You are on page 1of 7

Article

pubs.acs.org/IECR

Process Simulation of Laboratory Wastewater Treatment via


Supercritical Water Oxidation
Xiuqin Dong, Yaqi Wang, Xuqing Li, Yingzhe Yu,* and Minhua Zhang*
Key Laboratory for Green Chemical Technology of Ministry of Education, R & D Center for Petrochemical Technology, Tianjin
University, Tianjin 300072, China
S Supporting Information
*

ABSTRACT: Laboratory wastewater has neither a regular discharge cycle nor a regular discharge quantity, and its compositions
are so complex that they are rather dicult to dispose of. The purpose of this study is to set up a small laboratory wastewater
treatment plant, and it mainly focuses on the treatment of organic wastewater in the laboratory via supercritical water oxidation
(SCWO). The process conditions optimized experimentally were the following: 440 C, 26 MPa, longer than 70 s of residence
time, hydrogen peroxide as oxidant with a 2.6 times excessive rate. The reaction kinetics equation was obtained through study of
the degradation reaction of laboratory wastewater in supercritical water. The wastewater treatment process was simulated with
the program PRO/II, and a relatively complete design scheme of a laboratory wastewater treatment process by SCWO was
proposed from such aspects as the mass balance, heat balance, and equipment calculation. At the same time, an equipment
prototype was established, and thus, a small laboratory wastewater treatment plant could be set up.

1. INTRODUCTION
Wastewater treatment has become a signicant issue for
chemical processes on account of natural laws and rules to
maintain a cleaner environment.1 Laboratory wastewater mainly
means the wastewater discharged during research, education,
and industrial and agricultural product development by all kinds
of laboratories such as education research institution
laboratories, industrial research and development (R&D)
laboratories, analysis laboratories, medical and health testing
laboratories, etc. In addition, it also includes washing water of
containers and equipment, cooling water, cleaning groundwater, disinfecting water, the wastewater in the research
process, and so on. Laboratory wastewater has neither a regular
discharge cycle nor a regular discharge quantity, and its
components, especially the heavy metal elements and other
special toxic pollutants, are so complex that they are rather
dicult to dispose of by the biological treatment process in
sewage treatment plants. This paper mainly focuses on the
organic wastewater, which contains common organic solvents,
organic acids, ethers, organophosphorus compounds, phenols,
oils, greases, etc., which are the most dicult to treat with
various compositions and concentrations. At present, reports of
laboratory wastewater treatment technologies are rare and the
existing processes employed are physical,2 biochemical,3,4 and
chemical oxidation methods5 and the combination of the
aforementioned methods.6
Supercritical water (SCW) is a unique medium above the
thermodynamic critical point (374 C, 221 bar)7,8 with the
property that nonpolar compounds and organics can be
completely miscible in SCW.9 Supercritical water oxidation
(SCWO) is an advanced water oxidation technology rst
developed by the American scholar Modell10 in the mid-1980s,
and it has been rapidly developed since then. Attracting the
attention of many researchers, this technology is expected to
become an eective method to deal with organic waste11
2014 American Chemical Society

because of its advantages of high eciency, environmental


friendliness, and thorough organic removal. Numbers of
enterprises and research institutions have carried out the
study of the applications of SCWO technology. The studies are
mainly divided into two categories: one is the study of
degradation of model pollutants with supercritical water
oxidation. Phenol and phenolic substitute compounds are the
most common type of model pollutants that have been
mentioned above. A large number of literature works and books
have studied the degradation factors,12,13 reaction kinetics,14,15
and reaction mechanism16,17 of degradation of these compounds by SCWO. Another type of research is aimed at the
actual wastewater, including papermaking wastewater,18 chemical production wastewater,19 pharmaceutical industry wastewater,20 war industry wastewater,21 etc.
A novel method in SCWO research is using advanced
process simulation technology to simulate the process. Cocero
et al.22 used the program ASPEN to simulate a pilot
experimental device with the capacity of 2 m3/h, whose nhexane removal rate was 99.9% under the reaction conditions of
650 C and 23 MPa, and the results agreed well with the
experimental values. Lavric et al.23 also conducted the
simulation of 5 wt % hexane solution treatment process,
which showed that both the Brayton cycle (CBC) and Rankine
cycle (ORC) could be self-sucient in energy and the latter
was more realistic. Applying process simulation to the
supercritical water oxidation process will promote the development of new technologies and play a positive role in amplifying
the scale of and industrializing SCWO technologies.
Received:
Revised:
Accepted:
Published:
7723

December 30, 2013


April 9, 2014
April 16, 2014
April 16, 2014
dx.doi.org/10.1021/ie4044339 | Ind. Eng. Chem. Res. 2014, 53, 77237729

Industrial & Engineering Chemistry Research

Article

Raw materials rst ow into the liquid buer via highpressure plunger pump to ensure the smooth ow and, then,
enter the preheater. After that, the materials go into plug-ow
reactor to be heated and pressurized to supercritical conditions,
under which organics rapidly react with oxidant. The liquid
enters the quencher to be cooled. The pressure of system
should be controlled by the counterbalance valve, and then, the
mixture ows into gasliquid separator. Finally, the separated
liquid is collected and the separated gas is emitted
continuously.
The feedstock is automatically controlled by plunger pump.
Liquid preheater provides heat by single electric stove wires,
and the heating system of the reactor consists of a main heater
and three auxiliary heaters to ensure a constant temperature in
the reactor during the experiment. The counterbalance valve
can control the pressure of system, which uctuates within 0.2
MPa.
2.1.3. Suitable Process Conditions. The process of supercritical water oxidation is dicult to implement in engineering
due to the conditions of high temperature, high pressure, and
strong oxidative atmosphere which need equipment with
demanding requirements. So, this study tries to reduce the
operation pressure and temperature and extend residence time
under the premise of fully degrading the organics.
This study examined the inuence of such factors as
temperature, pressure, the selection and dosage of oxidant,
and residence time on the laboratory wastewater treatment by
SCWO, respectively. According to the experimental results
(shown in Figure S14 in the Supporting Information) and the
principles of optimizing process conditions, the reaction
pressure is set to 26 MPa, hydrogen peroxide is chosen as
oxidant with a 2.6 times excessive rate, and residence time
longer than 70 s. Beginning with low temperature ranging from
400 to 480 C, the eect of oxidation degradation of the
laboratory wastewater is investigated. The experimental results
are shown in Table 2 (TOC stands for total organic carbon).
Qualitative analysis of gaseous products under suitable
conditions indicates that CO2 has been found in the products
and neither of CO nor NOx has been detected, which is
consistent with the results of Xu et al.24

This research is thus threefold: First, the process conditions


of laboratory wastewater treatment by SCWO were researched
to select appropriate conditions. Second, the reaction kinetics
of the degradation was studied to lay the basis for the entire
process simulation and engineering design amplication.
Finally, the prgoram PRO/II was used to simulate the
wastewater treatment process, and a relatively complete design
scheme of a laboratory wastewater treatment process by SCWO
was proposed from such aspects as the mass balance, heat
balance, and equipment calculation, which could assist us in
setting up a small laboratory wastewater treatment plant.

2. MATERIALS AND METHODS


2.1. Experiment. 2.1.1. Compositions and Concentrations of Wastewater. This study focused on organic synthetic
laboratories. Methanol, ethanol, acetone, n-hexane, ethyl
acetate, etc., are commonly used and phenol, nitrobenzene,
etc., are common organic synthetic raw materials in these
laboratories. Furthermore, phenol and nitro compounds are
typical representatives which are the most dicult to degrade.
So, the aforementioned materials were chosen as the
compositions of laboratory wastewater. Specic concentrations
are shown in Table 1.
Table 1. Wastewater Compositions and Concentrations
compound

concentration/mgkg1

methanol
ethanol
acetone
ethyl acetate
n-hexane
phenol
nitrobenzene

800
1000
800
800
50
500
300

2.1.2. Experimental Device and Procedure. In Figure 1, the


experimental equipment used in this study is given. The unit
consists of a high pressure plunger pump, liquor preheater,
reactor, quencher, gasliquid separator, counterbalance valve,
etc.

Figure 1. Flowchart of supercritical water oxidation system upset: 1liquid storage tank, 2plunger pump, 3liquid buer, 4check valve, 5liquor
preheater, 6reaction tube, 7quencher, 8sampler, 9lter, 10counterbalance valve, 11vaporliquid separator, 12liquid tank.
7724

dx.doi.org/10.1021/ie4044339 | Ind. Eng. Chem. Res. 2014, 53, 77237729

Industrial & Engineering Chemistry Research

Article

Table 2. Experimental Results


experiment

temperature C

removal rate of nitrobenzene %

nitrobenzene mgkg1

TOC mgkg1

1
2
3
4
5
international emission standard

400
420
440
460
480

99.30
99.33
99.43
100
100

2.1
2.0
1.7

67.6
29.8
11.36
11.2
10.04
30

3.0

The simplex method was used to conduct the optimization


computation because of its easy convergence and low
requirements of initial values, despite the low calculation
speed.25 With MATLAB programming, the value of S was
reduced by modifying the parameters with the simplex method
and adjusting the initial value with the symmetry principle. The
desired parameter values are the ones when the S value meets
the convergence criteria. The reaction kinetics equation of
nitrobenzene degradation via supercritical water oxidation is

To ensure that laboratory wastewater can meet the standard


after the process, based on the experimental results of the
process, the proper process conditions determined are shown
in Table 3.
Table 3. Optimal Technological Conditions
temperature C

pressure MPa

residence time s

excessive rate of H2O2

440

26

>70

2.6

r = 8.851 106exp( 6.935 104 /RT )C NB1.545CO2 0.449

Where, r is the reaction rate of nitrobenzene in moles per liter


per minute and Ci denotes the concentration of the i
component in moles per liter.
The dynamic model obtained by experimental data
regression must be subject to the statistical test and analysis
of residual distribution to judge the reliability and accuracy of
the model. In Table 4, the statistical results of the kinetic model

2.2. Kinetic Model. The reaction kinetics of nitrobenzene


degradation by SCWO was studied, which was the typical
representative of the materials most dicult to degrade, in
order to further research the law of the reaction, further
understand supercritical water oxidation process, and provide
the guidance for design, optimization, and control of the
process in the industrial application.
A reaction kinetics equation with power exponents was used
to conduct this research because the products of the organic
pollutants treated by SCWO are too complex to describe with
elementary reactions. The mathematical model of nitrobenzene
degradation reaction kinetics is
FNB0 dXNB
s dz

Table 4. Statistical Results of the Kinetic Model of


Nitrobenzene

= A exp( Ea /RT )[NB]0 a (1 XNB)a

b
O2
[NB]0 XNB
[O2 ]0
NB

The initial conditions are z = 0, XNB = 0, [NB] = [NB]0, [O2] =


[O2]0.
In addition, the density of supercritical water is dierent from
that in normal condition and varies with changes in
temperature and pressure. Therefore, instead of directly using
the original experimental data, the original experiment data
should be processed with the reference to the PVT relationship
of reaction system. And then concentration and ow rate of
nitrobenzene and oxygen under reaction conditions were
calculated. The kinetics data are given in Table S1 in the
Supporting Information.
The fourth-order RungeKutta equation was chosen to
determine the parameters of A, Ea, a, and b in the kinetics
equation. Experimental data of nitrobenzene conversion and a
residual sum of squares of model calculation were used as the
objective function of parameter estimation:

result
20
4
0.931
81.145
4.44
5.61

of nitrobenzene are given. From this table, it is obvious that R2


> 0.9, F > 10F0.05, F > 10F0.01, and all the i are less than 10%,
which suggest that the kinetic equation is accurate.
2.3. Process Model. 2.3.1. Determination of Thermodynamics Method. The selection of the thermodynamics method
has a direct inuence on the precision and accuracy of the
analysis, process, optimization, and equipment calculation
results. So the selection of the appropriate thermodynamic
method is the key to the simulation.
The system studied here contained water, a small amount of
organics, O2, CO2, N2, etc. and was in supercritical state with
high temperature and high pressure. The PR equation could be
used to calculate uid properties of supercritical state.
Furthermore, the equation called PRM (PR-modied PanagiotopoulosReid) which introduces four adjustable interaction parameters is of higher calculation accuracy. So the PRM
equation was chosen for the models in this system such as the
reactor, heat exchanger, pump, counterbalance valve, and mixer
while the thermodynamics model of vaporliquid equilibrium
used the NRTL equation that was applicable to a water system.
2.3.2. Selection of Calculation Method. All streams
convergence and direct iteration convergence were adopted
in this study for the simplicity of supercritical water oxidation

S=

item
experiment groups
number of parameters to be estimated
correlation coecient R2
F test value
F ( = 0.05)
F ( = 0.01)

cal
exp 2
XNB
)
(XNB
i=1

Where, S stands for the residual sum of squares, q is the number


cal
exp
of parameters to be estimated, XNB
and XNB
represent
calculated conversion and experimental conversion of nitrobenzene, respectively.
7725

dx.doi.org/10.1021/ie4044339 | Ind. Eng. Chem. Res. 2014, 53, 77237729

Industrial & Engineering Chemistry Research

Article

Figure 2. Process owchart of laboratory wastewater treatment using SCWO.

Figure 3. Flowchart of amplied laboratory wastewater treatment using SCWO.

(4) Other: The pump and valve modules were also used in
simulation.
2.3.4. Model Verication. In order to verify the accuracy of
thermodynamics method and models that were selected in the
SCWO process, the partial physical properties of the
supercritical water were calculated, including density, enthalpy,
and thermal capacity under constant pressure. The results of
calculated and reported supercritical water density are shown in
Table S24 from the Supporting Information.
It can be seen from the tables that most of the calculation
results agree with those in the literature, while only the part at
low temperature and high pressure shows large relative
deviation. Therefore, the selected model can be used to
simulate a reaction system within the experiment scale and
guide the engineering design.
2.3.5. Parameter Calculation. According to the optimal
process conditions determined by experiment, calculation
parameters are as follows:
The feed pressure of wastewater and hydrogen peroxide is
0.1 MPa, and the temperature is 20 C. Methanol, phenol, etc.
contained in laboratory wastewater can react rapidly and are
degraded easily, while nitrobenzene is the most dicult to
degrade. So the pollutants after disposal can meet the national
discharge standard as long as nitrobenzene does. Therefore,
nitrobenzene is the only pollutant to be considered in the
wastewater of the simulation feedstock. The concentration of
wastewater is 300 mg/kg, hydrogen peroxide is chosen as the
oxidant, and the excess rate is 2.6. After reaction, the
concentration of nitrobenzene should be less than 3 mg/kg,

process. The direct iteration method is known as a successive


substitution method which is the most direct, simple, and quite
stable method, but its convergence speed is slow. The sequence
method in the process simulation was the Minimum Tear
Streams. It is the most commonly used method due to having
the least torn streams and the least variables associated with
those streams.
2.3.3. Establishment of Unit Models. The laboratory
wastewater oxidization process mainly consists of heat
exchange, reaction, and separation. The following unit models
were selected to build the process:
(1) Reactor: Organics, water, and oxygen are miscible for
little mass transfer resistance in supercritical water, so the
reaction is under homogeneous condition. The tubular
reactor in the experiment could be simulated by a plugow reactor.
(2) Heat exchanger: For heating and cooling streams, or the
heat exchange between two streams, the simple heat
exchanger module (Simple HX) in PRO/II software was
chosen to calculate a simple heat balance, not involving
the specic structure of a heat exchanger. Zone analysis
along the direction of temperature change was
conducted, and the temperature of streams in the middle
area was calculated to check driving force generated by
temperature dierence in heat exchangers.
(3) Vaporliquid separator: This is a ash unit in PRO/II,
which is applicable to both VLE and VLLE calculation,
and can be used to conduct balance calculation of any
dened parallel conditions.
7726

dx.doi.org/10.1021/ie4044339 | Ind. Eng. Chem. Res. 2014, 53, 77237729

Industrial & Engineering Chemistry Research

Article

Table 5. Mass Composition of Main Steams in Existing Laboratory-Scale Process


stream

S1

S2

S3

S4

S5

S6

S7

S8

water
CO2
N2
nitrobenzene
O2
T/C
p/MPa
ow/kg/h

98.5800
0.0000
0.0000
0.0300
1.3900
20.00
0.10
0.3000

98.5800
0.0000
0.0000
0.0300
1.3900
20.29
26.00
0.3000

98.5800
0.0000
0.0000
0.0300
1.3900
440.00
26.00
0.3000

98.5910
0.0643
3.41 1003
2.24 1005
1.3413
440.00
26.00
0.3000

98.5910
0.0643
3.41 1003
2.24 1005
1.3413
20.00
26.00
0.3000

98.5910
0.0643
3.41 1003
2.24 1005
1.3413
25.46
0.10
0.3000

1.5123
1.6017
0.2600
6.58 1009
96.6260
22.15
0.10
3.38 1003

99.6968
0.0467
4.85 1004
4.29 1005
0.2559
22.15
0.10
0.2966

Table 6. Mass Composition of Main Steams in Amplied Process


stream

S1

S3

S5

S6

S7

S8

S9

S11

S12

water
CO2
N2
nitrobenzene
H2O2
T/C
p/MPa
ow kg/h

0.0000
0.0000
0.0000
0.0000
100.0000
20.00
0.10
1.4100

99.9700
0.0000
0.0000
0.0300
0.0000
20.00
0.10
100.0000

98.5800
0.0000
0.0000
0.0296
1.3904
20.19
26.00
101.4100

98.5800
0.0000
0.0000
0.0296
1.3904
420.00
26.00
101.4100

98.5800
0.0000
0.0000
0.0296
1.3904
440.00
26.00
101.4100

98.5910
0.0634
3.36 1003
2.54 1005
1.3424
440.00
26.00
101.4100

98.5910
0.0634
3.36 1003
2.54 1005
1.3424
20.00
26.00
101.4100

1.5125
1.5801
0.2564
3.94 1009
96.6510
22.16
0.10
1.1430

99.6974
0.0461
4.78 1004
2.56 1005
0.2559
22.16
0.10
100.2671

3. CALCULATION RESULTS
3.1. Calculation Results of Existing Process. The main
stream data by simulation for the exiting laboratory-scale
process are listed in Table 5. It is clearly seen from calculation
results, the concentration of nitrobenzene is less than 0.5 mg/
kg after reaction under certain conditions. And the removal rate
of nitrobenzene is 99.86%, which is in excellent agreement with
the results obtained from experiments.
3.2. Calculation Results of Amplied Process. The
main stream data of amplied process by simulation are
included in Table 6. It is obvious from results that nitrobenzene
removal rate under the process conditions can reach 99.91%,
and the concentration after reaction is lower than 0.3 mg/kg,
which meets the national emission standard. The load of heat
exchanger E0 is 265 200 kJ/h, and the heat needed by the cold
stream is provided by the hot stream of the reactor outlet. The
heat supplement for preheater E1 is 11 000 kJ/h, that is, 3.056
kW.

that is to say, the nitrobenzene removal rate should be over


99%. The reaction temperature is supposed to be constant at
440 C for a low concentration of raw materials and minimal
heat eect, although it is an exothermic reaction. The stream
pressure of the reactor inlet is 26 MPa, and the residence time
in the reactor is supposed to be 70 s. Calculation is conducted
with the kinetic equation determined by experiment, r = 8.851
106 exp(6.935 104/RT)CNB1.545CO20.449. The stream ows
into quencher after reaction, and the temperature decreases to
20 C. The operational pressure of the vaporliquid separator
is 0.1 MPa, and adiabatic ash is applied. The wastewater pump
inlet pressure is atmospheric pressure, while the outlet pressure
is 26.0 MPa. The stream pressure decreases to 0.1 MPa after
the counterbalance valve.
2.3.6. Process. The existing experimental process simulated
by PRO/II is shown in Figure 2.The scale of calculation for
laboratory wastewater treatment is 0.3 kg/h. The length of the
reactor is 0.369 m, and the inner diameter is 12.8 mm.
Amplication and energy optimization have been conducted
on the basis of the existing process. The amplied technological
process is shown in Figure 3. Laboratory wastewater is mixed
with hydrogen peroxide before owing into thermal coupling
heat exchanger E0. The heated materials reach the specic
temperature through preheater E1, and then, organics are
degraded in tubular reactor R1 where organics rapidly react
with oxidant. The stream enters thermal coupling exchanger E0
to be cooled, passes counterbalance valve V1, and then ows
into vaporliquid separator F1 to continuously collect the
liquid; the vapor is emitted.
The scale of wastewater treatment is amplied to 100 kg/h.
The length of reactor is 4 m, and the inner diameter is 80 mm.
After calculation, the reactor volume is 20.42 L. Energy
optimization also has been employed to the existing process.
The cold stream temperature reaches 420 C through heat
exchanger E0 and becomes 440 C through preheater E1. The
rest of the unit operation parameters are the same as those
mentioned in section 2.3.5.

4. DESIGN OF THE PLANT


A vertical storage tank with volume of 2.50 m3 and DN 1400
1600 is used to store wastewater for a day and a night. For the
need of high pressure in supercritical water oxidation reaction, a
plunger pump is chosen as the feed pump. The maximum ow
is twice the normal ow, J5 type is chosen, the ow is 200 L/h,
and the highest pressure is 40.0 MPa. The maximum ow of the
hydrogen peroxide pump is 10 L/h, and the highest pressure is
40.0 MPa. Fluid state, residence time, and inlet temperature are
the same before and after amplication of the reactor26 which is
at a constant temperature of 440 C. On the basis of the
aforementioned principles, the calculated reactor eective
volume is Vr = 20.42 L. L/D 50 is set to ensure the uid
in the reactor stays in the state of plug ow, and Re > 10 000 is
set to ensure turbulence in the reactor. The nally determined
reactor diameter is 80.0 mm, and the length is 4.0 m. A doublepipe heat interchanger is chosen to ensure that the uid is in
the turbulent state which facilitates the heat transfer. The hot
stream ows into the tube while the cold stream ows between
the tubes. An electrical heating apparatus with adjustable power
7727

dx.doi.org/10.1021/ie4044339 | Ind. Eng. Chem. Res. 2014, 53, 77237729

Industrial & Engineering Chemistry Research

Article

Table 7. Equipment Information Table


operation conditions
equipment
code

equipment name

V-01

liquid storage tank

vertical type, 2.5 m3 DN 1400 1600

P-01

wastewater pump

metering pump, ow 200 L/h

P-02

metering pump, ow 10 L/h

E-00

hydrogen peroxide
pump
heat exchanger

R-01

tubular reactor

V-02

vaporliquid
separator

specication and structure

operational medium
lab organic
wastewater
lab organic
wastewater
hydrogen peroxide

double-pipe heat interchanger, A = 17.2 m2 inner pipe 32 3.5,


outer pipe 32 3.5
eective volume 20.42 L DN 80 4000
vertical type, 1.50 m3 DN 1000 1600

water, organics, N2,


O2, etc.
water, O2, and
organics
water, O2, N2, etc.

temperatureC
room
temperature
room
temperature
room
temperature
pipe: 20420
shell: 44050
440
room
temperature

pressure
MPa
0.1
0.1
0.1
pipe: 26
shell: 26
26.0
0.1

kinetics equation determined by the experiment. Material


balances and heat balances of the supercritical water oxidation
devices with a capacity of 100 kg/h were conducted. The
concentration of nitrobenzene was lower than 0.3 mg/kg, and
the removal rate was 99.91% after the reaction, which met the
national discharge standard. (4) The main equipment involved
in the process was selected, and a relatively complete design
scheme of the laboratory wastewater treatment process by
SCWO was established.

is equipped outside the double-pipe heat interchanger. There is


no hot stream to preheat the feed at the beginning of the
reaction, so the electrical heating apparatus is needed. The
electrical heating apparatus is used to supply only the
complementary heat after the equipment runs normally. A
stainless steel tube of 32 3.5 and material type 316 is
chosen as the heat exchange tube, which meets the strength
requirement after the thickness calculation and check, and a
stainless steel tube with 57 3.5 is selected as the outer tube.
A heat transfer area of 17.17 m2 is needed with 15% allowance,
so the length of heat exchanger is 210 m. Separation capacity is
selected to be 1.0 m3/(m3h) to ensure the eectiveness of
vaporliquid separation, and the separation volume of the
vapor phase is 1.05 m3 according to the vapor ow rate. The
liquid residence time is set to 5 min to make sure the vapor is
released completely and the liquid level of the separator is
maintained. After calculation, the volume is 86 L, and the total
volume is 1.17 m3 with a liquid proportion of 0.70 in the
separator. It is determined that the volume is 1.5 m3 and the
size is DN 1000 1600 with reference to the related design
manuals.27
The equipment information on laboratory wastewater
treatment process by supercritical water oxidation is
summarized in Table 7.

ASSOCIATED CONTENT

S Supporting Information
*

Eects of reaction temperature, pressure, H2O2 dose ratio, and


residence time on removal eciency of laboratory wastewater
components (Figure S14, respectively). Data of nitrobenzene
supercritical water oxidation kinetics (Table S1). Comparison
of the calculated and reported supercritical water density,
capacity, and enthalpy (Table S24, respectively). This
material is available free of charge via the Internet at http://
pubs.acs.org.

AUTHOR INFORMATION

Corresponding Authors

*E-mail: yuyingzhe@tju.edu.cn (Y.Y.).


*E-mail: mhzhang@tju.edu.cn (M.Z.).

5. CONCLUSIONS
This study focused on the degradation law of the main
pollutants in laboratory wastewater by supercritical water
oxidation technology. PRO/II software was used to simulate
and optimize the process, and the design principles of the main
equipment were established; thus, the following conclusions
were obtained: (1) An experiment investigated the reaction
temperature, pressure, selection of oxidant and its excess rate,
residence time, and other factors in the laboratory. Using
hydrogen peroxide as oxidant, a 2.6 times excess rate, a
temperature of 440 C, a pressure of 26 MPa, and a residence
time longer than 70 s suitable degradation process conditions of
the system were found. The contents of organic pollutants and
TOC met the discharge standard GB8978-1996 after the
laboratory wastewater treatment under the process conditions.
(2) Through the study of reaction kinetics, the reaction kinetics
equation of the nitrobenzene degradation by SCWO under
experimental conditions is r = 8.851 106exp(6.935 104/
RT)CNB1.545CO20.449. (3) PRO/II was used to simulate the
process of laboratory wastewater treatment by supercritical
water oxidation on the basis of the process conditions and the

Notes

The authors declare no competing nancial interest.

REFERENCES

(1) Sahu, G. C.; Garg, A.; Majozi, T.; Bandyopadhyay, S. Optimum


Design of Wastewater Treatment Network. Ind. Eng. Chem. Res. 2013,
52, 51615171.
(2) Xuan, X. M.; Jin, Z. H. Treatment of laboratory Organic
Wastewater with High Concentration by Fly Coal Ash Adoption and
Fenton Oxidation. Environ. Sanit. Eng. 2007, 15, 1824.
(3) Kobayashi, Hester; Rittmann, B. E. Microbial Removal of
Hazardous Organic Compounds. Environ. Sci. Technol. 1982, 16,
170A183A.
(4) Patil, S. S.; Shlnde, V. M. Biodegradation Studies of Aniline and
Nitrobenzene in Aniline Plant Wastewater by Gas Chromatography.
Environ. Sci. Technol. 1988, 22, 11601165.
(5) Matatov-Meytal, Y. I.; Sheintuch, M. Catalytic Abatement of
Water Pollutants. Ind. Eng. Chem. Res. 1998, 37, 309326.
(6) Bertanza, G.; Collivignarelli, C.; Pedrazzani, R. The Role of
Chemical Oxidation in Combined Chemical-physical and Biological
Processes: Experiences of Industrial Wastewater Treatment. Water Sci.
Technol. 2001, 44, 109116.

7728

dx.doi.org/10.1021/ie4044339 | Ind. Eng. Chem. Res. 2014, 53, 77237729

Industrial & Engineering Chemistry Research

Article

(7) Vadillo, V.; Garcia-Jarana, M. B.; Sanchez-Oneto, J.; Portela, J. R.;


Martinez de la Ossa, E. J. New Feed System for Water-insoluble
Organic and/or Highly Concentrated Wastewaters in the Supercritical
Water Oxidation Process. J. Supercrit. Fluids 2012, 72, 263269.
(8) Marrone, P. A. Supercritical Water Oxidation-Current Status of
Full-scale Commercial Activity for Waste Destruction. J. Supercrit.
Fluids 2013, 79, 283288.
(9) Huelsman, C. M.; Savage, P. E. Reaction Pathways and Kinetic
Modeling for Phenol Gasification in Supercritical Water. J. Supercrit.
Fluids 2013, 81, 200209.
(10) Modell, M.; Gaudet, G. G.; Simon, M. Supercritical Water:
Testing Reveals New Process Holds Promise. Solid Waste. Manage.
1982, 25, 2630.
(11) Brunner, G. Near and Supercritical Water. Part II: Oxidative
Processes. J. Supercrit. Fluids 2009, 47, 382390.
(12) Henrikson, J. T.; Chen, Z.; Savage, P. E. Inhibition and
Acceleration of Phenol Oxidation by Supercritical Water. Ind. Eng.
Chem. Res. 2003, 42, 63036309.
(13) Matsumura, Y.; Nunoura, T.; Urase, T.; Yamamoto, K.
Supercritical Water Oxidation of High Concentrations of Phenol. J.
Hazard. Mater. 2000, 73, 245254.
(14) Martino, C. J.; Savage, P. E. Total Organic Carbon
Disappearance Kinetics for the Supercritical Water Oxidation of
Monosubstituted Phenols. Environ. Sci. Technol. 1999, 33, 19111915.
(15) Oshima, Y.; Hori, K.; Toda, M.; Chommanad, T.; Koda, S.
Phenol Oxidation Kinetics in Supercritical Water. J. Supercrit. Fluids
1998, 13, 241246.
(16) Martino, C. J.; Savage, P. E. Supercritical Water Oxidation
Kinetics and Pathways for Ethylphenols, Hydroxyacetophenones, and
Other Monosubstituted Phenols. Ind. Eng. Chem. Res. 1999, 38, 1775
1783.
(17) Thornton, T. D.; Savage, P. E. Phenol Oxidation Pathways in
Supercritical Water. Ind. Eng. Chem. Res. 1992, 31, 24512456.
(18) Modell, M.; Larson, J.; Sobczynski, S. Supercritical Water
Oxidation of Pulp Mill Sludges. Tappi J. 1992, 75, 195202.
(19) Li, L.; Gloyna, E. F.; Sawicki, J. E. Treatability of DNT Process
Wastewater by Supercritical Water Oxidation. Water Environ. Res.
1993, 250257.
(20) Johnston, J. B.; Hannah, R. E.; Cunningham, V. L.; Daggy, B. P.;
Sturm, F. J.; Kelly, R. M. Destruction of Pharmaceutical and
Biopharmaceutical Wastes by the MODAR Supercritical Water
Oxidation Process. Nat. Biotechnol. 1988, 6, 14231427.
(21) Rofer, C. K.; Buelow, S. J.; Dyer, R. B.; Wander, J. D. Conversion
of Hazardous Materials Using Supercritical Water Oxidation. US patent
5133877 A, 1992.
(22) Cocero, M. J.; Alonso, E.; Sanz, M. T.; Fdz-Polanco, F.
Supercritical Water Oxidation Process under Energetically Selfsufficient Operation. J. Supercrit. Fluids 2002, 24, 3746.
(23) Lavric, E. D.; Weyten, H.; De Ruyck, J.; Plesu, V.; Lavric, V.
Delocalized Organic Pollutant Destruction Through a Self-sustaining
Supercritical Water Oxidation Process. Energy Convers. Manage. 2005,
46, 13451364.
(24) Xu, Y. W.; Dong, X. Q.; Zhang, M. H. Study on Catalytic
Supercritical Water Oxidation of Nitrobenzene Wastewater. Chem.
React. Eng. Technol. 2006, 22, 434438.
(25) Bard, Y. Nonlinear parameter estimation; Academic Press: New
York, 1974; Vol. 1209.
(26) Bruce, N. E. Chemical Reactor Design, Optimization, and Scale
Up; Wiley: Hoboken. NJ, 2008.
(27) Sinopec Shanghai Engineering Co. Ltd. Chemical Process Design
Handbook; Chemical Industry Press: Beijing, 2009; Vol. 2, pp 636
637.

7729

dx.doi.org/10.1021/ie4044339 | Ind. Eng. Chem. Res. 2014, 53, 77237729

You might also like