude.

FIGURE 8. Effects of shutting down the wet electrostatic precipitator FIGURE 8. Effects of shutting down the wet electrostatic precipitator (ESP) on particle-size distribution: (a) particle-size distribution in (ESP) on particle-size distribution: (a) particle-size distribution in the stack gas (80 °C) with ESP operating (b, green) and ESP shut the stack gas (80 °C) with ESP operating (b, green) and ESP shut off ([, red) and (b) 3D plot of the temporal course of the particleoff ([, red) and (b) 3D plot of the temporal course of the particlesize distribution in the APS range. size distribution in the APS range.
As
before,
the
real‐time
stark
contrast
between
ESP‐on
and
ESP‐off
can
be
seen.

At the lower At the lower ss equipment (17 nm equipment (17 nm concentration with concentration with small particles in g small particles in g gas- to particle-ph gas- to particle-pha centrations of ultra centrations of ultra with new formation with new formation

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

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