Study on the treatment of simulated coking wastewater by O3 and O3/Fenton processes in a rotating packed bed

Article abstract of DOI:10.1039/c5ra14198b

In this study, simulated coking wastewater was treated by the O₃/Fenton process in a rotating packed bed (RPB) and the results were compared with those by the O₃ process. Contrast experiments indicated that the degradation rates of phenol, aniline, quinoline and NH₃-N in the wastewater reached 100%, 100%, 95.68% and 100% respectively under the optimum operating conditions in the O₃/Fenton process and were much higher than those in the O₃ process. The BOD₅/COD value of the simulated coking wastewater treated in the O₃/Fenton process reached 0.46 and was 135% higher than that in the O₃ process. The degradation pathways of phenol, aniline, quinoline and NH₃-N in the simulated coking wastewater were also discussed. The results indicated that a combination of the advanced oxidation processes and the RPB can enhance the treatment efficiency of coking wastewater.

Full text of DOI:10.1039/c5ra14198b

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Study on the treatment of simulated coking
wastewater by O3 and O3/Fenton processes in
a rotating packed bed
Cite this: RSC Adv., 2015, 5, 93386
ab
Qing Wei,ab Shufeng Qiao,c Baochang Sun,ab Haikui Zou,
Jianfeng Chenab
*
ab
*
and Lei Shao
In this study, simulated coking wastewater was treated by the O3/Fenton process in a rotating packed bed
(RPB) and the results were compared with those by the O3 process. Contrast experiments indicated that the
degradation rates of phenol, aniline, quinoline and NH3–N in the wastewater reached 100%, 100%, 95.68%
and 100% respectively under the optimum operating conditions in the O3/Fenton process and were much
higher than those in the O3 process. The BOD5/COD value of the simulated coking wastewater treated in
the O3/Fenton process reached 0.46 and was 135% higher than that in the O3 process. The degradation
pathways of phenol, aniline, quinoline and NH3–N in the simulated coking wastewater were also
discussed. The results indicated that a combination of the advanced oxidation processes and the RPB
can enhance the treatment efficiency of coking wastewater.
Received 18th July 2015
Accepted 27th October 2015
DOI: 10.1039/c5ra14198b
www.rsc.org/advances
High gravity technology is carried out in a rotation packed
bed (RPB), which creates a simulated high gravity environment
1. Introduction
using centrifugal force generated by the rotation of a rotor in the
RPB. Liquid owing through the porous packing in the rotor is
split into micro- or nano-droplets, threads and thin lms, and
there is a huge and violently renewed gas–liquid interface,
leading to a signicant intensication of mass transfer and
micromixing.14,15 It is known that O3-related AOPs are limited by
O3 absorption into water.16 Thus high gravity technology can be
used to intensify these processes to improve the treatment effect
of wastewater.
This study employed the O3 and O3/Fenton AOPs and an RPB
as the reactor to treat a simulated coking wastewater containing
phenol, aniline, quinoline and ammonia. The effect of different
operating conditions on the degradation of phenol, aniline,
quinoline and ammonia was investigated, in an attempt to
provide a new process for the treatment of coking wastewater.
Coking wastewater is one of the largest industrial wastewaters
with many poorly biodegradable organics including phenol,
aniline, quinoline, as well as inorganic ammonia, which are
refractory and cause difficulties in biochemical treatment.1,2
Therefore, coking wastewater treatment processes are complex,
and combined treatment processes with various chemical and
physical methods are usually adopted in order to achieve
a certain effect, resulting in high operation costs.
In recent years, a variety of new technologies have emerged
for the treatment of wastewater with complex components,
among which advanced oxidation processes (AOPs), based on
chain reactions of hydroxyl radicals with pollutants, have
attracted wide attention due to their high efficiency and non-
selectivity.3 The most commonly used AOPs include O3, Fenton,
O3/Fenton, O3/H2O2, and so on.4–9 It was reported that AOPs are
efficient methods for coking wastewater treatment.10–12 In
O3-related AOPs, pollutants are degraded by reacting with O3
molecules (direct oxidation) or with hydroxyl radicals (indirect
oxidation), which are stronger oxidants produced through chain
reactions of ozone.13
2. Experimental section
2.1 Materials
The simulated coking wastewater was prepared in the labora-
tory and its composition and properties are shown in Table 1.
The chemical reagents used in the experiments include
ferrous sulfate heptahydrate, hydrogen peroxide (30%, w/w),
sodium hydroxide, sulfuric acid (98%), phenol ($99.0%),
aniline ($99.5%), quinolone ($99.5%) and ammonia
($99.0%). They are of analytical grade and were purchased from
Beijing Chemical Works, China. One mM Lꢀ1 of sodium
hydroxide and 1 mol Lꢀ1 of sulfuric acid were used to adjust pH
value of the solution.
aState Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical
Technology, P. O. Box 35, No. 15 Beisanhuan East Road, Beijing 100029, China.
E-mail: zouhk@mail.buct.edu.cn; Tel: +86 10 64443134
bResearch Center of the Ministry of Education for High Gravity Engineering and
Technology, Beijing 100029, China. E-mail: shaol@mail.buct.edu.cn; Fax: +86 10
64434784; Tel: +86 10 64421706
cQian'an Zhonghua Coal Chemical Co. Ltd., Tangshan, Hebei 064404, China
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Table
wastewater
1 Composition and properties of the simulated coking
2.2 Experimental procedures
The experimental setup is shown in Fig. 1. The simulated
coking wastewater was adjusted to a certain pH value and
divided into two portions with equal volume, one of which was
added with a certain amount of H2O2, and the other with
a certain amount of FeSO4$7H2O. The two liquid streams were
simultaneously pumped into the RPB via two respective liquid
Parameter
Value
Phenol (mg Lꢀ1
)
)
100
100
50
Aniline (mg Lꢀ1
Quinoline (mg Lꢀ1
)
NH3–N (mg Lꢀ1
)
83
pH
6.58 inlets with the same ow rate, while the ozone-containing gas
Chemical oxygen demand
588
147
0.25
was produced by an ozone generator and introduced into the
RPB via a gas inlet. The liquid streams and gas stream contacted
countercurrently in the RPB to achieve the mixing of liquid
streams and the absorption of O3 into the liquid as well as the
degradation of the pollutants. The remaining O3 in the gas
stream exiting the gas outlet was absorbed by the KI solution.
Samples were taken at the liquid outlet to analyze the pollutant
concentration, COD and BOD5.
(COD) (mg Lꢀ1
)
Biochemical oxygen demand
aer 5 days (BOD5) (mg Lꢀ1
)
BOD5/COD
The RPB consists mainly of a stationary casing and a packed
rotor. The rotor has an inner diameter of 40 mm, an outer
diameter of 120 mm, and an axial length of 15 mm. The
diameter of the casing is 170 mm. Stainless steel wire mesh
(Beijing Hongyahong Mesh Sale Center, Beijing, China) was
used as the packing material. For further information on the
RPB, please refer to our previous paper.17
2.3 Analytical methods
Ozone concentration was analyzed by a dual ultraviolet ozone
concentration detector (LM S-150, Guangzhou Li Mei Co.,
China).
Fig. 1 Experimental setup for the treatment of simulated coking wastewater in an RPB with the O3/Fenton process.
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COD was measured in terms of the Chinese Standard GB
HJ/T 399-2007 (water quality – determination of the chemical
oxygen demand – fast digestion – spectrophotometric method,
which is similar to the method by APHA18), and COD removal
rate was calculated according to the following eqn (1):
ðCODi ꢀ COD0Þ
h ¼
ꢁ 100%
(1)
COD0
where COD0 is the initial COD value of the wastewater, mg Lꢀ1
CODi is the COD value of the liquid samples taken at the liquid
outlet of the RPB, mg Lꢀ1
;
.
BOD5 was measured in terms of the Chinese Standard GB
7488-87 (water quality – determination of biochemical oxygen
demand aer 5 days – dilution and seeding method, which is
based on ISO 5815:1983 (ref. 19)), and BOD5 removal rate was
calculated according to the following eqn (2):
Fig. 2 Effect of rotation speed on the COD removal rate. (CO ¼ 30
ꢀ
ꢁ
3
mg Lꢀ1, pH ¼ 6.58, CFe( ¼ 0.4 mmol Lꢀ1, CH O ¼ 6.5 mmol Lꢀ1, G ¼
Vt ꢀ Ve
Vt
Ve
II
)
2
2
BOD5 ¼ ðC1 ꢀ C2Þ ꢀ
ðC3 ꢀ C4Þ
(2)
150 L hꢀ1, L ¼ 30 L hꢀ1).
Vt
where C1, C2: dissolved oxygen concentration measured
immediately aer the test specimen was prepared, and
measured aer the test specimen was cultivated for 5 days,
The B/C values were 0.24 and 0.38 at the rotation speed of
1000 rpm in the O3 and O3/Fenton processes respectively,
indicating that the wastewater treated by the O3/Fenton process
is suitable for subsequent bio-treatment.
A large amount of hydroxyl radicals is generated in the
O3/Fenton process through the reaction of O3 with Fenton. The
synergic mechanism of O3 and Fenton is shown by the following
eqn (3)–(12).20–23
respectively, mg Lꢀ1
.
C3, C4: dissolved oxygen concentration in a blank water
specimen measured immediately aer the specimen was
prepared, and measured aer the specimen was cultivated for
5 days, respectively, mg Lꢀ1
.
Ve, Vt: sample volume in the test specimen and total volume
of the test specimen, respectively, mL.
BOD5/COD (B/C) is the ratio of BOD5 to COD. B/C is
a biodegradable index, and a high B/C means high biodegrad-
ability of organic matters in wastewater. In general, wastewater
is suitable for biological treatment when B/C is higher than 0.3.
Phenol, aniline and quinoline concentrations were
measured with a high performance liquid chromatograph
(Waters 2695, USA), while NH3–N concentration was deter-
mined by a portable ammonia meter (GDYS-101SA, Xiaotiane
Instrument Co. Ltd., Changchun, China).
Fe2+ + O3 / Fe3+ + cO3
(3)
(4)
ꢀ
ꢀ
cO3 + H+ / O2 + cOH
Fe2+ + O3 / FeO2+ + O2
(5)
FeO2+ + O3 + H2O2 / Fe3+ + cOH + OHꢀ
(6)
ꢀ
H2O2 / H+ + HO2
(7)
ꢀ
ꢀ
O3 + HO2 / O2 + cOH + O2
(8)
ꢀ
ꢀ
O3 + O2 / O3 + O2
(9)
3. Results and discussion
O3 + H+ / cHO3
(10)
(11)
(12)
ꢀ
3.1 Effect of rotation speed
The effect of rotation speed on COD removal in the O3 and
O3/Fenton processes is presented in Fig. 2. It can be seen that
the highest COD removal rates of 39.36% and 17.5% were
reached at the rotation speed of 1000 rpm in the O3 and
O3/Fenton processes, respectively. When the rotation speed
increased initially, liquid was split into smaller droplets and
thinner lms, leading to a larger gas–liquid interface and better
absorption of O3 and thus higher COD removal rate. Neverthe-
cHO3 / O2 + cOH
Fe2+ + H2O2 / Fe3+ + cOH + OHꢀ
3.2 Effect of gas ow rate
less, a further increase in the rotation speed resulted in The effect of gas ow rate on the phenol, aniline, quinoline,
a reduction in liquid residence time in the RPB and thus NH3–N removal in the O3 and O3/Fenton processes is presented
a decrease in the COD removal. It is also found from Fig. 2 that in Fig. 3. It can be seen from Fig. 3 that the degradation of the
the O3/Fenton process has better effect on the COD removal pollutants increased with an increasing gas ow rate and ten-
than the O3 process due to the presence of H2O2 and Fe2+ to ded to stability at the gas ow rate of 300 L hꢀ1 in both the O3
enhance the generation of hydroxyl radicals.
and O3/Fenton processes. The phenol, aniline, quinoline,
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Fig. 3 Effect of gas flow rate on pollutants degradation in the O3 process (a) and O3/Fenton process (b) (CO ¼ 30 mg Lꢀ1, R ¼ 1000 rpm, pH ¼
3
6.58, L ¼ 20 L hꢀ1, CFe( ¼ 0.4 mM Lꢀ1, CH O ¼ 6.5 mM Lꢀ1).
II
)
2
2
Table 2 Effect of gas flow rate on the B/C value in the O3/Fenton
process
3.3 Effect of liquid ow rate
The effect of liquid ow rate on the phenol, aniline, quinoline,
NH3–N removal in the O3 and O3/Fenton processes is presented
in Fig. 4. It can be seen from Fig. 4(a) that the pollutants
degradation rate decreased as the liquid ow rate increased. An
increase in the liquid ow rate led to lower gas–liquid ratio,
resulting in reduced ozone mass transfer into per volume
liquid. In addition, higher liquid ow rate caused larger liquid
droplet size and shorter residence time of the liquid in the
reactor.14 All these were unfavorable for mass transfer between
ozone and the liquid and consequently resulted in decrease in
the removal rates of the pollutants.
Gas ow rate
150 (L hꢀ1
)
300 (L hꢀ1
)
COD (mg Lꢀ1
)
)
418.7
159.1
0.38
366.8
157.7
0.43
BOD (mg Lꢀ1
B/C
NH3–N degradation rates reached 61.97%, 98.78%, 60.0% and
100% respectively at the gas ow rate of 300 L hꢀ1 in the O3
process, while their degradation rates reached 91.51%, 100%,
88.78% and 100% at the gas ow rate of 300 L hꢀ1 in the
O3/Fenton process, indicating that the O3/Fenton process has
better effect than the O3 process. As the gas ow rate increased,
the pollutant degradation rates increased because higher gas
ow rate provided more ozone and higher mass transfer driving
force, promoting the mass transfer between ozone and liquid
and accelerating the degradation of the pollutants.
In order to maintain a reasonable throughput capacity, the
suitable liquid ow rate was determined as 20 L hꢀ1 in this
study. Fig. 4 also demonstrates that the O3/Fenton process has
better effect than the O3 process with the degradation rates of
phenol and quinoline reaching 76.4% and 78.63% respectively
in the O3/Fenton process but 55.69% and 50.96% respectively in
the O3 process at the liquid ow rate of 20 L hꢀ1
.
The effect of the gas ow rate on the B/C value in the
O3/Fenton process is given in Table 2, which shows that the B/C
value at the gas ow rate of 300 L hꢀ1 reached 0.43 and was
higher than that at the gas ow rate of 150 L hꢀ1, indicating that
the treated water is suitable for subsequent bio-treatment.
Table 3 gives the effect of the liquid ow rate on the B/C value
and shows that the B/C value reached 0.43 at the liquid ow rate
of 20 L hꢀ1 in the O3/Fenton process, indicating a high
biodegradability.
Fig. 4 Effect of liquid flow rate on pollutants degradation in the O3 process (a) and O3/Fenton process (b) (CO ¼ 30 mg Lꢀ1, R ¼ 1000 rpm, pH ¼
3
6.58, G ¼ 300 L hꢀ1, CFe( ¼ 0.4 mM Lꢀ1, CH O ¼ 6.5 mM Lꢀ1).
II
)
2
2
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Table 3 Effect of liquid flow rate on the B/C value in the O3/Fenton
process
Liquid ow rate
20 (L hꢀ1
)
50 (L hꢀ1
)
COD (mg Lꢀ1
)
373.4
160.6
0.43
449
152.7
0.34
BOD (mg Lꢀ1
B/C
)
3.4 Effect of initial pH
The solution pH plays an important role in the reaction of
organic compounds with ozone. The effect of initial pH on the
phenol, aniline, quinoline, NH3–N removal in the O3 and
O3/Fenton processes is presented in Fig. 5, which indicates that
the highest aniline, quinoline, NH3–N degradation rates were
attained at the initial pH 7 in both processes. At a lower pH, the
scavenging effect of hydroxyl radicals by H+ becomes obvious
Fig. 6 Effect of Fe(II) concentration on pollutants degradation in the
O3/Fenton process (CO ¼ 47 mg Lꢀ1, R ¼ 1000 rpm, pH ¼ 6.58, L ¼
and H2O2 reacted with H+ to form H3O2 , leading to an
+
3
20 L hꢀ1, G ¼ 300 L hꢀ1, CH O ¼ 6.5 mM Lꢀ1).
2
2
improved stability of H2O2 and weakened degradation effect.24
The pollutants degradation increased with a rising pH until
7 because the increase of hydroxyl ion concentration enhanced
the formation of hydroxyl radical, a more active oxidant than
ozone, through hydroxyl ion reaction with O3.15 In addition, the
increase of pH to 7 in the O3/Fenton process led to coagulation
whereby the pollutants were also removed by complexation
reactions due to the conversion of Fe2+ and Fe3+ to Fe(OH)n type
structures.25
When the pH was higher than 7, the degradation of phenol
constantly increased, while the degradation of aniline, quino-
line, NH3–N decreased with an increasing pH. The increasing
phenol degradation rate can be explained by the reaction of
phenol with more hydroxyl radicals induced by the increasing
hydroxyl ion concentration. It is deduced that aniline and
quinoline exist as the emprotid that is active and easy to react
with hydroxyl ions in acidic condition, but they exist as stable
molecules in basic condition, leading to a decreasing degrada-
tion rate with increasing pH.26
It can be seen from Fig. 5 that the phenol, aniline, quinoline,
NH3–N degradation rates reached 70.78%, 87.41%, 58.25% and
95.0% respectively at the initial pH of 7 in the O3 process, while
they increased to 88.39%, 94.97%, 76.31% and 100% respec-
tively at the initial pH of 7 in the O3/Fenton process. These
results conrmed that the O3/Fenton process has a higher
efficiency for coking wastewater treatment.
Table
5 Effect of Fe(II) concentration on the B/C value in the
O3/Fenton process
Table 4 Effect of initial pH on the B/C value in the O3/Fenton process
Fe(II) concentration
0
0.4 (mM Lꢀ1
)
0.8 (mM Lꢀ1
)
pH
3
5
6
7
9
12
COD (mg Lꢀ1
)
440.6
154.2
0.35
392.6
180.6
0.46
418.8
159.1
0.38
COD (mg Lꢀ1
)
424.3
148.5
0.35
419.5
155.2
0.37
400.1
176.2
0.44
386.6
190.2
0.49
422.4
167.2
0.40
426.5
153.5
0.36
BOD (mg Lꢀ1
B/C
)
BOD (mg Lꢀ1
B/C
)
Fig. 5 Effect of initial pH on pollutants degradation in the O3 process (a) and O3/Fenton process (b) (CO ¼ 47 mg Lꢀ1, R ¼ 1000 rpm, L ¼ 20 L hꢀ1
,
3
G ¼ 300 L hꢀ1, CFe( ¼ 0.4 mM Lꢀ1, CH O ¼ 6.5 mM Lꢀ1).
II
)
2
2
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Scheme 1
The natural pH of the simulated coking wastewater is 6.58,
which is close to 7 and was chosen as a suitable pH because
there was no need to adjust the pH of the wastewater with
reagents.
3.5 Effect of Fe(II) concentration
The effect of Fe(II) concentration on the phenol, aniline, quin-
oline, NH3–N removal in the O3/Fenton process is presented in
Fig. 6. It can be seen from Fig. 6 that the phenol, aniline, qui-
nolone and NH3–N degradation rates reached 100%, 100%,
95.68% and 100% respectively at the Fe(II) concentration of
0.4 mM Lꢀ1 in the O3/Fenton process. The combination of Fe(II)
and hydrogen peroxide can promote the generation of hydroxyl
radicals and improve the oxidation efficiency (eqn (3)–(12)).
Therefore, the increase in Fe(II) concentration enhanced the
formation of hydroxyl radicals, thus boosting coking wastewater
degradation. However, when Fe(II) concentration exceeded
0.4 mM Lꢀ1, hydroxyl radicals were consumed by the excess
Fe(II) (eqn (13) and (14)), leading to a decrease in coking
wastewater degradation efficiency. The optimum Fe(II) concen-
Scheme 2
The B/C values of the wastewater treated at different initial
pH in the O3/Fenton process are given in Table 4, which indi-
cates that the highest B/C value of 0.49 was attained at the pH 7.
tration was thus determined as 0.4 mM Lꢀ1
.
Fe2+ + cOH / Fe3+ + OHꢀ
(13)
Scheme 3
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Fe2+ + FeO2+ + 2H+ / 2Fe3+ + H2O
Paper
it is found that the O3/Fenton process was more effective due to
the synergistic effect of O3 and Fenton. The optimum operating
conditions for the degradation of phenol, aniline, quinoline
and NH3–N in the coking wastewater were determined as rota-
tion speed of 1000 rpm, gas ow rate of 300 L hꢀ1, liquid ow
(14)
Higher degradation rate and B/C value can be attained in the
O3/Fenton process due to the synergic effect of O3 and Fenton
reagent. Table 5 indicates that the B/C value reached 0.46 at the
Fe(II) concentration of 0.4 mM Lꢀ1, compared to 0.35 and 0.38 at
the Fe(II) concentration of zero and 0.8 mM Lꢀ1 respectively,
conrming that 0.4 mM Lꢀ1 was a suitable Fe(II) concentration.
rate of 20 L hꢀ1, CFe( ) of 0.4 mM Lꢀ1, CH O of 6.5 mM Lꢀ1 and
II
2
2
pH of 6.58. Under these conditions, phenol, aniline, quinoline
and NH3–N removal rates in the O3/Fenton process reached
100%, 100%, 95.68% and 100%, respectively, which are much
higher than those in the O3 process. The BOD5/COD value of the
simulated coking wastewater treated by the O3/Fenton process
reached 0.46 and was 135% higher than that treated by the O3
process. It can be deduced that the O3/Fenton process in an RPB
is a feasible way to increase biodegradability in the treatment of
coking wastewater.
3.6 Degradation pathways
The degradation pathways of the coking wastewater are
complex and involve mainly the oxidative ring-opening reac-
tion, nitration reaction, and so on. In the O3/Fenton process, the
Fenton reagent with Fe2+ and H2O2 can catalyze O3 decompo-
sition to produce hydroxyl radicals and thus improve the
degradation efficiency of the coking wastewater signicantly.
1) Phenol degradation pathway. The mechanism of oxida-
tive degradation of phenol is shown in Scheme 1. Intermediates
are generated by the attack of hydroxyl radicals on phenol, and
the main intermediate is hydroquinone. Then the generated
quinone substances are further oxidized to form small molec-
ular substances through ring-opening reaction and eventually
converted into carbon dioxide and water.27,28
2) Aniline degradation pathway. Aniline mineralization is
initiated by the attack of O3 and/or cOH on aniline to yield mainly
benzoquinonimine and some nitrobenzene. p-Benzoquinone is
subsequently produced by hydrolytic decomposition of benzo-
quinonimine. Further degradation of p-benzoquinone, as well as
of nitrobenzene with release of NO3ꢀ, leads to the formation of
maleic acid which is mineralized to CO2.29,30 The mechanism of
oxidative degradation of aniline is shown in Scheme 2.
3) Quinoline degradation pathway. The mechanism of
oxidative degradation of quinoline is shown in Scheme 3.
Hydroxyl radicals attack preferentially C3 and C6 sites at the
benzene ring to activate quinoline, which are quickly oxidized to
form 5,8-dicarbonyl quinolone. Aldehyde and acid are released
through the ring-opening reaction of 5,8-dicarbonyl quinolone,
and by-products, mainly pyridine, are produced. With the attack
of hydroxyl radicals and O2 on pyridine, NH3, N2, CO2, CO, H2O
and other small molecule compounds are generated.31
4) NH3–N degradation pathway. As shown in the following
eqn (15) and (16), NH3 is removed bꢀy the reaction with O3 and
hydroxyl radicals, and N2 and NO3 are produced. It is also
found that hydroxyl radical concentration in the solution has
a great inuence on the degradation rate of NH3–N.32
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 21276013, 20990221).
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