Chemical Engineering Journal 277 (2015) 3039

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Study on catalytic and non-catalytic supercritical water oxidation

of p-nitrophenol wastewater
Xiuqin Dong, Zhongdong Gan, Xianlin Lu, Wenzhu Jin, Yingzhe Yu , Minhua Zhang
Key Laboratory for Green Chemical Technology of Ministry of Education, R&D Center for Petrochemical Technology, Tianjin University, PR China
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 A new composite catalyst was

employed in the catalytic process and
a good performance was obtained.
 Economical process conditions were
achieved for both processes based on
several experiments.
 A new reaction mechanism was
proposed for the catalytic process.
 Probable reaction pathways were
speculated for the two processes.

a r t i c l e i n f o a b s t r a c t

Article history: Catalytic and non-catalytic supercritical water oxidation of p-nitrophenol contained in wastewater was
Received 13 February 2015 performed using compressed air and hydrogen peroxide as an oxidant, respectively. In catalytic process,
Received in revised form 15 April 2015 the supported Mn2O3/Ti-Al oxide composite catalyst was employed to accelerate the reaction rate.
Accepted 24 April 2015
Experiments were conducted to investigate the effect of temperature, pressure, oxygen excess or dosage
Available online 30 April 2015
of hydrogen peroxide and residence time on the destruction of p-nitrophenol. Appropriate reaction con-
ditions were obtained for both processes. Based on the products generated in reaction, possible reaction
Keywords:
pathways were speculated. A possible mechanism was also proposed for the catalytic process according
p-Nitrophenol
Supercritical water oxidation (SCWO)
to the experiments focused on the crystal structure transformation in catalyst MnO2. The comparison of
Composite catalyst the two processes indicated that hydrogen peroxide is a better oxidant without its cost taken into con-
Reaction mechanism sideration, and the reaction rate of catalytic process is much higher than that in non-catalytic process
Reaction pathway in spite of the better oxidant used in it.
2015 Elsevier B.V. All rights reserved.

1. Introduction chemical industry. However, the wide use of p-nitrophenol has

caused a serious problem in waste management due to its high
As an important organic chemical raw material, p-nitrophenol toxicity and persistence in the environment. In recent years, super-
has been used extensively in pharmaceutical and pesticide critical water oxidation (SCWO) has shown a fantastic potential for
clean and efcient decontamination of organic wastewater that is
hard to be handled by conventional methods [13]. SCWO is an
Corresponding authors at: Key Laboratory for Green Chemical Technology of
effective and advanced oxidation technology to break up organic
Ministry of Education, R&D Center for Petrochemical Technology, Tianjin University,
PR China. Tel.: +86 22 27405972; fax: +86 22 27406119 (Y. Yu). Tel./fax: +86 22 matters through the unique properties of supercritical water under
27406119 (M. Zhang). the typical operation conditions of 450600 C, 2428 MPa [4].
E-mail addresses: yzhyu@tju.edu.cn, yuyingzhe@tju.edu.cn (Y. Yu), Supercritical water (SCW) is a good medium for the complete
mhzhangtj@163.com (M. Zhang).

http://dx.doi.org/10.1016/j.cej.2015.04.134
1385-8947/ 2015 Elsevier B.V. All rights reserved.
 X. Dong et al. / Chemical Engineering Journal 277 (2015) 3039
decomposition of organic compounds. Organic compounds and
oxygen are both completely miscible with supercritical water,
which allows oxidation reactions to occur rapidly without any
interphase mass transport limitations [5]. Several recent review
articles provide more details on the properties of supercritical
water and on SCWO [68]. Most hydrocarbons and oxygenated
hydrocarbons are converted to CO2 and H2O while nitrogen in
the feed is converted to N2 or N2O [9].
However, because of high temperature and pressure as well as
the substantial amount of power required to pressurize the oxy-
genating reagent, supercritical water oxidation technologies are
very expensive. To reduce these costs, operation at lower temper-
atures, pressures and reduction in the amounts of oxidant will be
required, and this can only be achieved through increasing the oxi-
dation rate in supercritical water.
To improve the oxidation rate in supercritical water, numerous
researchers have investigated the application of catalysts. Krajnc
and Levec [1012] and Ding et al. [1316] were among the rst
to investigate the catalytic effect in supercritical water. So far,
precious metals such as platinum and metal oxides such as man-
ganese oxide, chromium oxide and vanadium oxide have been
studied. Oshima et al. [17] studied the SCWO of diluted coking
wastewater with MnO2 as the catalyst and obtained 90% or higher
conversions of both NH3 and TOC (total organic carbon) within 2 s
of contact time at 500 C. Savage et al. [18] used MnO2, TiO2, CuO/
Al2O3 catalysts for phenol degradation in supercritical water with
a tubular ow reactor and concluded that MnO2 is the best cata-
lyst for its highest activity and stability in the three catalysts.
Destruction of quinoline over MnO2/CuO mixed catalyst in super-
critical water was investigated to examine the effects of operation
conditions, and the results showed that the catalytic reaction
depended strongly on temperature and pressure [19]. However,
the supported Mn2O3/Ti-Al oxide composite catalyst has not yet
been applied to the SCWO of p-nitrophenol waste water
oxidation.
In this work, p-nitrophenol was decomposed by supercritical
water oxidation with the supported Mn2O3/Ti-Al oxide composite
catalyst. The aim is to investigate the effects of reaction conditions,
such as temperature, pressure, oxygen excess and residence time
on the destruction of p-nitrophenol. Furthermore, the mechanism
of supercritical water oxidation with the supported Mn2O3/Ti-Al
oxide composite catalyst was proposed to better understand the
process. At the end of the article, non-catalytic supercritical water
oxidation using hydrogen peroxide as oxidant is also presented.
2. Experimental details
2.1. Apparatus and procedure
Compressed air and hydrogen peroxide were chosen as an oxi-
dant, respectively. The scheme diagram of experimental apparatus
is shown in Scheme 1(a for compressed air, b for H2O2). The exper-
imental apparatus consists of feeding pumps, wastewater storage,
oxidant tank, preheater, a reactor, a cooler, heat exchanger, gas
liquid separator, back- pressure regulator, and so on. Main equip-
ment specications of the system are listed in Table 1. The wastew-
ater and oxidant feed streams, which were mixed at the reactor
inlet using a mixer after pressurized by two high-pressure pumps
and then preheated to reaction temperature separately in two dif-
ferent lines. Upon exiting the reactor, the efuent was quenched
immediately by passing through a shell-and-tube heat exchanger.
Subsequently, the product steam was depressurized by a back-
pressure regulator and separated into vapor and liquid phases in
a gasliquid separator. Gas and liquid products from gasliquid
separator were collected for analysis.
31
2.2. Materials and analytical methods
Concentration of p-nitrophenol in wastewater employed in this
work is 1000 mg/L. The oxidant feed stream was prepared by dilut-
ing an analytical reagent of hydrogen peroxide with deionized
water to the desired concentration. The p-nitrophenol concentra-
tions of wastewater and liquid efuents were analyzed by liquid
chromatography using an Agilent HP1100 series equipped with a
diode array UV detector and a Zorbax SB-C18 5 lm C-18,250 
4.6 mm column, and the total organic carbon (TOC) content was
measured using a Shimadzu TOC-VCPH. Hydrogen peroxide quanti-
cation was carried out by titration with a potassium permanganate
solution. GCMS (Anglilent 6892N-5973N, HP-Inno wax column)
was applied for qualitative analysis of the reaction products.
Reaction products are essential to be concentrated and extracted
with methylene chloride (C2H2Cl2) for analysis since the concentra-
tion of reaction products in the liquid phase is too low.
A commercial titanium-aluminum composite oxide was used as
the catalyst support. The supported Mn2O3/Ti-Al oxide composite
catalyst was prepared by incipient wetness impregnation method.
The titanium-aluminum composite oxide support was impreg-
nated by aqueous solution of manganese nitrate (Mn(NO3)2). The
samples were dried at 120 C for 4 h in vacuum and calcined at
600 C for 4 h after aging 18 h. The preparation of non-supported
MnO2 catalyst: mixed MnO2 powder with a certain amount of
methyl cellulose and tableted after evenly mixed, then dried the
samples at 120 C for 2 h in vacuum and calcined at 450 C for
3 h. The catalysts were sieved to a 2040 mesh size range for later
use. The preparation of non-supported Mn2O3 catalyst is the same
as MnO2 catalyst, just changed the calcination temperature to
600 C. A total of 6.5 g of catalyst was loaded into the reactor in
all experiments requiring a catalyst.
Removal efciency of p-nitrophenol (PNP) and TOC is calculated
using the following equation:
 
PNPt
X PNP 1   100% 1
PNP0
 
TOCt
X TOC 1   100% 2
TOC0
where [PNP]t (mg/L) is the residual concentration of PNP in wastew-
ater after reaction, and [PNP]0 (mg/L) is the initial concentration.
And [TOC]0 is the initial TOC concentration of wastewater (mg/L),
and [TOC]t is the residual TOC concentration of the liquid efuent
after the reaction (mg/L). The oxygen excess is dened as:
O2 actual
n  100% 3
O2 stoich
where [O2]actual is the concentration of O2 fed into the reactor (mg/
l), and [O2]stoich is the stoichiometric requirement concentration of
O2 to obtain complete oxidation of the feed wastewater (mg/L).
When hydrogen peroxide is used as oxidant, chemical reaction
equation is:
2C6 H5 NO3 23H2 O2 ! 12CO2 28H2 O N2 4
Dosage of hydrogen peroxide is dened as:
H2 O2 actual
k  100% 5
H2 O2 stoich
where [H2O2]actual is the concentration of H2O2 fed into the reactor
(mg/L), and [H2O2]stoich is the stoichiometric requirement concen-
tration of H2O2 for complete oxidation of wastewater (mg/L). The
residence time in the reactor is obtained using the equation below:
Vr
s 6
VF H2 O F O2
32 X. Dong et al. / Chemical Engineering Journal 277 (2015) 3039
Scheme 1. Schematic diagram of supercritical water oxidation system (a) O2, (b) H2O2.
where V r is the reactor volume (mL), V is the total volume of H2O
and O2 (mL), F H2 O and F O2 is the ow rate of H2O and O2,
respectively.
3. The process of catalytic SCWO
3.1. Effect of operation parameters
Non-supported catalysts MnO2, Mn2O3 and Mn2O3/Ti-Al oxide
composite catalyst were employed to evaluate the catalytic activity
by the criteria of PNP removal efciency under same reaction con-
ditions. Besides, a vacant test without a catalyst was performed to
make comparisons with the aforementioned catalytic SCWO pro-
cesses, and results are shown in Fig. 1.
Compared with non-catalytic supercritical water oxidation
reaction, the catalyst can improve the removal rate of supercritical
water oxidation of p-nitrophenol. Two of the non-supported cata-
lysts have shown good catalytic effect on the PNP removal
efciency while the supported Mn2O3/Ti-Al composite oxide cata-
lyst can further improve the removal rate of p-nitrophenol in
wastewater, especially in the low temperature region where its
activity is obviously higher compared with non-supported cata-
lysts. The effects of temperature, pressure, excess oxygen and res-
idence time on the removal efciency of p-nitrophenol in
wastewater with the supported Mn2O3/Ti-Al oxide composite cat-
alyst are illustrated in Figs. 25.
Experiments were conducted in a temperature range of 385
445 C with a constant pressure of 26 MPa, residence time of 1
2 s and 1000% excess oxygen. As is seen in Fig. 2, with the rising
temperature, removal efciency of p-nitrophenol is promoted
gradually. Effect of temperature on oxidative degradation of
organic compounds in supercritical water can be explained in
two ways. On the one hand, the reaction rate constant increases
with the temperature growth while the other conditions remain
unchanged. On the other hand, as the density of water is extremely
sensitive to temperature changes under supercritical conditions,
 X. Dong et al. / Chemical Engineering Journal 277 (2015) 3039 33

Table 1
Main equipment of the supercritical water oxidation system. 100

Name Specication Manufacturer

98
Plunger pump Maximum outlet pressure Thar Company
60 MPa
Maximum ow 50 g/min 96

Removal efficiency/%
Compressor Membrane compressor NOVA SWISS Company
Inlet pressure P 2 MPa 94
Maximum outlet pressure
100 MPa
92
Liquid preheater Maximum operating pressure Hangzhou Huali Pump
32 MPa Co., Ltd
90
Maximum operating
temperature 600 C
Material C-276 88
Gas preheater Maximum operating pressure Hangzhou Huali Pump
32 MPa Co., Ltd 86
Maximum operating
temperature 600 C 390 400 410 420 430 440 450
Material C-276 Temperature/C
Reactor Maximum operating pressure Hangzhou Huali Pump
32 MPa Co., Ltd Fig. 2. Effect of temperature on the removal efciency of p-nitrophenol (26 MPa, 1
Maximum operating 2 s, n = 5).
temperature 600 C
Material C-276
Diameter 12.8 mm
100
Quencher Center tube material C-276 Hangzhou Huali Pump
Coil Tube material 316L Co., Ltd 99
Maximum operating pressure
32 MPa 98
Removal efficiency/%

97

96
100

95

94
Removal efficiency/%

93
95

92
vacant test
Mn2O3
20 22 24 26 28
MnO2
Pressure/Mpa
90 Mn2O3/Ti-Al oxide
Fig. 3. Effect of pressure on the removal efciency of p-nitrophenol (400 C, 12 s,
n = 10).

380 390 400 410 420 430 440 100

Temperature/C

Fig. 1. PNP removal efciency of different catalysts and comparison with a vacant
Removal efficiency/%

98
test (26 MPa, n = 15, 12 s).

temperature increment will lead to a decline of water density, 96

thereby reducing the concentration of reactants, which in turn
lowers the reaction rate. It is by the aforementioned two opposite
effects that the temperature plays the combined role in the reac- 94
tion. As is shown in Fig. 2, the positive effect of temperature plays
a dominant role in the range of 385445 C. Once the temperature
exceeds 420 C, because of the relatively small concentration of p-
92
nitrophenol in the system, the rising temperature exhibits a small
effect on the removal efciency of p-nitrophenol. Consequently,
5 10 15 20 25
420 C is a good choice since the removal rate is approximately
99%. Oxygen excess (n)
Effect of pressure on the pollutant destruction in wastewater
Fig. 4. Effect of oxygen excess degree on the removal efciency of p-nitrophenol
was investigated in a pressure range from 20 MPa to 28 MPa at
(26 MPa, 12 s and 400 C).
34 X. Dong et al. / Chemical Engineering Journal 277 (2015) 3039
400 C. Results are illustrated in Fig. 3. It can be seen that as the
pressure rises, removal efciency of the p-nitrophenol keeps
increasing. It is known raising the pressure gives rise to the
increase of water density, thus more p-nitrophenol and oxygen
will be dissolved into supercritical water, resulting in promoted
reaction rate [2022]. However, in industrial practice, higher oper-
ating pressure leads to higher power requirement and also causes
problems regarding the reactor wall stress [23]. Therefore, 26 MPa
was selected as an optimal pressure in our study.
Effect of excess oxygen on removal efciency of p-nitrophenol
in wastewater was investigated at 400 C, 26 MPa and 12 s of res-
idence time. In these experiments, excess oxygen (n) varied from
2.5 to 25. Degradation of p-nitrophenol in supercritical water oxi-
dation is a process of oxidative pyrolysis, the higher excess oxygen
is, the better reaction it performs, and the higher the p-nitrophenol
removal efciency is. Dependence of phenol [22] and benzene [24]
conversion on the excess oxygen has been observed, and the
authors found that the conversions were higher in the experiments
with the higher oxygen concentrations. Though, it should be
stressed that the investigators performed experiments at low tem-
peratures. As can be seen in Fig. 4, with the increasing of oxygen
excess, p-nitrophenol removal efciency increased rapidly in the
range of 2.510. The variation trend of removal efciency is level-
ing off when the excess oxygen is greater than 15 because of the
low concentration of organic compounds left in the reactor.
100
Removal efficiency/%
98
96
94
92
1.0 1.5 2.0 2.5 3.0
Residence time/s
Fig. 5. Effect of residence time on the removal efciency of p-nitrophenol (26 MPa,
400 C, n = 10).
Fig. 6. X-ray diffraction pattern of catalyst after reaction (a) MnO2 (b) Mn2O3.
Another reason is that the concentration of oxygen adsorption on
the catalyst surface is saturated, and thereby continuously increas-
ing the amount of oxygen has no signicant effect on the reaction.
However, n = 20 is selected to ensure adequate oxidant in the
reaction.
Residence time is an important factor affecting the rate of
oxidative degradation of organic pollutants. The effect of residence
time on the removal efciency is displayed in Fig. 5. Organic
removal efciency in supercritical water goes up very fast with
the increasing of residence time in the range of 0.51.3 s, and after
that the increasing trend is slowing down due to the depletion of
reactants. In order to ensure the sufcient reaction, 6 s is chosen
for the operation parameter. It should be noted that in this work
residence time varies by adjusting the liquid ow rate.
3.2. Reaction mechanism
Manganese dioxide, as a transition metal oxide, has been widely
used in the SCWO process on account of its excellent catalytic per-
formance. But the mechanism of MnO2 in supercritical water oxi-
dation of organic matters is not yet very clear. Ding [14] thinks
oxygen adsorbed on the catalyst surface may participate in the cat-
alytic reaction when manganese oxide is used as a catalyst. Kengo
[25] believes MnO2 lattice oxygen participates in the catalytic reac-
tion in SCWO. In catalytic supercritical water oxidation, MnO2 is
about to convert to Mn2O3 at some time after the reaction. In order
to understand the mechanism of the catalytic oxidation of man-
ganese oxide, several experiments were carried out to analyze
structural characteristics of the catalyst to further investigate the
catalytic effect of the manganese oxide in supercritical water
oxidation.
3.2.1. Transformation of catalyst in aerobic conditions
The catalytic SCWO process was conducted at 24 MPa, 400 C,
n = 10 for 8 h using low strength wastewater (p-nitrophenol con-
centration 80 mg/L) with MnO2 and Mn2O3 catalyst, respectively.
The XRD results of MnO2 and Mn2O3 catalyst after reaction are
shown in Fig. 6. As is seen in Fig. 6(a), after the reaction some peaks
of Mn2O3 appear. Since the experiment was performed far from the
decomposition temperature of MnO2, it is inferred that MnO2 cat-
alyst partially transformed into Mn2O3, which indicates the lattice
oxygen of MnO2 catalyst itself may be involved in the supercritical
water oxidation reaction with organic compounds, causing the
transformation of crystal structure. While Fig. 6(b) shows that no
other peaks come up after reaction, which means there is no trans-
formation of crystal structure. This may be explained by the
adsorption of oxygen on Mn2O3 catalyst surface which is possibly
 X. Dong et al. / Chemical Engineering Journal 277 (2015) 3039
Fig. 7. X-ray diffraction pattern for catalyst after reaction without oxidant (a) MnO2 (b) Mn2O3.
involved in reaction with p-nitrophenol. Although the process of
Mn2O3 converting to MnO2 is feasible when oxygen is obtained
in thermodynamic conditions, it is hard to meet the dynamic con-
ditions, hence it is manifested that Mn2O3 is the stable structure in
supercritical water.
3.2.2. Transformation of catalyst in anaerobic conditions
To further investigate the role of lattice oxygen in the catalyst,
another experiment was conducted at 400 C, 24 MPa for 5 h to
examine the changes of catalyst during supercritical water oxida-
tion reaction without oxygen feeding. In the experiment, deionized
water was rst fed until stable supercritical state was obtained and
then p-nitrophenol wastewater was passed into the system. Both
deionized water and p-nitrophenol wastewater were degased to
eliminate inuences of dissolved oxygen and adsorbed oxygen on
catalyst surface. Catalyst was characterized by XRD after the reac-
tion, and the results are shown in Fig. 7. Experiments also exam-
ined the changes of p-nitrophenol removal efciency over
reaction time using MnO2 catalyst in the absence of oxygen, and
specic results are listed in Fig. 8.
From Fig. 7(a), after 5 h for MnO2 catalyst under anaerobic con-
ditions in supercritical water, the XRD pattern only detects a large
number of Mn3O4 diffraction peaks and a few Mn2O3 diffraction
peaks. Compared with the previous experiments under aerobic
96
95
Removal efficiency/%
94
93
92
91
0 1 2 3 4 5
Time/h
Fig. 8. Removal efciency of p-nitrophenol over time for MnO2 without oxidant
(24 MPa, 400 C, n = 0).
35
conditions, without the presence of oxygen in the system, MnO2
quickly transformed into Mn2O3, and can be further reduced to
Mn3O4.
Fig. 8 shows that at the beginning of the reaction p-nitrophenol
still has a relatively high removal rate even without the presence of
oxygen. With the increasing of reaction time, removal efciency of
p-nitrophenol decreases. And after about 2 h, the removal ef-
ciency remains stable since only pyrolysis reaction occurs at this
time. This shows that at some time in the start of the reaction,
MnO2 lattice oxygen in the catalyst became the reactive oxygen
and involved in the oxidation of organic compounds degradation,
resulting in the reduced valence state of Mn. Supercritical water
oxidation reaction suspended after the MnO2 catalyst became
Mn3O4, so the removal efciency line stays steady.
Similarly after 5 h use of Mn2O3 catalyst under anaerobic condi-
tions, Fig. 7(b) shows only a large number of Mn3O4 diffraction
peaks and a low intensity of Mn2O3 diffraction, which means dur-
ing the reaction, substantial Mn2O3 converted into a much lower
valence oxide namely Mn3O4. This also indicates that under anaer-
obic conditions, Mn2O3 lattice oxygen becomes reactive oxygen in
oxidative degradation of organics, leading to the reduction of
valence state.
3.2.3. Air sweeping for catalyst after reaction under anaerobic
conditions
In this section, catalyst after reaction under anaerobic condi-
tions was charged into the reactor at 400 C and 24 MPa for 6 h
to perform air sweeping to research the transfer behaviors of oxy-
gen during the reaction. After sweeping, XRD characterization was
performed, and the results are shown in Fig. 9. As is seen in the Fig.,
peaks of MnO2, Mn2O3 and Mn3O4 are all detected. Compared with
XRD pattern after catalytic reaction in the absence of oxygen,
Mn2O3 diffraction peaks in Fig. 9 account for the majority, and
the MnO2 diffraction peaks appear. This illustrates that by the re-
providing oxygen to the reaction system, Mn3O4 can reversibly
converts to Mn2O3 and MnO2. During the reaction, the change of
the lattice oxygen in the catalyst is a reversible process, and con-
sumed lattice oxygen during organics oxidation can be compen-
sated by externally supplied oxygen.
According to the results of above experiments, and based on
free radical mechanism of supercritical water oxidation process
by Li [26] and Ding [27], this work presents a mechanism describ-
ing a synergistic effect of adsorbed oxygen and lattice oxygen. In
supercritical conditions, water dissociation generates hydroxyl
radical (HO) with high activity, which can attack organic com-
pounds (RH) on the weak CH bond, wherein hydroxyl radical
combines with H to water producing R. Due to the strong oxidizing
36
5000
4000
Intensity,cps
3000
2000
1000
0 line with this process. Experiments also detected the presence of
10 20 30 40 50
2,degree
Fig. 9. X-ray diffraction pattern for catalyst after air sweeping.
ability of high valence manganese oxide ([MO]), lattice oxygen
can react with R and because of lattice oxygen consumption, oxy-
gen vacancy occurs on catalyst surface, meanwhile high valence
manganese oxide converts to low valence manganese oxide ([M]):
H2 O ! H HO
RH HO ! R H2 O
M  O R ! M ROO
The oxygen vacancy is the adsorption center, externally sup-
plied oxygen can be adsorbed on the oxygen vacancy, forming
adsorbed oxygen, the oxygen adsorbed on the catalyst surface
exists mainly in the form of O2, and it may continue to be broken
down into O [11]. [M]. . .Oads has a strong oxidizing ability which
can react with R, generating peroxide radicals (ROO). At the same
time, the catalyst surface can also adsorb organic compounds:
M O2 ! M . . . Oads
M . . . Oads R ! M ROO
M RH ! M . . . RH
Organic compounds adsorbed on the surface of the catalyst
([M]. . .RH) are capable of adsorbing either absorbed oxygen or lat-
tice oxygen or ROO, which are likely to generate peroxide prod-
ucts. After desorption of peroxides, the catalyst surface readsorbs
oxygen or organics to proceed further catalytic reaction cycle
[14]. Peroxide products generated above are very unstable which
will quickly break down into small molecular compounds which
may be ultimately decomposed to CO2 and H2O:
M . . . RH M . . . Oads ! M . . . ROOH
M . . . RH M  O ! M . . . ROOH
M . . . RH ROO ! M R ROOH
M . . . ROOH ! M ROOH
3.3. Reaction path speculation
GCMS was used to analyze oxidation products of p-nitrophe-
nol wastewater, and the results indicated that degradation inter-
mediates of p-nitrophenol in supercritical water were phenol,
X. Dong et al. / Chemical Engineering Journal 277 (2015) 3039
hydroquinone, benzoquinone, o-nitrophenol, 2-phenoxy phenol,
4-phenoxy phenol, dibenzofuran, 2-nitrodibenzofuran and so on.
MnO2 Based on the analytical results, the intermediates are mainly phe-
Mn2O3 nol, which is in accordance with the study results of non-catalytic
Mn3O4 supercritical water oxidation of p-nitrophenol by Martino et al.
[28]. According to Martino and Savage [29], phenol is mainly pro-
duced in the path of pyrolysis of p-nitrophenol. Further oxidative
degradation of phenol has been studied by Thornton and Krajnc
[3032].
It is generally believed that phenol degraded to hydroquinone
(or catechol), and then further oxidized to p-benzoquinone (or o-
benzoquinone) which nally decomposed to CO2 and H2O. Since
hydroquinone and phenol were detected, the description of the p-
nitrophenol degradation in catalytic supercritical water is also in
o-nitrophenol, which may attribute to the attack by the removed
60 70 80 nitro from p-nitrophenol. Meanwhile dibenzofuran was also
detected which may generate due to the coupling between the
intermediate products or intermediate products with free radicals.
Because of the more stable structure of benzene to ring structure,
the coupled products will eventually decompose to single ring com-
pounds, and then further oxidized to open the loop. Therefore, in
this paper pathways of p-nitrophenol degradation in supercritical
water oxidation reaction are speculated as shown in Fig. 10.
7 4. Process of non-catalytic SCWO
8 4.1. Effect of operation parameters
9 Effects of temperature, pressure, dosage of oxidant and resi-
dence time on the reaction were considered in experiments, results
are displayed in Fig. 11. It is obvious that within certain limits p-ni-
trophenol removal rate remains steady at a high level. In the range
of 400480 C, experiments were conducted keeping a constant
pressure of 24 MPa, residence time of 36 s and 2 dosage of H2O2.
As is seen in Fig. 11(a), within the temperature range investigated
p-nitrophenol removal rate keeps steady maintaining a high level
while TOC removal rate is increasing as the temperature increases.
10 In general, temperature increment is benecial to the degradation
of organics, however the higher temperature is, the more stringent
11 requirements the equipment needs. Therefore, we should try to
reduce the reaction temperature in the premise of ensuring the
12 degradation of organic matter, 420 C is a good option as the
removal efciency is already 98%.
From 23 MPa to 27 MPa, p-nitrophenol removal efciency keeps
at a high level but pressure has small inuence on TOC removal
after 24 MPa, as is shown in Fig. 11(b). Regarding with the dosage
of H2O2, the more H2O2 we use, the higher removal rate we will get.
In practice, the amount of hydrogen peroxide is preferably selected
twice as the stoichiometric amount after all the removal rate is
96.7% according to Fig. 11(c). Seen from Fig. 11(d), with the growth
of residence time, TOC removal rate increases. At beginning with
13 the residence time prolonging degradation of organics is rapid,
but as the reaction proceeds, due to the reducing concentration
14 of the reactants, the reaction rate is getting slow, effect of residence
time on degradation becomes smaller. Consequently, 23 s is chosen
15 when the TOC removal rate is high as 96.4%.
16
4.2. Reaction pathway speculation
The GCMS analytical results of p-nitrophenol wastewater
oxidative degradation products are phenol, p-benzoquinone,
o-nitrophenol, 4-phenoxyphenol, dibenzofuran and so on. Based
on analytical results, reaction pathways are speculated as dis-
played in Fig. 12.
 X. Dong et al. / Chemical Engineering Journal 277 (2015) 3039 37

Fig. 10. Possible reaction routes of p-nitrophenol in SCWO.

a 100
b
100

98 98
Rem oval efficiency / %

Removal efficiency / %

96 96

94 94
TOC TOC
92 p-nitrophenol 92 p-nitrophenol

90 90
400 420 440 o 460 480 23 24 25 26 27
Temperature / C Pressure / MPa
o
Pressure 24MPa,Dosage of H2O2 2,Residence time 36s Temperature 400 C,Dosage of H2O2 2,Residence time 36s

c d
100 100

98 98
Removal efficiency / %
Removal efficiency / %

96 96

94 94
TOC
p-nitrophenol TOC
92 92
p-nitrophenol

90 90
1 2 3 4 5 10 20 30 40 50 60
Dosage of oxidant Residence time / s
o o
Temperature 400 C,Pressure 24MPa,Residence time 36s Temperature 400 C,Pressure 24MPa,Dosage of H2O2 2

Fig. 11. Effect of operation parameters on removal efciency of p-nitrophenol and TOC.
38 X. Dong et al. / Chemical Engineering Journal 277 (2015) 3039
Fig. 12. Main reaction pathways of p-nitrophenol.
5. Conclusions
The SCWO of wastewater containing p-nitrophenol was investi-
gated with or without a catalyst using compressed air and hydro-
gen peroxide respectively. The main results obtained are shown as
follows (A: process with a catalyst, B: process without a catalyst):
(1) The effects of reaction temperature, pressure, residence time
and oxygen excess or hydrogen peroxide dosage on p-nitro-
phenol degradation in supercritical water are considered in
both two processes. p-Nitrophenol removal efciency
increases with the increase of these four factors, wherein
effect of temperature on removal efciency is much more
obvious than the others in the investigated temperature
range where the positive effect of the temperature plays a
dominant role. Oxygen excess or hydrogen peroxide dosage
and residence time have a suitable value of removal ef-
ciency, when greater than this limit, continuously increasing
the amount of oxidant and residence time has a small inu-
ence on the enhancement of removal efciency. Pressure
increment has a smaller effect on removal efciency in both
process A and B.
(2) Through the experimental study, the synergetic mechanism
of lattice oxygen and adsorbed oxygen in manganese-based
oxide catalysts is presented in supercritical water oxidation
process, based on which the transformation of the catalyst
before and after reaction is explained. The possible oxidative
degradation of p-nitrophenol reaction pathways are both
described according to the major intermediates of p-nitro-
phenol degradation in the catalytic process in supercritical
water oxidation obtained by GCMS analysis.
(3) Three catalysts were employed in experiments to make a
comparison and supported Mn2O3/Ti-Al oxide composite
catalyst performs better in catalytic SCWO than non-
supported catalysts MnO2 or Mn2O3. Suitable reaction condi-
tions were acquired for the catalytic and non-catalytic
supercritical water oxidation. Process conditions for A:
420 C, 26 MPa, oxygen excess n = 20, residence time >6 s.
Process conditions for B: 420 C, 24 MPa, residence time
>23 s, hydrogen peroxide dosage/stoichiometric dosage = 2.
(4) In this work, two different methods of processing wastew-
ater were systematically studied and both of them have
different advantages. Compared with the conditions of
both processes, it is concluded that hydrogen peroxide is
apparently a better oxidant for supercritical water oxida-
tion due to its identical temperature and lower pressure
without a catalyst if the cost of hydrogen peroxide is not
taken into consideration. Catalytic process with com-
pressed air being the oxidant has a dramatic advantage
to the non-catalytic process with H2O2 in industrial scale,
after all the price of hydrogen peroxide is too high and
the storage is difcult too. However, sometimes non-cat-
alytic process with H2O2 being an oxidant can show some
advantages in some special occasions, such as organic
wastewater in laboratory.
References
[1] M. Bermejo, F. Cantero, M. Cocero, Supercritical water oxidation of feeds with
high ammonia concentrations: pilot plant experimental results and modeling,
Chem. Eng. J. 137 (2008) 542549.
[2] I.V. Prez, S. Rogak, R. Branion, Supercritical water oxidation of phenol and 2,4-
dinitrophenol, J. Supercrit. Fluids 30 (2004) 7187.
[3] B. Veriansyah, T.J. Park, J.S. Lim, Y.W. Lee, Supercritical water oxidation of
wastewater from LCD manufacturing process: kinetic and formation of
chromium oxide nanoparticles, J. Supercrit. Fluids 34 (2005) 5161.
[4] B. Veriansyah, K. Jae-Duck, Retracted: supercritical water oxidation for the
destruction of toxic organic wastewaters: a review, J. Environ. Sci. 19 (2007)
513522.
[5] X. Du, R. Zhang, Z. Gan, J. Bi, Treatment of high strength coking wastewater by
supercritical water oxidation, Fuel 104 (2013) 7782.
[6] M. Bermejo, M. Cocero, Supercritical water oxidation: a technical review,
AIChE J. 52 (2006) 39333951.
[7] G. Brunner, Near and supercritical water. Part II: Oxidative processes, J.
Supercrit. Fluids 47 (2009) 382390.
[8] M. Kutz, Environmentally conscious materials and chemicals processing, Wiley
Online Library, 2007.
 X. Dong et al. / Chemical Engineering Journal 277 (2015) 3039
[9] P.A. Marrone, Supercritical water oxidationcurrent status of full-scale
commercial activity for waste destruction, J. Supercrit. Fluids 79 (2013) 283
288.
[10] M. Krajnc, J. Levec, Catalytic oxidation of toxic organics in supercritical water,
Appl. Catal. B 3 (1994) L101L107.
[11] M. Krajnc, J. Levec, Oxidation of phenol over a transition-metal oxide catalyst
in supercritical water, Ind. Eng. Chem. Res. 36 (1997) 34393445.
[12] M. Krajnc, J. Levec, The role of catalyst in supercritical water oxidation of acetic
acid, Appl. Catal. B 13 (1997) 93103.
[13] S.N. Aki, Z.Y. Ding, M.A. Abraham, Catalytic supercritical water oxidation:
stability of Cr2O3 catalyst, AIChE J. 42 (1996) 19952004.
[14] Z.Y. Ding, M.A. Frisch, L. Li, E.F. Gloyna, Catalytic oxidation in supercritical
water, Ind. Eng. Chem. Res. 35 (1996) 32573279.
[15] Z.-Y. Ding, S.N. Aki, M.A. Abraham, Catalytic supercritical water oxidation:
phenol conversion and product selectivity, Environ. Sci. Technol. 29 (1995)
27482753.
[16] L. Jin, Z. Ding, M.A. Abraham, Catalytic supercritical water oxidation of 1,4-
dichlorobenzene, Chem. Eng. Sci. 47 (1992) 26592664.
[17] Y. Oshima, K. Inaba, S. Koda, Catalytic supercritical water oxidation of coke
works waste with manganese oxide, Sekiyu Gakkai Shi 44 (2001) 343350.
[18] J. Yu, P.E. Savage, Catalyst activity, stability, and transformations during
oxidation in supercritical water, Appl. Catal. B 31 (2001) 123132.
[19] M.J. Angeles-Hernndez, G.A. Leeke, R.C. Santos, Catalytic supercritical water
oxidation for the destruction of quinoline over MnO2/CuO mixed catalyst, Ind.
Eng. Chem. Res. 48 (2008) 12081214.
[20] H.R. Holgate, J.W. Tester, Oxidation of hydrogen and carbon monoxide in sub-
and supercritical water: reaction kinetics, pathways, and water-density
effects. 2. Elementary reaction modeling, J. Phys. Chem. 98 (1994) 810822.
39
[21] M. Koo, W.K. Lee, C.H. Lee, New reactor system for supercritical water
oxidation and its application on phenol destruction, Chem. Eng. Sci. 52 (1997)
12011214.
[22] T.D. Thornton, P.E. Savage, Phenol oxidation in supercritical water, J. Supercrit.
Fluids 3 (1990) 240248.
[23] Y. Matsumura, T. Nunoura, T. Urase, K. Yamamoto, Supercritical water
oxidation of high concentrations of phenol, J. Hazard. Mater. 73 (2000) 245
254.
[24] J.L. Dinaro, J.W. Tester, J.B. Howard, K.C. Swallow, Experimental measurements
of benzene oxidation in supercritical water, AIChE J. 46 (2000) 22742284.
[25] K. Tomita, Y. Oshima, Stability of manganese oxide in catalytic supercritical
water oxidation of phenol, Ind. Eng. Chem. Res. 43 (2004) 77407743.
[26] L. Li, P. Chen, E.F. Gloyna, Generalized kinetic model for wet oxidation of
organic compounds, AIChE J. 37 (1991) 16871697.
[27] Z.Y. Ding, Catalytic Supercritical Water Oxidation of Aromatic Compounds on
Transition Metal Oxides, University of Tulsa, 1995.
[28] C.J. Martino, P.E. Savage, Oxidation and thermolysis of methoxy-, nitro-, and
hydroxy-substituted phenols in supercritical water, Ind. Eng. Chem. Res. 38
(1999) 17841791.
[29] C.J. Martino, P.E. Savage, Thermal decomposition of substituted phenols in
supercritical water, Ind. Eng. Chem. Res. 36 (1997) 13851390.
[30] M. Krajnc, J. Levec, On the kinetics of phenol oxidation in supercritical water,
AIChE J. 42 (1996) 19771984.
[31] T.D. Thornton, D.E. LaDue III, P.E. Savage, Phenol oxidation in supercritical
water: formation of dibenzofuran, dibenzo-p-dioxin, and related compounds,
Environ. Sci. Technol. 25 (1991) 15071510.
[32] T.D. Thornton, P.E. Savage, Phenol oxidation pathways in supercritical water,
Ind. Eng. Chem. Res. 31 (1992) 24512456.