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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
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
concentration/mgkg1
methanol
ethanol
acetone
ethyl acetate
n-hexane
phenol
nitrobenzene
800
1000
800
800
50
500
300
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
Article
temperature C
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
pressure MPa
residence time s
440
26
>70
2.6
b
O2
[NB]0 XNB
[O2 ]0
NB
result
20
4
0.931
81.145
4.44
5.61
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
Article
(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,
Article
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
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.
Article
equipment name
V-01
P-01
wastewater pump
P-02
E-00
hydrogen peroxide
pump
heat exchanger
R-01
tubular reactor
V-02
vaporliquid
separator
operational medium
lab organic
wastewater
lab organic
wastewater
hydrogen peroxide
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
ASSOCIATED CONTENT
S Supporting Information
*
AUTHOR INFORMATION
Corresponding Authors
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
REFERENCES
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