Water Research 110 (2017) 56e65

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Supercritical water oxidation of quinazoline: Reaction kinetics

and modeling
Yanmeng Gong a, b, Yang Guo a, c, *, Shuzhong Wang a, Wenhan Song a, Donghai Xu a
a
Key Laboratory of Thermo-Fluid Science and Engineering, Ministry of Education, School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an,
Shaanxi, 710049, China
b
Jiangsu Provincial Academy of Environmental Science, Jiangsu Province Key Laboratory of Environmental Engineering, Nanjing, Jiangsu, 210036, China
c
Xi'an Jiaotong University Suzhou Academy, Suzhou, Jiangsu, 215123, China

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

Article history: This paper presents a rst quantitative kinetic model for supercritical water oxidation (SCWO) of qui-
Received 12 May 2016 nazoline that describes the formation and interconversion of intermediates and nal products at 673
Received in revised form e873 K. The set of 11 reaction pathways for phenol, pyrimidine, naphthalene, NH3, etc, involved in the
6 December 2016
simplied reaction network proved sufcient for tting the experimental results satisfactorily. We
Accepted 10 December 2016
Available online 11 December 2016
validated the model prediction ability on CO2 yields at initial quinazoline loading not used in the
parameter estimation. Reaction rate analysis and sensitivity analysis indicate that nearly all reactions
reach their thermodynamic equilibrium within 300 s. The pyrimidine yielding from quinazoline is the
Keywords:
Quinazoline
dominant ring-opening pathway and provides a signicant contribution to CO2 formation. Low sensi-
Supercritical water oxidation tivity of NH3 decomposition rate to concentration conrms its refractory nature in SCWO. Nitrogen
Kinetics content in liquid products decreases whereas that in gaseous phase increases as reaction time prolonged.
Modeling The nitrogen predicted by the model in gaseous phase combined with the experimental nitrogen in
Reaction mechanism liquid products gives an accurate nitrogen balance of conversion process.
2016 Elsevier Ltd. All rights reserved.

1. Introduction biological and pharmacological activities, such as antimalarial,

Supercritical water oxidation (SCWO) is considered as a new
promising environmental technology for the treatment of waste-
water which was contaminated with high concentrations of organic
compounds (Akgn and So g
t, 2014; Gloyna and Li, 1995). During
the process, the organics can be thoroughly degraded to H2O and
CO2 within a remarkable short period of time via a single-phase
reaction with oxidant in supercritical water (Tc 647.15 K and
Pc 22.1 MPa), generally ranging from 673 to 923 K and 24e30 MPa
(Ploeger et al., 2008; Rice and Steeper, 1998). The salts are insoluble,
since supercritical water (SCW) behaves as a nonpolar solvent with
low dielectric constant (Vadillo et al., 2013). Besides, undesired by-
products known from incineration, such as dioxines, NOx, are
normally not generated (Kritzer and Dinjus, 2001).
As a N-containing heterocycle with a benzene ring and a py-
rimidine ring, quinazoline (C8H6N2) and its derivatives have diverse
* Corresponding author. Key Laboratory of Thermo-Fluid Science and Engineer-
ing, Ministry of Education, School of Energy and Power Engineering, Xi'an Jiaotong
University, Xi'an, Shaanxi, 710049, China.
E-mail address: Guoyang@mail.xjtu.edu.cn (Y. Guo).
antimicrobial, anti-inammatory, anticonvulsant, antihyperten-
sive, anti-diabetic and anticancer activities (Chandregowda et al.,
2009; Khan et al., 2014, 2015). Owing to the widespread applica-
tions in a variety of synthetic drugs, bioactive natural products,
pharmaceuticals and agrochemicals, quinazoline and its derivatives
are often detected in treated wastewater and environmental water
(Kaiser et al., 2014; Kosjek et al., 2009; McDowell et al., 2005).
Hence, the oxidative degradation of quinazoline and its derivatives
in SCW has captured our attention. Several researchers have
studied the reaction kinetics and mechanisms involved in advanced
oxidation process of other N-heterocyclic organic compounds, such
as quinoline (Pinto et al., 2006; Thomsen, 1998) and pyridine (Aki
and Abraham, 1999a,b; Crain et al., 1993). The global kinetic pa-
rameters of N-heterocyclic organic compounds in SCWO in the
literatures are summarized in Table 1. Crain and co-workers (Crain
et al., 1993) developed a simplied network of reaction pathways
for pyridine oxidation in SCW on the basis of identied compounds.
However, most of the previous kinetic models focused solely on
global rate expression of reactant conversion, but without
capturing the pathways resulted in the formation and intercon-
version of intermediate species.

http://dx.doi.org/10.1016/j.watres.2016.12.015
0043-1354/ 2016 Elsevier Ltd. All rights reserved.
 Y. Gong et al. / Water Research 110 (2017) 56e65 57

Table 1
Kinetic parameters comparison of N-heterocyclic organic compounds in SCWO.

Parameters Quinoline (Pinto et al., 2006) Pyridine (Crain et al., 1993) Pyridine (Aki and Abraham, 1999a) Pyridine (Aki and Abraham, 1999b)

A 2.7  10132 1013.11.65 1031.453.92 1025.36.7 1014.252.5 1014.323.6

Ea 226 19 209.5 22.4 299.28 40.39 287.26 75.61 196.42 27.8 227.61 47.85
a 0.8 0.1 1.0 0.30 1.82 0.22 2.25 0.18 1.12 0.13 0.42 0.18
b 0.3 0.1 0.20 0.16 0.42 0.13 0.43 0.28 1.14 0.23 0.73 0.28
Catalyst None None Pt/g-Al2O3 Pt/g-Al2O3 MnO2/CeO2 a-Al2O3

To ll this gap, a kinetic model aspect of quinazoline oxidation in
SCW was developed and tted with experimental data obtained
from our previous literature (Gong et al., 2016). The experimental
variables included temperatures (T) varying from 673 to 873 K,
residence times (t) varying from 60 to 120 s, water densities (r)
varing from 70.8 to 166.3 kg m3 and a xed oxidation coefcient
(OC) of 2.0. A simplied SCWO reaction network of quinazoline was
proposed rstly on the basis of the quantitative data of both liquid
and gaseous products. After parameter estimation and model
validation were described, the prediction ability of the model was
demonstrated by the comparison of the calculated results and the
experimental measurements. And then, the important reactions in
the model were also identied by reaction rate and sensitivity
analysis.
2. Model development
This model is based on the products distribution and reaction
pathways proposed in our previous study on the SCWO mecha-
nisms of quinazoline (Gong et al., 2016), as shown in Fig. 1. All
quantitative analysis data used in this work were shown in Table 2
(Gong et al., 2016). In details, the organic components (such as
phenol, pyrimidine and naphtalene) in liquid products were
determined quantitatively by gas chromatograph equipped with a
KB-Wax capillary column and a ame ionization detector after the
samples were extracted by dichloromethane. The amount of each
compound in the sample was obtained by using linear calibrations
prepared using standards of known organic matter concentrations.
The concentration of inorganic component (NH3) in liquid products
was analyzed based on Water quality e Determination of ammonia
nitrogen e Nessler's reagent spectrophotometry (Standard Method
HJ 535-2009, China). Besides, the CO2 concentration was measured
by another gas chromatograph equipped with a thermal conduc-
tivity detector and a supelco 60/80 mesh Carboxen 1000 packed
column, and helium served as an internal standard for gas product
analysis which was pressurized to 0.2 MPa in a SCWO reactor
before experiment. All experiments were performed in isothermal
batch coiled tube reactors in preheated sandbath.
A variety of organics (phenol, pyrimidine, naphtalene, benzene,
toluene, butyric acid, etc) were detected indicating oxidative
degradation of quinazoline involves complicated chemical pro-
cesses. The model provided an insight into the reactions involving

Fig. 1. Simplied reaction network of oxidative degradation of quinazoline in SCW.

58 Y. Gong et al. / Water Research 110 (2017) 56e65

Table 2
Data required to solve ODEs.

T/K r/kg$m3 t/s [CPyr] [CBA] [CNap] [CPhe] [CBip] [CQu] [CCO2] [CNH3]

mmol$L1

673 166.3 0 0.00E00 0.00E00 0.00E00 0.00E00 0.00E00 5.56E00 0.00E00 0.00E00
60 1.29E00 2.79E-01 1.70E-01 7.45E-01 8.60E-02 1.25E00 1.20E01 4.82E00
120 2.25E00 5.86E-01 2.64E-01 8.17E-01 9.29E-02 1.06E00 1.33E01 5.67E00
180 2.29E00 8.21E-01 3.03E-01 6.82E-01 1.11E-01 5.72E-01 2.25E01 6.60E00
240 2.54E00 9.21E-01 2.77E-01 5.17E-01 8.41E-02 2.32E-01 2.54E01 7.34E00
300 2.29E00 1.00E00 2.09E-01 3.77E-01 7.41E-02 1.04E-01 3.19E01 7.40E00
360 2.10E00 8.09E-01 2.08E-01 2.73E-01 7.54E-02 8.13E-02 3.07E01 7.11E00
420 2.20E00 7.49E-01 1.85E-01 1.99E-01 5.32E-02 4.02E-02 3.12E01 7.81E00
723 109.0 0 0.00E00 0.00E00 0.00E00 0.00E00 0.00E00 3.64E00 0.00E00 0.00E00
60 1.71E00 4.00E-01 4.94E-01 4.81E-01 7.30E-02 7.21E-01 1.57E01 4.57E00
120 1.50E00 6.19E-01 4.80E-01 2.66E-01 6.78E-02 1.51E-01 1.98E01 5.04E00
180 1.35E00 4.50E-01 4.07E-01 1.09E-01 3.22E-02 2.02E-02 2.10E01 6.25E00
240 1.27E00 2.47E-01 3.38E-01 8.63E-02 1.29E-02 2.10E-02 2.53E01 5.74E00
300 7.71E-01 2.24E-01 2.79E-01 2.65E-02 1.06E-02 1.10E-02 2.51E01 6.26E00
360 7.10E-01 1.56E-01 2.31E-01 1.13E-02 8.36E-03 1.50E-03 3.01E01 6.17E00
420 5.79E-01 1.07E-01 1.90E-01 1.29E-02 4.20E-03 3.58E-05 2.85E01 6.88E00
773 89.9 0 0.00E00 0.00E00 0.00E00 0.00E00 0.00E00 3.01E00 0.00E00 0.00E00
60 7.92E-01 5.28E-01 2.27E-01 1.51E-01 4.89E-02 1.33E-01 1.76E01 5.16E00
120 4.02E-01 2.14E-01 8.54E-02 6.09E-02 6.07E-03 5.26E-03 1.87E01 6.59E00
180 6.48E-02 1.01E-01 2.89E-02 2.10E-02 2.06E-03 1.22E-03 2.46E01 5.34E00
240 2.99E-02 3.79E-02 9.67E-03 4.34E-03 2.51E-04 1.92E-04 2.56E01 6.56E00
300 5.13E-02 1.55E-02 3.23E-03 2.07E-03 3.12E-05 1.10E-04 2.65E01 4.86E00
360 8.56E-03 8.73E-03 1.08E-03 6.51E-04 0.00E00 0.00E00 2.76E01 5.06E00
420 2.76E-03 5.60E-04 3.60E-04 5.16E-04 0.00E00 0.00E00 2.64E01 5.11E00
823 78.6 0 0.00E00 0.00E00 0.00E00 0.00E00 0.00E00 2.63E00 0.00E00 0.00E00
60 2.68E-01 1.27E-01 4.41E-02 2.28E-02 1.82E-03 1.99E-02 1.93E01 4.92E00
120 3.91E-02 1.63E-02 2.33E-02 9.48E-03 6.46E-04 1.51E-03 2.13E01 4.89E00
180 1.22E-02 3.03E-03 1.22E-03 4.86E-03 1.91E-04 1.14E-04 2.25E01 4.31E00
240 2.45E-03 1.55E-04 6.35E-04 2.53E-04 0.00E00 8.63E-05 2.24E01 4.37E00
300 2.77E-04 8.07E-05 3.31E-04 1.32E-04 1.51E-05 0.00E00 2.36E01 3.36E00
360 3.13E-04 4.20E-05 1.73E-04 0.00E00 4.23E-05 0.00E00 2.45E01 3.55E00
420 3.54E-04 0.00E00 0.00E00 0.00E00 0.00E00 0.00E00 2.44E01 2.64E00
873 70.8 0 0.00E00 0.00E00 0.00E00 0.00E00 0.00E00 2.37E00 0.00E00 0.00E00
60 2.63E-02 6.96E-03 8.21E-03 5.54E-03 2.61E-03 4.30E-02 2.10E01 3.95E00
120 2.14E-03 3.10E-03 4.15E-03 2.57E-03 2.01E-03 2.55E-03 2.16E01 2.42E00
180 2.70E-04 4.70E-03 5.52E-03 4.11E-03 2.34E-03 8.11E-03 2.26E01 1.85E00
240 7.00E-05 2.10E-03 2.28E-03 2.20E-03 1.20E-03 4.12E-03 2.36E01 1.52E00
300 0.00E00 1.60E-03 2.00E-03 0.00E00 1.70E-03 2.08E-03 2.16E01 1.80E00
360 0.00E00 1.42E-03 1.05E-03 0.00E00 0.00E00 0.00E00 2.22E01 8.60E-01
420 0.00E00 7.51E-04 2.52E-03 0.00E00 1.15E-03 1.31E-03 2.32E01 1.17E00

these liquid and gaseous species quantitatively identied. in the column we used, therefore benzene was ignored in the re-
Following, we dened and classied the reactions involved in this action network.
simplied model.
2) Polymerization reactions
1) Alternative ring-opening reaction of quinazoline

k1
C8 H6 N2 Quinazoline 4:5O2 !C4 H4 N2 Pyrimidine 2C8 H6 N2 Quinazoline 4O2
k3
4CO2 H2 O (1) 4H2 O!C10 H8 Naphthalene 6CO2 4NH3 (3)

k2
C8 H6 N2 Quinazoline O2 3H2 O!C6 H6 OPhenol
2CO2 2NH3
The oxidation of quinazoline was triggered by two alternative
ring-opening reactions. The rst ring-opening reaction, as Eq. (1)
shows, generated pyrimidine via oxidation without contribution
of H2O. The second pathway, in Eq. (2), yielded phenol as ring-
opening intermediate by attack of H2O and O2 with removal of 2
molecular of NH3. Webley et al., (1991) showed that, as the inter-
mediate product in degradation of nitrogenous organic compound,
NH3 was stable in SCWO reaction. We found benzene as an inter-
mediate product from GC-MS test in our previous work on SCWO of
Quinazoline (Gong et al., 2016), However, we cannot quantitatively
analyze it in GC-FID, probably due to benzene cannot be separated
2C8 H6 N2 Quinazoline 1:5O2
(2)
k4
5H2 O!C12 H10 Biphenyl 4CO2 4NH3 (4)
The quantitative analysis results in Table 2 suggested that some
intermediates with higher molecular weight, such as biphenyl and
naphthalene, existed in the liquid products instead of benzene se-
ries. Biphenyl and naphthalene probably were polymerization
products from benzene and phenyl free radical (Comandini et al.,
2012; Shukla et al., 2008). Given the results from literatures, we
assumed that they were generated from quinazoline directly, as
Eqs. (3) and (4) shown.
3) Oxidation reactions of intermediates
 Y. Gong et al. / Water Research 110 (2017) 56e65 59

 
k5 d CBip    
C12 H10 Biphenyl H2 O 0:5O2 !2C6 H6 OPhenol (5) k4 CQu  k5 CBip (16)
dt

k6
C6 H6 OPhenol 2O2 H2 O!C4 H8 O2 n  Butyric acid dCBA 
k6 CPhe   k10 CBA  (17)
dt
2CO2
(6) dCCO2   
4k1 2k2 3k3 2k4 CQu 2k6 6k9 CPhe 
dt
   
k7 4k7 CPyr 4k8 CNap 4k10 CBA 
C4 H4 N2 Pyrimidine H2 O 3:5O2 !4CO2 2NH3 (7)
(18)
k8
C10 H8 Naphthalene 5O2 !C6 H6 OPhenol 4CO2 dCNH3     
2k2 4k3 4k4 CQu 2k7 CPyr  k11 CNH3 
H2 O (8) dt
(19)

k9
C6 H6 OPhenol 6O2 !6CO2 3H2 O (9)
k10
C4 H8 O2 n  Butyric acid 5O2 !4CO2 4H2 O (10)
Once these intermediates yielded, they could undergo a variety
of oxidation reactions with or without participation of H2O and led
to the generation of lower molecular weight compounds (CO2 and
NH3). Anitescu and Tavlarides, (2005) demonstrated phenol was
one of intermediate products from SCWO degradation of biphenyl.
So we assumed that phenol was an intermediate product of
oxidation reaction of biphenyl and naphtalene. In addition, we
deduced that n-butyric acid was an intermediate product from the
degradation of phenol based on the quantitative analysis data
shown in Table 2.
4) Oxidation reaction of NH3
dCN2 
0:5k11 CNH3  (20)
dt
In the equations above, [CQu], [CPyr], [CPhe], [CNap], [CBip], [CBA],
[CCO2], [CNH3] and [CN2] were concentrations (mmol$L1) of qui-
nazoline, pyrimidine, phenol, naphthalene, biphenyl, n-butyric
acid, CO2, NH3 and N2 in the SCWO reactor, respectively.
Oxidation coefcient, OC, is dened as:

O2 add
OC  (21)
O2 need
where, [O2]add is the oxygen (mg) formed from the decomposition
of H2O2. [O2]need is the stoichiometric oxygen (mg) needed to
completely oxidize the feed to carbon dioxide, nitrogen and water.
In this experiment, the oxidation coefcient was controlled to the
value of 2.0.

k11 3. Results and discussion

NH3 0:75O2 !0:5N2 1:5H2 O (11)
There was a little NO 1 
2 (<1.2 mg L ) and no NO3 detected from 3.1. Parameter estimation
liquid products, which indicates NH3 was ultimately oxidized to N2.
On the basis of the mass action law, we described every reaction The Berkeley Madonna software developed by Berkeley Uni-
pathway in differential dynamic model, as Eqs. (12)e(20) shown. versity was applied to solve ordinary differential equations (ODEs)
We assumed that all reactions are irreversible and rst-order in above-mentioned (Macey et al., 2009). The data required to solve
each reactant. Since water and oxygen were present in excess to the ODEs are shown in Table 2, in which OC 2 and reaction time vary
stoichiometric amount needed in the reaction system, we did not from 60 to 420 s.
include them in the rate equations. Then, we obtained corre- After determining optimized values for the rate constants at
sponding rate constants for the individual reactions by tting the each temperature, the Arrhenius parameters were determined by
experimental concentrations to these differential equations, which using linear regression. Table 3 lists the rate constants, pre-
were applied to this reaction network and the constant-volume exponential factors and activation energy data under different
batch reactors used in the experiments. testing temperatures. The value of k1 was always higher than that of
  k2, k3 and k4 in all testing temperature conditions, suggesting that
d CQu   the alternative ring-opening of quinazoline for pyrimidine yielding
k1 k2 k3 k4 CQu (12)
dt was the dominant pathway. When the temperature reached 823 K,
k7 increased rapidly until close to k1. In this case, the ring-opening
  reaction of pyrimidine was accelerated obviously. High values of k5
d CPyr    
k1 CQu  k7 CPyr (13) and k6 at 873 K indicate high oxidation rates of biphenyl to phenol
dt
and further to n-butyric acid at the participation of water. By
comparing k9 and k10, without participation of water, oxidative
dCPhe        degradation of phenol was relatively slower than that of n-butyric
k2 CQu 2k5 CBip k8 CNap  k6 k9 CPhe 
dt acid due to its high molecular structural stability, in accordance
(14) with the previous literature (Weiss-Hortala et al., 2010).
As demonstrated, Ea for reaction 1 and 2 were relatively lower
  than the others and the values were 61.15 7.87 kJ mol1 and
d CNap    
k3 CQu  k8 CNap (15) 81.62 19.75 kJ mol1, respectively. It indicates that ring-opening
dt reaction of quinazoline was relatively easy. However, activation
energy for reaction 7 and 9 were high, illustrating that pyrimidine
60 Y. Gong et al. / Water Research 110 (2017) 56e65

Table 3
Chemical reaction rate constant and kinetic parameters.

Reaction rate k/s1 Temperature T/K lnA Activation energy Ea/kJ$mol1 R2

673 723 773 823 873

k1 6.44E-03 1.87E-02 2.59E-02 7.13E-02 7.29E-02 6.01 1.24 61.15 7.87 0.937
k2 4.12E-03 9.05E-03 1.64E-02 1.34E-01 6.81E-02 9.01 3.11 81.62 19.75 0.801
k3 8.44E-04 2.57E-03 8.21E-03 4.46E-02 4.87E-02 12.10 1.80 107.64 11.41 0.957
k4 3.34E-04 1.17E-03 3.55E-03 2.09E-02 1.06E-02 9.51 3.02 97.30 19.14 0.861
k5 2.77E-03 1.14E-02 3.79E-02 2.44E-01 2.29E-01 15.08 2.16 117.17 13.68 0.948
k6 9.49E-03 2.54E-02 6.50E-02 4.71E-01 3.13E-01 12.70 2.69 97.50 17.05 0.888
k7 9.57E-04 3.41E-03 1.60E-02 1.04E-02 7.23E-02 10.2 2.88 95.52 18.3 0.868
k8 1.84E-03 7.69E-03 1.93E-02 6.33E-03 1.19E-01 7.92 4.93 78.90 31.28 0.573
k9 1.93E-04 7.28E-04 1.74E-03 1.24E-02 1.48E-02 11.55 1.93 112.80 12.25 0.954
k10 4.56E-03 1.33E-02 3.76E-02 5.60E-02 1.88E-01 10.10 1.05 86.69 6.64 0.977
k11 1.59E-05 1.54E-04 5.46E-04 2.10E-03 8.60E-03 15.78 0.83 149.23 5.27 0.995

and phenol were difcult to be decomposed. Given the minimum
values of rate constants and the highest Ea value observed for re-
action 11, the degradation of NH3 was suggested to be the most
difcult pathway in the network, which was consistent with pre-
vious literatures (Al-Duri et al., 2008; Bermejo et al., 2008; Segond
et al., 2002).
3.2. Model validation
This section compares the model calculation results with the
experimental data to determine the kinetic parameters. Experi-
mental concentrations of reactants, intermediates and nal prod-
ucts presented above were utilized to validate the model. Fig. 2
provides a detailed assessment by showing the experimental
temporal variations of the concentrations of the major liquid and
gaseous products ([CQu], [CPyr], [CPhe], [CNH3], [CBip], [CNap], [CBA],
[CCO2]) along with the model calculations at testing temperatures.
As expected, residual quinazoline concentration decreased very fast
at initial stage of the reaction. Except for 673 K, nearly all the qui-
nazoline was completely consumed within 120 s. As the conse-
quences, the intermediates yielded from the decomposition of
quinazoline, as shown in Fig. 2 (b) e (g), were mainly formed in this
period and further decomposed as the time prolonged. The
oxidation of NH3 can only be observed above 773 K, whereas, at 723
and 673 K, [CNH3] increased with the time increasing giving a
maximum concentration of 6.88 and 7.81 mmol L1 at the longest
time investigated, respectively. [CCO2] reached maximum values in
the initial minutes and appeared to approach constant values in gas
phase, suggesting a possible thermodynamic equilibrium at tem-
perature higher than 773 K. As can be seen, in general, the model
identied the main trends for each compound and matched the
experimental data reasonably well in most cases. From graph (a),
the largest difference between experimental data and model pre-
dictions is at the shortest batch holding time, 60 s, and lowest
temperature, 673 K. This difference may be a consequence of both
model inadequacy and experimental error caused by the excessive
high experimental [CQu] collected at this point out of calibration
range for standard quinazoline concentrations. On account of high
reaction rates in SCWO condition, the intermediates, as shown in
Fig. 2 (b) e (g), generated rapidly and reached maximum values in
the initial stage of reaction, then further consumed at longer times
at high treating temperature. And the higher temperature, the
earlier maximum values occurred. When the temperature was
higher than 723 K, we didn't experimentally catch these maximum
values since most of them occurred earlier than our rst testing
point (<60 s). As reaction time prolonged, the experimental data for
[CNH3] is higher than model calculation results at 873 K, whereas, at
773 K, its experimental data is lower than model predictions.
After having shown that the model accurately captures all the
experimental data for each major product based on the parameter
values in Table 3, we now use the model to calculate quantities that
are not accessible experimentally. Fig. 3 shows the temporal vari-
ation of the concentrations of N2 calculated by the model for SCWO
of quinazoline at testing temperatures. From the oxidation reaction
produced almost no N2 at 673 K. The dependences of N2 yields on
times show nearly linear relationship at 673, 723, 773 and 823 K. N2
yield does not provide a linear trend at 873 K, but increases rapidly
in the rst half of the process, but further starts to level off at longer
times and reaches a maximum value of 2.98 mmol L1 at the end of
reaction.
Fig. 4 demonstrates the nitrogen balance (NB) of quinazoline
conversion in SCWO reaction. Here, NB is the sum of N atoms in
liquid (wN,L) and gaseous (wN,G) products derived from N atoms in
quinazoline feedstock. The former is total nitrogen in NH3, NO 3 and
NO 2 obtained from exprimental analysis, and the latter is nitrogen
in N2 calculated by the model. The results provide an overall trends
that, at testing temperatures, wN,L decreases but wN,G increases as
reaction time prolonged. This could be as a result of nitrogen
migration from liquid phase products to gaseous phase products at
longer times. NB values in the gure are in the range of
81.80e100.96%, giving a good accurate nitrogen balance of the
conversion process. The deviation from 100% NB can be attributable
to the existence of nitrogen containing intermediate compounds in
the liquid products.
3.3. Model prediction
Having shown that the model faithfully correlates experimental
data for the concentrations of major intermediate products, in this
section, we tested the predictive capability of the model. We used
exprimental results of [CNH3] and [CCO2] which are not used for
parameter estimation at 773 and 873 K by varying initial quina-
zoline feed concentrations to compare the corresponding results
calculated by the model. It reveals how the model predicts the
unknown outcomes as consequences of changing reaction vari-
ables. As demonstrated in Fig. 5 (a), at 773 K, overall experimental
NH3 concentrations are lower than predictions from model calcu-
lation. And the deviations become higher as initial quinazoline
concentration increases. At 873 K, by contrast, overall experimental
NH3 concentrations are slightly higher than the prediction values.
As for CO2, as shown in Fig. 5 (b), at both temperature and initial
quinazoline concentration ranges, the model predictions match
these experimental results satisfactorily.
3.4. Reaction rate analysis
In this section, we analyzed the variation trends in reaction rates
at different times in order to know how the reaction pathways
 Y. Gong et al. / Water Research 110 (2017) 56e65 61

Fig. 2. Comparison between experimental and model calculation results (a:[CQu], b:[CPyr], c:[CPhe], d:[CNH3], e:[CBip], f:[CNap], g:[CBA], h:[CCO2]) at 673, 723, 773, 823 and 873 K.
(scattered points: experiment data; solid lines: model predictions).
62 Y. Gong et al. / Water Research 110 (2017) 56e65
Fig. 3. Temporal variations of [CN2] predicted by the model at different temperatures.
Fig. 4. Nitrogen balance in SCWO of quinazoline at 120, 180 and 240 s under different
temperatures.
inuenced reactions of compounds in the process. Fig. 6 shows
reaction rates in the important pathways of quinazoline, phenol,
NH3 and CO2 at different reaction times, in which positive values
represent production rates whereas negative values mean decom-
position rates. By comparing the rates of quinazoline decomposing
Fig. 5. Comparison between model calculated value and experimental value for [CNH3] (a) and [CCO2] (b) at different initial [CQu].
from reaction 1 to 4, as clearly observed in Fig. 6 (a), all the re-
actions reach thermodynamic equilibrium within 100 s and their
contributions follow the order: reaction 1 > reaction 2 > reaction
3 > reaction 4. Fig. 6 (b) shows that reaction 2 is the most primary
reaction for the generation of phenol. The maximal rate of reaction
2 is found at the starting of the reaction, and rapidly decreases and
approaches zero when the equilibrium is reached. Once phenol as
an intermediate is formed, it decomposes immediately through
other pathways in which reaction 6 is the fastest one. The decom-
position rate for phenol decreases sharply and reaches a minimum
value of 0.0255 mmol L1$s1 at 22 s, and then increases at
prolonging reaction time as the phenol concentration reduces. By
contrast, reaction 2 and reaction 5 have little effects on the con-
version of phenol. Fig. 6 (c) shows that reactions 2 and 3 are the
most primary pathways for yielding NH3 in the initial stage of re-
action and both rates of them demonstrate basically the same
trends. Reaction 7 provides a positive increasing in NH3 formation
and the rate for it reaches a maximum value of
0.0276 mmol L1$s1 at 32 s, and further decreases as time pro-
longed. As the only reaction for NH3 conversion, however, as ex-
pected, reaction 11 does not give an obvious impact on the reaction
process, compared with other reactions. Reaction 1 provides a great
contribution for CO2 formation at the starting of reaction. All re-
actions 1, 2 and 3 show sharp decreasing trendencies in rate as time
elapses and trend to at within 100 s. The rates of CO2 conversion
from intermediates rstly increases and then decreases before
reaching the termination (<300 s).
3.5. Sensitivity analysis
In this section, sensitivity coefcient (S) is utilized to examine
the relative importance of different reaction pathways in SCWO of
quinazoline. It reveals how the model predictions (Ci, species
concentrations) change when a single model parameter (rate
constants (kj) in this case) is slightly perturbed (Resende and
Savage, 2010). The normalized S can be dened as in Eq. (22) as
reported in literature elsewhere (Guan et al., 2012). The larger ab-
solute value of S means more sensitive of concentration to the value
of the particular rate constant. We calculated the sensitivity coef-
cient (S) by Berkeley Madonna software.
DCi =Ci
S  (22)
0:001kj kj
Fig. 7 shows the variation tendencies of sensitivity coefcients
for generation of phenol, pyrimidine, NH3 and CO2 by giving a slight
change in rate constants in the time range from 0 to 300 s. Nearly all
S values appear to approach constant values in longer time
 Y. Gong et al. / Water Research 110 (2017) 56e65
Fig. 6. Reaction rates different paths for quinazoline (a), phenol (b), NH3 (c) and CO2 (d) at 773 K.
(>300 s), suggesting a possible reaction equilibrium, which is
excluded in this gure.
As shown in Fig. 7 (a), the concentration of phenol shows strong
negative sensitivity by giving a silght change in k6 at the initial
stage of reaction. This illustrates that the consumption rate of
phenol from reaction 6 increases sharply by bringing a small
perturbation on k6. As time increases, so does it for k1, but only
slightly, because alternative ring-opening reaction of quinazoline
from reaction 1 indirectly inuences the concentration of quina-
zoline as reactant for reaction 2. A strong positive sensitivity for
[Cphe] generation from reaction 2 is found at the beginning of re-
action and further decreases to 0.516 as time increases. S values
for [Cphe] generation inuenced by reaction 5 and reaction 4 do not
change obviously and uctuate between 0.463 0.233. But it from
naphthalene oxidation slightly increases and reaches its maximum
of 0.139 and further shows a linear decreasing trend at longer batch
holding time.
Sensitivity of pyrimidine production from reaction 1 has the
highest value of positive value of 0.989 at starting point of reaction
and then decreases to 0.320 at 155 s, as shown in Fig. 7(b), then
appears to approach constant values suggesting that these sensi-
tivities change very little as the reactions approach their thermo-
dynamic equilibrium. Reaction 1 plays a key role for the generation
of pyrimindine. In the initial stage of reaction, a tiny increment in k1
leads to a signicant reducing in pyrimidine concentration. As
competitive pathways, corresponding S values for reaction 2 and 3
are negative and demonstrate similar trends when giving a tiny
perturbation on k2 and k3, but the former is signicant lower than
the later. As expected, as the only direct oxidation pathway for
63
pyrimidine, S for reaction 7 displays a negative linear increasing
tendency with time increasing.
For NH3 and CO2, overall sensitivities vary in a relative narrow
range as shown in Fig. 7 (c) and (d). Under inuence of tiny per-
turbations on k1, k4 and k7, S values for NH3 concentrations change
in a range of 0.153e0.175. S value for reaction 7 increases with the
time rstly and then decreases as time prolonged, while that for
reaction 1 presents an obviously opposite trend. It is understand-
able that reaction 1 and reaction 7 separately dominate the for-
mation and decomposition of pyrimindine which directly affects
the formation of NH3. By adding a small increment to k2, k3, k4 and
k11, the corresponding S values for these reactions demonstrate
monotone decreasing trend in the modeling time range. As the only
decomposing reaction of NH3, k11 doesn't show an apparent
sensitivity (particularly in the initial phase of reaction). This re-
fractory characteristic of NH3 in SCW was experimentally
conrmed by the previous literatures (Al-Duri et al., 2008; Bermejo
et al., 2008; Segond et al., 2002). As shown in Fig. 7 (d), except for k1,
all sensitivity values for CO2 generation change in the range
of 0.036e0.191. The highest S value of k1 indicates greatest
contribution for CO2 yield from reaction 1 can be observed at the
starting point of reaction. This sensitivity further rapidly decreases
as the reaction progresses.
4. Conclusions
Based on qualitative and quantitative analysis of intermediate
products, we developed the reaction network and quantitative ki-
netic model for SCWO of quinazoline with 11 reaction pathways
64 Y. Gong et al. / Water Research 110 (2017) 56e65
Fig. 7. Sensitivity coefcient analysis of reaction rates for [CPhe](a), [CPyr](b), [CNH3](c), [CCO2](d) at 773 K.
involved, which had not been documented previously. The model
ts experimental concentration changes of major compounds rea-
sonablely well in the process. Reaction rate analysis shows that
reactions 1 to 4 reach their thermodynamic equilibrium within
100 s and their contributions to quinazoline decomposition follow
the order: reaction 1 > reaction 2 > reaction 3 > reaction 4. The
model results suggest the alternative ring-opening of quinazoline
for pyrimidine yielding (reaction 1) is the dominant pathway, and
the ring-opening reaction of pyrimidine (reaction 7) is accelerated
obviously when the temperature is above 823 K. Reaction 2 is the
dominate reaction for the generation of phenol and NH3. Degra-
dation of NH3 was quite difcult with the low value of conversion
rate constant and the high Ea value. As conrmed by sensitivity
analysis results, reaction 1 plays a key role for the generation of
pyrimidine. Nitrogen content in liquid products decreases whereas
that in gaseous phase increases as reaction time prolonged. The
nitrogen predicted by the model in gaseous phase combined with
experimental nitrogen in liquid products gives an accurate nitrogen
balance, which is in the range of 81.80e100.96%.
Acknowledgement
The work was supported by the National Natural Science
Foundation of China (51406146, 21576219), the Jiangsu Province
Natural Science Foundation of China (BK20151040, BK20140406)
and the Jiangsu Province Post Doctoral Fund of China (1501124B).
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