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Chemical Engineering Research and Design

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

Supercritical water oxidation of a pesticide

wastewater

Donghai Xu ∗ , Shuzhong Wang ∗ , Jie Zhang, Xingying Tang, Yang Guo,

Chuanbao Huang
Key Laboratory of Thermo-Fluid Science & Engineering, Ministry of Education, School of Energy and Power
Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi Province 710049, China

a b s t r a c t

In this research, we studied supercritical water oxidation (SCWO) of a pesticide wastewater under a wide range of
operation conditions in two reaction plants. The results show that reaction temperature, oxidant coefficient (OC), and
residence time (t) can improve the wastewater XCOD (removal efficiency of chemical oxygen demand). The residence
time and OC have important influences on XCOD at higher reaction temperatures (>500 ◦ C). It is significant to increase
the preheating rate for the XCOD improvement of the pesticide wastewater in SCWO. XCOD and XTN (removal efficiency
of total nitrogen) are 99.42% and 86.70% at 600 ◦ C, 25 MPa, OC = 3.0 and t = 2.0 min, respectively. More than 92 wt%
total organic carbon (TOC) and 86.70 wt% total nitrogen in the wastewater are converted into CO2 and N2 under the
above conditions, respectively. Inconel 625 can be used as the reactor material in the wastewater SCWO plant, and
its corrosion rate is approximately 0.6 mm/year at 600 ◦ C, 25 MPa and OC = 3.0 conditions. We also primarily design
a 100 t/d SCWO plant for the tested pesticide wastewater treatment on the basis of accomplished investigations.
SCWO together with traditional wastewater treatment methods is proposed to harmlessly dispose the complicated
wastewater. This information is valuable for guiding the large-scale SCWO plant design for pesticide wastewater
treatment.
© 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Supercritical water oxidation; Pesticide wastewater; Removal efficiency; Corrosion; Plant design

1. Introduction subsequent proper approaches. Thus, the above whole treat-

Pesticide wastewater, which usually comes from pesticide pro-
duction processes, commonly contains a large quantity of
biorefractory organic matters, biological inhibition or toxicity
matters. Traditional biological or physicochemical methods
are insufficient or ineffective to deal with this wastewa-
ter, particularly for wastewater with high concentration of
organic matters and complicated components (Baura et al.,
2005). One means to treat this variety of wastewater is first
to concentrate via multi-effect evaporation with the help of
vapor, and the concentrated fluid is incinerated with a certain
auxiliary fuel, and then the vapor condensate is adequately
diluted for further disposal by common biochemical methods.
Secondary pollutants such as dioxins and particulate mat-
ters, from the incineration process still require treatment by
ment means inevitably results in a relatively high operation
cost.
Supercritical water (T > 374.15 ◦ C, P > 22.12 MPa) can be used
as a reagent, acid–base catalyst or unique environmentally
safe solvent (Kruse and Dinjus, 2007; Galkin and Lunin, 2005).
Due to the decrease of the hydrogen bonding content, super-
critical water has different properties from ambient water on
the density, dielectric constant, etc. (Kus, 2012). In a com-
mon SCWO process, organic matters are rapidly, thoroughly
oxidized and composed into small molecular matters such
as CO2 , N2 , H2 O, and heterocyclic atoms are converted into
corresponding acids or organic salts. Reactions occur in a
single-phase environment because both organic matters and
oxidant are dissolvable in supercritical water. Hence, the
removal efficiency of organic matters can be boosted more

∗
Corresponding authors. Tel.: +86 29 82665157; fax: +86 29 8266 8703.
E-mail addresses: haidongxu93346423@aliyun.com (D. Xu), szwang@aliyun.com (S. Wang).
http://dx.doi.org/10.1016/j.cherd.2014.08.016
0263-8762/© 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

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Table 1 – Properties of the tested pesticide wastewater.
Item COD0 (NH3 -N)0 TN0
(mg/L) (mg/L) (mg/L)
Value 66,300 210 7300
than 99.9% within less than several minutes, and there are no
secondary pollutants like SO2 and NOx . Moreover, in general,
it can achieve heat self-sufficiency when the mass concentra-
tion of organic matters is higher than 2 wt%, and meanwhile
possibly surplus heat can be recovered to yield steam or hot
water, leading to a low operation cost (Shen et al., 2010).
Therefore, SCWO has a more promising future in comparison
with incineration for some organic wastewater treatments.
Presently, Marrone (2013) has summarized commercial SCWO
activities and future plans of current active SCWO companies,
and found that SCWO has been increasingly used in a variety
of full-scale designs and applications. However, extensively
industrial scale-up of SCWO plants has been delayed by some
drawbacks such as corrosion, and salt deposition (Vadillo et al.,
2011). Some new SCWO plants are even closed due to corro-
sion, plugging and operational problems associated with the
high pressure, high temperature and oxidative atmosphere
(Bermejo and Cocero, 2006).
Baura et al. (2005) reported that the destruction efficiency
of dissolved organic carbon in the biocide production waste-
water was higher than 99.99% in SCWO. However, systematical
studies and demonstration plants concerning pesticide waste-
water SCWO are extremely scarce now, especially for the
realistic pesticide production wastewater containing very
complicated components. To the best of our knowledge, no
adequate data are currently available. In this work, we chose
one kind of complicated pesticide wastewater from a pesticide
production company in China as the experimental sample.
SCWO tests were systematically conducted under wide oper-
ation parameter conditions to explore their influences on
organic matter removal in a continuous-flow reaction plant as
well as a batch reaction plant with oxygen as oxidant. Element
balances of carbon and nitrogen, reaction processes, auxiliary
treatments, reactor corrosion problems, etc., are also explored
at certain conditions. On the basis of these investigations,
a primary SCWO plant (100 t/d) construction is proposed to
effectively, economically achieve the harmless treatment of
the pesticide wastewater. This information is useful for guid-
ing the design and operation of a large-scale SCWO plant for
the pesticide wastewater treatment.
2. Materials and methods
2.1. Materials
The tested pesticide wastewater was identified to contain
complex substances, including methanol, toluol, cyclohexane,
triazole, tebuconazole, triazinone, flutriafol, dimethylform-
amide, etc., in which toluol, triazole and dimethylformamide
are main components. Table 1 illustrates the properties of the
wastewater. It can be observed that the wastewater contains
high concentrations of COD, inorganic salts, TN and chloride,
which reach up to 66,300 mg/L, 114,600 mg/L, 7300 mg/L and
5700 mg/L, respectively. Further identification indicates that
these inorganic salts mainly consist of Na2 SO4 and K2 SO4 .
They belong to the second kind of salt, which has a low
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http://dx.doi.org/10.1016/j.cherd.2014.08.016
Colority Salt content Chloride pH (–)
(multiple) (mg/L) content (mg/L)
400 114,600 5700 10.55
solubility near the critical temperature (Hodes et al., 2004). It
can also be found that the initial ammonia–nitrogen (NH3 -N)
content is much lower than the TN content, and the sub-
sequent analysis displays that nitrates hardly exist in the
wastewater. This suggests that N existence is mainly in the
form of organic N. Moreover, the brownish yellow wastewater
has a colority of 400 multiple and a pH value of 10.55.
2.2. Apparatuses and procedures
We used oxygen (99.9 wt% purity) as oxidant in this work,
because it is regarded as the most suitable oxidant in SCWO
(Zhang et al., 2011). H2 SO4 was applied to adjust the pH value
of the initial pesticide wastewater if necessary in the tests.
In order to investigate the corrosion rate of possible reactor
material, corrosion tests and parts of SCWO experiments were
conducted in a batch reaction plant similarly mentioned in
our previous literature (Guo et al., 2010). The reactor (250 mL)
is made of Hastelloy C276, which can withstand 600 ◦ C and
30 MPa. Oxygen can be added into the reactor and be quanti-
fied via its pressure and volume. In the experiments, the metal
sample for corrosion tests was first put into the reactor, and
N2 was used to purge the reactor for 5 min to minimize the
influence of oxygen in air on OC before each experiment. A cer-
tain volume of wastewater and oxygen calculated according to
the required OC were added into the reactor. The reactor was
heated by a temperature controller after sealed, so its pres-
sure increased with the temperature rising. For comparison
with the continuous plant, we defined the remained time as
the residence time at the set reaction temperature in the batch
reactor. The definition method is in accordance with those
reported by Williams and Onwudili (2005, 2006). After the res-
idence time, the reactor was quickly cooled to about 40 ◦ C by
cooling water as well as the separation of the reaction vessel
and the heating furnace. Finally, reaction products were col-
lected for the following analysis. Furthermore, the corrosion
sample was taken out and analyzed after the given test time.
Nevertheless, it is unfeasible to use a batch reaction plant
to deal with a large amount of wastewater owing to the compa-
rably low treatment capacity and the very high operation cost.
Therefore, we tested the wastewater SCWO in a continuous-
flow tubular reaction plant (see Fig. 1) to explore influences
of operation parameters on organic matter removal. On the
whole, the pesticide wastewater and oxygen were pressur-
ized and regulated their flow rates by high pressure metering
pumps, and then pumped into corresponding preheaters for
being preheated, respectively. These two kinds of reagents fur-
ther entered the mixer for sufficient mixing, and then flowed
into the tubular reactor (1700 mm length, 12.3 mm i.d., the
maximum treatment capacity of 1 L/h) for oxidation reactions.
Reactor effluent was quenched by the cooler, and then depres-
surized to the ambient pressure by the back pressure valve,
and further separated gaseous and liquid products via the gas-
liquid separator. A volumetric flow meter was used to measure
the gas yield, and gaseous and liquid products were collected
for following analysis. Notably, herein the supercharger was
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Fig. 1 – Schematic diagram of the continuous-flow tubular reaction plant for pesticide wastewater SCWO.

used to pressurize oxygen by that water pushed its inner In this work, COD removal efficiency (XCOD ), NH3 -N removal
piston to move upwards to compress upper oxygen. The burst- efficiency (XNH3 -N ), and TN removal efficiency (XTN ) are defined
ing disk device was applied for extra safety protection because as follows:
its inner bursting disk would creak to release fluid when the  COD1

reactor pressure exceeds its set safety pressure. Moreover, the XCOD = 1 − × 100% (1)
COD0
precisions of the volume flow, pressure, and temperature were
within ±0.02 L/h, ±0.1 MPa, and ±2 ◦ C, respectively. The resi-  
(NH3 − N)1
dence time was regulated through the control of the feedstock XNH3 -N = 1 − × 100% (2)
(NH3 − N)0
flow rate. Detailed experiment procedures can be seen in our
previous report (Xu et al., 2011).  TN1

A multi-parameter water analyzer (Model NOVA60) with XTN = 1 − × 100% (3)
TN0
Merck cells was utilized to measure COD, NH3 -N, TN and
nitrates concentrations of liquid. Both the pH value and where the subscripts 0 and 1 represent the original pesticide
the dissolved salt concentration were measured by a pro- wastewater and the reactor effluent, respectively.
fessional meter (Model PP-50) based on the H+ amount Oxidant coefficient (OC) is calculated by the following equa-
and the conductivity of liquid, respectively. The colority tion,
of liquid was determined by the standard method, which
is introduced in “Water quality-Determination of colority” O1
OC = (4)
(GB 11903-89). Its value is expressed by the dilution mul- O0
tiple via optical pure water so that the sample cannot be
where O1 is the practically added oxidant amount, and O0
seen its color compared with the pure water. The corrosion
is theoretically required oxidant amount for the complete
morphology of the tested sample was analyzed by a scan-
removal of organic matters.
ning electron microscope (SEM, Model JSM-6390A) with an
N gasification efficiency (GN ) is expressed by the following
energy dispersive spectrometer (EDS) for element component
equation,
analysis. Gaseous products were identified and quantified
by a gas chromatography (Model GC-112A) with a thermal  N yield 
2
conductivity detector. Additionally, residual organic matter GN = × 100% (5)
TN0
components of the reactor effluent were analyzed by a gas
chromatography–mass spectrometry analyzer (GC–MS, Model Many investigations have proved that reaction pressure
Agilent 6890-5973) fitted with a Agilent HP-5 capillary column has little effect on the removal of organic matters in SCWO,
(50 m × 200 ␮m × 0.33 ␮m). whereas high pressures will accelerate reactor corrosion

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(Kritzer, 2004), so many researchers commonly conduct SCWO

at 25 MPa (Shin et al., 2009; Veriansyah et al., 2011; Sögüt
et al., 2011a). We also chose 25 MPa as a constant reaction
condition in experiments. SCWO is usually used to handle
the wastewater with an organic matter concentration in the
range of 5–20 wt% (Vadillo et al., 2012). It is attributed to
that the high organic matters concentration can ensure heat
self-sufficiency in SCWO and evidently decrease its opera-
tion cost. Cocero et al. (2002) confirmed that the minimum
heat value of feedstock should be 930 kJ/kg, which is equal
to 2 wt% n-hexane solution. In this work, the tested pesticide
wastewater contains high concentration of organic matters
(COD0 = 66,300 mg/L), which will be beneficial to achieving heat
self-sufficiency and economic feasibility in a commercial pro-
cess in future. Thus, related investigation results will help
guide the design, realistic operation and industrial scale-up
of the pesticide wastewater SCWO plant.
In this research, three independent runs were conducted
at same conditions to determine uncertainties of experimen- Fig. 2 – Influences of OC and residence time on COD1 of
tal data. Results reported herein are average values, and the pesticide wastewater SCWO at 500 ◦ C.
uncertainties are calculated by the corrected sample standard
deviation, as expressed typically by the following equation: play an important role in organic matter decomposition.
Adding Na2 CO3 will inhibit the XCOD improvement in the pes-
 ticide wastewater SCWO at 400 ◦ C and 450 ◦ C. This suggests

1 
N
S=

2 that Na2 CO3 may result in some polymerization reactions or

(xi − x̄)
N−1
i=1
where S is a biased estimator for the population standard devi-
ation, N is experiments times, and x̄ is the average value.
3. Results and discussion
3.1. Influences of operation parameters
Table 2 elucidates the experimental results of pesticide waste-
water SCWO in the batch and continuous-flow plants under
different reaction conditions. We first performed experiments
(OC = 0) to determine the effect of the temperature on ther-
mal decomposition of the pesticide wastewater. This is very
necessary because the thermal decomposition will occur at
the preheating stage in SCWO with a preheating system. It
can be observed that XCOD increases from 72.3% to 74.7% with
the reaction temperature changing from 410 ◦ C to 450 ◦ C at
t = 1.5 min in the continuous-flow plant. According to previous
investigations concerning organic matter conversion in super-
critical water (Kritzer, 2004; Williams and Onwudili, 2006;
Garcia Jarana et al., 2008), the above relatively high XCOD can
be explained by that organic matters in the pesticide waste-
water are decomposed into CO2 , H2 O, H2 , CO, CH4 and other
small molecular compounds under above supercritical condi-
tions without oxidant. Correspondingly, the several flammable
gases in total gaseous products will further react with oxygen
to release heat energy in the SCWO reactor. It can be supposed
that consumed oxygen first converts these flammable gases
and then meanwhile further removes organic matters. This
may be one of the reasons why XCOD at 400 ◦ C and OC = 1.1 does
not have a remarkable difference from that at OC = 0. Another
explanation is perhaps that the temperature is too low and
this wastewater requires more extreme conditions, and this
will be proven by following tests.
It seems that there is no positive influence on COD removal
in the neutral case (pH = 7.5). However, the alkali reaction
environment helps improve XCOD , and hydroxyl ions may
(6)
decrease the decomposition of partial organic matters. More-
over, the addition of Na2 CO3 further brings the risk of reactor
plugging due to its very low solubility at supercritical condi-
tions. Thus, Na2 CO3 is not suitable for being used as a catalyst
or additive in SCWO of the tested pesticide wastewater. As
illustrated in Table 2, increasing t from 1.5 min to 4.0 min can
only change XCOD from 88.2% to 91.1% at 450 ◦ C and OC = 1.1
in the continuous-flow plant. This means that organic mat-
ter removal mainly occurs within a shorter residence time at
above conditions. It is also obvious that XCOD can be improved
with OC or reaction temperature increasing.
As listed in Table 2, the continuous-flow plant obtains a lit-
tle lower XCOD but just has slight difference compared with the
batch plant at the same conditions. Notably, in the batch plant,
the preheating time (preheating rate of 200 ◦ C/h) overlaps par-
tially with the reaction time, meaning a longer reaction time
than that in the continuous-flow plant. During the preheat-
ing time, organic matters take place complicated reactions
such as polymerization, decomposition and oxidation. As a
matter of fact, the continuous-flow plant has a shorter pre-
heating time (<4 min), meaning a higher preheating rate. It
suggests that the high preheating rate remarkably affects
organic matter removal in the pesticide wastewater SCWO.
Some polymerization reactions forming complex polymers or
intermediate products like char and tar may be inhibited, and
organic matter decomposition is promoted in the rapid pre-
heating process, leading to rapid organic matter removal in
the continuous-flow plant in spite of in a shorter reaction
time (≤4 min). This phenomenon is confirmed by supercrit-
ical water gasification of organic matters in many previous
reports (Kruse et al., 2003; Sýnag et al., 2004; Watanabe et al.,
2005). Hence, these two plants behave differently and induce
whole results differences, but the continuous-flow plant is
more efficient obviously. It reveals that it is very significant
to increase the preheating rate of the pesticide wastewater for
rapid organic matter removal.
Experiments were further conducted at the higher temper-
atures and OCs in the continuous-flow plant. Fig. 2 depicts the
influences of OC and the residence time on COD1 of pesticide

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Table 2 – Experimental results for pesticide wastewater SCWO in the batch and continuous-flow plants.
No. T (◦ C) OC t (min) XCOD (%) in the XCOD (%) in the
batch plant continuous-flow plant

1 400 0.0 1.5 74.1 ± 0.8 72.3 ± 0.9

2 400 1.1 1.5 82.5 ± 0.9 80.3 ± 0.8
3a 410 1.1 1.5 82.6 ± 0.8 80.5 ± 0.4
4 410 1.1 1.5 83.4 ± 0.7 81.6 ± 0.5
5b 410 1.1 1.5 82.9 ± 0.5 80.5 ± 0.7
6 430 0.0 1.5 75.1 ± 0.7 73.3 ± 0.6
7 450 0.0 1.5 76.5 ± 0.6 74.5 ± 0.5
8c 450 1.1 1.5 88.1 ± 0.7 86.7 ± 0.6
9 450 1.1 1.5 89.8 ± 0.5 88.2 ± 0.4
10 450 1.1 2.0 91.8 ± 0.6 89.2 ± 0.5
11 450 1.1 4.0 92.6 ± 0.7 91.3 ± 0.4
12 450 1.5 1.5 93.6 ± 0.4 92.2 ± 0.6
13 450 2.0 1.5 94.2 ± 0.5 93.1 ± 0.5
14 450 2.5 1.5 95.6 ± 0.7 94.0 ± 0.6
15 470 2.5 1.5 95.8 ± 0.3 94.8 ± 0.4
16 470 2.5 2.0 96.6 ± 0.4 95.5 ± 0.5

a
Regulating the pH value of the initial wastewater to 7.5.
b
Adding 0.5 g Na2 CO3 .
c
Adding 0.3 g Na2 CO3 .

wastewater SCWO at 500 ◦ C, and the experiment errors are
lower than 8%. It can be concluded that COD1 declines with the
increase of OC and the residence time. This may be attributed
to that the SCWO process of organic matters is mainly con-
trolled by kinetics but not thermodynamics at the higher
temperature. COD1 changes in the range of 6130–901.7 mg/L
(corresponding to XCOD = 90.75%–98.64%) within OC = 1.1–3.0,
t = 2.0–4.0 min at 500 ◦ C. Based on COD1 under the above high
OC and the long residence time conditions, it can be suspected
that COD removal mainly depends on reaction processes other
than on mass transfer processes.
Fig. 3 further displays COD1 of pesticide wastewater SCWO
at 550 ◦ C under different OCs and residence times conditions,
similarly within 8% experiment errors. It has similar variation
tendencies in comparison with those in Fig. 2 in that both OC
and the residence time have very important roles in reducing
COD1 . COD1 changes from 5251.0 mg/L to 543.7 mg/L (corre-
sponding XCOD from 92.08% to 99.18%) within OC = 1.1–3.0,
t = 2.0–4.0 min at 550 ◦ C. It can be clarified that OC has more
Fig. 3 – COD1 of pesticide wastewater SCWO at 550 ◦ C under
different OC and residence time conditions.
significant effect on COD1 reduction in the same residence
time case at 550 ◦ C compared with 500 ◦ C in terms of gradi-
ent variations. Furthermore, as listed in Table 2, XCOD rises
about 2.1% at 450 ◦ C, OC = 1.1 in the range of 2.0–4.0 min, how-
ever, it increases approximately 5.3% and 5.9% at 500 ◦ C and
550 ◦ C according to Figs. 2 and 3, respectively. Thus, residence
time has more important influences on COD1 at higher tem-
peratures conditions. A possible explanation is that some
intermediate products formed at high temperatures are dif-
ferent from those generated at low temperatures. Due to
complicated organic components in the pesticide wastewa-
ter, some polymers formed at low temperatures are likely to
be difficult to be decomposed by prolonging the residence
time and/or increasing OC. However, they may be compara-
tively easy to be destroyed at a higher temperature. Moreover,
another possible explanation is that some intermediate com-
pounds formed are difficult to be oxidized so that they need
the higher temperature and the longer residence time. In this
research, the relatively harsh reaction conditions suggest that
some organic matters in the pesticide wastewater are very
difficult to be destroyed.
Although COD1 is 543.7 mg/L at 550 ◦ C, OC = 3.0 and
t = 4.0 min, as indicated in Fig. 3, it still does not meet cor-
responding discharge standards in China. Temperature is
regarded as one of the main variables affecting organic matter
removal in SCWO (Sögüt et al., 2011b), so we attempted to fur-
ther carry out experiments at a higher temperature (600 ◦ C), as
displayed in Fig. 4. An important aim is to sufficiently remove
NH3 -N and TN in the pesticide wastewater. This is because
ammonia is often determined to be a main refractory nitrogen-
containing intermediate product (Zhou et al., 2013), and the
minimum reaction temperature should be 540 ◦ C to efficiently
destroy TN in sewage sludge SCWO (Gidner and Stenmark,
2001). Thus, some commercial SCWO plants commonly use a
reaction temperature as high as 600 ◦ C (Gidner and Stenmark,
2001; Griffith and Raymond, 2002). From Fig. 4, it can be seen
that COD1 , (NH3 -N)1 and TN1 remarkably decline with the resi-
dence time increasing. It can be attributed to that more organic
matters containing C and N are decomposed into CO2 , N2 and
H2 O with the residence time rising. COD1 , (NH3 -N)1 and TN1

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1600
1400
COD0: 66300 mg/L
COD1, (NH3-N)1, TN1 (mg/L)
1200 (NH3-N)0: 210 mg/L
1000
800
600
400
200
0
1 2
Residence time (min)
Fig. 4 – COD1 , (NH3 -N)1 and TN1 of reactor effluent for
pesticide wastewater SCWO treatment at 600 ◦ C and
OC = 3.0 with different residence times.
separately reach up to 76 mg/L, 12 mg/L and 19 mL/L at 600 ◦ C,
OC = 3.0 and t = 4.0 min conditions, which meet correspond-
ing discharge standards in China. However, OC of 3.0 is too
high and very costly, so this is the reason why surplus oxygen
must be recovered in real application. Some other SCWO pro-
cesses also adopt a high OC (Yang, 2003; Baura et al., 2005; An,
2010), and recover excess oxygen to improve the technology’s
sustainable potentialities (Svanström et al., 2004).
For a 100 t/d SCWO plant for the pesticide wastewater
treatment, our evaluation testifies that the reactor is very
expensive and becomes the largest part cost if it is made of
Inconel 625, whose corrosion properties will be reported in
the following section. Hence, we planned to decrease the resi-
dence time to 2.0 min, meaning half of the investment cost of
the 4.0 min reactor. In this work, a SCWO process at 600 ◦ C,
OC = 3.0 and t = 2.0 min together with traditional treatment
wastewater methods for the residual pollutants treatment
was considered and explored. This whole scheme is evalu-
ated to be more economic than that just SCWO at 600 ◦ C,
OC = 3.0 and t = 4.0 min. As elucidated in Fig. 4, COD1 , (NH3 -
N)1 , and TN1 at t = 2.0 min separately reach 386 mg/L, 351 mg/L
and 971 mg/L, and corresponding XCOD and XTN are around
99.42% and 86.70%. Therefore, the traditional methods are just
auxiliary for pollutants removal, however, they play a signifi-
cant role in reducing the investment cost of the whole system.
Moreover, our findings that the pH value of the reactor efflu-
ent is about 8.5 at above conditions, suggest that there must
be a small amount of acid formed in reaction processes and
neutralization is not necessary before drainage. Fig. 5 indicates
colority variations of the pesticide wastewater before and after
SCWO treatment at OC = 3.0, t = 2.0 min 550 ◦ C and 600 ◦ C. It can
be observed that the initial wastewater with a brownish yellow
color turns into slightly yellow at 550 ◦ C and becomes trans-
parent like distilled water at 600 ◦ C, without any suspended
matters and solids.
3.2. C and N balance analysis
In our tests, carbon (C) in gaseous products is confirmed to
exist in the form of CO2 and no other C-containing gases
are detected. Fig. 6 displays C balance and XTOC at 25 MPa,
OC = 3.0, t = 2.0 min within 480–600 ◦ C, and experiment errors
are within 1%. It can be calculated that more than 92 wt%
TOC0 is converted into CO2 in terms of CO2 yields in the above
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TN0: 7300 mg/L
COD1
(NH3-N)1
TN1
3 4
Fig. 5 – Colority variations of the pesticide wastewater
before and after SCWO treatment at OC = 3.0 and t = 2.0 min.
(a) Initial pesticide wastewater, (b) reactor effluent of 550 ◦ C,
(c) reactor effluent of 600 ◦ C.
temperature range. The ratio of the sum of C in gaseous prod-
ucts and TOC in liquid products to TOC0 ranges from 94.21% to
95.65%. Hence, the relative errors of C balance calculation are
less than 6%, which can be attributed to related measurement
errors and a certain amount of CO2 dissolving into liquid prod-
ucts. Additionally, it can be noticed that XTOC increases from
95.22% to 99.67% within 480–600 ◦ C. The CO2 yield and XTOC
reach up to 32,713 mg/L and 99.67% at 600 ◦ C, 25 MPa, OC = 3.0
and t = 2.0 min, respectively. This exhibits high CO2 conversion
and TOC removal, which is consistent with previous reports
(Baura et al., 2005).
It is well known that no NOx is formed in organic mat-
ter SCWO, so the N2 yield can be determined by N balance
calculation. Samples 1 and 2 were liquid effluents when the
pesticide wastewater was disposed at 600 ◦ C, 25 MPa, OC = 3.0
and t = 2.0 min in the batch plant and the continuous-flow
plant, respectively. Some measured values and calculated val-
ues regarding N balance calculation are listed in Table 3. Thus,
we can neglect very low nitrate concentrations in the feed-
stock and in reactor effluents. It can be noticed that TN in the
pesticide wastewater is much more than that in sample 1 or
2, meaning that most of N in N-containing organic matters
is converted into N2 . There are no NOx and SOx gases forma-
tions because the oxidation reaction temperature is too low to
form these pollutants. In terms of N balance calculation, the
N2 yield is 6558 mg/L in the batch plant and 6329 mg/L in the
100 100
80
95
C content (%)
60
C in gaseous products
XTOC (%)
TOC in liquid products 90
C in gaseous products + TOC in liquid products
40 OC=3.0
XTOC
t=2.0 min
25 MPa 85
20
0 80
480 510 540 o 570 600
Temperature ( C)
Fig. 6 – C balance and XTOC at different temperatures.
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Table 3 – N balance analysis at 600 ◦ C, OC = 3.0 and t = 2.0 min conditions.

Item Pesticide wastewater Sample 1 Sample 2

TN (mg/L) a
7300 ± 120 742 ± 45 971 ± 55
NH3 -N (mg/L)a 210 ± 14 285 ± 17 351 ± 21
Nitrate (mg/L)a 12 ± 3 3±2 4±3
XNH3 -N (%)b – −35.7 −67.1
N2 yield (mg/L)b – 6558 6329
GN or XTN (%)b – 89.8 86.7

a
Measured values.
b
Calculated values.

continuous-flow plant, and corresponding GN are 89.8% and
86.7%, respectively. These data are valuable for the subsequent
design of a large-scale SCWO plant.
Ammonia is regarded as a refractory compound and is
also mainly converted to N2 in SCWO (Zhang and Ma, 2011).
Nevertheless, in this research, owing to (NH3 -N)0 = 210 mg/L,
the increment of (NH3 -N)1 shown in Table 3 results in neg-
ative XNH3 -N . This can be explained by that partial NH3 -N
is converted into N2 but more extra NH3 -N is formed in
SCWO processes of N-containing organic matters. Gidner and
Stenmark (2001) reported that XTN could reach 99.72% (from
4400 mg/L to 12.5 mg/L) for sewage sludge SCWO at more than
540 ◦ C and t = 60 s. However, the relatively low XTN in this study
suggests that the pesticide wastewater contains some very
complicated N-containing organic matters like triazole, which
may be difficult to be converted into N2 . Herein, the rela-
tively higher GN and XTN in the batch plant compared with
the continuous-flow plant are also probably due to the really
longer reaction time, as mentioned before.
3.3. Reaction processes
Fig. 7 depicts residual organic matter components in the reac-
tor effluent for pesticide wastewater SCWO at 600 ◦ C, 25 MPa,
OC = 3.0 and t = 2.0 min. It contains formamide, N,N-dimethyl-
, phenol, benzamide, 1(3H)-isobenzofuranone, benzoic acid,
benzene, 1,3-bis(3-phenoxyphenoxy), etc., in trace, which can
also be regarded as the intermediate products of the longer
reaction time (4 min). These produced intermediate matters
lead to residual COD1 , (NH3 -N)1 , TN1 in the reactor effluent at
t = 2.0 min.
250000
1 and Dinjus, 2007), microscopic influences are very significant
1:Benzene, 1,3-bis(3-phenoxyphenoxy), 2:Formamide,
200000 N,N-dimethyl-, 3:Phenol, 4:Benzoic acid, 5: Cyclohex-
asiloxane, dodecamethyl-, 6: Cyclohexasiloxane, 7: Cy-
clohexasiloxane, dodecamethyl-, 8: Benzamide, 9: 1(3-
Aboundance
According to previous investigations, many researchers
explain the SCWO process by the free radical reaction
mechanism. For instance, this mechanism is used to reveal
ethylenediamine SCWO (Zhang and Ma, 2011). It has been
reported that organic matter degradation in SCWO occurs in
two simultaneous steps, i.e. thermal decomposition and oxi-
dation (Erkonak et al., 2008; Anikeev and Yermakova, 2011).
The former transforms organic matter into smaller gaseous
hydrocarbons (Sögüt et al., 2011b), and the latter leads to the
formations of CO2 and N2 , etc. These two processes take place
in the whole SCWO process, and there be also lots of parallel
reactions.
Pesticide wastewater SCWO involves very complicated
reaction processes, which should also be explained by the radi-
cal reaction mechanism. In this research, we only find CO2 and
N2 as main gaseous products, which is in accordance with pre-
vious findings for different organic wastes SCWO (Zhang and
Ma, 2011; Wang et al., 2011). Thus, it can be judged that most of
organic matters are converted into CO2 , H2 O and N2 in pesti-
cide wastewater SCWO. There are some other formed matters
in trace (see Fig. 7) leading to residual COD, TN, etc., in the reac-
tor effluent at a shorter residence time conditions. According
to product properties, the overall reaction equation at 600 ◦ C,
25 MPa, OC = 3.0 and t = 2.0 min conditions can be expressed by
the following equation:
Oragnicmattersinpesticidewastewater + O2 → CO2
+ N2 + H2 O + othersintrace (7)
Detailed reaction pathways for SCWO of organic matters in
the pesticide wastewater are too complicated for clear cogni-
tion. In fact, due to the polarity of the single molecule (Kruse
to relevant reactions in supercritical water. Therefore, a deep
insight into all properties of the phys-icochemical interactions
occurring at hydrothermal conditions on the molecular level,
is essential to reveal the reaction mechanisms in pesticide

150000 H)-Isobenzofuranone.
wastewater SCWO.

100000 3.4. Auxiliary treatment with traditional methods

9 The incomplete XCOD , XTN and XTN at 600 ◦ C, 25 MPa, OC = 3.0

50000
4 5 78 and t = 2.0 min, mean that some organic matters are still
2 3 6
present in the reactor effluent. As displayed in Fig. 7, the
0 identified components in trace include C3 H7 NO, C8 H6 O2 ,
0 2 4 6 8 10 12
Retention time (min) C21 H22 O11 , C30 H22 O4 , etc., if described in the form of molecu-
lar formulas, in which some molecular weights are more than
Fig. 7 – components of the reactor effluent for pesticide 400. We planned to remove these residual organic matters
wastewater SCWO at 600 ◦ C, OC = 3.0 and t = 2.0 min. by a biochemical treatment means or a physical adsorption

Please cite this article in press as: Xu, D., et al., Supercritical water oxidation of a pesticide wastewater. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.08.016
CHERD-1680; No. of Pages 11
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8 chemical engineering research and design x x x ( 2 0 1 4 ) xxx–xxx
method for improving the economic feasibility of the whole
treatment process. Thus, we further investigated the biochem-
ical treatment properties of the reactor effluent, and found the
ratio of BOD (biological oxygen demand, mg/L) to COD of the
liquid is higher than 0.3, meaning it can be disposed harm-
lessly by traditional biochemical methods such as activated
sludge process, biomembrance process, oxidation pond pro-
cess, anaerobic biological process. We also conducted some
adsorption experiments by using activated carbon in order to
remove residual COD, and testified that XCOD rises with an
increase in the activated carbon amount, and can reach 58.3%
when 0.3 g activated carbon is added into 8.0 mL liquid above.
Hence, activated carbon adsorption also plays a remarkable
role in the COD removal of the reactor effluent. However,
the traditional biochemical methods are more prevalent in
the environment field. In addition, the traditional desorption
method is also confirmed to be a desirable option for residual
NH3 -N removal.
3.5. Corrosion tests
SCWO environment may be oxidizing, acidic, basic, non-
ionic or highly ionic. Reactor corrosion is a key obstacle of
hindering SCWO extensive commercialization, and it even
causes industrial SCWO plants to be shut down after a few
months of operation (Marrone, 2013). In this study, the chloride
ion concentration in the pesticide wastewater is much high.
Obviously, common austenitic stainless steel materials are not
suitable for the wastewater SCWO environment, because they
are sensitive to chloride ions and easily susceptible to stress
corrosion crack. Nickel-base alloy is well known for its excep-
tional high temperature oxidation resistance, and possesses
a perfect corrosion resistance property. Taking into account
reactor material selection, we explored the corrosion prop-
erties of Inconel 625 under the pesticide wastewater SCWO
conditions of 600 ◦ C, 25 MPa and OC = 3.0 in the batch plant, as
indicated in Fig. 8.
From the corrosion morphology in Fig. 8(a), it can be
observed that the material surface almost displays general
corrosion after 70 h. According to the EDS diagram (line scan-
ning) of the end face of the sample, we discern the element
distributions in the basis layer and in the surface oxide layer,
which exhibits that the O content remarkably increases but
the contents of Mo and Ni evidently decline. Thus, on the basis
of the variations of the element contents, it can be determined
that the corrosion depth is about 4.0 ␮m and the corresponding
corrosion rate is approximately 0.6 mm/year at experiments
conditions.
Kritzer (2004) has reported that material parameters have
effect especially on corrosion initiation, and corrosion prod-
ucts coat the material surface and the material loss stops. Iron
oxides initially precipitating on the alloy surface are found
in Inconel 625 corrosion tests under different SCWO condi-
tions (Brunner, 2009). On the other hand, a small amount
of acid formed in reaction processes reduces the pH value
of the reaction fluid. These two reasons may help minimize
the corrosion rate of Inconel 625 in the test case. Moreover,
density strongly influences dissolution and dissociation pro-
cesses of both attacking species and corrosion products, and
these two processes play important roles in corrosion in high
temperature water (Kritzer, 2004). Therefore, the higher reac-
tion pressure is not recommended because it will lead to a
high density, meaning an increase in the reactor corrosion
rate.
Please cite this article in press as: Xu, D., et al., Supercritical water oxidation of a pesticide wastewater. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.08.016
3.6. Primary plant design
In this section, we will introduce a primary SCWO plant design
with the treatment capacity of 100 t/d for the tested pesticide
wastewater based on current investigations.
In SCWO, tank type reactors are first favored for over-
coming reactor corrosion and plugging problems, but tubular
reactors are preferred later (Brunner, 2009). This is because
the tubular reactor has a very simple construction and is
easy to achieve a large treatment capacity under a relatively
low investment condition. Reactor corrosion and plugging
problems can be overcome by the methods of corrosion
resistance metal material or coating, a high flow velocity
and periodical rinsing, etc. (Marrone et al., 2004; Marrone
and Hong, 2009). Thus, some commercial SCWO plants for
other wastewater treatment adopt tubular reactors (Gidner
and Stenmark, 2001; Griffith and Raymond, 2002). Herein, we
also use a tubular reactor to deal with this tested pesticide
wastewater.
Although high temperatures play important role in organic
matters removal, it is very difficult to select an appropri-
ate reactor material when the temperature is higher than
600 ◦ C. Hence, a high OC can be considered to further improve
the removal of organic matters in the pesticide wastewater
because OC hardly affects the reactor length and investment.
Nevertheless, excess oxidant must be recovered to reuse since
oxidant has the most contribution to the SCWO operation cost.
That is the reason why some SCWO plants adopt high OCs
and recover surplus oxidant (Yang, 2003; An, 2010). Moreover,
it has been clarified that most of organic matters in the pes-
ticide wastewater are removed in a shorter residence time in
SCWO. It is desirable to decrease the residence time as much
as possible in order to shorten the reactor length because
the reactor material is very expensive. Therefore, according to
experimental results and economy consideration, we choose
reactor operation parameters to be 600 ◦ C, 25 MPa, OC = 3.0 and
t = 2.0 min for the 100 t/d SCWO plant design, meaning that the
excess oxygen recovery is required. Additionally, Inconel 625
is selected as the reactor material, and its corrosion rate is
about 0.6 mm/year at the above conditions. According to C and
N balance studies, we have confirmed that carbon in gaseous
products exists in the form of CO2 and most of TN is converted
into N2 in pesticide wastewater SCWO. The yields of CO2 and
N2 are 32,713 mg/L and 6329 mg/L at above selected reaction
conditions, respectively. Hence, for the designed SCWO plant,
it is necessary to separate CO2 in order to recover excess oxy-
gen, and N2 should also be separated and emitted periodically
to ensure the recovered oxygen within a certain purity.
Plugging is another crucial problem of SCWO application.
High concentration of organic matters are easy to produce
tarry materials such as char and tar in supercritical water,
resulting in the decrease of the conversion efficiency (Xu
et al., 1996; Matsumura et al., 2000). However, we did not
find the formations of tarry matters and suspended matters,
and the liquid effluent is very clear, as indicated in Fig. 5.
Hence, it is not necessary to consider the plugging problem
induced by thermal degradation products during the preheat-
ing process of the pesticide wastewater in the design. Due to
very low solubilities of inorganic salts in supercritical water,
salt depositon problems should be considered adequately,
so many approaches are adopted to avoid reactor plugging
(Marrone et al., 2004). In fact, inorganic salt separation and
removal before the SCWO reactor is very necessary for avoid-
ing reactor plugging. Schubert et al. (2012) reported that it
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chemical engineering research and design x x x ( 2 0 1 4 ) xxx–xxx 9

Fig. 8 – Corrosion morphology and EDS analysis of the Inconel 625 sample in pesticide wastewater SCWO at 600 ◦ C, 25 MPa
and OC = 3.0 for 70 h. (a) Surface SEM diagram of 500 magnification, (b) EDS diagram (line scanning) of the end face.

could recover a maximum value in the brine effluent for the Part of reactor effluent is used to preheat the wastewater
Na2 SO4 and K2 SO4 mixture at a temperature of 450–460 ◦ C. feedstock via the heat exchanger (4), and the rest of it flows
Because the tested pesticide wastewater mainly contains inor- into the heat exchanger (17) to produce the desired steam.
ganic salts Na2 SO4 and K2 SO4 , we also propose to design a Cooling water pump (15) pumps cooling water into the heat
specific salt separator and control its inner fluid temperature exchanger (16) to cool down all of reactor effluent which fur-
at about 450 ◦ C to separate these inorganic salts. Of course, this ther enters the gas-liquid separator (18) for liquid and gaseous
requires to be systematically tested in a pilot scale salt separa- products separation. The separated gaseous products flow into
tor at around 450 ◦ C for the pesticide wastewater. Furthermore, the heat exchanger (12) and are cooled by liquid oxygen, so
we design suitable diameters for the reactor and preheating produced CO2 is liquefied and then enters the O2 /CO2 sepa-
pipelines to guarantee a high flow velocity and periodically rator (19), and obtained liquid CO2 is depressurized via the
rinse them to minimize the plugging risk. pressure reducing valve (22) and then is stored in the gas cylin-
We find that further improving reaction conditions, such der (23). The separated excess O2 from the O2 /CO2 separator
as increasing the reaction temperature, the residence time (19) flows into the gas buffer (20), and then is transported into
and OC will remarkably lead to the increment of the plant the gas buffer (13) by the compressor (21) to reuse the recov-
investment or the operation cost. Thus, traditional waste- ered oxygen. Due to a small amount of N2 formation in the
water treatment methods such as biochemical methods and reaction, it is necessary to periodically conduct gas emission
NH3 -N desorption methods are proposed to further remove a via the valve on the gas buffer (20) in order to ensure the purity
little residual pollutants after SCWO for ultimately meeting of the recovered oxygen.
corresponding discharge standards. According to our evalu- Removed salts via the hydrocyclone (5) first flow into the
ation and calculation, SCWO (at 600 ◦ C, 25 MPa, OC = 3.0 and salt-collecting tank (24), and then enter the expanding ves-
t = 2.0 min) combined with traditional wastewater treatment sel (25) to freely expand for drying, and ultimately the dried
methods has obvious economic advantage compared with just
SCWO (at 600 ◦ C, 25 MPa, OC = 3.0 and t = 4.0 min) for the harm-
less treatment of the 100 t/d pesticide wastewater.
Fig. 9 indicates the schematic diagram of the primary
design scheme for the pesticide wastewater SCWO plant with
the treatment capacity of 100 t/d. Pesticide wastewater is
transported and pressurized by the high pressure metering
pump (2), and then preheated up to approximately 450 ◦ C by
reactor effluent via the heat exchanger (4), and further enters
the hydrocyclone (5) for salt separation, and the clean fluid
after salt removal flows into the mixer (8) via the accessory
pipeline (6). The gas-fired heater (7) is only applied to com-
pensate the heat requirement at the plant starting stage due
to heat self-sufficiency in the normal running. Liquid oxygen
(−183 ◦ C and 1.6 MPa) stored in the tank (10) is pressurized
and its flow rate is regulated by the liquid oxygen pump (11),
and subsequently gasified into gaseous oxygen in the heat
exchanger (12), and then the gaseous oxygen enters the gas
buffer (13) for decreasing its fluctuation, and further mixes
with the preheated wastewater in the mixer (8), and finally
flows into the tubular reactor (9) made of Inconel 625 with
100 mm i.d. for oxidation reactions. Herein, liquid oxygen is
chosen as the oxidant of this plant because it is the most suit-
able and economic one systematically compared with other
kinds of oxidants such as gaseous oxygen, hydrogen peroxide Fig. 9 – Schematic diagram of the primary design scheme
and air (Xu et al., 2012). for the pesticide wastewater SCWO plant (100 t/d).

Please cite this article in press as: Xu, D., et al., Supercritical water oxidation of a pesticide wastewater. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.08.016
CHERD-1680; No. of Pages 11
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salts are collected and disposed periodically. The gained liquid
from the gas-liquid separator (18) is first depressurized to the
ambient pressure by the back pressure valve (26), and flows
into the water pond (27) and is further pumped into the tradi-
tional treatment unit (29) through the water pump (28). After
secondary treatments via traditional methods, the liquid is
finally drained without pollutants.
Investigations for industrial wastewaters SCWO have
demonstrated the possibility of working under heat self-
sufficient conditions, and also verified the economic feasibil-
ity, especially in view of energy recovery optimization (Vadillo
et al., 2011). In a large-scale process, SCWO together with
traditional treatment methods will effectively deal with the
pesticide wastewater with relatively low investment and oper-
ation costs. We have finished the primary scheme design
of the 100 t/d SCWO plant for pesticide wastewater treat-
ment on the basis of previous investigations. However, more
detailed exploration and economic evaluation are still nec-
essary to finally optimize the design. Currently, we are
conducting detailed design and optimization of the plant
according to more systematical and deeply studies, and it
will be demonstrated in the pesticide production company.
Detailed introduction will be reported in subsequent work.
4. Conclusions
In order to construct a 100 t/d SCWO plant to effectively and
economically dispose a pesticide wastewater, we have studied
its SCWO product properties, traditionally auxiliary treat-
ment processes, reactor material corrosion problems, etc., in a
continuous-flow tubular reaction plant as well as a batch reac-
tion plant with oxygen as oxidant. It is confirmed that reaction
temperature, oxidant coefficient, residence time can improve
the removal of organic matters in the wastewater. The reaction
temperature plays a very significant role in XCOD , while the
residence time and OC have important influences on XCOD at
higher reaction temperatures (>500 ◦ C). Increase the preheat-
ing rate of feedstock is significant for the XCOD improvement.
XCOD and XTN are 99.42% and 86.70%, and more than 92 wt%
TOC and 86.70 wt% TN in the wastewater are converted into
CO2 and N2 at 600 ◦ C, 25 MPa, OC = 3.0 and t = 2.0 min con-
ditions, respectively. A tubular reactor made of Inconel 625
is recommended and its corrosion rate is about 0.6 mm/year
at the selected conditions. A little residual pollutant in the
reactor effluent is proposed to be further harmlessly treated
by traditional wastewater treatment methods. According to
accomplished investigations, we conduct a primary SCWO
plant design for the tested pesticide wastewater, in which
excess oxygen will be recovered to reuse and traditional waste-
water treatment methods will be combined to improve the
whole system’s economic feasibility.
Acknowledgments
This work is supported by the Projects from National Natural
Science Foundation of China (No. 21206132), and the Spe-
cialized Research Fund for the Doctoral Program of Higher
Education (No. 20120201120069), the Fundamental Research
Funds for the Central Universities (No. xjj2012032), the
National Science Foundation for Post-doctoral Scientists of
China (No. 2013M540748), and the seventh batch of special
fund of the National Science Foundation for Post-doctoral Sci-
entists of China (No. 126568).
Please cite this article in press as: Xu, D., et al., Supercritical water oxidation of a pesticide wastewater. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.08.016
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