Process Safety and Environmental Protection 179 (2023) 168–179

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Process Safety and Environmental Protection

journal homepage: www.journals.elsevier.com/process-safety-and-environmental-protection

Thermodynamic and environmental analysis of self-thermal antibiotic

residues supercritical water gasification system for hydrogen and
power production
Wenwen Wei a, Shi Liu a, Xinyu Li a, Linhu Li a, Wen Cao a, b, *
a
State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xianning West Road, Xi’an 710049, China
b
Suzhou Academy of Xi’an Jiaotong University, No.99 Ren’ai Road, Suzhou, Jiangsu 215123, China

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

Keywords: Efficient treatment of antibiotic residue, containing a range of persistent organic compounds, is essential to
Thermodynamic analysis ensure the protection of both the environment and human health. Supercritical water gasification technology
Supercritical water gasification could achieve the clean and efficient energy conversion of antibiotic residues. In this paper, a self-thermal su­
Life cycle assessment
percritical water gasification system for antibiotic residues is developed to convert antibiotic residues to high-
Antibiotic residues
Hydrogen and power
purity H2 and electrical power. The system analysis results demonstrate that increasing the antibiotic residue
slurry concentration, elevating the gasification reactor temperature, and optimizing the ratio of water-to-dry
antibiotic residues effectively enhance system efficiency and H2 yield within specific ranges. The H2 yield and
net electrical power at optimal operating conditions are 634.52 kg/h and 2.3 MW with 10 t/h dry antibiotic
residue feeding. Meanwhile, the energy efficiency, exergy efficiency, and cold gas efficiency of the system are
61.32%, 63.05%, and 53.96%, respectively. The life cycle assessment analysis shows that the global warming
potential of the system is 20.77 kg CO2-eq/kg H2 with the above operating conditions. Taking into account the
emission reduction impact of the system on thermal power generation, the inclusion of CO2 capture and storage
units can potentially lead to a negative global warming potential for the system.

1. Introduction
Biopharmaceutical companies unavoidably generate a substantial
amount of pharmaceutical waste, encompassing fermentation residues
and wastewater. Without proper management, residues containing
antiretrovirals, antibiotics, non-steroidal anti-inflammatory drugs and
analgesics, steroid hormones, beta-blockers, lipid regulators, antipy­
retics, psychostimulants, etc. (Letsoalo et al., 2023), will inevitably leak
into the environment (Patel et al., 2019). Regrettably, the sluggish
natural decomposition rate of these persistent organic residues has
exacerbated the accumulation of drugs in the environment (Khan et al.,
2022). With the rise in microbial resistance, the diminishing effective­
ness of antibiotics and other medications poses growing challenges for
treating an expanding array of diseases and infections (Sharma et al.,
2022). The global concern of pharmaceutical contamination, particu­
larly within watershed environments, has come to the forefront.
Antibiotics are mainly produced by bacteria or fungi through the
industrial fermentative process (Han et al., 2024). However, only a few
basic materials are transformed into products and used for microbial life
activities. Among the various components, antibiotic residual waste
streams contain underutilized fermentation substrate, bacteria myce­
lium, unextracted antibiotics, and a plethora of other organic materials
that consistently persist (Hui et al., 2023). Globally, approximately 350,
000 tons of antibiotics are manufactured each year, with China leading
as both a major producer and consumer (Zhang et al., 2023). China
alone generates over 2 million tons of antibiotic residue waste annually
(Y. Chen et al., 2021; G. Chen et al., 2021), resulting in the inclusion of
antibiotic residue waste in China’s National Hazardous Wastes Cata­
logue (2021 Edition). Consequently, there is an imperative for the safe
treatment and resourceful utilization of antibiotic residues.
The current treatment methods reported for antibiotic residues can
be divided into biological fermentation treatment (Koumaki et al., 2017;
Tiwari et al., 2017), physical adsorption (Kim et al., 2018; Neha et al.,
2021), and chemical decomposition represented by advanced oxidation
(Rodriguez-Narvaez et al., 2017; Theerthagiri et al., 2018). Neverthe­
less, the aromaticity and intricate structure of pharmaceutical residues

* Correspondence to: State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, No.28 Xianning West Road, Xi’an 710049, China.
E-mail address: caowenxjtu@mail.xjtu.edu.cn (W. Cao).

https://doi.org/10.1016/j.psep.2023.09.014
Received 11 July 2023; Received in revised form 3 September 2023; Accepted 7 September 2023
Available online 9 September 2023
0957-5820/© 2023 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
W. Wei et al.
Fig. 1. The basic flow chart of the poly-generation system by SCWG self-thermal for antibiotic residue.
impose restrictions on the feasibility of biological fermentation treat­
ment. While physical adsorption, essentially a transfer process for con­
taminants, fails to fully eradicate antibiotics, it also incurs relatively
high operational expenses (Chen et al., 2023). Regarding the advanced
oxidation process, achieving the complete mineralization of antibiotics
comes at a considerable cost and might even generate potentially
harmful sub-active byproducts (Dantas et al., 2008). In recent times, the
adoption of thermochemical conversion for antibiotic residue waste has
emerged as a more comprehensive chemical decomposition treatment
(G. Chen et al., 2021; Y. Chen et al., 2021; Ge et al., 2022).
Supercritical water gasification (SCWG) has gained notable attention
as a thermochemical conversion technique for managing various organic
wastes (Cao et al., 2022c; Liu et al., 2022a). Due to the unique physi­
cochemical properties of supercritical water (SCW), including its low
dielectric constant, high diffusivity, high reactivity, and excellent solu­
bility for organic matter (Liu et al., 2023), recalcitrant organic pollutions
that challenge conventional decomposition methods can be effectively
eliminated (Cao et al., 2022a). Therefore, ongoing experimental in­
vestigations are underway to explore the application of SCWG in
handling antibiotic residues. Feng et al. (Feng and Yang, 2015) exam­
ined the catalytic decomposition of analgin pharmaceutical wastewater
in SCW with a continuous reactor. They found that adding sodium salts
facilitated the conversion of combustible hydrocarbons into CO2. Chen
et al.(Chen et al., 2023) comprehensively explored the mechanisms of
amoxicillin decomposition in SCW by experiment and ReaxFF reactive
molecular dynamics simulation. Their results demonstrate the feasibility
of treating amoxicillin by SCWG, wherein the OH radicals from SCW
play a pivotal role in benzene ring opening and carbon chain fragmen­
tation. Dias et al. (Dias et al., 2023) delved into the gasification char­
acteristics of antibiotic residue wastes in SCW using amoxicillin as a
model compound. Impressively, they achieved a 78.4% removal of total
organic carbon (TOC) from antibiotics-laden wastewater.
These experimental studies have convincingly showcased the
viability of SCWG technology in treating antibiotic residue. However,
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Process Safety and Environmental Protection 179 (2023) 168–179
these ongoing investigations primarily operate at the experimental and
molecular simulation levels. Limited research has addressed the ther­
modynamic characteristics of the SCWG process concerning antibiotic
residues, a critical aspect for its practical industrial implementation.
Encouragingly, numerous analogous studies have explored the ther­
modynamic systems associated with handling organic waste, such as
algae (Liu et al., 2021), pig manure (Ren et al., 2022), sludge (Ruya
et al., 2020), black liquor (Cao et al., 2018), and oilfield wastewater
(Peng et al., 2023), thereby furnishing valuable insights for probing the
thermodynamic framework for antibiotic residues. Moreover, the life
cycle assessment (LCA) analysis has been extensively used to examine
the potential environmental impacts of the system (Chen et al., 2019).
Organic Rankine Cycles (ORC) is a mature and effective waste heat re­
covery technology for power generation (Serafino et al., 2023). The
lower boiling point temperature of organic working fluids in comparison
to water renders the conversion of medium and low-grade heat energy
into electricity feasible through turbine expanders (Loni et al., 2021).
In order to complement relevant research on the SCWG process of
antibiotic residues, this paper reported a self-thermal antibiotic residues
SCWG polygeneration system for H2 and power production based on a
coupled network between SCWG, hydrogen oxidation, and ORC waste
heat recovery. Initially, the effect of operating parameters on system
efficiency, H2 yield, and net electrical power was explored to determine
the optimum operating parameters. The adjustment of these parameters
primarily encompasses the ratio of water-to-dry antibiotic residues, the
temperature of the gasification reactor, and the concentration of anti­
biotic residues slurry. Subsequently, LCA was employed to examine the
potential environmental impacts of this system. Moreover, an in-depth
analysis of the system’s mass and exergy flows is conducted. This
work applies SCWG technology to the eco-friendly and non-hazardous
management of antibiotic residue waste. The focus on H2 as the target
product aligns with forthcoming energy trends. The ORC subsystem,
functioning as a heat recovery unit, effectively converts waste heat into
electricity for localized utilization. This significantly alleviates concerns
W. Wei et al.
Table 1
Properties of antibiotic residue.
Sample Moisture/% Proximate analysisa (wt%)
Mad VM Ash
Antibiotic residues 87.89 5.45 61.59 17.66
a
On air dry basis.
b
By difference (O% =100% - Ash% - C% - H% - N% - S%).
associated with industrial steam consumption, which conventionally
arises from the waste heat recovery mode in typical SCWG systems. The
outcomes of this study are anticipated to offer valuable insights for the
sustainable management of antibiotic residue waste in practical
applications.
2. Methods and assumptions
2.1. System configuration design
The schematic diagram of the self-thermal SCWG polygeneration
system, designed for producing both hydrogen (H2) and electric power
from antibiotic residues, is depicted in Fig. 1. The antibiotic residue
slurry undergoes pressurization via a raw pump before being directed to
the cryogenic heat exchanger for preheating. Within this unit, oxygen is
pressurized by the liquid oxygen pump and subsequently heated using
the air bath preheater, also undergoing preheating. By passing through
the medium and high heat exchangers, the preheated water achieves a
supercritical state.
Subsequently, the SCW and the preheated antibiotic residue slurry
are fed into the gasification reactor to produce H2-rich gases. The
insolubility of inorganic salts and other substances in SCW causes ash to
settle at the gasification reactor’s bottom, subsequently being dis­
charged through the separator. The SCW, now containing dissolved H2-
rich gases, is then conveyed into the oxidation reactor, where hydrogen
oxidation reacts with oxygen preheated by the cryogenic heat
exchanger. This reaction releases the necessary heat for the self-thermal
process of the system. This unit yields high-temperature steam, which is
utilized to heat the incoming preheated water, feedstock slurry, and
oxygen through the respective heat exchangers. However, the mixed
steam at a lower temperature still retains recoverable heat after un­
dergoing heat exchange.
The ORC waste heat recovery technology is used here to recover
residual heat efficiently. During this process, the waste heat is absorbed
by the pressurized low boiling point organic working fluid (R245fa)
(Lakew and Bolland, 2010) at the heat exchanger (ORC-evaporator),
producing superheated organic steam for electric power generation
(ORC-turbine). Subsequently, the organic steam discharged from the
turbine is cooled to liquid by air in the storage tanks ((ORC-cooler) and
finally returns to the heat exchanger with the help of the pump (ORC-­
pump). The ORC waste heat recovery system offers electricity for all
power consumption devices in this system. The remaining electricity is
exported outside for use in the plant to save energy consumption.
Notably, the entirety of the ORC waste heat recovery system is metic­
ulously sealed to prevent any leakage of the organic working fluid,
ensuring no environmental contamination.
Post-waste heat recovery, the mixed steam is cooled, depressurized,
and introduced into the hydrogen separation unit. The separated high-
purity H2 is fed into the storage tank for further use, and the sepa­
rated liquid is fed into the pre-water pipeline for recycling. The sepa­
rated exhaust gas contains high concentrations of CO2, which can be
further utilized by carbon capture and storage (CCS) to reduce the CO2
emissions of this system.
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Process Safety and Environmental Protection 179 (2023) 168–179
Ultimate analysis (wt%)
FC C H N S Ob
15.30 38.01 5.72 5.27 2.29 25.60
2.2. Process modeling method
The antibiotic residue used in this research was collected from
Ningxia Qiyuan Pharmaceutical CO.LTD. Their properties are shown in
Table 1. Additionally, to provide further clarity on their constituents, the
GC-MS analysis was employed to detect the components. The results are
listed in Table S1.
This basic flow chart is established and simulated using Aspen Plus
V11, which is assumed to be a steady-state system (Prins et al., 2007).
The Peng-Robinson equation of state with Boston-Mathias modifications
(PR-BM), widely adopted for calculating thermophysical parameters in
the SCWG thermodynamic process, is used in this system (Hantoko et al.,
2019; Liu et al., 2022b). The system ignores the heat loss and pressure
drop of the units and pipe, mostly caused by on-way resistance and heat
dissipation, because these physical variables have far less impact on the
system than the exergy destructions caused by the heat exchangers (Guo
et al., 2021; Yuksel et al., 2019).
Unfortunately, due to its complex components, no conventional
substances from this software could represent antibiotic residues. An
unconventional substance is established to represent antibiotic residues
according to previous studies on oilfield wastewater and biomass studies
(Peng et al., 2023; Wang et al., 2022). Combined with the Calculator
module compiled with Fortran, the Rstoic reactor module (Stoic)
transforms antibiotic residues into the simplest elemental components
(C, S, N2, H2, and O2) and ash based on the provided ultimate and
proximate analysis. These components and ash then enter the Gibbs
reactor (Gasification reactor), undergo a range of gasification reactions,
and reach a state of chemical equilibrium based on the strict Gibbs free
energy minimization. Herein, it is assumed that the fixed carbon is
entirely reformed by SCW (Guo et al., 2023). The ash is regarded as an
inert solid and remains unchanged. Additionally, this study assumed
that N and S are separated along with the ash, and neither is present in
the gas products after the ash separator unit (Guo et al., 2021). The
mainly involved gasification reactions during the gasification process
are listed as follows (Ren et al., 2022).
Steam reforming : C + H2 O→CO + H2 • Δr H298k = 131.29kJ/mol (1)
Boudouard equilibrium : C + CO2 →2CO • Δr H298k = 172.46kJ/mol
(2)
Methanation : C + 2H2 →CH4 • Δr H298k = − 74.81kJ/mol (3)
Reforming : CH4 + H2 O→CO + 3H2 • Δr H298k = 206.10kJ/mol (4)
Water − gas shift : CO + H2 O→CO2 + H2 • Δr H298k = − 41.17kJ/mol
(5)
The oxidation reactor is also simulated by a Gibbs reactor based on
Gibbs free energy minimization. The gas products are partially oxidized
at a theoretical oxygen demand for this self-thermal system. The heat
exchangers are modeled by the HeatX (Medium heat exchanger and
High heat exchanger) and MheatX (Cryogenic heat exchanger) modules
and set as countercurrent heat exchangers whose heat loss is assumed to
be neglected (Liu et al., 2021). The minimum temperature approach is
kept at or above 10 ℃ between the hot and cold streams. A component
separator (Ash separator) removes the ash, N, and S components from
the gasification reactor according to predetermined split fractions. The
W. Wei et al. Process Safety and Environmental Protection 179 (2023) 168–179

Table 2 Ex,pre− water (kJ/h), Ex,liquid oxygen (kJ/h), Ex,H2 (kJ/h), Ex,exhaust gas (kJ/h), and
Essential operating parameters and key data of the main units. Ex,water (kJ/h) are the exergy flow rates of the material flow into and out of
Unit Type Essential operating parameters and key data this system. where Ex,Wpumps (kJ/h) and Ex,Wpower (kJ/h) represent the
Raw pump Pump Pump efficiency: 0.8; Driver efficiency: 0.98;
exergy flow rates of the consumed and produced electricity of the sys­
Outlet pressure: 25 MPa (Ren et al., 2022) tem. The electric power can be totally transformed, so the exergy used
Liquid oxygen Pump Pump efficiency: 0.8; Driver efficiency: 0.98; by pumps or produced by ORC turbine is provided by:
pump Outlet pressure: 25 MPa (Ren et al., 2022)
Pre-water pump Pump Pump efficiency: 0.8; Driver efficiency: 0.985; Ex,W = W (14)
Outlet pressure: 25 MPa
ORC-pump Pump Pump efficiency: 0.8; Driver efficiency: 0.98; The values of total exergy (Ex ) of steam, including its physical (Ex,ph )
Outlet pressure: 25 MPa (Ren et al., 2022) and chemical (Ex,ch ), can be calculated by equations as follows due to the
Cryogenic heat MheatX Cold stream outlet temperature: 200 ℃ values of kinetic exergy (Ex,ki ) and potential exergy (Ex,po ) are minimal
exchanger
that can be ignored:
Medium heat HeatX Cold stream outlet temperature: 350 ℃
exchanger Ex = Ex,ph + Ex,ch (15)
High heat HeatX Hot stream outlet temperature: ≥ 365 ℃
exchanger
ORC-evaporator HeatX Cold stream outlet temperature: 210 ℃ Ex,ph = Msteam × ex,ph (16)
ORC-cooler Heater Outlet temperature: 25 ℃; Outlet pressure:
0.15 MPa Ex,ch = Msteam × ex,ch (17)
Stoic Rstoic Decomposition temperature: 400 ℃;
Gasification RGibbs Gasification temperature: 550–690 ℃ where Ex (kJ/h) represent the exergy flow rates of the steam. The
reactor Ex,ph (kJ/h) and Ex,ch (kJ/h) represent the physical and chemical exergy
Oxidation reactor RGibbs Outlet pressure: 25 MPa flow rates of the steam. The ex,ph (kJ/kg) and ex,ch (kJ/kg) represent the
ORC- turbine Compr Isentropic efficiency: 0.9; Mechanical efficiency:
0.9 (Chen et al., 2019)
corresponding specific exergy of this steam.
Hydrogen Sep Operating temperature: 25 ℃; Operating The physical exergy of a pure component or a mixture (ex,ph (kJ/kg))
separator pressure:2.4 MPa; H2 separation rate: 99%(Liu can be calculated using the data of enthalpy and entropy as follows:
et al., 2021).
eix,ph = (Hi − H0 ) − TO (Si − S0 ) (18)

same module is used in the unit of the hydrogen separator. ∑

ex,ph = yi eix,ph (19)
The essential operating parameters and critical data of the main units i
of the system are summarized in Table 2.
where the mole fraction of pure component i is represented by yi . In
this research, the environment temperature and pressure are set to 25 ℃
2.3. Thermodynamic analysis method and 1 atm, and the standard enthalpy and standard entropy of the
component are H0 and S0 . This paper assumes that the physical exergy of
The energy efficiency, exergy efficiency, and cold gas efficiency are antibiotic residue under ambient conditions is zero.
used to evaluate the thermodynamics performance of this self-thermal The chemical exergy of the gas mixture (ex,ch (kJ/kg)) can be calcu­
SCWG system for antibiotic residues. lated as follow:
Energy efficiency (ηen,sys ) can be calculated by equations as follow: ∑ ∑
ex,ch = yi ε0,i + RTO yi lnyi (20)
Useful⋅energy⋅output EH2 + Wpower i i
ηen,sys = = (6)
Useful⋅energy⋅input Eantibiotic residue + Wconsumption where ε0,i is the standard chemical potential of a pure chemical
component i, based on the Guishan-Yoshida model (Dincer and Rosen,
EH2 = MH2 × HHV H2 (7)
2013). The standard chemical exergy of the involved components in this
study is listed in Table S2.
Eantibiotic = Mantibiotic × HHV antibiotic (8)
The chemical exergy of antibiotic residue (ε0,antibiotic residue kJ/kg) can
residue residue residue

Wpower = WORC− (9) be obtained by the following equation proposed in the literature (Guo
turbine
et al., 2021).
Wconsumption = Wpumps (10) ε0,antibiotic = QHHV antibiotic (21)
residue residue

where EH2 (kJ/h) and Eantibiotic residue (kJ/h) represent the energy flow The exergy loss of unit i (Eix,loss (kJ/h)) can be calculated by equations
rates of H2 and antibiotic residues. The MH2 (kg/h) and Mantibiotic residue (kg/
as follow:
h) represent the mass flow of H2 and antibiotic residue. The Wpower (kJ/h)
∑ ∑
and Wconsumption (kJ/h) represent the power generation and consumption i
Ex,loss = i
Ex,in − ( i
Ex,out i
+ Wnet ) (22)
of this system. The WORC− turbine (kJ/h) and Wpumps (kJ/h) represent the
power generated by the ORC waste heat recovery system and consumed where Eix,in (kJ/h) and Eix,out (kJ/h) represent the exergy flow rates of
by the pumps, including the raw pump, liquid oxygen pump, pre-water input and output of unit i. Winet (kJ/h) represent the exergy flow rates of
pump, and ORC pump, in this system. the net electricity consumption of this unit.
Exergy efficiency (ηex,sys ) can be calculated by equations as follow: The exergy loss rate (ηiex,loss ), which can be calculated as follows, is
Ex,out the ratio of individual unit exergy losses (Eix,loss (kJ/h)) to the total exergy
ηex,sys = (11) ∑
Ex,in losses ( Eix,loss (kJ/h)).

Ex,in = Ex,antibiotic + Ex,Wpumps + Ex,pre− + Ex,liquid (12) Ei

residue slurry water oxygen
ηiex,loss = ∑ x,loss
i (23)
Ex,loss
Ex,out = Ex,H2 + Ex,exhaust + Ex,water + Ex,Wpower (13)
Cold gas efficiency (ηc,en,sys ) can be calculated by equations as follow:
gas

where Ex,in (kJ/h) and Ex,out (kJ/h) represent the exergy flow rates of
input and output of this system. The Ex,antibiotic residue slurry (kJ/h),

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W. Wei et al. Process Safety and Environmental Protection 179 (2023) 168–179

Fig. 2. System boundary for LCA of the self-heat SCWG system for antibiotic residues.

Fig. 3. The system diagram of the autoclave for SCWG of antibiotic residues (Cao et al., 2022c).

Useful⋅chemical energy⋅output E H2 antibiotic residues. The conceptual framework, encompassing purpose

ηc,en,sys = = (24)
Useful⋅chemical energy⋅input Eantibiotic residue and scope definition, inventory analysis, impact assessment, and inter­
pretation of results, is illustrated in Fig. 2.
The major feedstocks for the self-thermal SCWG system are antibiotic
2.4. Life cycle assessment method residue slurry, oxygen, and water. The electrical energy generated by
the ORC waste heat recovery system meets the system demand and
The LCA analysis constitutes a method for evaluating the potential excess export electricity to the outside. Consequently, the principal
environmental impacts linked with the system. In this study, LCA is outputs of the system encompass electric power, purified H2, and CO2.
employed to scrutinize the environmental implications during the The environmental impact category includes many aspects, and
operational phase of the self-thermal SCWG system for handling Global Warming Potential (GWP) is a significant indicator. In this study,

172
W. Wei et al.
Fig. 4. Comparison between simulation results and experimental data of the
SCWG reactor.
only the GWP was considered (Ren et al., 2022; Wang et al., 2022).
According to the World Meteorological Organization (WMO), the
equivalent CO2, CO, and CH4 coefficients were 1, 2, and 296 kg
CO2eq/kg, respectively (Wmo, 2010). The equivalent coefficient for CO2
emissions corresponding to electricity consumption is 0.96 kg/kWh
based on China Life Cycle Database (Peng et al., 2023). In this study, the
basic functional unit (FU) is 1 kg/h of H2 output. All emissions are based
on this FU to provide a basis for comparing the systems studied.
Fig. 5. The H2 yield, net electric generation (a), system efficiency (a), and exergy destruction of the main units (c) at different ratios of water-to-dry antibiotic
residue. (feedstock concentration: 40%, gasification temperature: 650 ◦ C).
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Process Safety and Environmental Protection 179 (2023) 168–179
3. Results and discussion
3.1. Model validation
3.1.1. Experimental process
The SCWG experiments on antibiotic residue waste were conducted
using an autoclave reactor fabricated from Inconel 625, boasting a
chamber volume of 10 ml. The designed temperature and pressure of the
reactor were 800 ◦ C and 40 MPa, respectively. The schematic diagram
of the reactor system is shown in Fig. 3.
The primary components of the system comprise a reactor, an elec­
tric heat furnace, and a data acquisition system. For a comprehensive
understanding of the experimental procedure, in-depth details were
previously expounded upon in our prior work, and as such, will not be
reiterated in this paper (Cao et al., 2022a; Cao et al., 2022b). In the
verification experiments, the experimental conditions involved tem­
peratures of 650 ◦ C, 700 ◦ C, and 750 ◦ C, coupled with a pressure of
25 MPa. The concentration of the antibiotic residue was 12 wt%.
3.1.2. Reliability verification
Fig. 4 illustrates a comparison between the thermodynamic proper­
ties derived from simulation outcomes and experimental findings. The
molar fraction is used to evaluate the reliability of the model by
assessing the properties of the gaseous products obtained from the
simulation results and the experimental results.
the molar number of each gas product
molar fraction = × 100%
the total molar number of gas products
(25)
The findings demonstrate a favorable concurrence between the
molar fractions of gaseous product components obtained through sim­
ulations at varying temperatures and the corresponding outcomes of
experimental antibiotic residue SCWG trials. This verification of reli­
ability substantiates the soundness of the thermodynamic model
employed in this study.
W. Wei et al.
Fig. 6. The H2 yield, net electric generation (a), system efficiency (b), and exergy destruction of the main units (c) at different temperatures of the gasification
reactor. (feedstock concentration: 40%, ratios of water-to-dry antibiotic residue waste: 6).
3.2. The influence of the ratio of water-to-dry antibiotic residue
Alterations in operational parameters consistently exert a profound
influence on the system’s performance. In this work, the influence of the
ratio of water-to-dry antibiotic residue is first investigated. Simulation
results show that the ratio of water-to-dry antibiotic residue is a crucial
parameter affecting the efficiency of the system. The concentration of
antibiotic residue slurry and the temperature of the gasification reactor
are fixed at 40 wt% and 650 ℃.
As depicted in Fig. 5, the system’s efficiency and H2 yield exhibit an
initial increase followed by a subsequent decrease as the water-to-dry
antibiotic residue ratio is elevated. When the ratio of water-to-dry
antibiotic residue rises from 3 to 6, the H2 yield increases from
315.35 kg/h to 634.52 kg/h. And the energy efficiency, exergy effi­
ciency, and cold gas efficiency rise from 40.68%, 49.73%, and 26.82%,
to 61.32%, 63.05%, and 53.96%, respectively. Conversely, the trend
observed in net electric generation contrasts with the H2 yield, dimin­
ishing from 4.48 kW to 2.43 kW. However, with a further elevation of
the water-to-dry antibiotic residue ratio, there is a subsequent decline in
H2 yield and system efficiency, accompanied by an increase in net
electric generation.
With the increase in the preheated water flow rate, the CH4 yield
experiences a decline from 2163.65 kg/h to 1287.28 kg/h. There is only
a slight increase in CO yield from 226.24 kg/h to 230.5 kg/h. The reason
may be that, as the flow rate of preheated water increases, the equilib­
rium of the steam reforming, methane reforming, and water-gas shift
reactions in the gasification reactor shifts in the direction of H2 forma­
tion, resulting in an increase in H2 yield. Meanwhile, CO produced
through steam reforming and methane reforming reactions is swiftly
consumed by the water-gas shift reaction, thereby engendering minimal
fluctuations in CO yield.
Sustaining the desired temperature within the gasification reactor
hinges on the infusion of heat from preheated water. However, when the
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Process Safety and Environmental Protection 179 (2023) 168–179
ratio of water-to-dry antibiotic residue is low, the introduction of pre­
heated water into the system remains restricted. In that case, the pre­
heated water temperature must be kept very high, even exceeding
1400 ◦ C, to ensure an adequate heat influx into the gasification reactor.
Additionally, the relatively substantial temperature differential for heat
transfer exacerbates exergy losses within heat exchanger units, conse­
quently dampening the system’s efficiencies.
With increasing the ratio of water-to-dry antibiotic residue in the
lower range, the heat carrier temperature of preheated water can un­
dergo a notable reduction. Consequently, a relatively lower temperature
for the oxidation reactor is induced. Consequently, a relatively lower
temperature for the oxidation reactor is induced. This, in turn, curtails
the amount of waste heat within the system, thus diminishing net
electricity generation through the ORC system. However, with a further
rise in the water-to-dry antibiotic residue ratio, excess preheated water
flow increases significantly. This further leads to more H2 being
consumed for oxidative exotherm to heat the excessive preheated water
to ensure the temperature of the gasification reactor reaches the setting
values. These operation conditions of the system increase the waste heat,
which in turn raises the net electric generation of the system.
3.3. The influence of gasification reactor temperature
The temperature of the gasification reactor stands as another pivotal
parameter exerting influence over the system’s performance. The ratio
of water-to-dry antibiotic residue and the antibiotic residue slurry con­
centration are set at 6 and 40 wt%. As shown in Fig. 6(a) and (b), the
yield of H2 rises slowly from 632.60 kg/h to 642.55 kg/h as the gasifi­
cation temperature increases from 550 ◦ C to 590 ◦ C, and then falls to
580.55 kg/h rapidly with the gasification temperature further rise to
690 ◦ C. The changes in energy efficiency and cold gas efficiency of the
system show a similar trend. The exergy efficiency of the system shows a
decreasing trend with increasing gasification temperature, while the net
W. Wei et al. Process Safety and Environmental Protection 179 (2023) 168–179

Fig. 7. The H2 yield, net electric generation (a), and system efficiency (b) of the SCWG system at different concentrations of the antibiotic residue slurry. The input
and output exergy of the system (c) (gasification temperature: 650 ◦ C, ratios of water-to-dry antibiotic residue waste: 6).

Fig. 8. Influence of operating parameters, including the ratio of water-to-dry antibiotic residue waste (a), temperature (b), and concentration (c) on GWP.

175
W. Wei et al.
electric generation shows an opposite trend. When the gasification
temperature is 590 ◦ C, the H2 yield and system efficiency are 642.55 kg/
h, ηen,sys = 61.91%, ηex,sys = 63.29%, and ηc,en,sys = 54.65%, respectively.
Fig. 6(c) shows the exergy destruction trend of the main units in this
system. The results show that the exergy destruction of the gasification
reactor increases steadily with the rise of the temperature, while the
exergy destruction of the oxidation reactor decreases gradually. The
energy destruction of the heat-exchangers start to rise dramatically
when the gasification reactor temperature is above 650 ◦ C.
When the gasification temperature is relatively low, the increase in
gasification temperature promotes a positive shift of the endothermic
reaction equilibrium in the gasification reactor, resulting in a slow in­
crease in H2 yield. However, as the gasification temperature further
increases, the heat required by the gasification reactor also rises rapidly,
causing a large amount of H2 to be consumed in the oxidation reactor by
the rapid oxidation exotherm process. The H2 consumed is much more
than generated by the shift of equilibrium. This also further reduces the
efficiency of the system.
3.4. The influence of antibiotic residue slurry concentration
The concentration of antibiotic residue slurry is another essential
operational parameter affecting the performance of this SCWG self-
thermal system. The ratio of water-to-dry antibiotic residue and the
temperature of the gasification reactor are fixed at 6 and 650 ℃.
As shown in Fig. 7, there is a significant improvement in system ef­
ficiency and H2 yield with antibiotic residue slurry concentrations
increasing, while the net electric generation shows an opposite trend.
When the antibiotic residue slurry concentration is below 40%, this
improvement is very noticeable. The energy efficiency, exergy effi­
ciency, cold gas efficiency, and H2 yield of the system rapidly grew from
34.69%, 38.49%, 16.79%, and 197.45 kg/h to 61.32%, 63.05%,
53.96%, and 634.52 kg/h, respectively, with the antibiotic residue
slurry concentration increase from 30 wt% to 40 wt%. However, the
increase in antibiotic residue slurry concentration has a limited impact
on the increase in H2 yield and the growth in system efficiency when the
antibiotic residue slurry concentration rises further. In the simulated
parameter range, at the antibiotic residue slurry concentration of 60%,
the H2 yield and the net electric power of this system are 689.07 kg/h
and 2.06 MW. The corresponding efficiency is ηen,sys = 64.81%, ηex,sys
= 66.26%, and ηc,en,sys = 58.60%, respectively.
This is because with the fixed ratio of total water-to-dry antibiotic
residue, an increase in antibiotic residue slurry concentration results in a
decrease in preheated water flow, which lowers the amount of H2 used
in the exothermic process of the oxidation reactor. As a result, H2 yield
steadily rises, while net electricity generation from waste heat recovery
steadily declines. This variation is particularly noticeable when the
antibiotic residue slurry concentration is below 40%. It is worth noting
that the system will stop producing H2 when the antibiotic residue slurry
concentration falls below 27.55 wt%.
3.5. Life cycle assessment analysis
The change of GWP with different operating parameters is quantified
to determine the effects of operational parameters on the environment.
The simulation results are shown in Fig. 8.
It becomes evident that when the gasification reactor temperature
falls below 650 ◦ C, GWP experiences a rapid decline as the temperature
increases. Nonetheless, this decrease in GWP becomes less conspicuous
as the temperature continues to rise. Similar trends emerge concerning
the impact of the water-to-dry antibiotic residue ratio and the antibiotic
residue slurry concentration on GWP. Both parameters exhibit initial
declines followed by gradual increases, ultimately reaching a minimum
value, as the ratio or concentration rises.
The results can be explained by the relatively high methane content
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Process Safety and Environmental Protection 179 (2023) 168–179
in the gasification product when the temperature of the gasification
reactor is low. Methane’s GWP value surpasses that of other gas prod­
ucts, significantly augmenting the overall GWP of the system product. A
similar rationale holds for the relatively higher GWP at lower water-to-
dry antibiotic residue ratios. With a further increase in the ratio of
water-to-dry antibiotic residue, the production of CO, CH4, and CO2 in
the gas product stabilizes, while the yield of H2 in the final product is
decreased, resulting in a slight increase in the GWP of the system based
on the basic functional unit (FU) of 1 kg/h H2 of output. This phenom­
enon is also reflected in the effect of lower antibiotic residue slurry
concentration on GWP. As the concentration of the antibiotic residue
slurry increases further, the slight increase in the concentration of CH4
of the final gaseous product leads to a further rise in the GWP of this
system.
It’s noteworthy that the exhaust gas from this system bears a
considerably high concentration of CO2. Should an additional CCS unit
be implemented for the exhaust gas, the system’s GWP would undergo
further reduction. This could even lead to a negative GWP, considering
the emission reduction effect of the system on thermal power, among
other factors.
3.6. Optimization and analysis of system operating parameters
3.6.1. Optimization of system operating parameters
Optimizing the system’s operating parameters is essential for
achieving optimum performance while aligning with the practical de­
mands of manufacturing operations. A clear inference drawn from the
preceding analysis is that the system excels notably when the water-to-
dry antibiotic residue ratio is set at 6. However, for the optimization
process of the optimal gasification temperature of the system, a gasifi­
cation temperature of 590 ◦ C is challenging to ensure the complete
gasification of the antibiotic residue slurry. In the present study, a more
elevated gasification reactor temperature becomes imperative to ensure
a thorough gasification process. Gratifyingly, the system’s performance
experiences only marginal degradation as the gasification reactor tem­
perature ascends from 590 ◦ C to 650 ◦ C. To meet the needs of the actual
gasification process, the temperature of the gasification reactor in the
system is optimized at 650 ◦ C, a temperature compatible with the
gasification of most biomass waste (Cao et al., 2016).
As for the antibiotic residue slurry, a concentration of 40 wt% is
selected for this optimization process. The reason is that higher con­
centrations pose a huge challenge to the continuous feed system and the
pulping properties of the antibiotic residue slurry. Additionally, anti­
biotic wastewater is an important component of antibiotic waste, which
can be used to formulate slurries together with antibiotic residues, and
higher concentrations of slurry concentrations are not conducive to
antibiotic wastewater consumption.
Furthermore, it should be emphasized that the ORC subsystem, as an
integral part of the system, plays a pivotal role in determining the
overall system performance. Nevertheless, under the specified param­
eter configurations in this system, the ORC system demonstrates
remarkable stability compared to other operational parameters. The key
determinant affecting the efficiency of waste heat recovery and power
generation within the ORC system primarily hinges on the physico­
chemical properties of the ORC working fluid itself. In this system,
R245fa is regarded as appropriate and highly effective. The supple­
mentary materials elaborate on the process for selecting the ORC
working fluid.
In summary, in this system, the optimized system operating param­
eters were selected as the ratio of water-to-dry antibiotic residue is 6, the
temperature of the gasification reactor is 650 ℃, and the antibiotic
residue slurry of the feedstock concentration is 40 wt%. Fortunately, the
results of the LCA analysis show that the best operating parameters of
the self-heat SCWG system setting above are also in line with the envi­
ronmental optimization strategy, which further justifies the optimiza­
tion of our system operating parameters.
W. Wei et al. Process Safety and Environmental Protection 179 (2023) 168–179

Table 3
Detailed mass flow and conditions of the main streams in the simulation of SCWG self-thermal system for antibiotic residue waste.
Stream NO. Temperature/ ℃ Pressure/ MPa Mass flow/ kg/h component flow, kg/h

CH4 CO CO2 H2 H2O O2

1 25 0.1 25000 0 0 0 0 15000 0

2 27.33 25 250000 0 0 0 0 15000 0
3 200 25 25000 0 0 0 0 15000 0
4 400 25 25000 0 0 0 540.8 15545 2839.3
5 25 0.1 45000 0 0 0 0 45000 0
6 27.89 25 45000 0 0 0 0 45000 0
7 350 25 45000 0 0 0 0 45000 0
8 951.23 25 45000 0 0 0 0 45000 0
9 650 25 70000 1741.9 228.7 8030.4 497.4 57020.6 0
10 650 25 67519 1742.0 228.6 8030.3 497.4 57020.7 0
11 650 25 2481 0 0 0 0 0 0
12 25 0.1 2481 0 0 0 0 0 0
13 -195 1.8 5287.1 0 0 0 0 0 5287.1
14 -189.2 25 5287.1 0 0 0 0 0 5287.1
15 25 25 5287.1 0 0 0 0 0 5287.1
16 200 25 5287.1 0 0 0 0 0 5287.1
17 962 25 72,806.1 6.4 1098.9 11,424.0 640.9 59,635.8 0
18 366 25 72,806.1 6.4 1098.9 11,424.0 640.9 59,635.8 0
19 279.5 25 72,806.1 6.4 1098.9 11,424.0 640.9 59,635.8 0
20 247.2 25 72,806.1 6.4 1098.9 11,424.0 640.9 59,635.8 0
21 40 25 72,806.1 6.4 1098.9 11,424.0 640.9 59,635.8 0
22 210 25 290,473 0 0 0 0 0 0
23 31.69 0.15 290,473 0 0 0 0 0 0
24 25 0.15 290,473 0 0 0 0 0 0
25 36.2 25 290,473 0 0 0 0 0 0
26 25 25 72,806.1 6.4 1098.9 11,424.0 640.9 59,635.8 0
27 25 2.4 634.5 0 0 0 634.5 0 0
28 25 2.4 12,534.2 6.4 1098.9 11,407.2 6.4 15.2 0
29 25 2.4 59,637.5 0 0 16.8 0 59,620.7 0

Fig. 9. Sankey diagram of exergy flow in the SCWG system.

177
W. Wei et al.
Fig. 10. The exergy loss (a) and destructions in different system units (b).
3.6.2. Optimized system performance
Based on the optimized system operating parameters above, a self-
thermal antibiotic residue SCWG system for hydrogen and power pro­
duction is designed. According to Fig. 1, the process simulation results,
such as the pressure, temperature, and flow rate of the main streams in
the process, are given in Table 3. The self-heat SCWG system for anti­
biotic residues processing capacity of 10 t/h can produce 634.52 kg/h
H2 and an output of 2.3 MW net power generation. The cooled exhaust
gas contains a high concentration of CO2 and is available for further
separation and use by CCS. The energy efficiency, exergy efficiency, and
cold gas efficiency of the optimized system are ηen,sys = 61.32%, ηex,sys
= 63.05%, and ηc,en,sys = 53.96%, respectively.
3.6.3. Analysis of energy and exergy
A Sankey diagram of the SCWG self-thermal system for antibiotic
residues is displayed in Fig. 9 to demonstrate the exergy flow in the
system intuitively. The width of the lines represents the amount of
exergy of the streams from the system (Bang-Møller et al., 2011). Further
details of the system exergy destructions are shown in Fig. 10.
The gasification and oxidation units are the core modules of this
system. In the gasification stage, 46,338.91 kW of chemical exergy is fed
into the gasification reactor by the slurry of antibiotic residues. As the
gasification process is endothermic, the preheated water must carry
additional heat into the reactor (951.23 ℃ and 25 MPa). These pre­
heated water carry the 28,190.52 kW of physical exergy from the heat
exchanger process to ensure the reaction is carried out properly at the set
temperature. However, the gasification reactor is the main source of the
exergy destruction of the system. The value of exergy destructions of the
gasification reactor, represented by ED 8, is 3912.05 kW, which
accounted for 21.15% of the total system exergy destructions and 5.16%
of the input exergy of this unit. The oxidation reactor is another major
unit where exergy destructions represented by ED 11 occupy 28.31% of
the total system exergy destructions and 7.22% of its input exergy. This
is mainly caused by the irreversible loss of chemical energy from the
oxidation process.
The heat-regenerative units, including cryogenic heat-exchanger,
medium heat-exchanger, and high heat-exchanger, is another primary
source of exergy destruction of this system, which accounts for 6.6%,
17.7%, and 7.3% of the total system exergy destructions, respectively.
This exergy loss is mainly due to the difference in temperature between
the hot and cold fluids and the heat transfer process. In this system, the
medium heat exchanger has the most significant heat transfer temper­
ature differential, followed by the high heat exchanger and the cryo­
genic heat exchanger. As a result, the exergy loss produced in medium
heat-exchanger is significantly higher compared to cryogenic and high
heat-exchangers. The above units account for 81.1% of the total system
exergy destructions, corroborating with previous related studies (Gasafi
et al., 2007; Guo et al., 2021; Wang et al., 2022).
4. Conclusions
A self-thermal SCWG system designed for the production of
178
Process Safety and Environmental Protection 179 (2023) 168–179
hydrogen and power from antibiotic residues is established and
comprehensively scrutinized. Detailed analysis of the impact of the
operating parameters on the system performance, including the ratio of
water-to-dry antibiotic residues, the temperature of the gasification
reactor, and antibiotic residues slurry concentration, is carried out in
detail. Employing the LCA analysis method, a thorough evaluation of the
system’s environmental impact is conducted.
With a treatment capability of 10 t/h for antibiotic residues, a self-
thermal SCWG system has been developed for hydrogen and electric
power production. Employing univariate analysis, an in-depth investi­
gation into the specific impacts of operational parameters on the simu­
lation system was undertaken. Notably, the system’s efficiency is
profoundly shaped by the ratio of water-to-dry antibiotic residue, the
temperature of the gasification reactor, and the concentration of anti­
biotic residue slurry. The results pinpoint the optimized operating pa­
rameters for these variables as 6, 650 ℃, and 40 wt%, respectively. The
optimum energy efficiency, the exergy efficiency, and the cold gas ef­
ficiency are ηen,sys = 61.32%, ηex,sys = 63.05%, and ηc,en,sys = 53.96%,
respectively. At these conditions, the hydrogen production and net
electricity generation of the system are 634.52 kg/h and 2.3 MW. To
assess the potential environmental repercussions, an LCA was conduct­
ed. Under the optimal operating conditions, the system exhibited a GWP
of 20.77 kg CO2-eq/kg H2.
This system is envisaged as a pivotal strategy for waste management,
potentially propelling pharmaceutical plant production towards carbon
neutrality. By facilitating the clean treatment of antibiotic residue waste
and wastewater while simultaneously generating exportable electrical
power, the system holds great promise.
CRediT authorship contribution statement
Wenwen Wei: Investigation, Methodology, Data curation, Re­
sources, Writing – original draft. Shi Liu: Formal analysis, Investigation,
Writing – review & editing. Xinyu Li: Investigation, Writing – review &
editing. Linhu Li: Writing – review & editing. Wen Cao: Writing – re­
view & editing, Supervision, Project administration.
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.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (No. 52006173), the Basic Science Center Program
for Ordered Energy Conversion of the National Natural Science Foun­
dation of China (No. 51888103), and the Natural Science Foundation of
Jiangsu Province (No. BK20200243).
W. Wei et al.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.psep.2023.09.014.
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