Journal of Hazardous Materials 433 (2022) 128761

Contents lists available at ScienceDirect

Journal of Hazardous Materials

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

Review

Oily sludge treatment in subcritical and supercritical water: A review

Zhong Chen a, e, *, Zhijian Zheng b, Chunlan He c, Jumei Liu d, Rui Zhang a, Qiao Chen a, e, *
a
Key Laboratory of Reservoir Aquatic Environment, Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences, Chongqing 400714, China
b
State Key Laboratory Breeding Base of Nuclear Resources and Environment, East China University of Technology, Nanchang 330013, China
c
Chongqing Institute for Food and Drug Control, Chongqing 401120, China
d
School of Petroleum and Natural Gas Engineering, Chongqing University of Science and Technology, Chongqing 401331, China
e
Chongqing School, University of Chinese Academy of Sciences, Chongqing 400714, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Eight hydrothermal technologies for oily

sludge treatment are described in detail.
• A general reaction pathway for hydro­
thermal treatment of oily sludge is
presented.
• The global reaction pathways of model
petroleum compounds are illustrated.
• Guidelines for selecting a suitable hy­
drothermal technology are proposed.

A R T I C L E I N F O A B S T R A C T

Editor: Baiyang Chen Oily sludge, an inherent byproduct of the petroleum industry, presents dual characteristics of petroleum re­
sources and hazardous waste. Owing to the unique physicochemical properties of sub-/supercritical water, hy­
Keywords: drothermal technologies have been increasingly used for oily sludge treatment. This review is the first to focus on
Hydrothermal technology oily sludge treatment using sub-/supercritical water. Eight hydrothermal technologies used for different purposes
Reaction pathways
are summarized herein: pressurized hot water extraction (PHWE) for hydrocarbon separation, thermal hydrolysis
Long-chain alkanes
(TH) for dewaterability improvement, hydrothermal carbonization (HTC) for hydrochar production, wet air
Polycyclic aromatic hydrocarbons
Fuel recovery oxidation (WAO) for biodegradability improvement, hydrothermal liquefaction (HTL) for bio-oil production,
Harmless treatment supercritical water upgrading (SCWU) for light oil production, supercritical water oxidation (SCWO) for com­
plete degradation, and supercritical water gasification (SCWG) for H2-rich syngas production. Moreover, a
general reaction pathway for sub-/supercritical water treatment of oily sludge is presented, with a particular
focus on the chemical mechanism at temperatures above 350 ◦ C. Lastly, two reaction maps are included to
illustrate the reaction pathways of two groups of identifiable model compounds in oily sludge: aliphatic and
aromatic hydrocarbons. This review provides detailed information that can promote a better understanding of
various hydrothermal technologies, a guideline for selecting the suitable hydrothermal process for a particular
oily sludge, and recommendations for further researches.

1. Introduction industry, and in particular, during petroleum exploitation, storage,

transportation, and refining (Hochberg et al., 2022; Hu et al., 2013; Li
Oily sludge is generated during all processes in the petroleum et al., 2021b). The results of a survey involving 75 European oil

* Correspondence to: Chongqing Institute of Green and Intelligent Technology (CIGIT), Chinese Academy of Sciences, No. 266 Fangzheng Avenue, Beibei District,
Chongqing, 400714, China.
E-mail addresses: chenzhong@cigit.ac.cn, chen370353205@qq.com (Z. Chen), chenqiao@cigit.ac.cn (Q. Chen).

https://doi.org/10.1016/j.jhazmat.2022.128761
Received 30 December 2021; Received in revised form 8 March 2022; Accepted 20 March 2022
Available online 24 March 2022
0304-3894/© 2022 Elsevier B.V. All rights reserved.
Z. Chen et al.
refineries, which was conducted in 1986, suggested that the oily sludge
yield was only 0.13% of the crude oil throughput (Van Oudenhoven
et al., 1995). However, this yield was estimated to be as high as 1.5%
according to the Statistical Annual Report of National Agency for Pe­
troleum of Brazil in 2010 (da Silva et al., 2012). This increase was
attributed to the crude oil extracted worldwide becoming increasingly
heavier. It was estimated that, in 2013, 70–80% of the petroleum crude
reserves were unconventional petroleum resources comprising primarily
oil shale and oil sand bitumen (Yeletsky et al., 2020). As a result, it is
foreseeable that the amount of produced oily sludge will continue to
increase. In China, the annual oily sludge output exceeds 6 million tons,
and the total historical stock reached 143 million tons, according to
business statistics (Li et al., 2021b).
Oily sludge is a semi-solid waste that usually comprises 15–50%
petroleum hydrocarbons, 30–85% water, and 5–46% solid particles (Hu
et al., 2013). This composition confers oily sludge dual characteristics of
petroleum resources and hazardous waste. On one hand, 1 ton of oily
sludge yields 0.15–0.5 tons of crude oil, and the quality of the recovered
oil is typically higher than that of biodiesel derived from renewable
biomass. In 2020, 73.5% of the crude oil in China was imported (Wang
et al., 2021c). Therefore, oily sludge recycling is practical in China. On
the other hand, oily sludge has been recognized as a hazardous waste in
many countries, including China. Typically, solid wastes with white
spirit contents higher than 3% are classified as hazardous waste (Chinese
National Standard, 2007). Moreover, oily sludge contains several toxic
components, such as polycyclic aromatic hydrocarbons (PAHs), metal
salts, chemical additives, and asphaltene (Jerez et al., 2021). Therefore,
oily sludge without treatment will not only lead to massive loss of pe­
troleum resources, but also tend to threaten nearby residents and the
environment seriously.
Various technologies have been adapted for oily sludge treatment, as
summarized in relevant reviews (Hochberg et al., 2022; Hu et al., 2013;
Hui et al., 2020; Teng et al., 2021). Due to the high water content of oily
sludge, the traditional treatment technologies involve an indispensable
preprocess, namely dewatering. Oily sludge is a stable water-in-oil
emulsion; therefore, dewatering is a challenging process that requires
high energy consumption (Gao et al., 2021). Fortunately, hydrothermal
technology using sub-/supercritical water as a green medium is an
alternative treatment method for the valorization of oily sludge that do
not require dewatering. Moreover, sub-/supercritical water serves as an
Fig. 1. Chord diagram of petroleum waste type, reaction media, and year of publication. Data collected from the Web of Science as of December 28, 2021.
2
Journal of Hazardous Materials 433 (2022) 128761
adjustable-polarity solvent for extracting and recovering petroleum
hydrocarbons (Teo et al., 2010), and plays multiple roles in chemical
reactions, such as hydrogen donor, oxygen donor and catalyst (Arcelu­
s-Arrillaga et al., 2017; Wei et al., 2021).
Several hydrothermal technologies have been developed for oily
sludge treatment, including pressurized hot water extraction (PHWE),
thermal hydrolysis (TH), wet air oxidation (WAO), hydrothermal
carbonization (HTC), hydrothermal liquefaction (HTL), supercritical
water upgrading (SCWU), supercritical water oxidation (SCWO), and
supercritical water gasification (SCWG). These technologies are used for
recovering fuels (char, coke, oil, and H2-rich syngas) and/or decon­
taminating or mineralizing organic pollutants. Consequently, multiple
purposes of volume reduction, fuel recovery and harmless treatment can
be achieved by simply changing the operating parameters, such as
temperature (T), pressure (P), residence time (t), oxidation coefficient
(OC), and catalyst.
A total of 3645 relevant articles were retrieved using the Web of
Science as of December 28, 2021. Two topics were used for each search:
petroleum waste (oily sludge, petroleum hydrocarbons, heavy oil, PAHs,
and asphaltene) and the reaction medium (subcritical water, hydro­
thermal, and supercritical water). Some of the retrieved articles were
duplicates because two or more topics (keywords) were used in the same
publication. Nevertheless, the chord diagram was meaningful (Fig. 1).
Although only 82 articles on petroleum waste included information on
oily sludge, the primary components of oily sludge (petroleum hydro­
carbons, heavy oil, and PAHs) have been widely studied. In particular,
PAHs have attracted significant attention because they are high-profile
environmental pollutants that can be easily derived from petroleum,
coal, and biomass. Subcritical water has been the least frequently re­
ported reaction medium because most petroleum hydrocarbons are
stable at temperatures below 300 ◦ C. The chemical reactions underwent
by petroleum hydrocarbons typically require near-/supercritical water,
as discussed in Section 4. Moreover, our literature survey indicated that
the hydrothermal treatment of oily sludge and derived compounds has
recently attracted increasing attention. The number of articles on the
hydrothermal treatment of oily sludge and derived compounds pub­
lished between 2016 and 2020 was more than 2.5 times higher than that
published between 2011 and 2015. However, there is not yet a review
focusing on the special topic, i.e., oily sludge treatment in sub-/super­
critical water.
Z. Chen et al.
Herein, we briefly discuss the phase diagram and physicochemical
properties of water at different pressures and temperatures (Section 2),
followed by a step-by-step review of the sub-/supercritical water treat­
ment of oily sludge (Sections 3–5). In Section 3, eight hydrothermal
technologies used for oily sludge treatment are classified, introduced,
and compared. In Section 4, a general reaction pathway for oily sludge
treatment using sub-/supercritical water is proposed, and the reaction
mechanism at temperatures above 350 ◦ C is discussed in detail. In
Fig. 2. Phase diagram and physicochemical properties of sub-/supercritical water.
3
Journal of Hazardous Materials 433 (2022) 128761
Section 5, the hydrothermal conversion of various model petroleum
compounds is illustrated in detail using two reaction maps. In this re­
view, we comprehensively describe each hydrothermal technology for
non-expert readers, examine the behavior of oily sludge and petroleum
model compounds in sub-/supercritical water, and provide suggestions
for further fundamental studies and industrial development.
Z. Chen et al.
2. Physicochemical properties of sub-/supercritical water
Water at different pressures and temperatures can be categorized
into four phases: ice, liquid water, superheated steam, and supercritical
water (SCW) (Fig. 2A). Furthermore, liquid water can be subdivided into
ordinary water (0.0076 ◦ C< T ≤ 100 ◦ C) and subcritical water (100 ◦ C<
T ≤ 373.946 ◦ C). Subcritical water, which is also known as superheated
water, hot compressed water, or pressurized hot water (PHW), is a liquid
at pressures higher than the saturation vapor pressure (SVP). At pres­
sures and temperatures higher than the critical point (P = 22.064 MPa,
T = 373.946 ◦ C) water behaves as an a typical fluid, namely SCW
(Wagner and Kruse, 2007). At temperatures and pressures around the
critical point (350 ◦ C < T < 400 ◦ C, 18 MPa < P < 25 MPa), water is
known as near-critical water (NCW).
PHW, NCW, and SCW are collectively known as hydrothermal or
sub-/supercritical water. The physicochemical properties of sub-/su­
percritical water are different from those of room-temperature water.
The isobaric properties of water change significantly upon increasing
temperature from 25◦ to 600◦ C, and the curves are gentle upon
increasing pressure, as shown in Fig. 2 B–E. Water density (ρ) is a critical
property that has been widely used as a basic parameter for calculating
other properties, such as the dielectric constant (ε) (Uematsu and Frank,
1980), ionic product (Kw) (Marshall and Franck, 1981), inorganic salt
solubility (Ding et al., 2017), and hydrocarbon solubility (Adeniyi et al.,
2021). At temperatures and pressures above the critical point, the
density and viscosity of water decrease to less than one-fifth of those of
room-temperature water (Fig. 2B and C), thereby promoting mass
transfer. Furthermore, the hydrogen bond that is abundant in room
temperature water also becomes rare in SCW. Therefore, water polarity
changes from polar (ε = 80) at 25 ◦ C to non-polar (ε = 2.5) at 400 ◦ C
(Fig. 2D). Low-polar water can easily dissolve gases and small-molecule
organics, and a single homogeneous environment can be achieved under
supercritical conditions. Hence, chemical reactions occur easily and
quickly, which is the most important aspect of hydrothermal
technologies.
The chemical reactivity of water is primarily related to its ionic
product (Kw=[H+]⋅[OH− ]). Upon increasing temperature, Kw increases
slowly and then decreases sharply, reaching a maximum of 10− 11 at
approximately 300 ◦ C, which is approximately three orders of magni­
tude higher than that of room-temperature water (10− 14; Fig. 2E).
Higher Kw values indicate higher H+ and OH− yields; moreover, water
with higher KW values can easily participate in chemical reactions, such
as acid or base catalysis reactions (Savage, 2009), aquathermolysis
(Al-Muntaser et al., 2021) and pyrohydrolysis (Jin and Enomoto, 2011).
Upon further increasing temperature, Kw decreased sharply (Fig. 2E).
Therefore, the dominant reaction mechanism changes from an ionic
reaction in PHW to a free-radical reaction in SCW at an operating
pressure of no more than 30 MPa (Kritzer, 2004). However, the detailed
reactivity of sub-/supercritical water has not yet been elucidated.
3. Application of sub-/supercritical water in oily sludge
treatment
Although the chemical reactions of various model organic com­
pounds in sub-/supercritical water have been widely reported since the
1980 s (Savage, 1999), the application of sub-/supercritical water in real
oily sludge treatment was first reported in 2007 and has been increas­
ingly studied in the past few years, as summarized in Table 1. In this
section, we describe eight hydrothermal technologies and their appli­
cations in oily sludge treatment in an order of operating temperature,
namely PHWE, TH, HTC, WAO, HTL, SCWU, SCWO, and SCWG. Oily
sludge generated from different sources was divided into four types:
oilfield oily sludge (OOS), storage and transportation oily sludge
(STOS), refinery oily sludge (ROS) and accident oily sludge (AOS) (Li
et al., 2021b). Moreover, the reactors used in these studies were clas­
sified as batch reactor (BR), semi-continuous reactor (SCR,
4
Journal of Hazardous Materials 433 (2022) 128761
sub-/supercritical water continuously flows through the oily sludge) and
continuous reactor (CR), as shown in Table 1.
3.1. Pressurized hot water extraction (PHWE)
In 1994, Hawthorne et al. (1994) pioneered the extraction of organic
pollutants from environmental solids using sub-/supercritical water
instead of conventional organic solvents. They determined that polar,
moderately polar, and non-polar organics can be efficiently recovered by
sequentially increasing the operating temperature from 50◦ to 400◦ C.
The subsequent study of Yang et al. (1995) restricted the extraction
temperature to < 300 ◦ C, considering the drawbacks of SCW reaction
medium, such as decomposition of target analytes, reactor corrosion,
and high operating cost. In 2000, Lagadec et al. (2000) extended the
application of sub-/supercritical water from sample preparation to
remediation of organic-contaminated soil. Pilot-scale experiments
indicated that PAH- and pesticide-contaminated soil samples can be
remediated at mild temperatures (≤275 ◦ C). Subsequently, PHWE has
been widely used to extract various compounds from numerous
matrices, such as environmental, food, and botanical samples (Teo et al.,
2010) and, recently, to decontaminate oily sludge (Table 1).
Numerous individual reports have indicated that temperature played
a dominant role in PHWE, and the effect of pressure was negligible as
long as the pressure exceeded the SVP. Upon increasing temperature, ε
decreases significantly, whereas the effect of pressure on ε is limited
(Fig. 2D). Considering that most petroleum compounds are polar or­
ganics (Jerez et al., 2021), high-temperature water increases their sol­
ubility (Adeniyi et al., 2021). Conversely, upon increasing temperature,
the density and viscosity of water decrease (Fig. 2B and C), thereby
decreasing the mass transfer resistance during PHWE. In addition,
thermogravimetric analysis data indicated that more than 50% of the
total weight loss of oily sludge occurred at temperatures below 300 ◦ C
(Chen et al., 2018; Jerez et al., 2021), which coincided with the oper­
ating temperature range of low-temperature thermal desorption. In
summary, PHWE presents the advantages of low-temperature thermal
desorption and solvent extraction (Chen et al., 2018, 2019).
Water flow rate is the second most important parameter after tem­
perature. Kubátová et al. (2002) demonstrated that the thermodynamic
elution of pollutants from the matrix was the primary mechanism during
PHWE. Therefore, increasing the water flow rate is an efficient method
for improving extraction rate at a set temperature.
In addition, PHWE combined with in situ oxidation is an alternative
method for improving the extraction rate. Even in a pure PHW envi­
ronment, some unstable organics, such as polyaromatic hydrocarbons
(Islam et al., 2014) and trinitrotoluene (Kalderis et al., 2008), decom­
pose. In the presence of oxidants, heavy compounds, which are stable in
pure PHW decompose to produce small-molecule compounds. There­
fore, PHWE–WAO/SCWO can shorten extraction times, lower operation
costs, and minimize wastewater discharge (Dadkhah and Akgerman,
2002, 2006; Kronholm et al., 2002).
3.2. Thermal hydrolysis (TH)
The first commercial TH process, known as the “Porteous” process
dates back to 1938 (Kepp et al., 2000). TH is typically used to increase
the dewaterability of municipal sewage sludge (MSS) by destroying its
cytoderm, thereby promoting cell water release. In 1975, Stanford
University researchers extended the application of TH from a pretreat­
ment step before dehydration to a pretreatment step before anaerobic
digestion (Roger et al., 1978). Their results indicated that TH can effi­
ciently decompose the complex molecular compounds in MSS into
digestible compounds at mild temperatures (100–230 ◦ C) over a short
residence time (30 min). Since then, TH has been widely used and
commercialized as a pretreatment step for MSS treatment before dehy­
dration and anaerobic digestion (Phuong Linh et al., 2021).
Oily sludge from petroleum wastewater treatment plants contains
Z. Chen et al. Journal of Hazardous Materials 433 (2022) 128761

Table 1
Literature describing the sub-/supercritical water treatment of oily sludge.
Technology Oil Reactor Operating parameters Primary findings Reference
sludge (capacity)
T ( C)
◦
P (MPa) t (min) L/S (mL Additive
(wt% oil)
g− 1)

PHWE AOS SCR 100–200 2 30–60 1.25–7.5 None 99.8% of diesel was removed under Islam et al.
(0.60) (8.5 mL) optimal conditions (200 ◦ C, 60 min, and (2015)
L/Sof2.65).
PHWE AOS SCR 260 8 90 3 None An oil removal efficiency of approximately Islam et al.
(4.08) (1800 mL) 86% and an oil recovery efficiency of (2017)
approximately 39% were achieved.
PHWE OOS SCR 175–225 0.6–5.5 65 2.6–10.4 None The TOC removal rates for diesel- and Chen et al.
(13.18 (1960 mL) white-oil-based drill cuttings were 78.56% (2018)
and and 83.09%, respectively, under optimal
20.64) conditions (2.3 MPa, 225 ◦ C and L/S of
7.8).
PHWE OOS BR(330 mL) 200–300 SVP 20–60 1.5–3.5 None Temperature was the predominant Chen et al.
(13.18 parameter. White-oil-based drill cuttings (2019)
and were easier to decontaminate using PHWE
20.64) than diesel-based drill cuttings. PHWE
integrates the advantages of organic
solvent extraction and low-temperature
thermal desorption.
TH ROS BR 110–170 SVP 15–90 NA None The dewatering properties of OS were Yan et al.
(32.00) (1000 mL) improved significantly after TH treatment. (2014)
A maximum reduction rate of 88.2% was
achieved at 190 ◦ C and 30 min
TH ROS BR 160–240 SVP 30–90 NA None A reduction rate of ≥ 90% was achieved at Shi et al.
(14.05) (1000 mL) 200 ◦ C and 45 min. The heat value of the (2015)
solid product ranged between 18 and 19
MJ kg− 1.
TH ROS BR(NA) 140–180 SVP 15–60 NA None 42.3% of high-quality oil was recovered Tong et al.
(4.45) and 72.3% of asphaltene was removed (2021)
under optimal conditions (160 ◦ C, 30 min,
and 150 r min− 1).
TH OOS BR(NA) 100–300 5 120 0–10 NaOH A reduction rate of 84.7% was achieved at Zhang et al.
(10.53) (initial) 200 ◦ C and 120 min, in the absence of (2021)
additional water and NaOH.
TH ROS BR(500 mL) 120–240 SVP 120 10–60 None A minimum moisture content of 24.32% Gao et al.
(1.75) was achieved at 240 ◦ C and 60 min. The (2021)
heat value of the solid product ranged
between 10.72 and 11.58 MJ kg− 1.
TH ROS(NA) BR(250 mL) 180 SVP 60 NA NaOH and CaCl2 CaCl2 outperformed NaOH in terms of Deng et al.,
liquid product yield and moisture removal 2022
efficiency, whereas hydrochar exhibited
higher combustion performance and
combustion stability in the presence of
NaOH.
WAO STOS BR(500 mL) 250–330 NA 1–9 NA H2O2 and Ni2+, The catalytic efficiency of metal ions Jing et al.
(42.8) Mn2+, Fe3+ decreased as follows: Ni2+>Mn2+> Fe3+. (2012a),
The COD removal efficiency was increased (2012b),
from 88.40% to 99.70% upon the addition (2013)
of Ni2+ (200 mg/L) at 330 ◦ C, 9 min,
OC= 1.8 and an initial COD of 20000 mg/
L.
WAO ROS BR(500 mL) 220–340 10 15–55 4 Air, FeSO4 and The total petroleum hydrocarbon content Yuan et al.
(36.54) Na2S2O8 of oily scum was decreased from 92.63% (2018)
to 16.75% upon the addition of FeSO4
(47 mg/L) and Na2S2O8 (273 mg/L) at
310 ◦ C over 45 min. The degradation rate
was approximately 3.38 times higher than
that of the WAO process without additives.
WAO ROS(15) BR 240–280 12 30–90 0.73–1.27 H2O2 and Na2CO3 A maximum oil removal efficiency of Zhao et al.
(1000 mL) 89.28% was achieved at 240 ◦ C and (2019)
90 min using WAO. This was further
improved to 93.1% using a two-stage WAO
treatment. The biodegradability of the
residuals was also enhanced.
HTC STOS BR(250 mL) 150–250 SVP 480 20 None HTC destroyed the structure of OS and Pauline and
(60.42) yielded hydrochar. 75.7–78.9% of the Joseph
energy and 74.81–78.62% of the carbon (2021a)
from the OS were retained as hydrochar. (2021b)
The bioavailability, ecological risk, and
toxicity of hydrochar were decreased
significantly.
HTL ROS BR(58 mL) 275–350 SVP 30–75 1.5–9 None A maximum oil yield of 45.52% on a dry-
(48.0) ash-free basis was achieved at 290 ◦ C,
(continued on next page)

5
Z. Chen et al. Journal of Hazardous Materials 433 (2022) 128761

Table 1 (continued )
Technology Oil Reactor Operating parameters Primary findings Reference
sludge (capacity)
T (◦ C) P (MPa) t (min) L/S (mL Additive
(wt% oil)
g− 1)

60 min, and L/S of6.25. The primary Nazem and

compounds in the recovered oil were fatty Tavakoli
acids and aliphatic and carboxylate (2017)
compounds.
HTL ROS BR(NA) 150–250 SVP 30 NA TiO2 Upon the addition of 1.5% TiO2, the oil Dang et al.
(5.14) removal efficiency increased by 35% and (2021)
reached 82.69%; moreover, the oil
recovery rate increased by 55% and
reached 77.68% at 230 ◦ C.
SCWU ROS BR(100 mL) 350–450 21.5–30 60 1–3 None Temperature significantly affected the Gungoren
(0.90) total product yield and composition of oil et al. (2007)
and gaseous products. The yields of
gaseous, liquid, and solid products ranged
between 42.0% and 44.4%, 15.3%
and20.4%, and 35.2% and42.7%,
respectively.
SCWU ROS(NA) BR 400–420 24.1 30 1.1–1.4 None SCW served as the unique solvent and Radfarnia
(2052 mL) dispersant agent. 2.9% of H2–rich syngas et al. (2015)
and 15.7% of oil (primarily naphtha and
light gasoil) were recovered at 420 ◦ C and
30 min
SCWU ROS(NA) BR(140 mL) 350–400 25–35 30–120 0–10 None A high oil yield of 78.6% and low yields of Khan et al.
coke (7.0 wt%) and gas (0.05 wt%) were (2019)
achieved at 400 ◦ C, 30 MPa and L/S of 5.
The total acid number was decreased by
81.8%, and the amounts of metallic and
non-metallic impurities were significantly
decreased. Alkyl– and aryl–CO2 bond
cleavage were the primary deacidification
mechanisms.
SCWU OOS BR(20 mL) 350–450 SVP 45 5 Five types of solid High-quality oil was obtained via the Chen et al.
(20.64) wastes SCWU treatment of oil-based drill cuttings (2021a)
upon the addition of electroplating sludge.
The dehydration of metal hydroxides in
electroplating sludge played a critical role
during the co-treatment.
SCWO STOS BR(650 mL) 390–450 23–27 1–10 NA H2O2 A high COD removal rate of 92% was Cui et al.,
(58.5) achieved at 450 ◦ C, 25 MPa, 10 min, and (2009, 2011)
OC of4.27. The primary refractory
intermediate was CO and the minor one
wasCH3COOH. The oxidation of OS
occurred via a parallel-consecutive
reaction pathway.
SCWO STOS BR(500 mL) 380–440 22.5–30 3–10 NA H2O2 A high COD removal rate of 92.20% was Xu and Lu
(37.78) achieved at 420 ◦ C, 24 MPa, (2016)
10 min pH= 10 and OC of 4. The COD of
the effluents exceeded the discharge limit
(100 mgL− 1).
SCWO OOS BR(330 mL) 400–500 25 0.5–10 31.8–50 H2O2 A high TOC removal rate of 89.2% was Chen et al.
(20.64) achieved at 500 ◦ C, 25 MPa, 10 min, and (2017)
OC of2.5. The reaction pathway comprised
a combination of homogeneous and
heterogeneous reactions.
SCWO ROS(NA) BR 440–600 NA 1–10 NA H2O2 Relatively mild reaction conditions Li et al.
(125.6 mL) (520 ◦ C, 25 MPa, OC of 1.1) were selected (2020a)
as the basic operating parameters for
designing a SCWO plant with a capacity of
50 tons per day featuring ammonia
distillation and biochemical treatment
units.
SCWO OOS CR(2 L/h) 409–495 25 1–2 NA O2, Air, MSS and A mixed sludge (oil-based drill cuttings Chen et al.,
(13.18 electroplating and MSS/electroplating sludge) with a (2020, 2021b)
and sludge record-high ash content of approximately
20.64) 30% was continuously treated using a
novel SCWO reactor. The TOC removal
efficiency was increased from 98.44%
(MSS) to 99.96% (electroplating sludge)
owing to the metal compounds in the
electroplating sludge, which served as
catalysts.
SCWG ROS(NA) BR(600 mL) 530–650 26–42 3.3–6 NA K2CO3 Increasing temperature and residence time Zhang et al.
promoted gasification efficiency; (2016)
moreover, relatively low temperatures
(continued on next page)

6
Z. Chen et al. Journal of Hazardous Materials 433 (2022) 128761

Table 1 (continued )
Technology Oil Reactor Operating parameters Primary findings Reference
sludge (capacity)
T (◦ C) P (MPa) t (min) L/S (mL Additive
(wt% oil)
g− 1)

caused an increase in the hydrogen

fraction. K2CO3 significantly increased the
gas yield and hydrogen fraction.
SCWG OOS(30) BR(160 mL) 400–544 1–2.2 15–150 0.06–9 None A maximum H2 yield of 5.92 mol kg− 1 Jiang et al.
(initial) was achieved at 544 ◦ C, 2.2 MPa (initial), (2020)
150 min, and L/S of 9. The reaction
parameters were optimized using the
uniformity design method.
SCWG ROS BR(100 mL) 350–450 NA 30 10 None OS was converted from hazardous waste (Wang et al.,
(41.90) into general waste via SCWG treatment. 2021a)
44.98–59.64% of oil was decomposed into
aqueous and gaseous products. The
aqueous product was the primary product,
and the H2 yield was as low as
0.26 mol kg− 1 at 450 ◦ C.
SCWG OOS BR(1.4 mL) 400–750 23 5–30 NA None A maximum H2 yield of 19.79 mol kg− 1 Peng et al.
(47.09) was achieved at 750 ◦ C, 23 MPa, and (2021)
25 min. Gaseous products were generated
by two intermediates through steam
reforming and pyrolytic reactions.
Naphthalene and phenanthrene were the
primary compounds that hindered
complete gasification.

NA: not available.

considerable amounts of biological flocs (Jerez et al., 2021), which are
the primary organic components of MSS. Therefore, oily sludge treat­
ments present the same dehydration shortcomings as the MSS treat­
ments. Moreover, the interfacial stability of oily sludge enhances
dehydration difficulty (Liu et al., 2021). TH is typically used for oily
sludge treatment in the temperature range of 140–250 ◦ C (Table 1). The
primary purpose of TH is to improve the dewatering properties of oily
sludge by breaking down both biological flocs and emulsifying system
simultaneously. Typically, TH pretreatment followed by compression
filtration can remove ≥ 85% of moisture from oily sludge and simulta­
neously recycle solid fuel (Gao et al., 2021; Shi et al., 2015) or oil (Tong
et al., 2021).
To decrease operating time and improve dehydration efficiency, Gao
et al. (2021) combined TH pretreatment and compression filtration into
a one-pot process. They designed an autoclave with an in situ mechan­
ical compression function. Using their protocol, the moisture content of
floating oily sludge can be reduced from 91.20% to 24.32% in one step
under optimal conditions (240 ◦ C and 60 min). Further analysis indi­
cated that most of the heavy metals were stabilized in solid residuals
owing to the adsorption effect of the hydroxyl groups formed during the
TH reactions (Duan et al., 2022).
Catalysts can suitably enhance TH efficiency. Deng et al. (2021) used
NaOH and CaCl2 as additives to enhance TH efficiency. Their results
indicated that NaOH did not affect the dewatering properties of oily
sludge after TH treatment, which was in agreement with the findings of
Zhang et al. (2021). However, the moisture removal capacity of CaCl2
was higher than that of NaOH. The moisture contents of the solid
products were reduced below 8% using 0.3–1.0% CaCl2 at 180 ◦ C for
60 min (Deng et al., 2021).
3.3. Wet air oxidation (WAO)
The WAO process was developed in the early 1900 s (Marrone and
Hong, 2007), and the first commercial application of WAO was devel­
oped by Zimmermann in 1954 (Kim and Ihm, 2011). WAO was designed
as an upgraded TH process, and it was used to decrease the chemical
oxygen demand (COD) in MSS by up to 65% (Neyens and Baeyens,
2003). Subsequent studies indicated that abundant hydroxyl radicals,
which are highly reactive and present high oxidation potential, can be
generated in subcritical water in the presence of air at relatively high
temperatures (200–325 ◦ C) and pressures (5–15 MPa) (Sushma et al.,
2018). Thereafter, WAO was widely investigated and commercialized as
an advanced oxidation process for the degradation of refractory waste­
water and sludge.
However, WAO does not efficiently treat oily sludge because of the
high oil content and refractory nature of oily sludge. Catalysts are
commonly used during WAO to enhance the degradation of organic
pollutants (Sushma et al., 2018). Jing et al. (2012a), (2012b), (2013)
used Fe3+, Mn2+, and Ni2+ as homogeneous catalysts for the WAO
treatment of oily sludge and determined that Ni2+ was the most active
catalyst. The concentration of oily sludge in their experiments was lower
than 1%, leading to low treatment capacities. Therefore, WAO is better
suited as a pretreatment step than as an end step in the treatment of oily
sludge. The residual liquid products of WAO comprise small-molecule
organics, which are more biodegradable than those generated during
TH. In addition, a fraction of oil can be recycled (Zhao et al., 2019).
3.4. Hydrothermal carbonization (HTC)
Friedrich Bergius, who won the Nobel Prize in 1931, studied the
hydrothermal transformation of cellulose into coal-like materials and
revealed the mechanism of natural coalification in 1913. His work was
regarded as the inception of the HTC process (Wang et al., 2019). The
operating temperature range of HTC is similar to that of TH, i.e.,
140–250 ◦ C; however, the reaction time of HTC is significantly longer
than that of TH, and it ranges between 2 and 4 h. During HTC treatment,
wet feedstock is hydrolyzed into fragments at low temperature (pre­
heating step), followed by dehydration, decarboxylation, and polymer­
ization of the fragments at high temperatures over long residence times
(maintenance step). Lastly, hydrochar is obtained as the main product
(Wang et al., 2018). Therefore, HTC is also known as wet torrefaction
(Lachos-Perez et al., 2021). Raw wet biomass and MSS with a moisture
content of 75–85% can be directly processed using HTC without
requiring pretreatment steps or additional water (Wang et al., 2019).
Hydrochar is primarily used for energy production because its good fuel
properties, such as high carbon content, high energy density, high
heating value, and low oxygen content, are superior to those of the raw
materials or solid fuel obtained via TH (Li et al., 2020c). Moreover,

7
Z. Chen et al.
hydrochar presents abundant surface functional groups, large surface
area, and adjustable reactivity. Therefore, hydrochar can also be used in
various other areas, such as soil remediation, soil amendment, carbon
sequestration, gas adsorption, and adsorption treatment of exhaust gas
and wastewater (Kambo and Dutta, 2015).
Recently, Pauline and Joseph (2021a) (2021b) adapted HTC for
valorizing bottom oily sludge from a petroleum refinery in India. Their
results indicated that the structure of the oily sludge was destroyed
through various reactions, including dehydration, decarboxylation, and
condensation. Hydrochar with an energy recovery rate of 75.7–78.9%
was obtained. The prepared hydrochar comprised abundant linear
long-chain alkanes (C7–C20); therefore, it presented a low ignition point
of 250 ◦ C. The heavy metals in the initial oily sludge were converted
from mobile, unstable, and acid-soluble fractions into stable fractions
after HTC. Consequently, the ecological risk and toxicity of the hydro­
char decreased significantly.
3.5. Hydrothermal liquefaction (HTL)
In 1934, Berl (1934) pioneered the co-treatment of cellulose and
natural alkaline materials, such as limestone magnesite, dolomite, and
zeolite, in a hydrothermal environment at temperatures above 230 ◦ C,
and obtained a plastic material termed “proto product”. As long as the
post-processing of cracking or hydrogenation, the “proto product” shows
the almost same compositions with that of natural oil. Since then,
scattered research had continued to convert the renewable biomass into
bio-oil (or bio-crude oil), as a viscous crude oil replacement (Peterson
et al., 2008). Recently, this topic has become increasingly popular owing
to the exhaustion of natural oil resources.
Unlike HTC, HTL requires higher temperatures (240–400 ◦ C) and
shorter residence times (15–90 min). In addition, the moisture content
of feedstock should exceed 90% during HTL. Abundant water can dilute
the biomass or sludge and yield larger amounts of H+ and OH– ions
under subcritical conditions, further promoting the hydrolysis reaction
and simultaneously hindering the polymerization reaction (Lacho­
s-Perez et al., 2021). In brief, HTL generates a moderate hydrothermal
environment to balance hydrolysis and polymerization reactions, and is
typically used for producing bio-oil, neither oxygen-containing organics
in TH nor hydrochar in HTC. Therefore, the temperature, residence time,
and water content are critical HTL parameters.
Nazem and Tavakoli (2017) optimized the operating conditions for
the HTL treatment of ROS using a response surface method and deter­
mined that the significance of the parameters in an order of
liquid-to-solid ratio (L/S) > T > > t. The primary constituents of the
obtained oil were aliphatic, saturated, and unsaturated fatty acids and
mono- and polyaromatic compounds. Therefore, post-processing or
catalytic upgrading is necessary for high-quality oil production. Dang
et al. (2021) used nano-TiO2 as the catalyst during the HTL treatment of
ROS in the low temperature range of 150–250 ◦ C. Their results indicated
that subcritical water was split into O2 and H2 in the presence of
nano-TiO2. O2 promoted the oxidative cracking of heavy hydrocarbons,
whereas H2 improved the H/C ratio of the recovered oil through hy­
drogenation. Consequently, the oil removal efficiency and oil recovery
rate were increased by 35% and 55%, respectively, over 1.5% nano-TiO2
at 230 ◦ C.
3.6. Supercritical water upgrading (SCWU)
Shell Oil Co. took the lead in adopting steam injection for heavy
crude oil recovery. The first pilot test was performed in the Yorba Linda
Field in 1958 (Burns, 1969), and a large-scale project was subsequently
implemented in the Tia Juana Field, Western Venezuela in 1969
(Dehaan and Vanlooke, 1969). Since then, steam injection has been
tested and used under various reservoir conditions worldwide (Alvarado
and Manrique, 2010; Guo et al., 2016). However, the specific role of
steam was first described by Hyne et al. until 1980s (Al-Muntaser et al.,
8
Journal of Hazardous Materials 433 (2022) 128761
2021). They concluded that steam/hot water served as a heat carrier to
physically decrease the viscosity of heavy oil via heat transfer and as a
reactant to chemically decrease the viscosity of heavy oil via in situ
hydrocracking the heavy compounds and termed the process “aqua­
thermolysis” (Hyne et al., 1982). Over the same period (1980 s), SCW
began to display its talent in fuel conversion and waste destruction
(Marrone and Hong, 2007). In late 1980s, extraction/upgrading of
heavy oil in SCW were carried out by Berkowitz and Calderon (1990)
and Paspek and Klein (1990). That is the SCWU.
The SCWU of heavy crude oil and residual oil has been widely
studied, and relevant reviews have been published by Arcelus-Arrillaga
et al. (2017) and Timko et al. (2015). In this section, we focus on the
SCWU of oily sludge (Table 1). Compared with the operating tempera­
ture of HTL, that of SCWU was higher and reached the near- and su­
percritical range (350–450 ◦ C). This was ascribed to the upgrading
reaction of heavy compounds becoming significant only at temperatures
above 350 ◦ C (Al-Muntaser et al., 2020). Gungoren et al. (2007) sub­
jected oily sludge to SCWU treatment for the first time in 2007. Although
they termed the process extraction, it was actually an upgraded process
because it required the same operating parameters (350–450 ◦ C,
21.5–30 MPa) as SCWU. Toluene was selected as the contrast solvent
and the operating temperature and pressure ranged between 300 and
450 ◦ C and 8.5 and 20 MPa, respectively. The results suggested that
water outperformed toluene in three aspects: higher yield of total
products (liquids and gases), lower yield of heavy compounds in resi­
dues, and free of drying pretreatment. During SCWU, water serves as an
excellent dispersant and solvent for cracking, decarboxylation, and
demetalization reactions (Khan et al., 2019); however, its
hydrogen-donating capacity is negligible (Radfarnia et al., 2015).
Similar to other hydrothermal processes, temperature was the predom­
inant parameter for SCWU. Upon increasing temperature, the oil yield
increased, oil quality improved, and coke formation was accelerated.
Catalyst addition is an alternative approach for improving SCWU
efficiency. Metal oxides (MOn) are the most commonly used catalysts for
the SCWU of heavy oil (Golmohammadi et al., 2016; Kosari et al., 2017;
Yeletsky et al., 2020). However, MOn are vulnerable in a sub-/­
supercritical water environment (Jocz et al., 2018a, 2018b). Hetero­
atoms (primarily N and S) in oily sludge and sub-/supercritical water
corrode MOn, causing their deactivation. Therefore, our research group
used several types of industrial waste as inexpensive catalyst for the
SCWU treatment of oil-based drill cuttings (Chen et al., 2021a). Our
results indicated that electroplating sludge outperformed red mud and
hot steaming steel slag owing to the in situ pyrolysis of metal hydroxides
in the electroplating sludge. The in situ pyrolysis reaction yielded highly
active ferrite, MOn, and micro-mixtures of the active compounds with
heavy oil compounds. Consequently, high-quality asphaltene-free oil
with a low heteroatom content was recovered at a relatively mild tem­
perature of 350 ◦ C.
3.7. Supercritical water oxidation (SCWO)
In 1980, MIT researcher Michael Modell patented a process for the
degradation of organic pollutants in SCW with the participation of
oxidant, such as air and O2 (Modell, 1982), and founded a commercial
company (MODAR Inc.) for developing the process, which was termed
SCWO (Marrone and Hong, 2007). Similar to WAO, SCWO is an
advanced oxidation process, which occurs primarily via a free-radical
reaction mechanism (Li et al., 1991). However, the reaction medium
for SCWO is SCW, which can dissolve gases (oxidants) and
small-molecule organics (pollutants) to form single homogeneous reac­
tion environments. The interface transport resistance between the liquid
and gas phases, which is a major challenge during WAO, is negligible
during SCWO. Consequently, the residence time can be decreased to less
than 1 min under conventional operating condition (22.5–30 MPa and
400–600 ◦ C). Moreover, the COD/total organic content (TOC) removal
efficiency is typically up to 99%, and the products (primarily H2O, CO2,
Z. Chen et al.
and N2) are environmentally friendly. Owing to these unique advan­
tages, SCWO has been considered to be a promising end-of-pipe tech­
nology. Over the past four decades, SCWO has been widely studied and
used for the treatment of various organic pollutants (Bermejo and
Cocero, 2006; Li et al., 2020a; Marrone, 2013; Yang et al., 2019). SCWO
is particularly superior to traditional technology in treating some special
wastes, such as chemical weapons (Marrone et al., 2005), explosive
wastewater (Chang and Liu, 2007; Zhang et al., 2015), organic radio­
active wastes (Kim et al., 2010; Qin et al., 2017; Wang et al., 2021b; Xu
et al., 2020), and hazardous wastes(Al-Duri et al., 2015; Chen et al.,
2021b; Fedyaeva and Vostrikov, 2012).
As a hazardous waste, oily sludge was also reported to be treated by
SCWO, as listed in Table 1. It was found that oily sludge was more re­
fractory than MSS and general wastewater. The COD/TOC removal rate
during the SCWO treatment of oily sludge was only approximately 90%
(Chen et al., 2017; Cui et al., 2009, 2011; Xu and Lu, 2016). By contrast,
the COD/TOC removal rate during the SCWO treatment of MSS or
general wastewater reached 99%. Further increasing the operating pa­
rameters (T, t, OC) can increase the COD/TOC removal rate to 100%;
however, this would diminish the reliability and safety and increase the
cost of the SCWO treatment. Li et al. (2020a) proposed a commercial
SCWO plant coupled with follow-up units of ammonia distillation and
biochemical treatment. Fist, petrochemical sludge was degraded in the
SCWO unit, which was designed to be operated under relatively mild
conditions (520 ◦ C, 25 MPa, OC=1.1). Thereafter, the effluent from the
SCWO unit, which contained considerable amounts of ammonia and
small-molecule organics, was subjected to distillation, followed by
biochemical treatment. As a result, an environment-friendly economical
SCWO plant is expected to develop for treatment of petrochemical
sludge or other industrial wastes.
MOn have been widely used as catalysts for SCWO to decrease the
temperature, pressure, and residence time and enhance the degradation
of organics (Abdpour and Santos, 2021). Similar to the deactivation
short comings of the SCWU treatment, MOn is subjected to a harsher
environment during SCWO than during other hydrothermal processes
because of the presence of excess O2. Considering the high cost and
inevitable deactivation of MOn, our group subjected oil-based drill
cuttings to continuous SCWO treatment using high-Ni-content electro­
plating sludge as the additive (Chen et al., 2021b). In addition to
providing active MOn species, the electroplating sludge served as a
diluent, which homogeneously dispersed the oil-based drill cuttings. It
was suggested that the heat value of the feed during continuous SCWO
should not exceed 4500 J g− 1, which translated into a reaction tem­
perature range of 700–750 ◦ C (Bermejo and Cocero, 2006). However,
the heat value of real oily sludge with an oil content of ≥ 10% usually
exceeds this limit. Considering the reliability, safety, and cost of SCWO
treatment, the operating temperature in an SCWO plant should not
exceed 600 ◦ C. Therefore, dilution is indispensable for the SCWO
treatment of high-oil-content sludge. However, when water is used as
the only diluent, the oil, water, and solid phases in oily sludge become
layered, which can lead to fluctuations or even plugging problems
during continuous feeding. It was determined that electroplating sludge
can effectively suspend oil-based drill cuttings. A mixed sludge
comprising 67% electroplating sludge and 33% oil-based drill cuttings
was safely and efficiently treated in a continuous SCWO reactor. The
TOC content in the effluent was as low as 8 mg/L. Considering both of
them are type of hazardous wastes, this method provides an alternative
way for the SCWO co-processing of organics-rich hazardous wastes and
metals-rich hazardous wastes (Chen et al., 2021b).
3.8. Supercritical water gasification (SCWG)
In 1975, Modell and co-workers observed an interesting phenome­
non during the reforming of glucose in sub-/supercritical water. That is
the amount of char, which is a considerable byproduct when subcritical
water or superheated steam are used as reforming media, was negligible
9
Journal of Hazardous Materials 433 (2022) 128761
when SCW was used as the reforming medium (Marrone and Hong,
2007). This suggests that SCWG is a promising method for achieving
complete gasification. In 1978, Modell et al. (1978) patented their
method. Therefore, SCWG predates SCWO. However, Modell and
co-workers preferred to develop the SCWO process at the end of the last
century. The SCWG became noticeable until 2000 as the global demand
for clean and renewable energy increased. The SCWG focuses on con­
verting biomass into H2-and/or CH4-rich syngas through various re­
actions, including hydrolysis, partial oxidation, reforming, methanation,
and the water-gas shift reaction (WGSR) (Ibrahim and Akilli, 2019).
Compared with other hydrothermal technologies, SCWG should be
performed at higher temperatures, i.e., catalytic SCWG at 374–500 ◦ C
and non-catalytic SCWG at 500–800 ◦ C. Hence, catalysts are critical for
SCWG as they can decrease the operating temperature, increase gasifi­
cation efficiency, and enhance the H2 yield. Related information can be
found in a recent review by Abdpour and Santos (2021).
According to the data in Table 1, temperature is the predominant
parameter during the SCWG treatment of oily sludge. The H2 yield in
SCWG of oily sludge was determined to be 0.26 mol kg− 1 at 450 ◦ C
(Wang et al., 2021a), 5.92 mol kg− 1 at 544 ◦ C (Jiang et al., 2020), and
19.79 mol kg− 1 at 750 ◦ C (Peng et al., 2021). However, the gasification
efficiency achieved by subjecting oily sludge to SCWG treatment was
lower than that achieved by subjecting biomass to SCWG treatment. This
was ascribed to the stable molecular structure of the organic compounds
in oily sludge. Peng et al. (2021) concluded that naphthalene and
phenanthrene were the primary compounds that prevented the complete
SCWG of polymer-containing oily sludge. Naphthalene and phenan­
threne are intermediate products of the aquathermolysis reaction of
asphaltene. Real oily sludge contains asphaltene, which causes a sig­
nificant decrease in gasification efficiency. In addition, as much as 50%
of the organics in oily sludge are transformed into aqueous products via
SCWG (Wang et al., 2021a), thereby rises the difficulty of wastewater
post-processing. The primary organics in the aqueous products are
oxygen-containing compounds, such asphenols and organic acids.
Considering the positive effect of oxygen-containing organics on gasi­
fication efficiency, Jin et al. (2017) designed an external recycling
process of the residual liquid for the SCWG treatment of lignite. Their
results indicated that, at a mild temperature of 530 ◦ C, upon increasing
the cycling flow rate from 0 to 70 g min− 1, the H2 yield increased from
24 to 32 mol kg− 1 and the gasification efficiency increased from 74% to
99%. This method may be also suitable for the efficient gasification of
oily sludge, but relative study has not been performed to date.
3.9. Comparison of various hydrothermal technologies
Table 2 summarizes the aforementioned hydrothermal technologies.
Each technology presents advantages and disadvantages. Using the data
in Table 2, a guideline for developing a pertinent hydrothermal process
for a given oily sludge is proposed as follows.
(1) The PHWE is suggested to treat the petroleum-contaminated soil
and drill cuttings, better the oily sludge with little or no heavy com­
pounds (resins and asphaltenes). These types of oily sludge usually
contain 1–15% petroleum hydrocarbons, 1–10% moisture, and 75–98%
solids. The solids can provide abundant pores for subcritical water to
easily flow through and easily extract and remove petroleum hydro­
carbons. PHWE is a physical process rather than a chemical process
because petroleum hydrocarbons are stable at T < 300 ◦ C. However,
PHWE cannot easily remove heavy compounds (resins and asphaltenes)
because they are insoluble in subcritical water (Adeniyi et al., 2021).
(2) TH, WAO, and HTC can be considered as the same hydrothermal
technology for the treatment of oily sludge. These technologies are
suggested for the treatment of oily wastewater sludge and oily scum
generated by petroleum wastewater treatment plants, which contain
abundant biological flocs. These types of oily sludge can be considered
to be mixtures of MSS and petroleum hydrocarbons. The primary goal of
these hydrothermal technologies is the improvement of the dewatering
Z. Chen et al. Journal of Hazardous Materials 433 (2022) 128761

Table 2
A comparison of different hydrothermal technologies used for oily sludge treatment.
Technology T (◦ C) P (MPa) t (min) Oxidant Catalyst Purpose Byproducts

PHWE 150–300 0.5–10 15–60 No No • Separating petroleum • Oily wastewater (refractory)

hydrocarbons • Solid residues (environmentally
acceptable)
TH 150–250 0.5–4 30–90 No Yes • Increasing dewaterability • Oily wastewater (refractory)
(optional) • Oil recovery
• Hydrochar production
WAO 220–350 5–20 30–60 Yes (OC>1) Yes • Partial degradation of organics • Organic wastewater (biodegradable)
• Oil recovery • Solid residues (low heat value)
• Increasing biodegradability
HTC 150–250 0.5–4 120–360 No No • Hydrochar production • Oily wastewater (refractory)
• Oil recovery • Organic gases (traces)
HTL 250–400 4–25 15–90 No Yes • Bio-oil production • Oily wastewater (refractory)
(optional) • Solid residues (high heat value)
• Organic gases (moderate)
SCWU 350–450 18–35 30–90 Yes (optional, Yes • Light oil production • Oily wastewater (refractory)
OC<1) • Solid residues (high heat value)
• Organic gases (moderate)
SCWO 400–600 23–30 1–10 Yes (OC>1) Yes • Complete degradation • Brine (salts and heavy metals)
(optional) • Heat production • Solid residues (free of organics)
SCWG 400–750 23–30 15–90 Yes (optional, Yes • H2-rich syngas production • Oily wastewater (biodegradable)
OC<1) • Solid residues (low heat value)

properties of oily sludge by simultaneously breaking down its biological
flocs and emulsifying system. Subsequently, oily wastewater, bio-oil,
and hydrochar are obtained as liquid, oily, and solid products, respec­
tively. The addition of O2 (namely WAO) can increase treatment effi­
ciency by degrading a fraction of the organic compounds and improving
the biodegradability of wastewater. The quality of the recovered oil is
poor because a fraction of the oil originates from biological flocs (Chen
et al., 2021a). Therefore, upgrading is critical for post-processing the
recovered oil. Unlike the composition of hydrochar derived from
biomass or MSS, that of the hydrochar obtained from oily sludge is
complex and includes hazardous compounds, such as heavy metals,
PAHs, and asphaltenes. The potential environmental pollution risk
should be evaluated before recycling the hydrochar.
(3) HTL and SCWU can also be regarded as the same hydrothermal
technology, considering that both are used for recycling oil. Aging and
bottom oily sludge are the suitable types of feedstock for HTL and
SCWU. Typically, the oil content of these types of oily sludge is high
(>30%); therefore, their recycling is justified. However, the oil in aging
and bottom oily sludge comprises primarily heavy components (resins
and asphaltenes) because of the volatilization and conversion of light
components and the accumulation and precipitation of heavy compo­
nents during the lengthy synthesis process (Liu et al., 2021). The per­
centage of heavy components in aging and bottom oily sludge typically
reaches ≥ 50% of the total oil content. Correspondingly, HTL and SCWU
treatments can crack and upgrade the heavy compounds to produce light
oil using the solvent and reaction characteristics of sub-/supercritical
water.
(4) SCWO can be used to treat highly toxic oily sludge. The oily
sludge generated by some petrochemical plants contains highly toxic
and high-risk compounds. Recycling this type of oily sludge can cause
significant secondary pollution; moreover, the benefits are negligible.
Therefore, SCWO is a suitable method for completely and efficiently
mineralizing all types of organic pollutants in oily sludge, and producing
a lot of heat (Cocero et al., 2002; García-Rodríguez et al., 2015;
Jimenez-Espadafor et al., 2011; Lavric et al., 2005; Zhang et al., 2020a).
The residual solids obtained after SCWO treatment can be easily
disposed via direct discharging or landfilling, as they are free of or­
ganics. The liquid product should be desalted before discharging to
ensure that the amounts of inorganic salts and heavy metals do not
exceed the recommended limits.
(5) The SCWG is suggested to serve as a post-processing of oily
wastewater, instead of oily sludge itself. This is because the feedstock
should be dispersed in SCW as uniformly as possible to achieve complete
gasification. Obviously, it is difficult for oily sludge as the presence of
solid and heavy compounds. In contrast, the SCWG treatment of oily
wastewater is more practical (Kou et al., 2018, 2021; Xie et al., 2016; Xu
et al., 2019b, 2021; Yan and Tan, 2015). As summarized in Table 2, oily
wastewater is an inevitable byproduct of all types of hydrothermal
treatments of oily sludge except for SCWO. Therefore, SCWG can be used
as a post-processing treatment for oily wastewater for harvesting H2-rich
syngas as well as to achieving zero discharge (Cherad et al., 2016; Duan
et al., 2018; Shan et al., 2021; Taufer et al., 2021; Xu et al., 2019b; Zhang
et al., 2011).
4. General reaction pathways of oily sludge in sub-/supercritical
water
The products derived from oily sludge using sub-/supercritical water
treatment can be classified into four categories: gas, oil, liquid, and
solid. Carbon distribution in these types of products is an important
indicator for evaluating the SCW process and optimizing the operating
parameters. However, to date, most studies have only focused on the
target products, such as the solid products of HTC, oil products of HTL
and SCWU, and gas products of SCWG. Consequently, only a few articles
have reported the carbon distribution data, and the results are summa­
rized in Fig. 3. It can be seen that the carbon distribution curves reported
by different researchers were significantly different. Two aspects are
responsible. On one hand, the physical compositions of oily sludge from
different sources were different, as reported by Li et al. (2021b). On the
other hand, different SCW processes should be performed under
different operating conditions, namely temperature, pressure, residence
time, OC, and catalysts. Therefore, it is necessary to first distinguish the
organic compounds in oily sludge.
The primary organic compounds in real oily sludge are biological
flocs and petroleum hydrocarbons. Biological flocs are present only in
oily wastewater sludge and oily scum. The chemical reactions of bio­
logical flocs in sub-/supercritical water have been reported in several
reviews on MSS (Linh et al., 2021; Lachos-Perez et al., 2021; Qian et al.,
2016; Wang et al., 2019). In this section, we focus on the chemical re­
actions of petroleum hydrocarbons. The chemical composition of the
petroleum hydrocarbons in oily sludge is complex and includes thou­
sands of organic compounds, which can be generally divided into
saturated, aromatic, resin, and asphaltene (SARA) fractions. SARA
analysis is a common method for heavy oil characterization (Djimasbe
et al., 2021). In addition, oily sludge contains small amounts of
water-soluble organics and fixed organic carbons, which originate from

10
Z. Chen et al. Journal of Hazardous Materials 433 (2022) 128761

Fig. 3. Carbon distribution as a function of reaction temperature during the sub-/supercritical water treatment of oily sludge.
Data were retrieved from Gungoren et al. (2007) (•), Chen et al. (2017) (▀), Khan et al. (2019) (▴), and Wang et al. (2021a) (◆).

the chemical additives and natural degradation of petroleum hydro­
carbons. However, their amounts are usually negligible compared with
those of the SARA fractions. Therefore, only the SARA fractions in oily
sludge are considered in the following discussion.
The phase behavior of organic pollutants in sub-/supercritical water
significantly affects their chemical reactions (Adeniyi et al., 2021). The
water solubility of small-molecule organics increases with increasing
temperature, and a single homogeneous reaction environment can be
achieved under supercritical conditions, as mentioned in Section 2.
However, oily sludge contains abundant macromolecular organics, such
as asphaltenes, resins, and aromatics (heavy PAHs). Molecular dynamics
simulations indicated that light PAHs, such as naphthalene, can
completely dissolve in SCW, whereas heavy PAHs, such as benzo[ghi]
perylene and benzo[a]pyrene, formed droplets in SCW (Ding et al.,

Fig. 4. General reaction pathways for the hydrothermal treatment of oily sludge.

11
Z. Chen et al.
2020). The SCW–bitumen interface was visually observed using a sap­
phire window autoclave (Sato et al., 2012; Vilcáez et al., 2012). It was
determined that under sub-/supercritical conditions the oily sludge
+ water system comprised an upper water-rich phase (homogeneous)
and a lower oil-rich phase (heterogeneous) (Hosseinpour et al., 2016a;
Liu et al., 2013; Vilcáez et al., 2012), as illustrated in Fig. 4.
At T ≤ 300 ◦ C, the chemical reactions of the SARA fractions are slow
and imperceptible. Although oil viscosity can be decreased, the mass
percentages of the SARA fractions did not change significantly, and only
small amounts of light hydrocarbons (C1–C4) and inorganic gases, such
as H2S, CO2 and H2, are generated (Al-Muntaser et al., 2020). Moreover,
the residence time reached 24 h. It is preferred for applications in the
field of steam injection for heavy crude oil recovery (Alvarado and
Manrique, 2010; Guo et al., 2016). However, biological flocs are reac­
tive at this temperature. Therefore, TH, WAO, and HTC can be used to
treat oily wastewater sludge and oily scum, for which the treatment
target is biological flocs rather than SARA fractions (Section 3.9).
At T ≥ 350 ◦ C, the chemical reactions of the SARA fractions become
significant, and the residence time decreases to hours or even minutes.
As water under these conditions is near-/supercritical, the predominant
reaction mechanism is a free-radical reaction. The proposed general
reaction pathways are illustrated in Fig. 4 and are discussed below.
(1) Upgrading. As mentioned in Section 3.6, upgrading is performed
in an oxygen-free or oxygen-deficient environment at 350–450 ◦ C. The
reactions primarily occur between the SARA fractions and involve the
successive formation of asphaltenes, resins, aromatics, and saturates.
Small amount of secondary products are also obtained, as shown in
Fig. 4. The relevant free radical reactions were summarized based on the
previous literatures (Hosseinpour et al., 2015, 2016a, 2016b; Li et al.,
2020b; Liu et al., 2013, 2017, 2018; Yeletsky et al., 2020):
Thermal cracking: R1–R2 → R1• + R2•, (1)
Water reforming: R1–R2 + H2O → R1• + R2O• + 2H•, (2)
Partial oxidation: R1–R2 + 0⋅5O2 → R1• + R2O•, (3)
Catalytic cracking: R1–R2 + MOn → R1•+ R2O• + MOn− 1, (4)
Water decomposition: H2O → HO• + H•, (5)
Decarbonylation: R2O•→ R3• + CO, (6)
H-abstraction: R1•+ R4 → R1 + R4•, (7)
β-scission: R1→ R5• + alkanes, (8)
WGSR: CO + H2O⇄CO2 + 2H•, (9)
Catalyst regeneration: MOn− 1 + H2O → MOn + 2H•, (10)
H•-condensation: H• + H•→ H2, (11)
H•-addition: R1+ H•→ R1H (light oil), (12)
H•-addition: R2O•+ H•→ R2OH (aqueous organics), (13)
HO•-addition: R1 + HO• →R1OH (aqueous organics), (14)
HO•-addition: R2O•+ HO•→ R2OOH (aqueous organics), (15)
Radical condensation: R1 + R2 + R3 +⋅⋅⋅→ R1− R2− R3− ⋅⋅⋅(coke)⋅ (16)
During the initiation stage, heavy compounds represented by R1–R2
can undergo direct thermal cracking (Eq. (1)), reforming using water
(Eq. (2)), partial oxidation in the presence of oxidants, such as air, O2,
and H2O2 (Eq. (3)), and/or catalytic cracking over catalysts, such as MOn
(Eq. (4)). Furthermore, near-/supercritical water decomposes to pro­
duce HO• and H• species (Eq. (5)). During the propagation stage, hy­
drocarbon radicals (R1•, R2•, and R2O•) propagate quickly to produce
more radicals via decarbonylation, H-abstraction, and β-scission re­
actions (Eqs. (6), (7), and (8), respectively). CO, which is a byproduct
12
Journal of Hazardous Materials 433 (2022) 128761
can react with H2O to produce H• species via a classical WGSR (Eq.(9)).
Moreover, the reduced catalyst (MOn− 1) acquires O from water, re­
generates into its MOn form, and produces H• species (Eq.(10)). Once
the amount of radicals exceeds a critical value, the reaction changes
from the propagation to the termination stage, in which the radicals
condense with each other (Eqs. (11)–(16)). The addition of H• to the
hydrocarbon radicals (R1•, R2•, R3•,⋅⋅⋅) is the desired reaction pathway
(Eq. (12)), by which light oil can be produced. When the H• species are
scarce, the hydrocarbon radicals condense into undesired coke (Eq.
(16)). Therefore, H• species is the most important radical during the
upgrading reactions because they can simultaneously increase the light
oil yield and suppress coke formation. Several approaches have been
considered for generating more H• species from water, such as
increasing the water-to-oily-sludge molar ratio (Eq. (2)) (Hosseinpour
et al., 2016a), adding oxidants (Eqs. (3), (6), and (9)) (Arai et al., 2000;
Sato et al., 2012), using MOn as catalysts (Eqs. (4) and (10)) (Golmo­
hammadi et al., 2016; Kosari et al., 2017; Yeletsky et al., 2020), and
adding CO (Eq. (9)) (Sato et al., 2015, 2013).
(2) Gasification. As mentioned in Section 3.8, high temperatures (up
to 800 ◦ C), high water-to-oily-sludge ratios (>95%), the presence of
catalysts, and an oxygen-efficient reaction medium are preferred for
gasification. Gasification is used to completely decompose the SARA
fractions to produce gaseous and aqueous products, and finally to har­
vest H2-rich syngas, as shown in Fig. 4.
The reaction pathways of the SARA fractions during gasification are
similar to those followed during upgrading, i.e., Eqs. (1)–(16). However,
the production of aqueous organics (Eqs. (13)–(15)) is remarkable
during gasification. This can explain the presence of abundant organics
in the aqueous product (Wang et al., 2021a). Of which, the WGSR (Eq.
(9)) is the desired reaction pathway. After the destruction of the SARA
fractions, the secondary products further decompose. The alkanes and
olefins in the gaseous product can be reformed with water (Eq. (17)).
The phenols, aldehydes, ketones, and organic acids in the aqueous
product can be deoxidized into hydrocarbon radicals (R1•, R2•, R3•,⋅⋅⋅)
(Eqs. (6) and (18)), which can be further decomposed by repeating the
reactions described by Eqs. (1)–(4). Furthermore, coke can be partly
gasified with water according to the reaction described by Eq. (19) (Peng
et al., 2021; Rana et al., 2019). Lastly, the H• species generated from
different reactions condense with themselves to form the desired prod­
uct, i.e., H2 (Eq. (11)).
Water reforming: CH4 + 3H2O ⇄ CO + 6H•, (17)
Decarboxylation: R2OOH → R6• + CO2, (18)
Coke gasification: C + H2O ⇄ CO + 2H•⋅ (19)
(3) Oxidation. The most remarkable characteristic of oxidation is the
presence of excess O2. Therefore, all the SARA fractions are completely
mineralized as CO2 and H2O, and coke formation is inhibited. In 1991, Li
et al. (1991) proposed a simplified pathway for the oxidation of organic
compounds in sub-/supercritical water. They divided organic substances
into three groups: Group A (comprising the initial and intermediate
organics except for CH3COOH), Group B (comprising the refractory in­
termediates represented by CH3COOH), and Group C (comprising the
final products and CO2). Based on this, a triangular model was estab­
lished. However, subsequent studies have suggested that this model was
not suitable for the SCWO of heavy oil. It was found that CO was the
primary refractory intermediate, and CH3COOH was only a minor re­
fractory intermediate (Chen et al., 2017; Cui et al., 2009; Portela et al.,
2001). Given this, Cui et al., (2009, 2011) selected CO and CH3COOH as
refractory intermediates and proposed a new quadrangular model to
describe the reaction pathways. This model was adopted in this review,
as illustrated in Fig. 4.
Based on the previous reaction pathways (Eqs. (1)–(15), (17), and
(18)), the primary and secondary products (denoted as CxHyOz) can be
directly degraded into the final products (Eq. (20)), or via CH3COOH
Z. Chen et al.
(Eq. (21)) or CO intermediates (Eqs. (6), (17), (22)). Lastly, CO is
attacked by HO• species and converts into CO2 (Eq. (23)) (Li et al.,
2021a).
Direct oxidation: CxHyOz + (x+0⋅25y − 0⋅5z)O2 → xCO2 + 0.5yH2O, (20)
Complete oxidation: CH3COOH + 2O2 → 2CO2 + 2H2O, (21)
Partial oxidation: CH3COOH + O2 → 2CO + 2H2O, (22)
CO oxidation: CO + HO• → CO2 +H•⋅ (23)
5. Conversion of model petroleum compounds in sub-/
supercritical water
Considering the unpredictable chemical structures of the resins and
asphaltenes in oily sludge, only a few identifiable model compounds of
saturates and aromatics were selected, and the information is summa­
rized below.
5.1. Long-chain alkanes and fatty acids
Long-chain alkanes with more than 12 C atoms are among the pri­
mary identifiable organics in oily sludge. They are also the main com­
ponents of diesel oil. Compared with other organics in the oily sludge,
long-chain alkanes presented the best value. Therefore, long-chain al­
kanes are typically regarded as resources rather than pollutants. With
regard to the hydrothermal treatment of long-chain alkanes, current
studies have focused on producing H2-rich syngas via SCWG. Only a few
model compounds have been reported to date, including n-dodecane
(Guerra et al., 2020; Sanchez-Hernandez et al., 2018), n-hexadecane
(Alshammari and Hellgardt, 2012, 2015, 2016; Watanabe et al., 2001,
2003) and diesel, which is a mixture (Kou et al., 2022; Pinkwart et al.,
2004; Susanti et al., 2014; Xu et al., 2019a). Long-chain fatty acids are
also present in oily sludge as chemical additives and biodegradation
products; furthermore, they are the intermediate products during the
SCWG of long-chain alkanes(Kong et al., 2019). Therefore, the reaction
pathways of long-chain alkanes and fatty acids using SCW are
Fig. 5. Reaction pathways involved in the SCWG of long-chain alkanes and fatty acids.
13
Journal of Hazardous Materials 433 (2022) 128761
summarized based on the previously published literature (Jin et al.,
2010; Sanchez-Hernandez et al., 2018; Watanabe et al., 2003; Xu et al.,
2019a; Youssef et al., 2011), as shown in Fig. 5.
In a pure SCW environment, long-chain alkanes crack directly at high
temperatures, and C–C cleavage is the predominant reaction. The pri­
mary products of the C–C cleavage reaction are alkenes and short-chain
alkanes. Short-chain alkanes can be further decomposed to produce
shorter-chain alkenes and alkanes. At insufficient water concentrations
(low CH2O), the alkenes are cyclized as PAHs and further polymerized as
char/tar. In contrast, at high water concentrations (high CH2O), alkenes
are dispersed and the cyclization and polymerization reactions are
suppressed. Moreover, water participates in these reactions. Alkanes and
alkenes can be hydrolyzed into oxygenated compounds, such as ketones,
aldehydes, and organic acids. Lastly, small-molecule compounds (pri­
marily C2–C4) can be further gasified into syngas or remain as liquid
products.
In the presence of oxidants (O2 or lattice O from MOn), long-chain
alkanes are partly oxidized into ketones and aldehydes. Thereafter, the
ketones and aldehydes are converted via three pathways. The first
pathway consists of a cracking reaction in the presence of bases. The
products are primarily alkenes and formaldehyde (HCHO). The reaction
pathways of alkenes have been described in the previous paragraph, and
HCHO is thermally decomposed into CO and H2. The second pathway
consists of a cyclization reaction at low CH2O. Phenols are the primary
products, and they are further decomposed via ring-opening reactions.
The phenol reaction pathways are discussed in detail in Section 5.2. The
third pathway consists of an oxidation/hydrolysis reaction at high CH2O,
and the produced ketones and aldehydes are further oxidized into fatty
acids. Immediately thereafter, the fatty acids are decomposed into short-
chain alkanes and CO2 via decarboxylation. Subsequently, the short-
chain alkanes are further oxidized into ketones and aldehydes
following the same steps, i.e., the repetition of the Cn→Cn− 1 reactions, as
illustrated in Fig. 5. Lastly, the C2–C4 fractions are reformed with water
to produce syngas.
In summary, the addition of oxygen, use of catalysts, and increase in
CH2O are efficient methods for suppressing char and tar formation and
promoting H2 production. However, more detailed reaction informa­
tion, such as the effect of chain length, have not yet been elucidated. To
Z. Chen et al.
date, only a few model petroleum compounds have been studied, and
more works should focus on alkanes and fatty acids with different chain
lengths, especially those with more than 20 C atoms.
5.2. Benzenes and polycyclic aromatic hydrocarbons (PAHs)
Benzenes and PAHs, which are also the primary identifiable organics
in oily sludge, are usually regarded as environmental pollutants owing
to their toxic and hazardous characteristics. Herein, we summarize the
reaction pathways of nine typical compounds in sub-/supercritical water
based on the previous literature, i.e., benzene (Yong and Matsumura,
2014), phenol (Gopalan and Savage, 1994; Guan et al., 2011; Huelsman
and Savage, 2013; Krajnc and Levec, 1996; Xu et al., 2011; Zhang et al.,
2020b), biphenyl (Onwudili and Williams, 2007b), fluorene (Onwudili
and Williams, 2007b), naphthalene (Han et al., 2019; Onwudili and
Williams, 2007a; Wang et al., 2016), anthracene (Daud et al., 2021;
Reina et al., 2016), phenanthrene (Onwudili and Williams, 2007a),
pyrene (Daud et al., 2021; Onwudili and Williams, 2006), and benzo[a]
pyrene (Daud et al., 2021; Fang and Kozinski, 2000; Jiang et al., 2017).
These compounds are aromatic hydrocarbons with one to five rings and
are marked as pink color in Fig. 6. As indicated in Section 5.1 and
illustrated in Fig. 5, at low CH2O, benzenes and PAHs tend to polymerize
as char and tar. To simplify the reaction pathways, in Fig. 6 we only
illustrate the degradation pathways.
Typically, PAHs undergo successive degradation according to the
equation Rn→Rn− 1 (R–ring, n = 1–5). Although the reaction pathways
appear to be complex, they can be broadly classified into two primary
categories: thermal cracking and hydroxylation/oxidation. Thermal
cracking primarily occurs in oxygen-free environments with low CH2O,
whereas hydroxylation/oxidation requires aerobic environments with
high CH2O. Distinct boundaries for the operating conditions for these two
types of reaction pathways have not yet been established. Therefore, It is
usually considered that thermal cracking and hydroxylation/oxidation
can occur independently, alternately, or simultaneously during PAH
degradation in sub-/supercritical water. The reaction pathways in Fig. 6
can be described as follows.
(1) Degradation from five to four rings. The reaction pathways for
the degradation of five-ring PAHs into four-ring PAHs have been rarely
described in the literature. Recently, Daud et al. (2021) studied the
partial oxidation of three-, four, and five-ring PAHs in sub-/supercritical
water and concluded that reactivity decreased as follows: anthracene
> benzo[a]pyrene > pyrene. General reaction pathways were also pro­
posed based on the identified products, and they are summarized in the
first three lines in Fig. 6. Benzo[a]pyrene is degraded into chrysene and
3,4-dihydro-benz[a]anthracene-1-(2 H)-one through central-ring-op
ening reactions or into pyrene and 7 H benz[de]anthracene-7-one
through terminal-ring-opening reactions. Subsequently, the four-ring
PAHs are further cracked to produce three-ring PAHs, namely 2-phenyl­
naphthalene and phenanthrene.
Jiang et al. (2017) proposed more detailed pathways for benzo[a]
pyrene using ReaxFF reactive molecular dynamics simulations. They
identified three degradation pathways, as follows: benzo[a]pyrene was
attacked by OH• species during SCWG (Route 1), O2 molecules during
SCWO (Route 2), and OH• species and O2 and H2O2 molecules during
SCWO (Route 3). For Route 1, the OH• species removed H atoms from
benzo[a]pyrene to form H2O molecules, and then the six-membered ring
of benzo[a]pyrene was converted into a polycyclic compound
comprising one five-membered ring and one three-membered ring via
the loss of a H atom. Because its structure was unstable, the
three-membered ring was attacked by an OH• species, leading to ring
opening. For Route 2, the O2 molecule bound to the C atoms of benzo[a]
pyrene, causing breakdown of the conjugated structure and distortion of
the aromatic rings. Subsequently, the O atom inserted into the
six-membered ring to form a heterocyclic compound. As the C–O bonds
were unstable, they were easily attacked by H atoms to achieve ring
opening. For Route 3, the OH• species and O2 molecules simultaneously
14
Journal of Hazardous Materials 433 (2022) 128761
attacked the aromatic ring. One ring of benzo[a]pyrene was converted
into a seven-membered ring, in which one O atom was inserted into the
ring and the other two O atoms were bonded to C atoms. Lastly, ring
opening occurred via C–O bond cleavage.
Therefore, two-, three-, and four-ring PAHs can be obtained via
benzo[a]pyrene degradation following the aforementioned routes.
(2) Degradation of four-ring PAHs into one-ring aromatic hydro­
carbons. Onwudili and Williams (2006, 2007a, 2007b) described in
detail the degradation pathways of biphenyl, fluorene, naphthalene,
phenanthrene and pyrene. In addition, Reina et al. (2016) studied the
catalytic cracking of anthracene in SCW. Using their results, the reaction
pathways of two-, three-, and four-ring PAHs were summarized, and the
results are illustrated in lines 3–8 in Fig. 6. Thermal cracking is a simple
reaction pathway in which ring opening (Rn→Rn− 1) is achieved directly
via C–C bond cleavage. For example, pyrene → phenanthrene, 2-phenyl­
naphthalene → naphthalene, anthracene → naphthalenes, and biphenyl
→ phenylethene.
In contrast, the hydroxylation/oxidation reaction pathway is com­
plex. Typically, three steps are required for Rn → Rn− 1 terminal-ring-
opening reactions, i.e., hydroxylation, oxidation, and ring opening.
For example, phenanthrene → hydroxyphenanthrene → phenan­
threnequinone → dialdehyde, and naphthalene → 1,4-naphthol → 1,4-
napthoquinone → phthalic acid. In contrast, four steps are necessary
for Rn → Rn− 1 central-ring-opening reactions, i.e., hydroxylation,
oxidation, epoxidation, and ring opening. For example, anthracene →
anthrone → 1,4-napthoquinone → xanthone → phenol and benzalde­
hyde, fluorene → 9-hydroxyfluorene → 9 H-fluorenone → 4-hydroxy-
9 H-fluorenone → xanthone → phenol and benzaldehyde. Isomerization
is another common reaction pathway. For example, phenylethen-2-ol ⇄
acetophenone, 2-hydroxybiphenyl ⇄ 4-hydroxybiphenyl, and phenan­
threnequinone ⇄ 1,4-napthoquinone.
Lastly, phenol was obtained as the primary one-ring product through
six routes, as illustrated in Fig. 6.
(3) Phenol degradation. Phenols are not only the main toxic pollut­
ants in wastewater, but also the important intermediates during hy­
drothermal conversion of biomass. Therefore, phenol degradation in
sub-/supercritical water has been widely investigated (Gopalan and
Savage, 1994; Guan et al., 2011; Huelsman and Savage, 2013; Krajnc
and Levec, 1996; Xu et al., 2011; Zhang et al., 2020b). The reaction
pathways for phenol degradation are summarized in the last three lines
in Fig. 6. First, phenol is hydroxylated or oxidized to benzenediols, and
then benzenediols are oxidized to benzoquinones. Subsequently ring
opening occurs because benzoquinones present unstable structures. For
example, 3-hydroxy-acrylic acid, 1,2-dialdehyde, and 1,4-but-2-dienal
are unstable and are further converted into C2–C4 aldehydes, ketones,
alcohols, and acids. It must be pointed out that C2–C4 compounds are
also generated as fragments through the aforementioned degradation
pathways illustrated in lines 1–8 in Fig. 6. Lastly, the C2–C4 compounds
are gasified to harvest syngas under oxygen-poor conditions or
completely mineralized as CO2 and H2O under oxygen-rich conditions.
6. Conclusion and future perspectives
Hydrothermal technology provides a green route for oily sludge
treatment. Dehydration, an indispensable preprocessing step of tradi­
tional treatment technologies, is not required for hydrothermal treat­
ment because the reaction medium is water. Furthermore, sub-/
supercritical water serves as both solvent and reactant. Based on these,
oily sludge can be efficiently treated for different purposes, such as
hydrocarbon separation via PHWE, dewaterability improvement via TH,
hydrochar production via HTC, biodegradability improvement via
WAO, bio-oil production via HTL, light oil production via SCWU, com­
plete degradation via SCWO, and H2-rich syngas production via SCWG.
The key findings of this review are summarized as follows:
Z. Chen et al. Journal of Hazardous Materials 433 (2022) 128761

Fig. 6. Reaction networks of nine aromatic hydrocarbons in sub-/supercritical water.

15
Z. Chen et al.
(1) Various hydrothermal technologies. Eight hydrothermal tech­
nologies are systematically described, i.e., PHWE, TH, HTC,
WAO, HTL, SCWU, SCWO, and SCWG, including their develop­
ment, technical principles, and applications in oily sludge treat­
ment. The information summarized herein is helpful for non-
expert readers to identify the similarities and differences be­
tween the aforementioned hydrothermal technologies. Moreover,
a guideline is proposed for developing pertinent hydrothermal
processes for any type of oily sludge.
(2) Oily sludge behavior in sub-/supercritical water. The general
reaction pathways of oily sludge in sub-/supercritical water are
summarized. With the excess oxygen, increasing temperature and
prolonged time, the organics in oily sludge degrade in the
following order: SARA fractions → gaseous and aqueous organics,
hydrochar → CO, and CH3COOH → H2-rich syngas or CO2 and
H2O. Particularly, the chemical mechanism at temperatures
above 350 ◦ C are discussed in detail.
(3) Reaction pathways of model petroleum compounds. The reaction
pathways of aliphatic and aromatic hydrocarbons are summa­
rized and discussed deeply combining with two reaction maps.
Typically, hydrocarbons degrade through two primary pathways:
thermal cracking under oxygen-free and low CH2O conditions and
hydroxylation/oxidation under oxygen-rich and high CH2O
conditions.
Hydrothermal treatment of oily sludge has been widely studied in
laboratory, and the findings suggest its industrialization is great po­
tential. However, the relevant commercial activities are still rare to date.
To fill the gap between laboratory study and industrial application,
several aspects are recommended for future researches.
(1) Phase behavior. The solubility of some heavy PAHs, resins, and
asphaltenes in SCW is limited. The inorganic salts in oily sludge
and heterogeneous catalysts are present as solid particles.
Therefore, the chemical reactions involved to real oily sludge is
heterogeneous instead of homogeneous. The phase behavior
significantly affects the chemical reactions, but relevant funda­
mental data are scarce.
(2) Interaction between biological flocs and petroleum hydrocar­
bons. Biological flocs and petroleum hydrocarbons are the two
primary types of organics in oily sludge. Although the hydro­
thermal treatment of individual compounds has been widely
investigated, their interactions in sub-/supercritical water have
not been thoroughly studied to date.
(3) Detailed reaction pathways. Because of the limited information
obtained from traditional experiments, some reaction pathways,
such as the ring-opening step of heavy PAHs and C–C cleavage of
long-chain alkanes have not yet been elucidated enough.
Computational simulation is a powerful tool because it can pro­
vide complementary information that is difficult to obtain
experimentally. In addition, a visual reactor featuring a sapphire
window or silica capillary can be a promising tool for observing
reactions in situ. Both of computational simulations and in situ
observations are recommended for further investigation.
(4) By products. All the aforementioned hydrothermal technologies
except for SCWO generate byproducts more or less, which usually
have been neglected in the previously published literature.
Product distribution (carbon balance) is important for evaluating
the target product yield, and a well-designed hydrothermal pro­
cess is crucial for achieving the zero discharge. Besides, there may
be some toxic compounds in by-products, such as PAHs and
heavy metals. Therefore, potential environmental pollution risk
should be evaluated before recycling or discharging.
(5) Catalyst. Catalyst is vulnerable in the harsh reaction environment
of sub-/supercritical water. Given this, both high-stable catalyst
and disposable catalyst are recommended. The high-stable
16
Journal of Hazardous Materials 433 (2022) 128761
catalyst is developed for the mild hydrothermal technologies,
such as TH, HTC, WAO and HTL. Although the high-stable cata­
lyst is costly, it can be used repeatedly. On the contrary, dispos­
able catalyst is suitable for the SCW processes, such as SCWU,
SCWO, and SCWG. The disposable catalyst is costless because it is
usually derived from the nature minerals or industrial wastes.
(6) Technology problems. Corrosion, plugging and high energy
consumption are well known as the main technology problems in
hydrothermal technologies. Of which, corrosion and plugging
can occur in any high pressure and high temperature sections,
such as preheater, reactor, cooler and heat exchanger. The high
energy consumption is results from both power (high operation
pressure) and heating (high operation temperature). Therefore, a
well-designed process (not only the reactor) is the most efficient
way to minimize or even overcome these technology problems.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was financially supported by National Natural Science
Foundation of China (22108268), Natural Science Foundation of
Chongqing, China (cstc2019jcyj-msxmX0415, cstc2021jcyj-
msxmX0187), Natural Science Foundation of Beibei, Chongqing, China
(2021-8). West Light Foundation (Young Scholar) of the Chinese Acad­
emy of Sciences, China (Y93A030M10, E2296201), Open Project Pro­
gram of the State Key Laboratory of Petroleum Pollution Control, China
(PPC2019005).
References
Abdpour, S., Santos, R.M., 2021. Recent advances in heterogeneous catalysis for
supercritical water oxidation/gasification processes: insight into catalyst
development. Process Saf. Environ. Prot. 149, 169–184.
Adeniyi, K.I., Zirrahi, M., Hassanzadeh, H., 2021. Phase equilibria of water-hydrocarbon
(pentane to heavy oils) systems in the near-critical and supercritical water regions - a
literature review. J. Supercrit. Fluid. 178, 105356.
Al-Duri, B., Alsoqyani, F., Kings, I., 2015. Supercritical water oxidation for the
destruction of hazardous waste: Better than incineration. Philos. T. R. Soc. A 373,
2057.
Al-Muntaser, A.A., Varfolomeev, M.A., Suwaid, M.A., Yuan, C., Chemodanov, A.E.,
Feoktistov, D.A., Rakhmatullin, I.Z., Abbas, M., Domínguez-álvarez, E.,
Akhmadiyarov, A.A., Klochkov, V.V., Amerkhanov, M.I., 2020. Hydrothermal
upgrading of heavy oil in the presence of water at sub-critical, near-critical and
supercritical conditions. J. Petrol. Sci. Eng. 184, 106592.
Al-Muntaser, A.A., Varfolomeev, M.A., Suwaid, M.A., Feoktistov, D.A., Yuan, C.,
Klimovitskii, A.E., Gareev, B.I., Djimasbe, R., Nurgaliev, D.K., Kudryashov, S.I.,
Egorova, E.V., Fomkin, A.V., Petrashov, O.V., Afanasiev, I.S., Fedorchenko, G.D.,
2021. Hydrogen donating capacity of water in catalytic and non-catalytic
aquathermolysis of extra-heavy oil: deuterium tracing study. Fuel 283, 118957.
Alshammari, Y.M., Hellgardt, K., 2012. Thermodynamic analysis of hydrogen production
via hydrothermal gasification of hexadecane. Int. J. Hydrog. Energ. 37 (7),
5656–5664.
Alshammari, Y.M., Hellgardt, K., 2015. Partial oxidation of n-hexadecane through
decomposition of hydrogen peroxide in supercritical water. Chem. Eng. Res. Des. 93,
565–575.
Alshammari, Y.M., Hellgardt, K., 2016. Sub and supercritical water reforming of n-
hexadecane in a tubular flow reactor. J. Supercrit. Fluid. 107, 723–732.
Alvarado, V., Manrique, E., 2010. Enhanced oil recovery: an update review. Energies 3
(9), 1529–1575.
Arai, K., Adschiri, T., Watanabe, M., 2000. Hydrogenation of hydrocarbons through
partial oxidation in supercritical water. Ind. Eng. Chem. Res. 39 (12), 4697–4701.
Arcelus-Arrillaga, P., Pinilla, J.L., Hellgardt, K., Millan, M., 2017. Application of water in
hydrothermal conditions for upgrading heavy oils: a review. Energ. Fuel. 31 (5),
4571–4587.
Berkowitz, N., Calderon, J., 1990. Extraction of oil sand bitumens with supercritical
water. Fuel Process. Technol. 25 (1), 33–44.
Berl, E., 1934. Origin of asphalts, oil, natural gas and bituminous coal. Science 80 (2071),
227–228.
Bermejo, M.D., Cocero, M.J., 2006. Supercritical water oxidation: a technical review.
AIChE J. 52 (11), 3933–3951.
Z. Chen et al.
Burns, J., 1969. A review of steam soak operations in california. J. Petrol. Technol. 21,
25.
Chang, S., Liu, Y., 2007. Degradation mechanism of 2,4,6-trinitrotoluene in supercritical
water oxidation. J. Environ. Sci. 19 (12), 1430–1435.
Chen, Z., Chen, Z., Yin, F., Wang, G., Chen, H., He, C., Xu, Y., 2017. Supercritical water
oxidation of oil-based drill cuttings. J. Hazard. Mater. 332, 205–213.
Chen, Z., Zhou, J., Chen, Z., Chen, H., Chen, Q., He, C., Liu, X., Xu, Y., 2018. A laboratory
evaluation of superheated steam extraction process for decontamination of oil-based
drill cuttings. J. Environ. Chem. Eng. 6 (5), 6691–6699.
Chen, Z., Li, D., Tong, K., Chen, Z., Chen, H., Chen, Q., Xu, Y., 2019. Static
decontamination of oil-based drill cuttings with pressurized hot water using
response surface methodology. Environ. Sci. Pollut. R. 26 (7), 7216–7227.
Chen, Z., Zheng, Z., Li, D., Chen, H., Xu, Y., 2020. Continuous supercritical water
oxidation treatment of oil-based drill cuttings using municipal sewage sludge as
diluent. J. Hazard. Mater. 384, 121225.
Chen, Z., Tong, K., He, C., Xue, M., Lyu, C., Chen, H., Chen, Q., Xu, Y., 2021a. High
quality oil recovery from oil-based drill cuttings via catalytic upgrading in presence
of near-/supercritical water and different industrial wastes. J. Clean. Prod., 129061
Chen, Z., Tong, K., Xu, F., Xue, M., Chen, H., Chen, Q., Wang, D., Xu, Y., 2021b.
Development of supercritical water oxidation technology for application to
hazardous waste treatment: an extreme case study. J. Environ. Chem. Eng. 9 (4),
105296.
Cherad, R., Onwudili, J.A., Biller, P., Williams, P.T., Ross, A.B., 2016. Hydrogen
production from the catalytic supercritical water gasification of process water
generated from hydrothermal liquefaction of microalgae. Fuel 166, 24–28.
Chinese National Standard, 2007. GB 5085.6–2007, Identification Standards for
Hazardous Wastes-identification for Toxic Substance content. Integrated
Environmental Protection Agency of China,, Beijing.
Cocero, M., Alonso, E., Sanz, M., Fdz-Polanco, F., 2002. Supercritical water oxidation
process under energetically self-sufficient operation. J. Supercrit. Fluid. 24 (1),
37–46.
Cui, B., Cui, F., Jing, G., Xu, S., Huo, W., Liu, S., 2009. Oxidation of oily sludge in
supercritical water. J. Hazard. Mater. 165 (1–3), 511–517.
Cui, B., Liu, S., Cui, F., Jing, G., Liu, X., 2011. Lumped kinetics for supercritical water
oxidation of oily sludge. Process Saf. Environ. Prot. 89 (3), 198–203.
da Silva, L.J., Alves, F.C., de Franca, F.P., 2012. A review of the technological solutions
for the treatment of oily sludges from petroleum refineries. Waste Manag. Res. 30
(10), 1016–1030.
Dadkhah, A.A., Akgerman, A., 2002. Hot water extraction with in situ wet oxidation:
PAHs removal from soil. J. Hazard. Mater. 93 (3), 307–320.
Dadkhah, A.A., Akgerman, A., 2006. Hot water extraction with in situ wet oxidation:
Kinetics of PAHs removal from soil. J. Hazard. Mater. 137 (1), 518–526.
Dang, Z., Zhu, X., Wang, L., Ji, G., 2021. Titanium dioxide catalytic hydrothermal
liquefaction to treat oily sludge: as hydrogen production catalyst. Chem. Eng. J. Adv.
8, 100139.
Daud, A.R.M., Berrueco, C., Hellgardt, K., Millan, M., Kandiyoti, R., 2021. Oxidative
cracking of three to five-member ring polycyclic aromatic hydrocarbons in
subcritical and supercritical water. J. Supercrit. Fluid. 167, 105050.
Dehaan, H.J., Vanlooke, J., 1969. Early results of first large-scale steam soak project in
tia juana field western venezuela. J. Petrol. Technol. 21, 101.
Deng, S., Yu, S., Tan, H., Lu, X., Wang, X., 2021. A comparative study on the effects of
NaOH and CaCl2 additives on dewatering properties and product characteristics of
oily scum via hydrothermal treatment. Fuel 310, 122398.
Ding, W., Jin, H., Zhao, Q., Chen, B., Cao, W., 2020. Dissolution of polycyclic aromatic
hydrocarbons in supercritical water in hydrogen production process: A molecular
dynamics simulation study. Int. J. Hydrog. Energ. 45 (52), 28062–28069.
Ding, X., Lei, Y., Shen, Z., Yu, Y., Zhou, Q., Wei, J., Fang, T., 2017. Experimental
determination and modeling of the solubility of sodium chloride in subcritical water
from (568 to 598) K and (10 to 25) MPa. J. Chem. Eng. Data 62 (10), 3374–3390.
Djimasbe, R., Varfolomeev, M.A., Al-muntaser, A.A., Yuan, C.D., Suwaid, M.A.,
Feoktistov, D.A., Rakhmatullin, I.Z., Milovankin, A.A., Murzakhanov, F.,
Morozov, V., Gafurov, M., Farhadian, A., Davletshin, R.R., 2021. Deep insights into
heavy oil upgrading using supercritical water by a comprehensive analysis of GC,
GC-MS NMR, and SEM-EDX with the aid of EPR as a complementary technical
analysis. ACS Omega 6 (1), 135–147.
Duan, P., Yang, S., Xu, Y., Wang, F., Zhao, D., Weng, Y., Shi, X., 2018. Integration of
hydrothermal liquefaction and supercritical water gasification for improvement of
energy recovery from algal biomass. Energ 155, 734–745.
Duan, Y., Gao, N., Sipra, A.T., Tong, K., Quan, C., 2022. Characterization of heavy metals
and oil components in the products of oily sludge after hydrothermal treatment.
J. Hazard. Mater. 424, 127293.
Fang, Z., Kozinski, J.A., 2000. Phase behavior and combustion of hydrocarbon-
contaminated sludge in supercritical water at pressures up to 822 MPa and
temperatures up to 535 degrees C. P. Combust. Inst 28, 2717–2725.
Fedyaeva, O.N., Vostrikov, A.A., 2012. Disposal of hazardous organic substances in
supercritical water. Russ. J. Phys. Chem. B. 6 (7), 844–860.
Gao, N., Duan, Y., Li, Z., Quan, C., Yoshikawa, K., 2021. Hydrothermal treatment
combined with in-situ mechanical compression for floated oily sludge dewatering.
J. Hazard. Mater. 402, 124173.
García-Rodríguez, Y., Mato, F.A., Martín, A., Bermejo, M.D., Cocero, M.J., 2015. energy
recovery from effluents of supercritical water oxidation reactors. J. Supercrit. Fluid.
104, 1–9.
Golmohammadi, M., Ahmadi, S.J., Towfighi, J., 2016. Catalytic cracking of heavy
petroleum residue in supercritical water: study on the effect of different metal oxide
nanoparticles. J. Supercrit. Fluid. 113, 136–143.
17
Journal of Hazardous Materials 433 (2022) 128761
Gopalan, S., Savage, P.E., 1994. Reaction-mechanism for phenol oxidation in
supercritical water. J. Phys. Chem. 98 (48), 12646–12652.
Guan, Q., Wei, C., Chai, X.-S., 2011. Pathways and kinetics of partial oxidation of phenol
in supercritical water. Chem. Eng. J. 175, 201–206.
Guerra, P., Zaker, A., Duan, P., Maag, A.R., Tompsett, G.A., Brown, A.B., Schmidt-
Rohr, K., Timko, M.T., 2020. Analysis of coke formed during zeolite-catalyzed
supercritical dodecane cracking: effect of supercritical water. Appl. Catal. A-Gen.
590, 117330.
Gungoren, T., Saglam, M., Yuksel, M., Madenoglu, H., Isler, R., Metecan, I.H., Ozkan, A.
R., Ballice, L., 2007. Near-critical and supercritical fluid extraction of industrial
sewage sludge. Ind. Eng. Chem. Res. 46 (4), 1051–1057.
Guo, K., Li, H., Yu, Z., 2016. In-situ heavy and extra-heavy oil recovery: a review. Fuel
185, 886–902.
Han, Y., Ma, T., Chen, F., Li, W., Zhang, J., 2019. Supercritical water gasification of
naphthalene over iron oxide catalyst: a ReaxFF molecular dynamics study. Int. J.
Hydrog. Energ. 44 (57), 30486–30498.
Hawthorne, S.B., Yang, Y., Miller, D.J., 1994. Extraction of organic pollutants from
environmental solids with sub- and supercritical water. Anal. Chem. 66 (18),
2912–2920.
Hochberg, S.Y., Tansel, B., Laha, S., 2022. Materials and energy recovery from oily
sludges removed from crude oil storage tanks (tank bottoms): a review of
technologies. J. Environ. Manag. 305, 114428.
Hosseinpour, M., Ahmadi, S.J., Fatemi, S., 2015. Successive co-operation of supercritical
water and silica-supported iron oxide nanoparticles in upgrading of heavy petroleum
residue: Suppression of coke deposition over catalyst. J. Supercrit. Fluid. 100, 70–78.
Hosseinpour, M., Ahmadi, S.J., Fatemi, S., 2016a. Deuterium tracing study of
unsaturated aliphatics hydrogenation by supercritical water in upgrading heavy oil.
Part I: non-catalytic cracking. J. Supercrit. Fluid. 107, 278–285.
Hosseinpour, M., Fatemi, S., Ahmadi, S.J., 2016b. Deuterium tracing study of
unsaturated aliphatics hydrogenation by supercritical water in upgrading heavy oil.
Part II: hydrogen donating capacity of water in the presence of iron(III) oxide
nanocatalyst. J. Supercrit. Fluid. 110, 75–82.
Hu, G., Li, J., Zeng, G., 2013. Recent development in the treatment of oily sludge from
petroleum industry: a review. J. Hazard. Mater. 261 (0), 470–490.
Huelsman, C.M., Savage, P.E., 2013. Reaction pathways and kinetic modeling for phenol
gasification in supercritical water. J. Supercrit. Fluid. 81, 200–209.
Hui, K., Tang, J., Lu, H., Xi, B., Qu, C., Li, J., 2020. Status and prospect of oil recovery
from oily sludge: a review. Arab. J. Chem. 13, 6523–6543.
Hyne, J.B., Clark, P.D., Clarke, R.A., Koo, J., Greidanus, J.W., Tyrer, J.D., Verona, D.,
1982. Aquathermolysis of heavy oils. Rev. Tec. Intevep 2 (2), 87–94.
Ibrahim, A.B.A., Akilli, H., 2019. Supercritical water gasification of wastewater sludge
for hydrogen production. Int. J. Hydrog. Energ. 44 (21), 10328–10349.
Islam, M.N., Park, J.-H., Shin, M.-S., Park, H.-S., 2014. Decontamination of PCBs-
containing soil using subcritical water extraction process. Chemosphere 109, 28–33.
Islam, M.N., Park, H.-S., Park, J.-H., 2015. Extraction of diesel from contaminated soil
using subcritical water. Environ. Earth Sci. 74 (4), 3059–3066.
Islam, M.N., Jung, S.-K., Jung, H.-Y., Park, J.-H., 2017. The feasibility of recovering oil
from contaminated soil at petroleum oil spill site using a subcritical water extraction
technology. Process Saf. Environ. Prot. 111, 52–59.
Jerez, S., Ventura, M., Molina, R., Pariente, M.I., Martínez, F., Melero, J.A., 2021.
Comprehensive characterization of an oily sludge from a petrol refinery: A step
forward for its valorization within the circular economy strategy. J. Environ. Manag.
285, 112124.
Jiang, D., Wang, Y., Zhang, M., Zhang, J., Li, W., Han, Y., 2017. H2 and CO production
through coking wastewater in supercritical water condition: reaxFF reactive
molecular dynamics simulation. Int. J. Hydrog. Energ. 42 (15), 9667–9678.
Jiang, H., Duan, Y., Wang, Y., Zou, S., Zhang, L., Li, J., Wang, B., 2020. Supercritical
water gasification of oily sludge to produce hydrogen based on uniform design
method. Chem. Ind. Eng. Prog. 39 (9), 3819–3825.
Jimenez-Espadafor, F., Portela, J.R., Vadillo, V., Sanchez-Oneto, J., Becerra
Villanueva, J.A., Torres Garcia, M., Martinez de la Ossa, E.J., 2011. Supercritical
water oxidation of oily wastes at pilot plant: simulation for energy recovery. Ind.
Eng. Chem. Res. 50 (2), 775–784.
Jin, F., Enomoto, H., 2011. Rapid and highly selective conversion of biomass into value-
added products in hydrothermal conditions: chemistry of acid/base-catalysed and
oxidation reactions. Energ. Environ. Sci. 4 (2), 382–397.
Jin, F., Zeng, X., Cao, J., Kawasaki, K., Kishita, A., Tohji, K., Enomoto, H., 2010. Partial
hydrothermal oxidation of unsaturated high molecular weight carboxylic acids for
enhancing the cold flow properties of biodiesel fuel. Fuel 89 (9), 2448–2454.
Jin, H., Fan, C., Guo, L., Liu, S., Cao, C., Wang, R., 2017. Experimental study on hydrogen
production by lignite gasification in supercritical water fluidized bed reactor using
external recycle of liquid residual. Energ. Convers. Manag. 145, 214–219.
Jing, G., Luan, M., Han, C., Chen, T., Wang, H., 2012a. An effective process for removing
organic compounds from oily sludge using soluble metallic salt. J. Ind. Eng. Chem.
18 (4), 1446–1449.
Jing, G., Luan, M., Chen, T., 2013. Wet air oxidation of oily sludge using Ni2+ catalyst.
Environ. Prog. Sustain. Energ. 32 (1), 99–102.
Jing, G.L., Luan, M.M., Han, C.J., Chen, T.T., 2012b. Pretreatment of oily sludge by wet
air oxidation. J. Energ. Inst. 85 (4), 240–242.
Jocz, J.N., Savage, P.E., Thompson, L.T., 2018a. Thermodynamic analysis of catalyst
stability in hydrothermal reaction media. Ind. Eng. Chem. Res. 57 (26), 8655–8663.
Jocz, J.N., Thompson, L.T., Savage, P.E., 2018b. Catalyst oxidation and dissolution in
supercritical water. Chem. Mater. 30 (4), 1218–1229.
Kalderis, D., Hawthorne, S.B., Clifford, A.A., Gidarakos, E., 2008. Interaction of soil,
water and TNT during degradation of TNT on contaminated soil using subcritical
water. J. Hazard. Mater. 159 (2–3), 329–334.
Z. Chen et al.
Kambo, H.S., Dutta, A., 2015. A comparative review of biochar and hydrochar in terms of
production, physico-chemical properties and applications. Renew. Sust. Energ. Rev.
45, 359–378.
Kepp, U., Machenbach, I., Weisz, N., Solheim, O.E., 2000. Enhanced stabilisation of
sewage sludge through thermal hydrolysis - three years of experience with full scale
plant. Water Sci. Technol. 42 (9), 89–96.
Khan, M.K., Cahyadi, H.S., Kim, S.-M., Kim, J., 2019. Efficient oil recovery from highly
stable toxic oily sludge using supercritical water. Fuel 235, 460–472.
Kim, K., Son, S.H., Kim, K., Han, J.H., Do Han, K., Do, S.H., 2010. Treatment of
radioactive ionic exchange resins by super- and sub-critical water oxidation (SCWO).
Nucl. Eng. Des. 240 (10), 3654–3659.
Kim, K.-H., Ihm, S.-K., 2011. Heterogeneous catalytic wet air oxidation of refractory
organic pollutants in industrial wastewaters: a review. J. Hazard. Mater. 186 (1),
16–34.
Kong, L., Liu, S., Luo, L., Wang, Y., Dai, L., 2019. Enhanced methane yield from
supercritical water gasification of pentadecanoic acid. Fuel Process. Technol. 193,
48–52.
Kosari, M., Golmohammadi, M., Ahmadi, S.J., Towfighi, J., Chenari, A.H., 2017. On the
catalysis capability of transition metal oxide nanoparticles in upgrading of heavy
petroleum residue by supercritical water. J. Supercrit. Fluid. 126, 14–24.
Kou, J., Xu, J., Jin, H., Guo, L., Zhang, D., Cao, W., 2018. Evaluation of modified Ni/ZrO2
catalysts for hydrogen production by supercritical water gasification of oil-
containing wastewater. Int. J. Hydrog. Energ. 43 (30), 13896–13903.
Kou, J., Yi, L., Li, G., Cheng, K., Wang, R., Zhang, D., Jin, H., Guo, L., 2021. Structural
effect of ZrO2 on supported Ni-based catalysts for supercritical water gasification of
oil-containing wastewater. Int. J. Hydrog. Energ. 46 (24), 12874–12885.
Kou, J., Feng, H., Wei, W., Wang, G., Sun, J., Jin, H., Guo, L., 2022. Study on the detailed
reaction pathway and catalytic mechanism of a Ni/ZrO2 catalyst for supercritical
water gasification of diesel oil. Fuel 312, 122849.
Krajnc, M., Levec, J., 1996. On the kinetics of phenol oxidation in supercritical water.
AIChE J. 42 (7), 1977–1984.
Kritzer, P., 2004. Corrosion in high-temperature and supercritical water and aqueous
solutions: a review. J. Supercrit. Fluid. 29 (1–2), 1–29.
Kronholm, J., Kalpala, J., Hartonen, K., Riekkola, M.L., 2002. Pressurized hot water
extraction coupled with supercritical water oxidation in remediation of sand and soil
containing PAHs. J. Supercrit. Fluid. 23 (2), 123–134.
Kubátová, A., Jansen, B., Vaudoisot, J.-F., Hawthorne, S.B., 2002. Thermodynamic and
kinetic models for the extraction of essential oil from savory and polycyclic aromatic
hydrocarbons from soil with hot (subcritical) water and supercritical CO2.
J. Chromatogr. A 975 (1), 175–188.
Lachos-Perez, D., Torres-Mayanga, Cesar, Abaide, P., Zabot, E.R., De Castilhos, G.L., F,
2021. Hydrothermal carbonization and Liquefaction: differences, progress,
challenges, and opportunities. Bioresour. Technol. 343, 126084.
Lagadec, A.J.M., Miller, D.J., Lilke, A.V., Hawthorne, S.B., 2000. Pilot-scale subcritical
water remediation of polycyclic aromatic hydrocarbon- and pesticide-contaminated
soil. Environ. Sci. Technol. 34 (8), 1542–1548.
Lavric, E.D., Weyten, H., De Ruyck, J., Ple?u, V., Lavric, V., 2005. Delocalized organic
pollutant destruction through a self-sustaining supercritical water oxidation process.
Energ. Convers. Manag. 46 (9–10), 1345–1364.
Li, G.X., Fan, M.J., Lu, Y.J., Glarborg, P., 2021a. Kinetic modeling of carbon monoxide
oxidation and water gas shift reaction in supercritical water. J. Supercrit. Fluid. 171,
105165.
Li, J., Wang, S., Li, Y., Ren, M., Jiang, Z., Zhang, J., Yang, C., 2020a. Experimental
research and commercial plant development for harmless disposal and energy
utilization of petrochemical sludge by supercritical water oxidation. Chem. Eng. Res.
Des. 162, 258–272.
Li, J., Lin, F., Li, K., Zheng, F., Yan, B., Che, L., Tian, W., Chen, G., Yoshikawa, K., 2021b.
A critical review on energy recovery and non-hazardous disposal of oily sludge from
petroleum industry by pyrolysis. J. Hazard. Mater. 406, 124706.
Li, L., Chen, P., Gloyna, E.F., 1991. Generalized kinetic model for wet oxidation of
organic compounds. AIChE J. 37 (11), 1687–1697.
Li, N., Zhang, X., Zhang, Q., Chen, L., Ma, L., Xiao, X., 2020b. Reactivity and structural
changes of asphaltene during the supercritical water upgrading process. Fuel 278,
118331.
Li, Y., Liu, H., Xiao, K., Jin, M., Xiao, H., Yao, H., 2020c. Combustion and pyrolysis
characteristics of hydrochar prepared by hydrothermal carbonization of typical food
waste: influence of carbohydrates, proteins, and lipids. Energ. Fuel. 34 (1), 430–439.
Liu, J., Xing, Y., Chen, Y.-X., Yuan, P.-Q., Cheng, Z.-M., Yuan, W.-K., 2018. Visbreaking
of heavy oil under supercritical water environment. Ind. Eng. Chem. Res. 57 (3),
867–875.
Liu, J., Zhang, Y., Peng, K., Zhao, X., Xiong, Y., Huang, X., 2021. A review of the
interfacial stability mechanism of aging oily sludge: heavy components, inorganic
particles, and their synergism. J. Hazard. Mater. 415, 125624.
Liu, Q.-K., Xu, Y., Tan, X.-C., Yuan, P.-Q., Cheng, Z.-M., Yuan, W.-K., 2017. Pyrolysis of
asphaltenes in subcritical and supercritical water: influence of h-donation from
hydrocarbon surroundings. Energ. Fuel. 31 (4), 3620–3628.
Liu, Y., Bai, F., Zhu, C.-C., Yuan, P.-Q., Cheng, Z.-M., Yuan, W.-K., 2013. Upgrading of
residual oil in sub- and supercritical water: an experimental study. Fuel Process.
Technol. 106, 281–288.
Marrone, P.A., 2013. Supercritical water oxidation-Current status of full-scale
commercial activity for waste destruction. J. Supercrit. Fluid. 79, 283–288.
Marrone, P.A., Hong, G.T., 2007. Supercritical water oxidation. Environ. Conscious
Mater. Chem. Process. 385–453.
Marrone, P.A., Cantwell, S.D., Dalton, D.W., 2005. SCWO system designs for waste
treatment: application to chemical weapons destruction. Ind. Eng. Chem. Res. 44
(24), 9030–9039.
18
Journal of Hazardous Materials 433 (2022) 128761
Marshall, W.L., Franck, E.U., 1981. Ion product of water substance, 0–1000 ◦ C, 1–10,000
bars New International Formulation and its background. J. Phys. Chem. Ref. Data 10
(2), 295–304.
Modell, M., 1982. Processing methods for the oxidation of organics in supercritical
water. U.S. Patent, NO. 4338199.
Modell, M., Reid, R.C., Amin, S.I., 1978. Gasification process. U.S. Patent, NO. 4113446.
Nazem, M.A., Tavakoli, O., 2017. Bio-oil production from refinery oily sludge using
hydrothermal liquefaction technology. J. Supercrit. Fluid. 127, 33–40.
Neyens, E., Baeyens, J., 2003. A review of thermal sludge pre-treatment processes to
improve dewaterability. J. Hazard. Mater. 98 (1), 51–67.
Onwudili, J.A., Williams, P.T., 2006. Flameless incineration of pyrene under sub-critical
and supercritical water conditions. Fuel 85 (1), 75–83.
Onwudili, J.A., Williams, P.T., 2007a. Reaction mechanisms for the decomposition of
phenanthrene and naphthalene under hydrothermal conditions. J. Supercrit. Fluid.
39 (3), 399–408.
Onwudili, J.A., Williams, P.T., 2007b. Reaction mechanisms for the hydrothermal
oxidation of petroleum derived aromatic and aliphatic hydrocarbons. J. Supercrit.
Fluid. 43 (1), 81–90.
Paspek, S.C., Klein, M.T., 1990. Shale oil upgrading in supercritical water solutions. Fuel
Sci. Technol. Int. 8 (6), 673–687.
Pauline, A.L., Joseph, K., 2021a. Hydrothermal carbonization of crude oil sludge –
characterization of hydrochar and hydrothermal liquor. Process Saf. Environ. Protect
154, 89–96.
Pauline, A.L., Joseph, K., 2021b. Hydrothermal carbonization of oily sludge for solid fuel
recovery – investigation of chemical characteristics and combustion behaviour.
J. Anal. Appl. Pyrol. 157, 105235.
Peng, P., Guo, S., Li, L., Jin, H., Ge, Z., Guo, L., 2021. Supercritical water gasification
mechanism of polymer-containing oily sludge. Int. J. Hydrog. Energ. 46 (53),
26834–26847.
Peterson, A.A., Vogel, F., Lachance, R.P., Froeling, M., Antal Jr., M.J., Tester, J.W., 2008.
Thermochemical biofuel production in hydrothermal media: A review of sub- and
supercritical water technologies. Energ. Environ. Sci. 1 (1), 32–65.
Phuong Linh, N., Udugama, I.A., Gernaey, K.V., Young, B.R., Baroutian, S., 2021.
Mechanisms, status, and challenges of thermal hydrolysis and advanced thermal
hydrolysis processes in sewage sludge treatment. Chemosphere 281, 130890.
Pinkwart, K., Bayha, T., Lutter, W., Krausa, M., 2004. Gasification of diesel oil in
supercritical water for fuel cells. J. Power Sources 136 (2), 211–214.
Portela, J.R., Nebot, E., Mart??nez de la Ossa, E., 2001. Generalized kinetic models for
supercritical water oxidation of cutting oil wastes. J. Supercrit. Fluid. 21 (2),
135–145.
Qian, L., Wang, S., Xu, D., Guo, Y., Tang, X., Wang, L., 2016. Treatment of municipal
sewage sludge in supercritical water: a review. Water Res 89, 118–131.
Qin, Q., Wang, S., Wang, H., Ma, H., Chen, K., Qiao, Y., He, L., Qian, Z., Liu, X., Li, Z.,
Xia, X., 2017. Treatment of radioactive spent extraction solvent by supercritical
water oxidation. J. Radioanal. Nucl. Chem. 314 (2), 1169–1176.
Radfarnia, H.R., Khulbe, C., Little, E.C., 2015. Supercritical water treatment of oil sludge,
a viable route to valorize waste oil materials. Fuel 159, 653–658.
Rana, R., Nanda, S., Maclennan, A., Hu, Y., Kozinski, J.A., Dalai, A.K., 2019.
Comparative evaluation for catalytic gasification of petroleum coke and asphaltene
in subcritical and supercritical water. J. Energ. Chem. 31, 107–118.
Reina, T.R., Yeletsky, P., Bermudez, J.M., Arcelus-Arrillaga, P., Yakovlev, V.A.,
Milian, M., 2016. Anthracene aquacracking using NiMo/SiO2 catalysts in
supercritical water conditions. Fuel 182, 740–748.
Roger, T.Haug, James, D.C.S., Gossett, M., Perry, L., McCarty, 1978. Effect of thermal
pretreatment on digestibility and dewaterability of organic sludges. Water Pollut.
Control Fed. 50 (1), 73–85.
Sanchez-Hernandez, A.M., Martin-Sanchez, N., Jesus Sanchez-Montero, M.,
Izquierdo, C., Salvador, F., 2018. Effect of pressure on the gasification of dodecane
with steam and supercritical water and consequences for H-2 production. J. Mater.
Chem. A 6 (4), 1671–1681.
Sato, T., Trung, P.H., Tomita, T., Itoh, N., 2012. Effect of water density and air pressure
on partial oxidation of bitumen in supercritical water. Fuel 95, 347–351.
Sato, T., Tomita, T., Trung, P.H., Itoh, N., Sato, S., Takanohashi, T., 2013. Upgrading of
bitumen in the presence of hydrogen and carbon dioxide in supercritical water.
Energ. Fuel. 27 (2), 646–653.
Sato, T., Sumita, T., Itoh, N., 2015. Effect of CO addition on upgrading bitumen in
supercritical water. J. Supercrit. Fluid. 104, 171–176.
Savage, P.E., 1999. Organic chemical reactions in supercritical water. Chem. Rev. 99 (2),
603–621.
Savage, P.E., 2009. A perspective on catalysis in sub- and supercritical water.
J. Supercrit. Fluid. 47 (3), 407–414.
Shan, Y.-Q., Yin, L.-X., Djandja, O.S., Wang, Z.-C., Duan, P.-G., 2021. Supercritical water
gasification of waste water produced from hydrothermal liquefaction of microalgae
over Ru catalyst for production of H-2 rich gas fuel. Fuel 292, 120288.
Shi, P., Wu, Y., Li, F., Bai, C., 2015. Research on thermal hydrolysis oxidation process of
oily sludge. J. Dalian Univ. 36 (03), 61–65.
Susanti, R.F., Dianningrum, L.W., Yum, T., Kim, Y., Lee, Y.-W., Kim, J., 2014. High-yield
hydrogen production by supercritical water gasification of various feedstocks:
Alcohols, glucose, glycerol and long-chain alkanes. Chem. Eng. Res. Des. 92 (10),
1834–1844.
Sushma, Kumari, M., Saroha, A.K., 2018. Performance of various catalysts on treatment
of refractory pollutants in industrial wastewater by catalytic wet air oxidation: a
review. J. Environ. Manag. 228, 169–188.
Taufer, N.L., Benedetti, V., Pecchi, M., Matsumura, Y., Baratieri, M., 2021. Coupling
hydrothermal carbonization of digestate and supercritical water gasification of
liquid products. Renew. Energ. 173, 934–941.
Z. Chen et al.
Teng, Q., Zhang, D., Yang, C., 2021. A review of the application of different treatment
processes for oily sludge. Environ. Sci. Poll. Res. 28, 121–132.
Teo, C.C., Tan, S.N., Yong, J.W.H., Hew, C.S., Ong, E.S., 2010. Pressurized hot water
extraction (PHWE). J. Chromatogr. A 1217 (16), 2484–2494.
Timko, M.T., Ghoniem, A.F., Green, W.H., 2015. Upgrading and desulfurization of heavy
oils by supercritical water. J. Supercrit. Fluid. 96, 114–123.
Tong, K., Xie, J., Nie, F., Li, H., Zhang, M., 2021. Treatment of dehydrated oily sludge by
hydrothermal coupled low temperature drying. Nat. Gas. Ind. 41 (04), 153–159.
Uematsu, M., Frank, E.U., 1980. Static dielectric constant of water and steam. J. Phys.
Chem. Ref. Data 9 (4), 1291–1306.
Van Oudenhoven, J.A.C.M., Cooper, G.R., Cricchi, G., Gineste, J., Potzl, P., Martin, D.E.,
1995. Oil refinery waste, disposal methods and costs 1993 survey. Oil Refin. Waste,
Dispos. Methods Costs 1993 Surv. 1–39.
Vilcáez, J., Watanabe, M., Watanabe, N., Kishita, A., Adschiri, T., 2012. Hydrothermal
extractive upgrading of bitumen without coke formation. Fuel 102, 379–385.
Wagner, W., Kruse, A., 2007. International Steam Tables – Properties of Water and Steam
Based on the Industrial Formulation IAPWS-IF97, second ed. Springer,, Berlin, p. 5.
Wang, C., Wu, C., Zhang, H., Lai, J., Luo, X., Liang, Y., Tian, J., 2021a. Hydrothermal
treatment of petrochemical sludge in subcritical and supercritical water: Oil phase
degradation and syngas production. Chemosphere 278, 130392.
Wang, L., Chang, Y., Li, A., 2019. Hydrothermal carbonization for energy-efficient
processing of sewage sludge: a review. Renew. Sust. Energ. Rev. 108, 423–440.
Wang, L., Yi, L., Wang, G., Li, L., Lu, L., Guo, L., 2021b. Experimental investigation on
gasification of cationic ion exchange resin used in nuclear power plants by
supercritical water. J. Hazard. Mater. 419, 126437.
Wang, T., Zhai, Y., Zhu, Y., Li, C., Zeng, G., 2018. A review of the hydrothermal
carbonization of biomass waste for hydrochar formation: process conditions,
fundamentals, and physicochemical properties. Renew. Sust. Energ. Rev. 90,
223–247.
Wang, Y., Wang, S., Zhao, G., Guo, Y., Guo, Y., 2016. Hydrogen production by partial
oxidation gasification of a phenol, naphthalene, and acetic acid mixture in
supercritical water. Int. J. Hydrog. Energ. 41 (4), 2238–2246.
Wang, Y., Fan, D., Li, W., 2021c. Analysis and outlook of domestic and international oil
and gas recourse situation in 2020. China Min. Mag. 30 (1), 18–23.
Watanabe, M., Mochiduki, M., Sawamoto, S., Adschiri, T., Arai, K., 2001. Partial
oxidation of n-hexadecane and polyethylene in supercritical water. J. Supercrit.
Fluid. 20 (3), 257–266.
Watanabe, M., Inomata, H., Osada, M., Sato, T., Adschiri, T., Arai, K., 2003. Catalytic
effects of NaOH and ZrO2 for partial oxidative gasification of n-hexadecane and
lignin in supercritical water. Fuel 82 (5), 545–552.
Wei, N., Xu, D., Hao, B., Guo, S., Guo, Y., Wang, S., 2021. Chemical reactions of organic
compounds in supercritical water gasification and oxidation. Water Res 190,
116634.
Xie, R., Liu, Y., Bu, T., Yao, Y., Deng, K., Yang, Z., 2016. Supercritical water gasification
of petrochemical wastewater for hydrogen production. Environ. Prog. Sustain.
Energ. 35 (2), 428–432.
Xu, D., Wang, S., Guo, Y., Tang, X., Gong, Y., Ma, H., 2011. Catalyzed partial oxidative
gasification of phenol in supercritical water. Ind. Eng. Chem. Res. 50 (8),
4301–4307.
Xu, D., Liu, L., Wei, N., Guo, Y., Wang, S., Wu, Z., Duan, P., 2019a. Catalytic supercritical
water gasification of aqueous phase directly derived from microalgae hydrothermal
liquefaction. Int. J. Hydrog. Energ. 44 (48), 26181–26192.
19
Journal of Hazardous Materials 433 (2022) 128761
Xu, J., Kou, J., Guo, L., Jin, H., Peng, Z., Ren, C., 2019b. Experimental study on oil-
containing wastewater gasification in supercritical water in a continuous system. Int.
J. Hydrog. Energ. 44 (30), 15871–15881.
Xu, J., Peng, Z., Rong, S., Jin, H., Guo, L., Zhang, X., Zhou, T., 2021. Model-based
thermodynamic analysis of supercritical water gasification of oil-containing
wastewater. Fuel 306, 121767.
Xu, T., Wang, S., Li, Y., Zhang, J., Li, J., Zhang, Y., Yang, C., 2020. Optimization and
mechanism study on destruction of the simulated waste ion-exchange resin from the
nuclear industry in supercritical water. Ind. Eng. Chem. Res. 59 (40), 18269–18279.
Xu, X., Lu, J., 2016. Treatment of oily sludge by supercritical water oxidation process.
Environ. Prot. Chem. Ind. 36 (06), 681–685.
Yan, X., Qiao, W., Li, P., Ye, J., Zhou, Q., 2014. Reduction of oily sludge by hydrothermal
method. Environ. Prot. Chem. Ind. 34 (04), 340–343.
Yan, Z., Tan, X., 2015. Hydrogen generation from oily wastewater via supercritical water
gasification (SCWG). J. Ind. Eng. Chem. 23, 44–49.
Yang, J., Wang, S., Li, Y., Zhang, Y., Xu, D., 2019. Novel design concept for a
commercial-scale plant for supercritical water oxidation of industrial and sewage
sludge. J. Environ. Manag. 233, 131–140.
Yang, Y., Bowadt, S., Hawthorne, S.B., Miller, D.J., 1995. Subcritical water extraction of
polychlorinated-biphenyls from soil and sediment. Anal. Chem. 67 (24), 4571–4576.
Yeletsky, P.M., Zaikina, O.O., Sosnin, G.A., Kukushkin, R.G., Yakovlev, V.A., 2020.
Heavy oil cracking in the presence of steam and nanodispersed catalysts based on
different metals. Fuel Process. Technol. 199, 106239.
Yong, T.L.-K., Matsumura, Y., 2014. Kinetics analysis of phenol and benzene
decomposition in supercritical water. J. Supercrit. Fluid. 87, 73–82.
Youssef, E.A., Nakhla, G., Charpentier, P.A., 2011. Oleic acid gasification over supported
metal catalysts in supercritical water: hydrogen production and product distribution.
Int. J. Hydrog. Energ. 36 (8), 4830–4842.
Yuan, X., Guan, R., Wu, Z., Jiang, L., Li, Y., Chen, X., Zeng, G., 2018. Effective treatment
of oily scum via catalytic wet persulfate oxidation process activated by Fe2.
J. Environ. Manag. 217, 411–415.
Zhang, F., Ding, Y., Su, C., Chen, Z., 2020a. Energy self-sufficiency of a supercritical
water oxidation system with an improved cooled-wall reactor for power generation.
Appl. Therm. Eng. 172, 115158.
Zhang, H., Zhang, X., Ding, L., 2020b. Partial oxidation of phenol in supercritical water
with NaOH and H2O2: Hydrogen production and polymer formation. Sci. Total
Environ. 722, 137985.
Zhang, J., Gu, J., Han, Y., Li, W., Gan, Z., Gu, J., 2015. Supercritical water oxidation vs
supercritical water gasification: which process is better for explosive wastewater
treatment? Ind. Eng. Chem. Res. 54 (4), 1251–1260.
Zhang, L., Champagne, P., Xu, C., 2011. Supercritical water gasification of an aqueous
by-product from biomass hydrothermal liquefaction with novel Ru modified Ni
catalysts. Bioresour. Technol. 102 (17), 8279–8287.
Zhang, L., Zhang, Y., Zhao, T., 2016. Gasification of petrochemical sludge in supercritical
water. P. I. Civ. Eng. -Wat. M. 169 (6), 285–290.
Zhang, Y., Lin, J., Dong, P., Zhang, L., Yue, M., Xie, J., Guo, X., Ren, A., 2021.
Application of hydrothermal method in dewatering of oily sludge from waste oil-
based drilling fluid. Energy Chem. Ind. 42 (03), 47–50.
Zhao, Y., Yan, X., Zhou, J., Li, R., Yang, S., Wang, B., Deng, R., 2019. Treatment of oily
sludge by two-stage wet air oxidation. J. Energ. Inst. 92 (5), 1451–1457.