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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.
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 31
decomposition of organic compounds. Organic compounds and 2.2. Materials and analytical methods
oxygen are both completely miscible with supercritical water,
which allows oxidation reactions to occur rapidly without any Concentration of p-nitrophenol in wastewater employed in this
interphase mass transport limitations [5]. Several recent review work is 1000 mg/L. The oxidant feed stream was prepared by dilut-
articles provide more details on the properties of supercritical ing an analytical reagent of hydrogen peroxide with deionized
water and on SCWO [68]. Most hydrocarbons and oxygenated water to the desired concentration. The p-nitrophenol concentra-
hydrocarbons are converted to CO2 and H2O while nitrogen in tions of wastewater and liquid efuents were analyzed by liquid
the feed is converted to N2 or N2O [9]. chromatography using an Agilent HP1100 series equipped with a
However, because of high temperature and pressure as well as diode array UV detector and a Zorbax SB-C18 5 lm C-18,250
the substantial amount of power required to pressurize the oxy- 4.6 mm column, and the total organic carbon (TOC) content was
genating reagent, supercritical water oxidation technologies are measured using a Shimadzu TOC-VCPH. Hydrogen peroxide quanti-
very expensive. To reduce these costs, operation at lower temper- cation was carried out by titration with a potassium permanganate
atures, pressures and reduction in the amounts of oxidant will be solution. GCMS (Anglilent 6892N-5973N, HP-Inno wax column)
required, and this can only be achieved through increasing the oxi- was applied for qualitative analysis of the reaction products.
dation rate in supercritical water. Reaction products are essential to be concentrated and extracted
To improve the oxidation rate in supercritical water, numerous with methylene chloride (C2H2Cl2) for analysis since the concentra-
researchers have investigated the application of catalysts. Krajnc tion of reaction products in the liquid phase is too low.
and Levec [1012] and Ding et al. [1316] were among the rst A commercial titanium-aluminum composite oxide was used as
to investigate the catalytic effect in supercritical water. So far, the catalyst support. The supported Mn2O3/Ti-Al oxide composite
precious metals such as platinum and metal oxides such as man- catalyst was prepared by incipient wetness impregnation method.
ganese oxide, chromium oxide and vanadium oxide have been The titanium-aluminum composite oxide support was impreg-
studied. Oshima et al. [17] studied the SCWO of diluted coking nated by aqueous solution of manganese nitrate (Mn(NO3)2). The
wastewater with MnO2 as the catalyst and obtained 90% or higher samples were dried at 120 C for 4 h in vacuum and calcined at
conversions of both NH3 and TOC (total organic carbon) within 2 s 600 C for 4 h after aging 18 h. The preparation of non-supported
of contact time at 500 C. Savage et al. [18] used MnO2, TiO2, CuO/ MnO2 catalyst: mixed MnO2 powder with a certain amount of
Al2O3 catalysts for phenol degradation in supercritical water with methyl cellulose and tableted after evenly mixed, then dried the
a tubular ow reactor and concluded that MnO2 is the best cata- samples at 120 C for 2 h in vacuum and calcined at 450 C for
lyst for its highest activity and stability in the three catalysts. 3 h. The catalysts were sieved to a 2040 mesh size range for later
Destruction of quinoline over MnO2/CuO mixed catalyst in super- use. The preparation of non-supported Mn2O3 catalyst is the same
critical water was investigated to examine the effects of operation as MnO2 catalyst, just changed the calcination temperature to
conditions, and the results showed that the catalytic reaction 600 C. A total of 6.5 g of catalyst was loaded into the reactor in
depended strongly on temperature and pressure [19]. However, all experiments requiring a catalyst.
the supported Mn2O3/Ti-Al oxide composite catalyst has not yet Removal efciency of p-nitrophenol (PNP) and TOC is calculated
been applied to the SCWO of p-nitrophenol waste water using the following equation:
oxidation.
PNPt
In this work, p-nitrophenol was decomposed by supercritical X PNP 1 100% 1
PNP0
water oxidation with the supported Mn2O3/Ti-Al oxide composite
catalyst. The aim is to investigate the effects of reaction conditions,
TOCt
such as temperature, pressure, oxygen excess and residence time X TOC 1 100% 2
TOC0
on the destruction of p-nitrophenol. Furthermore, the mechanism
of supercritical water oxidation with the supported Mn2O3/Ti-Al where [PNP]t (mg/L) is the residual concentration of PNP in wastew-
oxide composite catalyst was proposed to better understand the ater after reaction, and [PNP]0 (mg/L) is the initial concentration.
process. At the end of the article, non-catalytic supercritical water And [TOC]0 is the initial TOC concentration of wastewater (mg/L),
oxidation using hydrogen peroxide as oxidant is also presented. 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
2. Experimental details n 100% 3
O2 stoich
2.1. Apparatus and procedure where [O2]actual is the concentration of O2 fed into the reactor (mg/
l), and [O2]stoich is the stoichiometric requirement concentration of
Compressed air and hydrogen peroxide were chosen as an oxi- O2 to obtain complete oxidation of the feed wastewater (mg/L).
dant, respectively. The scheme diagram of experimental apparatus When hydrogen peroxide is used as oxidant, chemical reaction
is shown in Scheme 1(a for compressed air, b for H2O2). The exper- equation is:
imental apparatus consists of feeding pumps, wastewater storage,
2C6 H5 NO3 23H2 O2 ! 12CO2 28H2 O N2 4
oxidant tank, preheater, a reactor, a cooler, heat exchanger, gas
liquid separator, back- pressure regulator, and so on. Main equip- Dosage of hydrogen peroxide is dened as:
ment specications of the system are listed in Table 1. The wastew- H2 O2 actual
ater and oxidant feed streams, which were mixed at the reactor k 100% 5
H2 O2 stoich
inlet using a mixer after pressurized by two high-pressure pumps
and then preheated to reaction temperature separately in two dif- where [H2O2]actual is the concentration of H2O2 fed into the reactor
ferent lines. Upon exiting the reactor, the efuent was quenched (mg/L), and [H2O2]stoich is the stoichiometric requirement concen-
immediately by passing through a shell-and-tube heat exchanger. tration of H2O2 for complete oxidation of wastewater (mg/L). The
Subsequently, the product steam was depressurized by a back- residence time in the reactor is obtained using the equation below:
pressure regulator and separated into vapor and liquid phases in
Vr
a gasliquid separator. Gas and liquid products from gasliquid s 6
VF H2 O F O2
separator were collected for analysis.
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 efciency while the supported Mn2O3/Ti-Al composite oxide cata-
and O2 (mL), F H2 O and F O2 is the ow rate of H2O and O2, lyst can further improve the removal rate of p-nitrophenol in
respectively. wastewater, especially in the low temperature region where its
activity is obviously higher compared with non-supported cata-
3. The process of catalytic SCWO lysts. The effects of temperature, pressure, excess oxygen and res-
idence time on the removal efciency of p-nitrophenol in
3.1. Effect of operation parameters wastewater with the supported Mn2O3/Ti-Al oxide composite cat-
alyst are illustrated in Figs. 25.
Non-supported catalysts MnO2, Mn2O3 and Mn2O3/Ti-Al oxide Experiments were conducted in a temperature range of 385
composite catalyst were employed to evaluate the catalytic activity 445 C with a constant pressure of 26 MPa, residence time of 1
by the criteria of PNP removal efciency under same reaction con- 2 s and 1000% excess oxygen. As is seen in Fig. 2, with the rising
ditions. Besides, a vacant test without a catalyst was performed to temperature, removal efciency of p-nitrophenol is promoted
make comparisons with the aforementioned catalytic SCWO pro- gradually. Effect of temperature on oxidative degradation of
cesses, and results are shown in Fig. 1. organic compounds in supercritical water can be explained in
Compared with non-catalytic supercritical water oxidation two ways. On the one hand, the reaction rate constant increases
reaction, the catalyst can improve the removal rate of supercritical with the temperature growth while the other conditions remain
water oxidation of p-nitrophenol. Two of the non-supported cata- unchanged. On the other hand, as the density of water is extremely
lysts have shown good catalytic effect on the PNP removal 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
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).
Fig. 1. PNP removal efciency of different catalysts and comparison with a vacant
Removal efficiency/%
98
test (26 MPa, n = 15, 12 s).
400 C. Results are illustrated in Fig. 3. It can be seen that as the Another reason is that the concentration of oxygen adsorption on
pressure rises, removal efciency of the p-nitrophenol keeps the catalyst surface is saturated, and thereby continuously increas-
increasing. It is known raising the pressure gives rise to the ing the amount of oxygen has no signicant effect on the reaction.
increase of water density, thus more p-nitrophenol and oxygen However, n = 20 is selected to ensure adequate oxidant in the
will be dissolved into supercritical water, resulting in promoted reaction.
reaction rate [2022]. However, in industrial practice, higher oper- Residence time is an important factor affecting the rate of
ating pressure leads to higher power requirement and also causes oxidative degradation of organic pollutants. The effect of residence
problems regarding the reactor wall stress [23]. Therefore, 26 MPa time on the removal efciency is displayed in Fig. 5. Organic
was selected as an optimal pressure in our study. removal efciency in supercritical water goes up very fast with
Effect of excess oxygen on removal efciency of p-nitrophenol the increasing of residence time in the range of 0.51.3 s, and after
in wastewater was investigated at 400 C, 26 MPa and 12 s of res- that the increasing trend is slowing down due to the depletion of
idence time. In these experiments, excess oxygen (n) varied from reactants. In order to ensure the sufcient reaction, 6 s is chosen
2.5 to 25. Degradation of p-nitrophenol in supercritical water oxi- for the operation parameter. It should be noted that in this work
dation is a process of oxidative pyrolysis, the higher excess oxygen residence time varies by adjusting the liquid ow rate.
is, the better reaction it performs, and the higher the p-nitrophenol
removal efciency is. Dependence of phenol [22] and benzene [24] 3.2. Reaction mechanism
conversion on the excess oxygen has been observed, and the
authors found that the conversions were higher in the experiments Manganese dioxide, as a transition metal oxide, has been widely
with the higher oxygen concentrations. Though, it should be used in the SCWO process on account of its excellent catalytic per-
stressed that the investigators performed experiments at low tem- formance. But the mechanism of MnO2 in supercritical water oxi-
peratures. As can be seen in Fig. 4, with the increasing of oxygen dation of organic matters is not yet very clear. Ding [14] thinks
excess, p-nitrophenol removal efciency increased rapidly in the oxygen adsorbed on the catalyst surface may participate in the cat-
range of 2.510. The variation trend of removal efciency is level- alytic reaction when manganese oxide is used as a catalyst. Kengo
ing off when the excess oxygen is greater than 15 because of the [25] believes MnO2 lattice oxygen participates in the catalytic reac-
low concentration of organic compounds left in the reactor. 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
100
structural characteristics of the catalyst to further investigate the
catalytic effect of the manganese oxide in supercritical water
oxidation.
Removal efficiency/%
98
Fig. 6. X-ray diffraction pattern of catalyst after reaction (a) MnO2 (b) Mn2O3.
X. Dong et al. / Chemical Engineering Journal 277 (2015) 3039 35
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 conditions, without the presence of oxygen in the system, MnO2
Mn2O3 converting to MnO2 is feasible when oxygen is obtained quickly transformed into Mn2O3, and can be further reduced to
in thermodynamic conditions, it is hard to meet the dynamic con- Mn3O4.
ditions, hence it is manifested that Mn2O3 is the stable structure in Fig. 8 shows that at the beginning of the reaction p-nitrophenol
supercritical water. still has a relatively high removal rate even without the presence of
oxygen. With the increasing of reaction time, removal efciency of
3.2.2. Transformation of catalyst in anaerobic conditions p-nitrophenol decreases. And after about 2 h, the removal ef-
To further investigate the role of lattice oxygen in the catalyst, ciency remains stable since only pyrolysis reaction occurs at this
another experiment was conducted at 400 C, 24 MPa for 5 h to time. This shows that at some time in the start of the reaction,
examine the changes of catalyst during supercritical water oxida- MnO2 lattice oxygen in the catalyst became the reactive oxygen
tion reaction without oxygen feeding. In the experiment, deionized and involved in the oxidation of organic compounds degradation,
water was rst fed until stable supercritical state was obtained and resulting in the reduced valence state of Mn. Supercritical water
then p-nitrophenol wastewater was passed into the system. Both oxidation reaction suspended after the MnO2 catalyst became
deionized water and p-nitrophenol wastewater were degased to Mn3O4, so the removal efciency line stays steady.
eliminate inuences of dissolved oxygen and adsorbed oxygen on Similarly after 5 h use of Mn2O3 catalyst under anaerobic condi-
catalyst surface. Catalyst was characterized by XRD after the reac- tions, Fig. 7(b) shows only a large number of Mn3O4 diffraction
tion, and the results are shown in Fig. 7. Experiments also exam- peaks and a low intensity of Mn2O3 diffraction, which means dur-
ined the changes of p-nitrophenol removal efciency over ing the reaction, substantial Mn2O3 converted into a much lower
reaction time using MnO2 catalyst in the absence of oxygen, and valence oxide namely Mn3O4. This also indicates that under anaer-
specic results are listed in Fig. 8. obic conditions, Mn2O3 lattice oxygen becomes reactive oxygen in
From Fig. 7(a), after 5 h for MnO2 catalyst under anaerobic con- oxidative degradation of organics, leading to the reduction of
ditions in supercritical water, the XRD pattern only detects a large valence state.
number of Mn3O4 diffraction peaks and a few Mn2O3 diffraction
peaks. Compared with the previous experiments under aerobic 3.2.3. Air sweeping for catalyst after reaction under anaerobic
conditions
In this section, catalyst after reaction under anaerobic condi-
96
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
95
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
Removal efficiency/%
3000
duced in the path of pyrolysis of p-nitrophenol. Further oxidative
degradation of phenol has been studied by Thornton and Krajnc
2000 [3032].
It is generally believed that phenol degraded to hydroquinone
(or catechol), and then further oxidized to p-benzoquinone (or o-
1000 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
0 line with this process. Experiments also detected the presence of
o-nitrophenol, which may attribute to the attack by the removed
10 20 30 40 50 60 70 80 nitro from p-nitrophenol. Meanwhile dibenzofuran was also
2,degree detected which may generate due to the coupling between the
intermediate products or intermediate products with free radicals.
Fig. 9. X-ray diffraction pattern for catalyst after air sweeping. 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
ability of high valence manganese oxide ([MO]), lattice oxygen
this paper pathways of p-nitrophenol degradation in supercritical
can react with R and because of lattice oxygen consumption, oxy-
water oxidation reaction are speculated as shown in Fig. 10.
gen vacancy occurs on catalyst surface, meanwhile high valence
manganese oxide converts to low valence manganese oxide ([M]):
H2 O ! H HO 7 4. Process of non-catalytic SCWO
M . . . ROOH ! M ROOH 16
4.2. Reaction pathway speculation
3.3. Reaction path speculation The GCMS analytical results of p-nitrophenol wastewater
oxidative degradation products are phenol, p-benzoquinone,
GCMS was used to analyze oxidation products of p-nitrophe- o-nitrophenol, 4-phenoxyphenol, dibenzofuran and so on. Based
nol wastewater, and the results indicated that degradation inter- on analytical results, reaction pathways are speculated as dis-
mediates of p-nitrophenol in supercritical water were phenol, played in Fig. 12.
X. Dong et al. / Chemical Engineering Journal 277 (2015) 3039 37
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
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