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361-377, 1993
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ORIGINAL CONTRIBUTION
A D V A N C E D C H E M I C A L O X I D A T I O N : ITS P R E S E N T
R O L E A N D P O T E N T I A L F U T U R E IN H A Z A R D O U S
WASTE TREATMENT
C. P. Huang* Chengdi Dong, and Zhonghung Tang
Department of Civil Engineering, Universityof Delaware, Newark, DE 19716
ABSTRACT.Chemical
oxidation reactions involving hydroxyl radicals have been extremely effective in the destruction of organic
pollutants. These advanced chemical oxidation processes (AOP) generally use a combination of oxidation agents (such as H202 or
O3), irradiation (such as uv or ultrasound), and catalysts (such as metal ions or photocatalysts) as a means to generate hydroxyl radical. The hydroxyl radical is one of the strongest inorganic oxidants next to elemental fluorine. The hydroxyl radical is stable over a
wide pH range, up to pH 10. The hydroxyl radical reacts with organic by three major mechanisms: hydroxy addition, hydrogen abstraction, and electron transfer. Several AOP systems are reviewed first. The merits as well as limitations of these systems are discussed. The potential of AOP for future hazardous wastes treatment is then demonstrated by four AOP systems, H202/Fe 2+,
TiO2/uv/O2, H2Oz/uv/O2, and TiO2/uv/H202, exemplified by chlorophenols. A reaction scheme can be generalized for the oxidation of halogenated phenols by advanced chemical oxidation, specifically, ones involving hydroxyl radicals. Upon the attack of a
halogenated phenol, ArXnOH, by a hydroxyl radical, OH., a free radical, Ar(OH)2Xn., is formed. This free radical can undergo two
reaction paths: (l)hydroxylation without dechlorination (Type A) and (2) hydroxylation with deehlorination (Type B). It has been
observed that mono-halogenated phenols (n=l) only follow Type A path; dichlorophenols (n = 2 ) and trichlorophenols (n = 3 ) can
have both Type A and Type B reaction pathways; tetrahalogenated (n = 4) and pentahalogenated (n = 5) phenols only follow Type B
reaction pathway.
INTRODUCTION
Oxidative destruction o f chemicals provides ultimate solutions for the treatment o f hazardous wastes. Oxidative
destruction o f organic pollutants can be accomplished by
various means: biological, chemical and physical (thermal). While there are differences in the mode of operation, the basic principle o f energy dissipation process,
intrinsic to oxidative destruction o f organic matters, is
largely the same among these systems.
Traditionally, attention received by biological oxidation processes far exceeds that o f the chemical and physical oxidation systems, due in part to its cost effectiveness
and versatility in handling a wide variety o f organic pollutants. Since its introduction in the 1900s, several biological treatment systems have evolved and been adopted
*To whom correspondence may be addressed.
is supported by a grant (No.
R815081) from the Exploratory Research Program, US
Environmental Protection Agency. Contents of this publication
do not necessarily reflect the views or policy of the funding
agency. Any conclusions or mention of chemicals and
processes are made by the authors only and should not be
implied as their endorsement by the funding agency.
Acknowledgements-This work
361
362
363
TABLE 1
(8)
Eo (NHE)
volt, 25C
F2 + 2e = 2F-
2.87
OH + H+ + e = H20
2.33
03 + 2H + 2e = 0 2 + H 2 0
2.07
H202 + 2H + 2e = H302+
1.76
MnO4- + 4 H + + 3e = MnO2 + 2 H 2 0
1.68
HCIO2 + 3 H + 4e = C l + 2 H 2 0
1.57
MnO4- + 8H+ + 5e = Mn 2+ + 4 H 2 0
1.49
HOCI + H + 2e = C I + H 2 0
1.49
C12 + 2e = 2CI-
1.36
H B r O + H + 2e = B r + H 2 0
1.33
03 + H 2 0 + 2e = 0 2 + 2 O H
1.24
CIO2(g) + e = CIO2-
1.15
Br2 + 2e = 2 B r
1.07
HIO + H + 2e = I + H 2 0
0.99
Hydroxyl Radical
CIO2(aq) + e = CIO2-
0.95
C I O + 2 H 2 0 + 2e = C I + 2OH-
0.90
The hydroxyl radical is one of the most reactive free radicals and one of the strongest oxidants (16):
H202 + 2H + + 2e = 2 H 2 0
0.87
CIO 2 + 2 H 2 0 + 4e = C I + 4OH-
0.78
BrO" + H 2 0 + 2e = Br" + 4 O H
0.70
12 + 2e = 2 1
0.54
13 + 3e = 3 1
0.53
I O + H 2 0 + 2e = I- + 2 O H
0.49
ing the early seventies (11). It was thought that molecular ozone was the major oxidation species. Hoigne et al.
(9,10) proposed that 03 can have two reaction modes: direct ozonation reactions and free radical (such as hydroxyl radical) decomposition reactions (9,10). The
direct 03 reaction involves molecular 03 which is highly
selective and produces a relatively slow reaction. The
typical rate constants are on the order of 1-103 (M-1 sec-1).
As a result, there is no complete mineralization and a
variety of intermediates could be formed (12). The hydroxyl radical formed during the ozone decomposition
reacts much more rapidly with organic compounds than
[1]
OH. + C6H6 ~
.C6H6OH
[2]
TABLE 2
HzOz/uv
electronbeam
ultrasound(us)
[3]
H202/us
uv/us
without irradiation
O3/[t202
O3/OH
HEO2/Fe2+ (Fenton's)
Heterogeneous Systems
with irradiation
[4]
TiO2/O2/ultraviolet
TiO2/HEOE/ultraviolet
without irradiation
electro-Fenton
364
HOOC-C4H~COOH+OH.
+H2OCO2+H20
HOOC-COOH
H202/uv system. UV photolysis of H202 generates OH':
[Sl
H202 + hv = 2'OH
[6]
Sundstrom et al. (28,29,30) have studied the destruction of individual aliphatic and aromatic compounds by
uv catalyzed oxidation with hydrogen peroxide. The results demonstrated that the system can destroy a wide variety of hazardous compounds present in water at low
concentration levels. For chlorinated aliphatic compounds, the organic chlorine was converted to chloride
ion, indicating that the chlorinated structures were effectively destroyed. In the case of aromatic compounds,
many intermediates were formed which could be eliminated by extending the treatment time. It was found that
benzene and trichloroethylene have similar reaction rates,
with trichloroethylene (TCE) having a slightly faster rate
than benzene. The oxidation rate increases with increasing hydrogen peroxide and decreases with increasing organic concentration. The rate constant for hydroxyl
radical addition to benzene ring is 7.8109 M-lsec~. The
addition of hydroxyl radical to TCE is 4.O109 Mlsec ~
(31). Thus, hydroxyl radical addition to benzene is about
twice as fast as that to TCE. The TCE oxidation rate
should be expected to be reduced by half at the constant
organic carbon concentration. The decomposition of
H202 by uv has much lower efficient than that of ozone
due to the much lower extinction coefficient of H202 by
uv photolysis.
Processes such as HzO2/uv, O3/uv, and H202/O3/uv
have been shown to be effective for groundwater decontamination and soil remediation. Because the activation
energy between active radicals, such as hydroxyl radicals
and organics is close to zero, oxidation occurs rapidly.
However, these systems are not without disadvantages.
First, when the processes involve ozone, mass transfer
between gaseous ozone and aqueous solution becomes
the major limiting factor (31). Second, although H202
can eliminate the mass transfer limitation, the decomposition of H202 by uv has been proved inefficient. This is
365
'OH (2.7) = H30 + (2.7) > e" (2.6) > H202 (0.71)
> H' (0.55)
I7]
e" + H + = 1/2H2
H + 02 = HO2; k = 2.11010 ( M l s e c 1)
[9]
Ultrasound (us) system. Ultrasound (us) can affect organic oxidation through three mechanisms: nucleation,
growth, and cavitation. Cavitation which is created by
the collapse of a gas- or vapor-filled bubble in a body of
liquid is the most important phenomenon. The instantaneous pressure and temperature at the center of the collapsing bubble has been estimated to be about 75,000 psi
and 13,000F respectively (36). Due to this high local
pressure and temperature, it has been recognized that
cavitation can enhance the rate of chemical reactions significantly. Next, solvent will be compressed and refracted by the rapid movement of fluids caused by a
variation of sonic pressure. Then, a large amount of energy will be put into a small volume with little heating.
The phenomenon is called microstreaming.
US radiation is known to decompose water vapor
molecules in the bubbles into free radicals, such as hydroxyl radicals, hydrogen radicals, and hydroperoxyl
radicals (37,38). Prasad et al. studied the liberation of a
chloride ion in a saturated aqueous solution of chlorobenzene and m-dichlorobenzene by ultrasound (US) (40).
More than 90% dechlorination of chlorobenzene and mdichlorobenzene occurs in 60 and 100 minutes, respectively (40). It is believed that the hydroxyl radical
formed by the reaction between H and O2 is responsible
for the oxidation of chlorobenzene and m-dichlorobenzene in water. Although hydrogen peroxide can be produced by application of US alone to a diluted aqueous
solution, the amount may be too small to be significant.
Hydrogen peroxide can be added to this process as an initiator to increase free radical concentration in the solution.
H202/us system. Chen et al. (41) investigated the oxidation of chloroform by us/H202 process. The optimal molar ratios of H202 to CHCI3 are between 30 and 50.
When the ratio of H202 to CHCI3 is 50:1, the best percentage removal (94%) was achieved. The overall reaction can be presented as follows:
[8]
CHCI3 + 2'OH ~
CO2 + 3Cl" + 3H +
[10]
366
[11]
[121
These products can form OH radicals through the following initiation steps:
02- + 03 ~
[13]
[14]
[15]
[16]
[17]
03- + "HO2 ~
[181
202 + H O
367
03/01-1- system. At neutral to high pH, ozone decomposes into hydroxyl radicals through the following initiation steps (9, 48):
[19]
[2Ol
-OH + R ~
The above initial steps result in the hydroxyl radicals
as the major oxidation species. This is the reason that alkaline oxidation rates by ozone are several orders of
magnitude higher than those in acidic media (49). Several investigators classified the ozonation at alkaline condition as advanced oxidation process (50). The catalytic
effect of a hydroxide ion has been recognized for a long
time in the ozonation of organic pollutants. Niegowski
reported pH of 11.8 as the optimal value (51). Jones indicated that phenol oxidation proceeds most efficiently at
a pH of 11.4(52).
Fe 2+ + H202 = Fe 3+ + O H + O H
[21]
OH + R ~
'R + H20 ~
oxidized products
[25]
Fe 3+ + R --~ Fe 2+ + products
[26]
[27]
Fe 2+ + R + H + --~ Fe 3+ + RH (reduction)
[28]
Fe2++OH ~
Fe 2+ + O H = Fe 3+ + OH"
[231
(Fe-OH) 2+
[29]
[22]
The rate constant is k2 = 3108 ( M l s e c q) (54,55). The expected stoichiometry of the reaction is given in Eq. [23].
Protons have been added to show formation of water:
368
contact with the H202. The accelerator in H202 decomposition will yield more free hydroxyl radicals.
If a small amount of F e E+ ion is needed, a chain reaction occurs through regeneration of Fe E+of Eq. [6]. If all
the oxidation is effected by hydroxyl radical formed by
reaction 1, non-chain reactions take place. Since there
are extra Fe 2+ present, considerable loss of the hydroxyl
radical proceeds via equation 2.
As the pH is raised, there is some evolution of oxygen
due to the reactions:
HO-OH = HO-O" + H +
[301
Fe 3+ + H O - O ~
HO-O ~
Fe 2+ + H O - O
H+ + ( O - O f
Fe 3+ + ( O - O f ~
H202 + (.O-O)- ~
[31]
[321
Fe 2+ + 02
[331
.HO + OH" + 02
[34]
tion of electricity from solar irradiation. Upon irradiation, electrons are produced at the conduction band (cb)
and positive holes are formed in the valence band (vb)
(56). If the semiconductor is in an aqueous suspension,
the electrons, which are reducing agents, can migrate to
dark surfaces and react with oxidizing chemicals. The
positive holes, which are oxidizing agents, will remain at
the surface of the semiconductor. In the absence of oxidizable substances such organic compounds, the positive
holes will react with the semiconductor and corrode the
solar cells (57). A coating of organic paint on the semiconductor is commonly applied to protect the solar cells
(56,57). The organic compound will consume the positive holes while being oxidized. Another way to harvest
the solar energy is with the production of hydrogen and
oxygen gases from water by semiconductor material irradiated with sunlight or an artificial light source (58). In
contrast to electricity generation, the solar energy is converted into chemical energy, in the form of hydrogen.
Since the separation of hydrogen from the gas mixture is
difficult, researchers have tried to suppress the oxidation
of water by adding organic chemicals to water (58). The
following illustration shows that in the presence of organic chemicals, the positive holes will be used by the
organic compounds rather than water. In fact this concept
has been used as corrosion control of solar cells.
[351
Haber and Weiss (53) suggest that this reaction contributed to the maintenance of a chain reaction sequence
under the acidic conditions of their study. Under neutral
pH, the sum of Eqs. [21] and [30] gives Eq. [33]. In this
superoxide-driven Fenton's reaction, iron functions as
the true catalyst as the result of the recycling mechanism
where iron has been canceled after summation of Eq.
[10] and [1].
n2o
C02
Org~aies
Three kinds of semiconductors can be recognized: (1)
R-type, (2) O-type and (3) RO-type. The classification
is made on the bandgap position of the semiconductors
with respect to the water reduction (H+/H:) and the water
oxidation (OdH20) potentials. The O-type semiconductors, such as WO3, Fe203, and MoS2, have valance bands
located below the EMF of the water oxidation and can
oxidize water to oxygen. The R-type semiconductors,
such as CdTe, CdSe, and Si, have conduction band located above the EMF of the water reduction and can
readily reduce water to hydrogen. The RO-type semiconductors, such as TiO2, CdS and SrTiO3, a combination of the above two types, can split water into O: and
H2. It must be noted that the presence of organic compounds can greatly enhance the decomposition of water
by one to three orders of magnitude.
Organic Matter
acetic acid
propionic acid
n-butylic acid
v-valeric acid
pivalic acid
tluene
benzene
acetopbenone
lactam
369
TABLE 3
Photocatalytic Dissociation of
Organic-Water Mixture by TiO2-Pt.
Organic Matter
glucose
ethanol
cellulose
pyruvic acid
gylcine
polyethylene
polyvinyl alcohol
polyvinyl chloride (PVC)
proline
End-Product
CH3CHO; C2HsOH; (CH3)2CO; H2
C2H6;CH3CHO; CH3COOH;H2
C2H6; C2H5OH; (CH3)2CO; H2
20H; H2
NH3; H2
CO2; H2
CO2; H2
CO2; HCI; H2
CO2; NH3; H2
stearic acid
CO2; H2
potato
fatty oil
cherry wood
white dutch clover
golden rod
water hyacinth
dead cockroach
human excrement
teflon
trichlorbenzene
trichloroethylene
CH3OH; (CH3)2CO; H2
C2H6; H2
C2H6; CH3OH; (CH3)zCO;H2
CH4; CH3OH; C2HsOH; NH3; H2
CH3OH; NH3; H2
NH3; H2
NH3; H2
NH3; CH3OH
HF; CO2; H2
HCI; CO2; H2
HCI; CO2; H2
TABLE 4
Other Work on the Photocatalytic Dissociation of Organic Matters on TiO2
End-Product
Reference
CH4; CO2; C2H6; H2
Kruatler and bard (72)
ethane; ethylene; CO2; H2
propane; CO2; H2
n-butane; CO2; H2
isobutane; isobutylene; CO2; H2
benzaldehyde; biphenyl; cresols
Fujihira et al. (62, 63)
phenol; bephenyl
Kawai and Sakata (59-61)
hydroxyacetophenone; phenol
imides
Pavlik and Tantayanon (73)
370
+ 0.5(4a+b-2c-3d-e)H2
[39]
C7F15COO + H + = C7F15COOH
[40]
[361
[38]
CnF2n+IOH + O H ~
[42]
CnF2n(OH)2 or
CnF2n+I(OH)
[43]
CASES OF ADVANCED C H E M I C A L
OXIDATION OF C H L O R O P H E N O L S
The oxidation of chlorophenols has been studied by
Huang and co-workers using Fenton's reagent and photocatalytic oxidation processes (80). Fig. 1 shows the results of the decomposition of the parent compounds,
mono-, di-, tri-, tetra- and penta-chlorophenois by the
Fenton's reagent. The results clearly indicate that the
degradation of chlorophenols is very fast and follows a
first order kinetic expression in terms of the parent compound concentration. Under the experimental conditions,
a total removal of chlorophenols is possible in less than 5
minutes, except perhaps for tetra- and penta-chlorophenols. The order in the destruction of these chlorophenols
is as follows:
371
1o0%
100%
-.<>-2-chlorophenol
--c3-3-dalorophenol
--<>-4-chlorophenol
80%
o
60%
k . . . , . . . . , . . . . ,
80%
~~1~
2o~
....
i....i
....
,....,
....
-o-2,34ichlomphenol
-o-2,44ich10rophenol
--o-23<lichlorophen01
"~-2'6 4ichlrphenl
--o-3,44ichloro~nol
3.54ichlorophenol
20%
0%
0%
1
Time (min)
Time (min)
--o-2j,4-trichl0mpl~01
8o~ ~
~\
-o-2.~,~-~d~o~h~ot
60% ~'~
"*-2,4,5-ttichJ~ophmol
---23,6-trich10t0pheml
2o%~icl~bmol
It~
80%~k
--o-phenol
i
--o-2,3,4,6-tetrachl0rophenol ~
.-o--pentachlorophenol
:
60%
"
@ 20%
o%
I
Time (rain)
0%
Time (min)
F I G U R E 1. Destruction o f Chlorophenols by Fenton's Reagent Oxidation. Experimental conditions: Concentration of organic was 10 "3 M except
2,3,4,6-tetrachlorophenol and pentachlorophen, for which concentration was 5x10 "5 M; Fe +2 = 10 -3 M; H202 = 6.7x10 4 M per minute; pH = 3.0;
reaction volume = 2 liter; ionic strength = 5x10 2 M NaNO3; room temperature.
35DCP > 23DCP > 25DCP > 34DCP > 24DCP -26 DCP (for dichlorophenols)
This order is slightly different from that o f the Fenton's reagent process, except that in both processes,
26DCP and 246TCP are the most difficult ones for oxidation.
For the purpose of comparison, the oxidation of these
chlorophenols was also conducted with the H202/uv system (Fig. 3). It must be mentioned that the uv light
source used in this experiment was the same as that used
in the photocatalytic oxidation process reported above;
the wavelength (350 nm) o f this uv light source is longer
than other systems such as H202/uv and O J u v o f other
researchers. The rate o f oxidation is the same as that o f
C . P . H U A N G , C. D O N G , A N D Z. T A N G
372
100%
100%
-o-2~orophenol
--o-3-chl0r0phen01
80~
=
o
=
~.
60%
40%
4O%
2O%
2O%
~.
I~.~
0~
40
80
120
160
200
40
80
100%
"
'
"
-o-23,5-trich10rophenol
...-2,3,6-tfichlorophenol
....-a-2,4,5-tddaloropheno[
2,4,6adchlorophenol
60%
60%
40%
2O%
20%
80
120
200
-o-2,3,4,6.tetrachl0r0phenol.'
--o-PCP
e~ 80~
4O%
40
160
" -~-2,3,4~@[alo~phe~]
80%
120
Time (rain)
100%
0%
0
\~,-~ +~,4~!ch~o~o~i
Time (min)
_o
--o- 2,Ydichlorophenol:
"-o-2,4-dichlo~ophenol~
"o"2,5-dichlor~phenol
'.
~2,6-dichlorophenol.
80%
60%
0%
0
160
0%
0
200
40
Time (rain)
80
120
160
200
Time (rain)
FIGURE 2. Destruction of Chlorophenols by UV/TiO2 Oxidation. Experimental conditions: Concentration of organic was 103 M except
2,3,4,6-tetrachlorophenol and pentachlorophen, for which concentration was 5x10 -5 M; TiO2 = 1 g/L; pH = 4.0; ionic strength = 5x10 2 M NaNO3;
room temperature.
100% I . . .
, . ..
, . ..
,...
'00% ]k .....
,...
-o- 2-chlomphenol
-t~-34a10r0~nol
--e-4-ch]rl~nl
s0%
=g 60% ~
,, 80%[.['~
-o-2,4-dichlorophenol:
[~l k
60%tl ~ ,
0%
. . . . .
40
80
120
:=,...
160
0%
0
200
40
Time (min)
100%
~-~i~:
-o-23~.
80%
80
120
160
200
160
200
Time (min)
100%
' "
--*- 2,6-dicMompheaol.
L/ ~ ' ~
--*-2~oro~
--~--2,4~,
80%
-o-Z3,4~
6O%
40%
20%
0%
40
80
120
Time (min)
160
200
0%
0
40
g0
1211
Time (min)
FIGURE 3. Destruction of Chlorophenols by UV/H202 Oxidation. Experimental conditions: Concentration of organic was 10-3 M except
2,3,4,6-tetrachlorophenol and pentachlorophenol, for which concentration was 5xl 0.5 M; H202 = 0.1 M per minute; pH = 4.0; reaction volume = 1
373
It is interesting to note that the most difficult chlorophenols for oxidation by this method are the same as the
above two methods, 26DCP and 246TCP.
The oxidation of these chlorophenols by a modified
photocatalytic oxidation process, TiO2/uv/H202, was also
conducted. Fig. 4 shows that the rate of chlorophenol
oxidation is extremely fast. Tseng has reported that the
rate of chlorophenol oxidation follows a first-order expression of the Langmuir-Hinshelwood type as adsorption onto the TiO2 surface controls the oxidation process
(82). Depending on the degree of chlorine substitution,
the rate of oxidation generally follows the order:
O"
OH
=
OH
X~
(n --1
x.
OH
to 5)
OH
XR.HX
OH
TYPE A
(hydroxylation without
dechlorination)
OH(o,p) Xn
(Y
OH
H O 2.
-0 2
OH
Xn.1
TYPE B
(hydroxylation with
dechlorlnation)
OH(o,p) Xn-1
374
n = 0 (phenol)
OH
~
OH
@ O
OH
OH
H
OH
c1_5%~,
~
OH
OH
~CI
or
n -- I ( m o n o c h i o r o p h e n o l s )
OH
OH
CI
OH
cI
..
El
n = 4 (tetrachlorophenol$)
CI
OH
OH
C~[CI
n ~ 2 (dichiorophenols)
OH
OH
~CI
A O~CI
el
C~OH
T C l
Cl
or
OH
OH
o~.,.,,Cll~.)j~ or C ~ C '
~ CI
CI
T C I
CI
~I~ -El
OH
n = 5 (pentaehlorophenol)
CI
OH
OH
C~[CI
OH
~ H cI
or
Ci ~f
ci
Cl
Ci
i 8o%I
c]
c i ~f- c!
oH
--o-2-dal0r0phen01
--o3-chlorophenol
-o-4<hl0~phenol
80%
" 60%
OH
C~,~C|
or
CI ~ f
ci
100%
OH
C~.OH
60%
I .
40%
. i
..~-dichloro~nol.
I
-o-2,3-dichlor0phenol
--o-2,44ichlor01~erml
--o-2,54ich10r0~nol
-a--2,6-dich/orophenol
-4-3,44ich10~lSen01
20%
. . . .
40
~"..., . . .
80 120 160 200
0%
40
80 120 160
Time (min)
Time (rain)
100%lf.m . . , . . . . . . . . . . . . . . .
100%
--o-2,3,4-trichl0tophenol
--o-2,334fichlor0phenol
- ' ~ 2,3,6-tfrdll~phenol
80~ [~\
I.
Lil
I~
- -
. i
--o-phenol
8O%
-,s'-2,4,5-trichlotophend
40% [ ~
'
200
-~- 2,4,646ch10mphen01
2,4,646ch10mtSen01
6o%
4o%
20%
40
80 120 160
Time (rain)
200
0%
40
80 120 160
Time (rain)
200
FIGURE 4. Destruction of Chlorophenols by UV/TiO2/H202 Oxidation. Experimental conditions: Concentration of organic was 10.3 M except
2,3,4,6-tetrachlorophenol and pentachlorophen, for which concentration was 5x 10-5 M; TiO2 = 1 g/Liter; H202 = 0.1 M per minute; pH = 4.0; ionic
strength = 5x102 M NaNO3; room temperature.
375
tO000
0000
6000
4000
2000
Raw Leachate
REFERENCES
FIGURE 5. COD removal by H202 and Fe +2 + H202 with and without
precipitation. Experimental conditions: Initial COD = 8,500 ppm,
H202 = 5x10 "2 M; FeSO4 = 2x10 "3 M, pH = 3.0 (with H2SO4).
CONCLUSION
10
o~
0
20
40
60
80
I00
120
Time (rain)
376
20. Eisenhauer, H. R. Oxidation of phenolic wastes. J. Water Poll.
ControlFed 36:1116 (1964).
21. Bishop, D. F., Stem, G., Fleischman, M., and Marshall, L. S.
Hydrogen peroxide catalytic oxidation of refractory organics in
municipal wastewaters. Ind. & Eng. Chem. Design and Develop.
7:110 (1968).
22. Bowers, A. R., Gaddipati, P., Eckenfelder, W. W., Jr., and Monsen,
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