Regeneration of Phenol-Saturated Activated

Carbon by Supercritical Water: Effect of H2O2

and Alkali Metal Catalysts
Yuechao Zhang 1; Dian Yang 2; Ping Ning 3; Yingjie Li 4; Senlin Tian 5; and Junjie Gu 6
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Abstract: The aim of this work was to study the supercritical water (SCW) regeneration of phenol-saturated activated carbon (AC) with the
H2 O2 and alkali metal catalyst (Na2 CO3 , NaOH, K2 CO3 , and KOH) addition. The results showed that SCW could effectively regenerate AC in
the 385–425°C range without any additives, but large and small amounts of phenol and dibenzofuran were present in the liquid phase, re-
spectively, which would result in secondary pollution. The H2 O2 addition enhanced the decomposition of phenol and increased the CO2 yield.
With the addition of H2 O2 and an alkali metal catalyst, SCW further decreased the phenol and dibenzofuran yields but increased the H2 and CO2
yields. Active component-supported (Cu-Ce-O, Fe-Ce-O, Ni-Zn-Pt, and Ni-Co-Pt) AC adsorbents might have decomposed some of the phenol
during the phenol adsorption process, which resulted in relatively small amounts of phenol adsorbed on the AC and a decrease of the liquid
(phenol and dibenzofuran) and gaseous (H2 and CO2 ) yields. SCW regeneration increased the surface area and pore volume of the AC and raised
the adsorption capacity. The H2 O2 and alkali metal catalyst addition can be used to achieve the rapid, efficient, and harmless regeneration of AC
in SCW at a lower temperature (385°C). DOI: 10.1061/(ASCE)EE.1943-7870.0001601. © 2019 American Society of Civil Engineers.
Author keywords: Supercritical water regeneration; Phenol; Activated carbon; H2 O2 ; Alkali metal catalysts.

Introduction phenol from wastewater, including microbial degradation (Juang

Phenol and its derivatives are very important raw materials or in-
termediates for various manufacturing processes, such as in the
chemical, pharmaceutical, petroleum, coal gasification, papermak-
ing, wood, rubber, dye, insecticide, explosive, and pesticide indus-
tries (Cheng et al. 2016; Podkościelny and Nieszporek 2011; Zhang
et al. 2012). Excessive exposure to phenol and its derivatives is
toxic to humans and aquatic life at low concentrations. Phenols
in such wastewaters are considered priority pollutants by the United
States Environmental Protection Agency (USEPA) (Singh et al.
2008; Radhika and Palanivelu 2006) and the Chinese integrated
wastewater discharge standard (GB 8978-1996) (Yin et al. 2010).
Consequently, various technologies have been developed to remove
1
Ph.D. Student, Faculty of Environmental Science and Engineering,
Kunming Univ. of Science and Technology, Wenchang Rd. 68, Kunming
650093, PR China. Email: zycnh1314@163.com
2
Postgraduate Student, Faculty of Environmental Science and Engineer-
ing, Kunming Univ. of Science and Technology, Wenchang Rd. 68,
Kunming 650093, PR China. Email: 2014311797yd@gmail.com
3
Professor, Faculty of Environmental Science and Engineering,
Kunming Univ. of Science and Technology, Wenchang Rd. 68, Kunming
650093, PR China. Email: ningping1958@163.com
4
Lecturer, Faculty of Environmental Science and Engineering,
Kunming Univ. of Science and Technology, Wenchang Rd. 68, Kunming
650093, PR China (corresponding author). Email: yjli@kmust.edu.cn
5
Professor, Faculty of Environmental Science and Engineering,
Kunming Univ. of Science and Technology, Wenchang Rd. 68, Kunming
650093, PR China. Email: tiansenlin@outlook.com
6
Professor, Faculty of Environmental Science and Engineering,
Kunming Univ. of Science and Technology, Wenchang Rd. 68, Kunming
650093, PR China. Email: junjie_gu@rogers.com
Note. This manuscript was submitted on January 3, 2019; approved on
March 29, 2019; published online on September 24, 2019. Discussion per-
iod open until February 24, 2020; separate discussions must be submitted
for individual papers. This paper is part of the Journal of Environmental
Engineering, © ASCE, ISSN 0733-9372.
and Wu 2007), electrochemical oxidation (Yavuz and Koparal
2006), photochemical oxidation (Zhou et al. 2011), ultrasonic deg-
radation (Kubo et al. 2007), enzymatic polymerization (Li et al.
2010), membrane separation (Das et al. 2008), solvent extraction
(Yang et al. 2006), chemical oxidation (Kang et al. 2002), and ad-
sorption (Banat et al. 2000; Lin et al. 2009; Przepiórski 2006; Yang
et al. 2014; Gokce and Aktas 2014; Mangrulkar et al. 2008). In this
context, as an excellent adsorbent with a large surface area, well-
developed pore structure, and tunable surface chemistry (Yang et al.
2014; Gokce and Aktas 2014), activated carbon (AC) is effective
and widely used for the removal of phenols (Przepiórski 2006;
Yang et al. 2014; Gokce and Aktas 2014).
In spite of the widespread use of AC as a cheap and efficient
adsorbent, efficient regeneration of AC saturated with phenol or
other organic pollutants is a key issue that must be solved. Recov-
ering the original adsorption capacity of AC adsorbents is the major
objective of regeneration. However, if not properly treated, these
adsorbents, which were exhausted with dangerous pollutants,
may result in secondary pollution. Accordingly, there have been
many studies on the regeneration of AC exhausted with pollutants.
This regeneration process mainly involves the following two tech-
nical routes. The first is the desorption of adsorbed pollutants from
the AC surface, but there are no reactions with AC. The second is
the degradation of adsorbed pollutants on the AC such that the deg-
radation reaction is able to completely mineralize the pollutants.
There are several well-established methods for the regeneration
of AC that can be categorized as (1) thermal and gas regenerations
(Álvarez et al. 2004); (2) chemical oxidation regenerations (Okawa
et al. 2007); (3) biological regeneration (Dewalle and Chian 1977);
(4) electrochemical regeneration (Wang and Balasubramanian
2009); (5) supercritical fluid regeneration (Tan and Liou 1989;
Madras et al. 1993; Charinpanitkul and Tanthapanichakoon 2011;
Salvador et al. 2013); and (6) other methods, including microwave
(Liu et al. 2004), ultrasound (Lim and Okada 2005), and photo-
chemical treatments (Muranaka et al. 2010).

© ASCE 04019083-1 J. Environ. Eng.

J. Environ. Eng., 2019, 145(12): 04019083

 As the regenerated by-products in the regeneration process can
lead to secondary pollution, more focus on the elimination of the
adsorbed pollutants and by-products of the regeneration process is
needed. Presently, supercritical fluid regeneration has attracted much
attention for regenerating adsorbents (Tan and Liou 1989; Madras
et al. 1993; Charinpanitkul and Tanthapanichakoon 2011; Salvador
et al. 2013). Supercritical CO2 can dissolve and extract some organic
compounds and therefore has been widely used in this field (Tan and
Liou 1989; Madras et al. 1993). Supercritical CO2 has been em-
ployed as an effective method for regenerating AC exhausted with
volatile organic compounds, but it is insufficient for complete regen-
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ratio of Ni and Co was 4∶3. The Pt loading on the AC was fixed at a
nominal 1% by weight. Appropriate amounts of metallic precursors
were dissolved in ultrapure water, after which AC (20–40 mesh)
was added to the solution. After the excess water was evaporated
at 60°C, the slurry was dried in air at 100°C for 12 h and calcined in
N2 at 400°C for 3 h (Cu-Ce-O/AC, Fe-Ce-O/AC) or in H2 at 300°C
for 2 h and then at 400°C for 2 h (Ni-Co-Pt/AC and Ni-Zn-Pt/AC).
Supercritical Water Regeneration Processes
Each adsorbent (0.1 g) was suspended in contaminated water

eration of some saturated AC adsorbents, like phenol adsorption on
the AC with a strong interaction (Humayun et al. 1998).
It is well recognized that supercritical water (SCW) would be
suitable for removing and decomposing organic pollutants in waste-
waters by SCW oxidation, gasification, and extraction at high tem-
peratures and pressures. Moreover, previous studies indicated that
SCW treatment could develop pore structures and increase the sur-
face area of the AC. SCW can be used for the rapid and efficient
regeneration of AC, but there have been few studies (Charinpanitkul
and Tanthapanichakoon 2011; Salvador et al. 2013) on the SCW
regeneration process of phenol or other organic pollutants. Further-
more, there have been few investigations on the degradation path-
ways of phenol adsorbed on AC during SCW regeneration.
This main purpose of the present work is to investigate regener-
ation efficiency of AC saturated with phenol using SCW with various
reaction temperatures, hydrogen peroxide contents, alkali salts, and
active components supported on AC. Hydrogen peroxide and alkali
salts (Na2 CO3 , NaOH, K2 CO3 , and KOH) were used as the oxidizer
and gasification catalysts, respectively. Furthermore, the effect of
SCW regeneration on the gaseous and liquid products with additives
(hydrogen peroxide and alkali salts) was also investigated.
(100 mL) to become saturated with phenol using a bath at 25°C
for 24 h. The phenol concentrations in contaminated water were
200; 400; 800; 1,200; 1,600; 2,000; 2,400; 2,800; and 3,200 mg=L,
respectively. Phenol-exhausted adsorbents were filtered and dried
for 12 h at 100°C before SCW experiments. Experimental solutions
were composed of the adsorbents, water, and reagents. All regen-
eration processes were accomplished by a sus 316 batch autoclave
reactor (inner volume ¼ 150 mL).
The quantitative adsorbents and experimental solution were
added to the autoclave reactor. The reactor was heated to the setting
temperature (regeneration temperature T f ) at a rate of 3.8°C=min
and maintained for the setting time (regeneration time tf ) with the
regeneration pressure Pf as described in our previous study (Zhang
et al. 2018). Residual solid samples, which were the adsorbents
after SCW regeneration processes, were washed, filtered, and dried
for 12 h at 100°C. The regeneration conditions are listed in Table 1.
The resulting adsorbent particles were isolated from the mixture
using a membrane filter, washed several times with ultrapure
water to remove residues, and dried at 100°C for 12 h in an oven.
The regeneration conditions are shown in Table 1.

Methods and Materials

Table 1. Summary of regeneration conditions
Materials Concentration T f Pf tf
Samples Solutions (%) (°C) (MPa) (min)
AC (coconut shell activated carbon, 20–40 mesh size) was purchased
from Tangshan Tianhe AC (Fengrun District, Tangshan City, Hebei AC-Oa — — — — —
Province, China). Analytical-grade phenol was obtained from AC-385°C Pure water — 385 23.0  0.2 20
AC-405°C Pure water — 405 23.0  0.2 20
Tianjin Zhiyuan Chemical Reagent (Dongli District, Tianjin City,
AC-425°C Pure water — 425 23.0  0.2 20
China). Analytical-grade CuðNO3 Þ2 · 3H2 O, FeðNO3 Þ3 · 9H2 O, AC-5% H2 O2 H2 O2 5b 425 23.0  0.2 20
ZnðNO3 Þ2 · 3H2 O, NiðNO3 Þ2 · 6H2 O, and H2 O2 were acquired AC-10% H2 O2 H2 O2 10b 425 23.0  0.2 20
from Tianjin Fengchuan Chemical Reagent (Dongli District, Tianjin AC-15% H2 O2 H2 O2 15b 425 23.0  0.2 20
City, China). Analytical-grade CeðNO3 Þ3 · 6H2 O and CoðNO3 Þ2 · AC-NaOH NaOH 5c 425 23.0  0.2 20
6H2 O were purchased from Shanghai Aladdin (Pudong District, AC-Na2 CO3 Na2 CO3 5c 425 23.0  0.2 20
Shanghai City, China). Analytical-grade H2 PtCl6 · 6H2 O was ob- AC-KOH KOH 5c 425 23.0  0.2 20
tained from Shanghai Siyu Chemical Technology (Jinshan District, AC-K2 CO3 K2 CO3 5c 425 23.0  0.2 20
Shanghai City, China). Ultrapure water was prepared in the labora- Cu-Ce-O — — — — —
tory using an ultrapure water production system (Sichuan Wo Te Cu-Ce-O H2 O2 10b 425 23.0  0.2 20
Fe-Ce-O — — — — —
Instruments Equipment, Qingyang District Industrial Development
Fe-Ce-O H2 O2 10b 425 23.0  0.2 20
Zone, Chengdu City, Sichuan, China). Ni-Zn-Pt — — — — —
Ni-Zn-Pt H2 O2 10b 425 23.0  0.2 20
Adsorbent Preparation Ni-Co-Pt — — — — —
Ni-Co-Pt H2 O2 10b 425 23.0  0.2 20
A series of different adsorbents were prepared by the coimpregna- SCW-treated ACd Pure water — 385 23.0  0.2 20
tion method using the above AC and metallic precursors (Cu, Fe, SW-treated ACe Pure water — 365 18.5  0.2 20
Zn, Ni, and Pt). The prepared carbon-based adsorbents are denoted a
The original activated carbon.
as Cu-Ce-O/AC, Fe-Ce-O/AC, Ni-Co-Pt/AC, and Ni-Zn-Pt/AC. b
H2 O2 and ultrapure water mass ratios.
In the Cu-Ce-O/AC and Fe-Ce-O/AC adsorbents, the CuO c
Alkali metal catalysts and activated carbon mass ratios.
(Fe2 O3 ) and CeO2 loadings on the AC were fixed at nominal values d
SCW-treated AC was that the original activated carbon without the
of 7.5 and 2.5% by weight, respectively. In the Ni-Co-Pt/AC and adsorption process was treated by supercritical water.
Ni-Zn-Pt/AC adsorbents, the Ni and Co loadings on the AC were e
SW-treated AC was that the original activated carbon without the
fixed at nominal values of 10% by weight, and the nominal mass adsorption process was treated by subcritical water.

© ASCE 04019083-2 J. Environ. Eng.

J. Environ. Eng., 2019, 145(12): 04019083

 Characterization of AC
The structural properties of the ACs were performed by N2
adsorption–desorption measurements at 77 K using a Micromerit-
ics ASAP 3020 surface area analyzer. The Brunauer–Emmett–
Teller (BET) surface area (SBET ) was calculated using the BET
method. The micropore and mesopore distributions were obtained
according to the Horvath–Kawazoe (H-K) and Barrett–Joyner–
Halenda (BJH) methods, respectively.
The powder X-ray diffraction patterns of the ACs were inves-
tigated by an Empyrean analytical diffractometer with Cu-Kα
radiation (k ¼ 1.54 Å) at 45 kV and 40 mA.
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The morphologies of the samples were observed by a tabletop
scanning electron microscope (Hitachi TM3030, Japan) with a
backscattered electron detector and an accelerating voltage of 15 kV.
Semiquantitative microanalysis performed by EDS was done by
using an EDAX detector attached to the scanning electron micro-
scope, and the collected data were processed through the EDAX
Genesis program.
The surface chemistry of samples was analyzed by X-ray
photoelectron spectroscopy (XPS). The analysis was carried out
on an XSAM-800 spectrometer (Kratos) with Al-Kα radiation
(1486.6 eV) under ultrahigh vacuum (UHV); the C1s peak
(284.8 eV) was used for calibration of the binding energies.
Sample Analysis
The gas phase was analyzed by a gas chromatograph (GC, Agilent,
7820A, TCD, helium carrier gas) using a stainless steel column
packed with Carboxen 1000 (Supelco) on 60–80 mesh. The liquid
phase was obtained after rinsing (10-mL dichloromethane), filter-
ing, and separating the liquid and solid fractions in the reactor.
The liquid phase was analyzed by gas chromatography/mass spec-
trometry (GC/MS, PE SQ 8T-680, Elite-5MS capillary column).
Results and Discussion
Effect of SCW on the Characteristics of AC
Previous studies demonstrated the obvious effect of SCW treatment
on the surface chemistry and physical structure of carbon materials
(Ashraf et al. 2013; Zhang et al. 2018); accordingly, it is important
to research the effect of the treatment on the surface characteristics
of the original AC before the regeneration study. As shown in Fig. 1,
the original activated carbon (AC-O), SCW-treated AC, and SW-
treated AC were characterized by BET analysis. The isotherms
Fig. 1. N2 adsorption–desorption isotherms of AC-O, SCW-treated
AC, and SW-treated AC.
© ASCE 04019083-3
J. Environ. Eng., 2019, 145(12): 04019083
Table 2. BET surface area and pore volume of AC-O, SCW-treated AC,
and SW-treated AC
BET surface Total pore Mass
Samples area (m2 =g) volume (cm3 =g) loss (%)
AC-O 765 0.346 —
SCW-treated AC 814 0.363 2.4
SW-treated AC 795 0.354 1.9
of the three samples present a sharp increase at very low relative
pressure (P=P0 < 0.1) indicating the existence of micropores con-
sistent with type I isotherms according to the IUPAC classification.
The isotherms show a type H4 hysteresis loop with the presence of
mesopores.
The main textural parameters and mass loss of the three samples
are listed in Table 2. The BET surface areas of AC-O, SCW-treated
AC, and SW-treated AC were 765, 814, and 795 m2 =g, while the total
pore volumes were 0.346, 0.363, and 0.354 cm3 =g, respectively. The
mass losses were less than 2.5% after the SCW and SW treatments.
The absence of CO in the gaseous products indicated that the SCW
treatment was unable to gasify the activated carbon at that tempera-
ture, which is in agreement with a previous study (Matsumura et al.
1997). Accordingly, a possible explanation for the increased BET sur-
face area and mass of SCW-treated AC is the removal of ash and min-
eral material contained in the AC because of a strong corrosive effect
of the SCW system on AC, resulting in flaking of the AC surface and
exposing pore structures with the formation of more micropores and
the increase of the surface areas and pore volumes (Zhang et al. 2018).
As also shown in Fig. 2, the surface of the AC treated with SCW was
seriously destroyed, which exposed well-developed porous structures
compared to the surface of AC-O without any treatment. The micro-
graphs revealed that the surface texture of coconut shell-activated
carbon (AC-O) contained some agglomerates attributed to the uni-
form cellulosic structure of the coconut shell (Charinpanitkul and
Tanthapanichakoon 2011). After SCW and SW treatment, the num-
ber of agglomerates significantly decreased. Moreover, the decrease
in the SCW was more obvious than that in SW. Further analysis
showed that SCW treatment was more beneficial for the development
of porosity, and SCW became completely miscible with organic com-
pounds like phenol and gases like oxygen (Portela et al. 2001). SCW
treatment can also increase the point of zero charge (pHPZC ) value of
the AC (Zhang et al. 2018), which is beneficial for the adsorption of
phenol that is acidic. Consequently, the SCW reaction environment is
especially suitable for the regeneration of AC.
Fig. 2. SEM images of AC-O, SCW-treated AC, and SW-treated AC.
J. Environ. Eng.
 Gaseous Products in SCW Regeneration Processes NaOH þ CO → HCOONa ð3Þ
The composition of the gaseous products, shown in Table 3, can
be found using a numerical proportion method. In addition, the HCOONa þ H2 O → NaHCO3 þ H2 ð4Þ
H2 produced from the AC after SCW regeneration at 405°C,
23.0  0.2 MPa, and 20 min was used as the standard value, 1.0. 2NaHCO3 → CO2 þ Na2 CO3 þ H2 O ð5Þ
There have been some studies on the oxidation and gasification of
phenol with H2 O2 (Matsumura et al. 2002), NaOH (KOH) (Li et al. H2 O þ CO → H2 þ CO2 ð6Þ
2015), and Na2 CO3 (K2 CO3 ) (Li et al. 2015; Xu et al. 2011) in
The catalysis of NaOH or Na2 CO3 resulted in the formation of
SCW reaction environments, which were beneficial for the decom-
formate salt, which could react with water to produce hydrogen. As
position and conversion of phenol. Furthermore, the presence of
shown in Table 3, the addition of NaOH, Na2 CO3 , KOH, and
AC could also improve the catalytic decomposition of phenol
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K2 CO3 significantly increased the gasification rate, and the H2

(Matsumura et al. 2002).
Generally, the gaseous products of phenol after catalytic SCW
gasification and oxidation are H2 , CO, CO2 , and CH4 (Li et al.
2015; Xu et al. 2011). As shown in Table 3, with increasing regen-
eration temperature (385°C, 405°C, and 425°C), a possible explan-
ation for the small increase of H2 , CO2 , and CH4 yields was that the
AC improved the catalytic gasification of phenol, but the gasifica-
tion efficiency was very low. In addition, there were no obvious
changes in the H2 , CO, and CH4 yields as the H2 O2 content
(5%, 10%, and 15%) increased, but the CO2 yield increased sig-
nificantly. This may have occurred because the C–C bonds of
the adsorbed phenol were broken into small molecular compounds
due to an oxidation reaction, and some of these compounds further
decomposed into H2 , CO, CO2 , and CH4 . However, an inappropri-
ate concentration of oxidant might promote the conversion of CO
and CH4 to CO2 or a reaction with H2 , resulting in a low H2 yield
(Xu et al. 2011).
During the subsequent regeneration processes, alkali metal cat-
alysts (NaOH, Na2 CO3 , KOH, and K2 CO3 ) (Li et al. 2015; Xu et al.
2011) and metal-supported catalysts (Cu-Ce-O/AC, Fe-Ce-O/AC,
Ni-Co-Pt/AC, and Ni-Zn-Pt/AC) (Liou and Chen 2009; Carriazo
et al. 2005; Guan et al. 2016; Jia et al. 2017) were employed in
the degradation and conversion of the phenol adsorbed on AC
and promoted catalytic gasification and catalytic oxidation of phe-
nol. Moreover, AC could also be activated by chemical activation
with the alkali metal catalysts (Gil et al. 2014; Alrahbi and
Williams 2016). Early work showed that, during SCW gasification
of phenol, the existence of NaOH or Na2 CO3 can promote the
water-gas shift reaction in the positive direction to promote H2
yield, as shown in the following equations (Li et al. 2015):
2NaOH þ CO2 → Na2 CO3 þ H2 O ð1Þ
Na2 CO3 þ H2 O → NaHCO3 þ NaOH ð2Þ
and CO2 yields increased significantly. The reason why the H2
yields using NaOH or KOH were higher than those of Na2 CO3
or K2 CO3 might be due to the higher amount of substance of NaOH
(KOH) than that of Na2 CO3 (K2 CO3 ) with the same mass. How-
ever, when the metal-supported ACs (Cu-Ce-O/AC, Fe-Ce-O/AC,
Ni-Co-Pt/AC, and Ni-Zn-Pt/AC) were used as phenol sorbents, the
H2 and CO2 yields were very low after the regeneration processes.
Previous studies proved that phenol could be catalytically degraded
by copper oxide/AC and iron oxide/AC with reaction temperatures
below 100°C (Liou and Chen 2009; Carriazo et al. 2005). Accord-
ingly, a possible reason for the low yields is that in the adsorption
processes, the interaction of adsorption and catalytic degradation
decreased the actual amount of phenol adsorbed on the activated
carbon-supported adsorbents. Accordingly, the same reasoning
can be used to explain the low yields of H2 and CO2 for
Ni-Co-Pt/AC and Ni-Zn-Pt/AC.
Liquid Products in SCW Regeneration Processes
The composition of liquid products, shown in Table 4, can be found
with a numerical proportion method. The dibenzofuran content
produced from Fe-Ce-O/AC after SCW regeneration at 385°C,
23.0  0.2 MPa, 20 min, and 10% H2 O2 was used as the standard
value 1.0. There have been some studies on the liquid products of
phenol with activated carbon, H2 O2 , and Na2 CO3 in SCW reaction
environments (Matsumura et al. 2002; Xu et al. 2011). The pres-
ence of AC could not only enhance the phenol decomposition ef-
ficiency, but also decrease the yield of phenol dimers (Matsumura
et al. 2002; Xu et al. 2011) and suppress the production of tarry
materials (Matsumura et al. 2002). There are three possible explan-
ations for the enhancement of phenol degradation efficiency. The
first is that the enhancement was due to the catalytic effect of AC.
The second is that the increase of temperature inside the reactor due

Table 3. Gaseous products of all the samples during the SCW regeneration Table 4. Liquid products of all the samples during the SCW regeneration
processes processes
Samples H2 CO CH4 CO2 Samples Phenol Dibenzofuran
AC-385°C 0.8 0.105 0.949 5.4 AC-385°C 1,170.3 4.9
AC-405°C 1.0 0.151 1.19 5.9 AC-405°C 1,230.1 7.4
AC-425°C 1.2 0.153 1.49 6.7 AC-425°C 1,260.0 9.4
AC-5% H2 O2 1.2 0.154 1.17 7.1 AC-5% H2 O2 496.2 5.7
AC-10% H2 O2 1.3 0.166 1.24 9.5 AC-10% H2 O2 334.7 10.9
AC-15% H2 O2 1.2 0.154 1.22 11.3 AC-15% H2 O2 127.9 5.6
AC-NaOH 19.3 0.0368 1.63 10.4 AC-NaOH 167.4 3.9
AC-Na2 CO3 9.1 0.0415 1.58 11.6 AC-Na2 CO3 218.2 6.1
AC-KOH 18.6 0.0292 1.75 10.2 AC-KOH 188.1 4.3
AC-K2 CO3 8.3 0.0318 1.54 11.3 AC-K2 CO3 225.7 6.9
Cu-Ce-O/AC 1.9 0.0423 0 7.4 Cu-Ce-O/AC 63.8 1.8
Fe-Ce-O/AC 2.1 0.0275 0 7.9 Fe-Ce-O/AC 82.1 1.0
Ni-Co-Pt/AC 2.2 0.322 0 6.8 Ni-Co-Pt/AC 71.1 1.1
Ni-Zn-Pt/AC 1.8 0.293 0 6.5 Ni-Zn-Pt/AC 67.5 1.3

© ASCE 04019083-4 J. Environ. Eng.

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 to the oxidation of AC improved the reaction rate of phenol oxi- Table 5. BET surface area, pore volume, and regeneration efficiency of all
dation in SCW. Third, the oxidation of activated carbon might lead the samples before and after the SCW regeneration processes
to the local temperature increase in the AC surface, and phenol BET surface Pore volume Regeneration Regeneration
might have reacted at a faster reaction rate in the surface pores Samples area (m2 =g) (cm3 =g) efficiency (%) yield (%)
(Matsumura et al. 2002). Accordingly, the regeneration processes AC-O 765 0.346 — —
also involved three reactions at least: homogeneous phenol oxida- AC-385°C 740 0.332 97 95.8
tion, heterogeneous phenol oxidation on the surface of AC, and AC-405°C 813 0.359 107 95.2
combustion of AC (Nunoura et al. 2002). AC-425°C 809 0.358 104 94.8
Generally, the liquid products of phenol after catalytic SCW gas- AC-5% H2 O2 876 0.400 115 93.8
ification and oxidation include p-benzoquinone, p-hydroxybenzoic, AC-10% H2 O2 778 0.348 102 93.1
hydroquinone, 2-phenoxyphenol, 4-phenoxyphenol, 2,2-biphenol, AC-15% H2 O2 800 0.355 104 92.3
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dibenzofuran, cyclohexanol, cyclohexanone, and phenol, as well AC-NaOH 854 0.381 111 98.6
as formic, malonic, acetic, oxalic, and maleic acids (Matsumura AC-Na2 CO3 731 0.350 98 97.5
AC-KOH 832 0.377 109 98.1
et al. 2002; Quintanilla et al. 2006). Different reaction processes
AC-K2 CO3 768 0.346 102 97.7
formed different intermediate products. In this study, the main Cu-Ce-O/AC 948 0.436 — —
products were phenol and dibenzofuran, possibly because the ac- Cu-Ce-O-H2 O2 709 0.326 72.9 94.3
tivated carbon sorbents effectively decreased intermediate product Fe-Ce-O/AC 942 0.437 — —
yield (Matsumura et al. 2002; Xu et al. 2011), causing a low yield. Fe-Ce-O-H2 O2 684 0.328 71.1 94.6
As shown in Table 4, the phenol and dibenzofuran yielded in the Ni-Zn-Pt/AC 895 0.404 — —
liquid phase increased with increasing regeneration reaction tem- Ni-Zn-Pt-H2 O2 652 0.323 76.3 95.2
perature (385°C, 405°C, and 425°C). A possible explanation for Ni-Co-Pt/AC 876 0.389 — —
the increase of the phenol yield is that the increasing temperature Ni-Co-Pt-H2 O2 634 0.303 72.3 95.4
improved the nonpolar property of SCW as a nonpolar solvent,
which was propitious to the dissolution of organics, and promoted
the desorption and dissolution of phenol from the AC surfaces. The
reason for the increase of the dibenzofuran yield is that the increas- SCW regeneration. Accordingly, the surface area (pore volume) of
ing temperature promoted the catalytic degradation of the phenol AC-O was lower than that of AC-405°C and AC-425°C, but higher
adsorbed on the AC in SCW. In addition, the phenol yield remark- than that of AC-385°C. A possible explanation for the lower values
ably decreased due to the enhancement of the SCW oxidation by is that after SCW regeneration at 385°C, the remaining phenol on
the H2 O2 addition. However, the dibenzofuran yield increased ini- the AC blocked the pores of the AC, though SCW treatment could
tially and subsequently decreased with the gradual increase of increase these values (Table 2). The H2 O2 addition (5%, 10%, and
H2 O2 concentration (5%, 10%, and 15%). The oxidation improved 15%) was beneficial for the regeneration of phenol-saturated AC
the degradation of phenol to dibenzofuran, but with increasing and could enhance the values of the surface area and pore volume
H2 O2 content, the enhancement of oxidation promoted the gasifi- due to the catalytic oxidation of phenol by the AC and the oxidation
cation of dibenzofuran to CO2 (Table 3), which resulted in a de- of the AC, which directly resulted in the decrease of phenol ad-
crease in the dibenzofuran yield. Based on the phenol yields at sorbed on the AC and the exposure of pore structure.
5%, 10%, and 15% H2 O2 shown in Table 4, it was speculated that Previous studies have proved that alkali metals (NaOH, Na2 CO3 ,
phenol could be completely decomposed during the SCW regen- KOH, and K2 CO3 ) could be used not only for chemical activation of
eration process with about 25% H2 O2 . AC (Gil et al. 2014; Alrahbi and Williams 2016) but also for catalytic
When the H2 O2 addition was 10% at 385°C, 23.0  0.2 MPa, gasification of phenol in supercritical water (Li et al. 2015; Xu et al.
and 20 min, the alkali metal catalysts (NaOH, Na2 CO3 , KOH, 2011). During the regeneration processes of the adsorbent containing
and K2 CO3 ) significantly decomposed phenol and dibenzofuran alkali metal catalysts, the values of the surface area and pore volume
and further decreased their yields, which was due to the catalyzed of AC-Na2 CO3 (KOH) were higher than that of AC-Na2 CO3
oxidative gasification by the AC and alkali metal catalysts (K2 CO3 ). As shown in Tables 3 and 4, compared to AC-Na2 CO3
(Matsumura et al. 2002; Xu et al. 2011). In addition, with the lower (K2 CO3 ), AC-NaOH (KOH) produced lower and higher yields of
and higher yields of phenol and H2 , respectively, the catalytic phenol and H2 , respectively, and was more effective for phenol con-
gasification effect of NaOH (KOH) was stronger than Na2 CO3 version from the liquid to the gas phase, which led to a higher level of
(K2 CO3 ) (Guo et al. 2012). When the sorbents of phenol were phenol degradation and higher surface area.
Cu-Ce-O/AC, Fe-Ce-O/AC, Ni-Co-Pt/AC, and Ni-Zn-Pt/AC, the After calcination, the AC catalysts supported by Cu-Ce-O,
phenol and dibenzofuran yields in the liquid phase were similar Fe-Ce-O, Ni-Zn-Pt, and Ni-Co-Pt increased the values of surface
to the H2 and CO2 yields in the gaseous phase due to the decrease area and pore volume, which was ascribed to the development of
of the actual amount of adsorbed phenol on the sorbents, which pore structure in the AC during the calcination process. However,
might be attributed to the joint influence of adsorption and catalytic SCW regeneration significantly decreased the values of all the AC-
degradation of the phenol in the sorbents. supported catalysts, which might be attributed to the high reactivity
of carbon with SCW. The flaking of the AC surface stripped the
active components (Cu-Ce-O, Fe-Ce-O, Ni-Zn-Pt, and Ni-Co-Pt)
Regeneration Efficiency of Phenol-Saturated AC from the surface and caused the active components to block the
As depicted in Fig. S1, the isotherms of the original and SCW- pore channels. A decrease of Cu, Fe, Ce, Ni, Zn, or Co content
treated ACs are type I based on the IUPAC classification, with a after SCW treatments was observed from the data of the scanning
type H3 or H4 hysteresis loop indicating the presence of slit-shaped electron microscopy with energy dispersive X-ray spectrometry
pores (Zhang et al. 2018). The BET surface area and pore volume (SEM-EDS) in Table 6. The change of O content was under
of the original and SCW-treated ACs are given in Table 5. 0.6% after SCW=H2 O2 =alkali metal catalyst treatments. The
The gradual increase of the regeneration temperature enhanced obvious increase of O content in Cu-Ce-O/AC, Fe-Ce-O/AC,
the desorption and dissolution of adsorbed phenol on AC during the Ni-Zn-Pt/AC, and Ni-Co-Pt/AC could be due to the increase of

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 Table 6. SEM-EDS elemental composition of all the samples before and after the SCW regeneration processes
Samples C O Na K Cu Fe Ce Ni Zn Co
AC-O 93.47 5.73 — — — — — — — —
AC-385°C 93.50 6.07 — — — — — — — —
AC-405°C 95.97 3.57 — — — — — — — —
AC-425°C 95.57 4.27 — — — — — — — —
AC-5% H2 O2 96.73 3.27 — — — — — — — —
AC-10% H2 O2 94.02 5.82 — — — — — — — —
AC-15% H2 O2 94.67 5.28 — — — — — — — —
AC-NaOH 94.23 5.10 0.63 — — — — — — —
AC-Na2 CO3 93.26 5.60 0.77 — — — — — — —
— — — — — — —
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AC-KOH 92.83 5.13 1.90

AC-K2 CO3 91.53 6.47 — 1.23 — — — — — —
Cu-Ce-O/AC 82.90 7.63 — — 7.80 — 1.67 — — —
Cu-Ce-O-H2 O2 90.75 6.75 — — 1.2 — 1.4 — — —
Fe-Ce-O/AC 67.60 10.03 — — — 14.37 2.97 — — —
Fe-Ce-O-H2 O2 77.6 12.77 — — — 8.73 0.73 — — —
Ni-Zn-Pt/AC 69.90 10.47 — — — — — 9.70 10.00 —
Ni-Zn-Pt-H2 O2 78.63 9.10 — — — — — 6.20 5.30 —
Ni-Co-Pt/AC 65.27 17.07 — — — — — 9.00 — 7.67
Ni-Co-Pt-H2 O2 75.33 12.23 — — — — — 6.80 — 1.97

the relative content of Oσ obtained from the XPS data. The addition
of NaOH, Na2 CO3 , KOH, and K2 CO3 resulted in the increase of
Na and K content.
The X-ray patterns of Cu-Ce-O/AC, Fe-Ce-O/AC, Ni-Zn-Pt/
AC, and Ni-Co-Pt/AC before and after SCW regeneration treat-
ments are shown in Fig. 3. The significant formation of metallic
Cu in Cu-Ce-O-H2 O2 was observed, which could be due to the
reducing action of AC to copper oxides. But SCW oxidation re-
sulted in the enhancement of the characteristic peaks of Fe2 O3 ,
NiO, and ZnO in relatively high crystallinity. Fe2 O3 , NiO, and
ZnO could also be agglomerated in SCW.
As shown in Fig. S2, the binding energy at around 529–530 eV
is the lattice oxygen (O2− ) (hereafter denoted as Oα ) and the
binding at around 531–533 eV is assigned to defect oxide or the
surface oxygen ions with a low coordination situation (hereafter
denoted as Oβ ). Only Oβ could be observed before and after
SCW=H2 O2 =alkali metal catalyst treatments in Figs. S2(a–c),
but in Figs. S2(d and e), there were two surface oxygen species
(Oα and Oβ ) in the O1s XPS spectra of Cu-Ce-O/AC, Fe-Ce-O/
AC, Ni-Zn-Pt/AC, and Ni-Co-Pt/AC. As shown in Table 7, Oα ob-
viously decreased, and the decrease in Cu-Ce-O-H2 O2 was worst,
which might be due to the significant formation of metallic Cu in
Cu-Ce-O-H2 O2 according to the XRD data. SCW regeneration
treatment resulted in the relatively high crystallinity of Fe2 O3 ,
NiO, and ZnO in Fig. 3, and then decreased the relative content
of Oα .
In Fig. S3, the two peaks at the banding energies of 932.9 and
934.1 eV corresponded to metallic Cu (or Cuþ ) and Cu2þ (Dai et al.
2001; Liu et al. 2014); the peaks at 711.1 and 712.9 eV corre-
sponded to Fe2þ and Fe3þ (Reddy et al. 2011); the peaks at 882.7,
888.2, 898.6, 899.1, 902.1, 909.8, and 917.8 eV corresponded to
Ce4þ ; the peaks at 883.9, 886.2, and 905.3 eV corresponded

Fig. 3. XRD patterns of Cu-Ce-O/AC, Fe-Ce-O/AC, Ni-Zn-Pt/AC, and Ni-Co-Pt-H2 O2 before and after the SCW regeneration processes.

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 Table 7. O1s XPS data of samples before and after the SCW regeneration as the maximum capacity, was also calculated from the Langmuir
processes model. The K values are in the 0–1 range (0.0089–0.0184), sug-
O1s gesting that the adsorption of phenol on AC was favorable (Lin
et al. 2009). The correlation coefficients (R2 ) were used to deter-
Oα =ðOα þ Oβ Þ Oβ =ðOα þ Oβ Þ
Samples Oα Oβ (%) (%) mine the relationship between the experimental data and the pre-
dicted model in most previous studies. All the R2 values exceeded
Cu-Ce-O/AC 532.0 530.2 85.9 14.1
0.97 in this study, suggesting that the Langmuir model is suitable
Cu-Ce-O-H2 O2 532.2 530.3 96.2 3.8
Fe-Ce-O/AC 532.2 530.6 63.2 36.8
for all the cases, with values in the range of 0.974–0.998 (Lin et al.
Fe-Ce-O-H2 O2 532.4 530.6 64.1 35.9 2009). The change of the adsorption capacities in the regenerated
Ni-Zn-Pt/AC 531.6 529.7 69.8 30.2 AC samples and their regeneration efficiencies is also important to
Ni-Zn-Pt-H2 O2 532.0 530.2 78.0 22.0 consider. Generally, the regeneration efficiency can be calculated
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Ni-Co-Pt/AC 531.6 530.1 74.1
Ni-Co-Pt-H2 O2 532.1 530.3 84.2
to Ce3þ (Bêche et al. 2008); the peaks at 779.7 and 781.3 eV cor-
responded to Co3þ and Co2þ (Liotta et al. 2006); and the peaks at
854.4, 854.9, 860.4, 861.8, 863.9, 856.3, and 857.9 eV corre-
sponded to Ni2þ and metallic Ni (Biesinger et al. 2009).
According to the XPS data in Table 8, the percentage of
Ce3þ =Ce4þ in Cu-Ce-O-H2 O2 and Fe-Ce-O-H2 O2 decreased, and
the relative content of Ce4þ increased. The percentage change of
ðCu þ Cuþ Þ=Cu2þ was not obvious, but the formation of metallic
Cu was observed from the XRD data, which should be due to the
amorphous structure of some Cu2þ that could not be detected by
XRD. The percentage of Fe2þ =Fe3þ decreased, and the increase
of the relative content of Fe3þ was consistent with the XRD data.
As listed in Table 9, the percentage of Ni=Ni2þ in Ni-Co-Pt-
H2 O2 and Ni-Zn-Pt-H2 O2 increased, but the characteristic peak of
Ni was not obvious according to the XRD data. The reason should
be due to the amorphous structure and the high dispersion of
some metallic Ni. In Fig. S3, two bands, Zn 2p3/2 (1,021.9 eV)
and Zn 2p1/2 (1,044.7 eV), indicated the presence of divalent zinc
with oxygen Zn2p1=2 and Zn2p2=3 before and after SCW treatment,
leading to the increase of Zn2p1=2 =Zn2p2=3 . According to the
SEM-EDS, XRD, and XPS data, the content, the structures, and
the valence states of the active components on the surface of the AC
were changed obviously.
The experimental and predicted adsorption isothermals of phe-
nol for all the AC samples at 25°C, obtained using the Langmuir
model, are presented in Fig. S4. Table S1 shows the isotherm
parameters obtained using a nonlinear curve fitting analysis based
on the Langmuir adsorption isotherm. Q (mg=g), which is defined
25.9 using the equation: regeneration efficiency = regenerated adsorp-
15.8 tion capacity/previous adsorption capacity × 100%. The maximum
adsorption capacities (Q) of the different samples before and after
SCW regeneration are shown in Fig. 4. The regeneration efficien-
cies are listed in Table 5.
In Fig. 4(a), it is shown that the adsorption capacity
(242 mg=g) of AC-385°C, under the regeneration conditions
385°C, 23.0  0.2 MPa, and 20 min, was lower than that of
AC-O (249 mg=g) due to the remaining phenol in the AC. The
regeneration adsorption capacities of AC-405°C and AC-425°C
were 267 and 260 mg=g, respectively, and the corresponding val-
ues of regeneration efficiency were 107% and 104%. The increase
in the reaction temperature was beneficial for the enhancement of
the regeneration efficiency. However, as shown in Table 5, the
regeneration efficiency of the three samples exceeded 100% with
the H2 O2 addition at different concentrations (5%, 10%, and 15%)
after the SCW regeneration process, which could improve the
degradation of phenol adsorbed on the AC and the oxidation
of the AC, resulting in an increase in surface area and adsorption
capacity.
The regeneration efficiencies for the regeneration processes
with added alkali metal catalysts (NaOH, Na2 CO3 , KOH, and
K2 CO3 ) at 385°C, 23.0  0.2 MPa, 20 min, and 10% H2 O2 ,
are shown in Table 5. The addition of Na2 CO3 and K2 CO3
significantly increased the degradation of phenol, and their regen-
eration efficiencies (98% and 102%, respectively) were similar to
the regeneration efficiency of AC-10% H2 O2 (102%). However,
the addition of AC-NaOH (111%) and AC-KOH (109%) not
only improved the decomposition and gasification of phenol
but also increased the surface area and the adsorption capacity
compared to the Na2 CO3 and K2 CO3 addition. The adsorption
capacities of Cu-Ce-O-H2 O2 , Fe-Ce-O-H2 O2 , Ni-Zn-Pt-H2 O2 , and

Table 8. XPS data of Cu-Ce-O/AC and Fe-Ce-O/AC before and after the SCW regeneration processes
Ce3d Cu2p Fe2p
3þ 4þ 3þ 4þ þ 2þ þ 2þ 2þ 3þ
Samples Ce (%) Ce (%) Ce =Ce Cu þ Cu (%) Cu (%) Cu þ Cu =Cu Fe (%) Fe (%) Fe2þ =Fe3þ
Cu-Ce-O/AC 65.2 34.8 1.87 50.2 49.8 1.01 — — —
Cu-Ce-O-H2 O2 62.6 37.4 1.67 50.6 49.4 1.02 — — —
Fe-Ce-O/AC 69.1 30.9 2.24 — — — 48.6 51.4 0.94
Fe-Ce-O-H2 O2 65.7 34.3 1.92 — — — 43.2 56.8 0.76

Table 9. XPS data of Ni-Co-Pt/AC and Ni-Zn-Pt/AC before and after the SCW regeneration processes
Ni2p Co2p (Zn2p)
Samples Ni (%) Ni2þ (%) Ni=Ni2þ Co2þ (%) Co3þ (%) Co2þ =Co3þ Zn2p1=2 (%) Zn2p2=3 (%) Zn2p1=2 =Zn2p2=3
Ni-Co-Pt/AC 32.4 67.6 47.9 95.0 5.0 19.0 — — —
Ni-Co-Pt-H2 O2 38.3 61.7 62.1 98.1 1.9 51.6 — — —
Ni-Zn-Pt/AC 33.8 66.2 51.1 — — — 38.3 61.7 0.62
Ni-Zn-Pt-H2 O2 36.6 63.4 57.7 — — — 60.0 40.0 1.50

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Fig. 4. Maximum adsorption capacities (Q) of all the samples from Langmuir isotherm constants before and after the SCW regeneration processes:
(a) AC-O, AC-385°C, AC-405°C, and AC-425°C; (b) AC-O, AC-5% H2 O2 AC-10% H2 O2 , and AC-15% H2 O2 ; (c) AC-O, AC-K2 CO3 , AC-KOH,
AC-Na2 CO3 , and AC-NaOH; (d) AC-O, Cu-Ce-O/AC, Cu-Ce-O-H2 O2 , Fe-Ce-O/AC, Fe-Ce-O-H2 O2 , Ni-Zn-Pt/AC, Ni-Zn-Pt-H2 O2 , Ni-Co-Pt/AC,
and Ni-Co-Pt-H2 O2 .

Ni-Co-Pt-H2 O2 (221, 216, 209, and 204 mg=g, respectively) after
SCW regeneration decreased significantly compared to those of
Cu-Ce-O/AC, Fe-Ce-O/AC, Ni-Zn-Pt/AC, and Ni-Co-Pt/AC (303,
304, 280, and 282 mg=g, respectively). A possible reason is that
the flaking of the AC surface resulted in the stripping of active com-
ponents (Cu-Ce-O, Fe-Ce-O, Ni-Zn-Pt, and Ni-Co-Pt) from the sur-
face, which blocked the pore channels. Additionally, the content, the
structures, and the valence states of the active components were
changed during SCW regeneration owing to the combined action of
H2 O2 (oxidation) and AC (catalytic reduction), which significantly
changed the catalytic properties of the samples.
Conclusions
In this study, we explored the regeneration of AC saturated with
phenol in SCW under different reaction conditions. Phenol ad-
sorbed on the AC could not be completely decomposed during the
SCW regeneration process without additives or catalysts. This pro-
cess resulted in the effective regeneration of the AC. The values of
the regeneration efficiency of AC-385°C, AC-405°C, and AC-425°C
were 97%, 107%, and 104%, respectively. The liquid products were
phenol (main) and dibenzofuran. The main product was CO2 with a
small amount of H2 , CH4 , and CO in the gas phase.
The addition of a small amount of H2 O2 (5%) improved the de-
composition of phenol and increased the regeneration efficiency
(115%). The gradual increase of H2 O2 content further improved
the decomposition of phenol and the oxidation of the AC, resulting
in a decrease of the regeneration efficiency. The H2 O2 addition
accelerated the decomposition of phenol and dibenzofuran and in-
creased the CO2 yield. It was speculated that the complete decom-
position of phenol could be achieved in the SCW regeneration
process with the addition of about 25% H2 O2 .
Alkali metals (Na2 CO3 , NaOH, K2 CO3 , and KOH), which
were used as gasification catalysts, accelerated the further decom-
position of phenol and dibenzofuran and resulted in a significant
and small increase of the H2 and CO2 yields, respectively. Com-
pared to Na2 CO3 (K2 CO3 ), NaOH (KOH) produced a lower yield
of phenol, dibenzofuran, and CO2 , and a higher yield of H2 , which
produced a stronger effect on the decomposition and gasification
of phenol. The supported active components (Cu-Ce-O, Fe-Ce-O,
Ni-Zn-Pt, and Ni-Co-Pt) increased the adsorption ability of
the AC, including adsorption and catalytic decomposition. This
phenomenon resulted in a decrease of the liquid (phenol and
dibenzofuran) and gaseous products (H2 and CO2 ) after SCW
regeneration. The regeneration efficiency of all the metal-
supported adsorbents was less than 90%. During the SCW regen-
eration process, the addition of H2 O2 and alkali metal catalysts
(Na2 CO3 , NaOH, K2 CO3 , and KOH) obviously increased the re-
generation efficiency of the AC and effectively enhanced the
decomposition of phenol at a lower SCW temperature (385°C).

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 SCW regeneration with additives can be used as a rapid, efficient,
and harmless process.
Data Availability Statement
No data, models, or code were generated or used during the study.
Acknowledgments
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This work was supported by the National Nature Science
Foundation of China (41761072 and 21277064), High-Level Talent
Foundation of Kunming University of Science and Technology
(1411909411), and the Analysis and Testing Foundation of
Kunming University of Science and Technology (2017T20160073).
We thank LetPub (www.letpub.com) for linguistic assistance
during the preparation of this manuscript.
Supplemental Data
Figs. S1–S4 and Table S1 are available online in the ASCE Library
(www.ascelibrary.org).
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