Journal of Environmental Chemical Engineering 7 (2019) 102932

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Journal of Environmental Chemical Engineering

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Pilot study of magnetic nanoparticles via SuperPro simulation using T

catalytic hydrothermal carbonization process
⁎
Chan Zhi Yieh, Xin Lee, Yann Ling Dua, Yong Siew Yien, Yoshiko Bong Kah Yee, N.M. Mubarak
Department of Chemical Engineering, Faculty of Engineering and Science, Curtin University, 98009 Sarawak, Malaysia

A R T I C LE I N FO A B S T R A C T

Keywords: Nanoparticles can be utilised in many field applications such as environmental analysis, water and wastewater
Nanoparticle treatment and medical treatment due to its unique physical and biomedical properties. Magnetic nanoparticles
Hydrothermal carbonization are excellent absorbent to treat large volumes of water or wastewater. Magnetic nanoparticles not just only have
Catalytic the same properties as nanoparticles, yet it has magnetic characteristic. Iron oxides magnetic nanoparticles react
Magnetic
with different functional groups and ligands, which can achieve specific contaminants removal. Despite of that,
Simulation
Economic
magnetic nanoparticles are still not commercially available for water and wastewater treatment. Thus, this pilot
study was conducted based on the most economical and feasible approach to produce magnetite (Fe3O4) na-
noparticles. Magnetite (Fe3O4) nanoparticles are synthesized via Hydrothermal Carbonization (HTC) process
using sugarcane bagasse as carbon precursor followed by 400 ℃ heat treatment for tannin removal but still
retain its good magnetic property. This pilot study was carried out based on a production capacity of 5000 tonnes
per annum magnetite (Fe3O4) nanoparticles with the least of 95% purity. Financial analysis for this pilot study
was conducted. Total annualized cost for base case was rated to be USD $ 129,294,635 per annum. Total revenue
for base case was estimated to be USD $4,452,949,096 with a payback period of 1.3 years. Net profit is USD
$41,134,543 per annum with returned on investment (ROI) of 75% for base case. Thus, a plant scale-up is
feasible for this pilot study.

1. Introduction
In the recent decades, synthesis and utilization of nanoparticles
have gained special attention due to its unique properties such as large
surface to volume ratio, simple surface modification and separation,
special adsorption properties and disinfect capability [1]. Nanoparticles
can be utilised in many field applications such as environmental ana-
lysis, water and wastewater treatment, medical treatment and more [1].
Nanoparticles can be employed in the nanofiltration process in waste-
water treatment. Sepheric et al. had studied on the effect of nitrifiers
community on fouling mitigation in a membrane bioreactor following
with filterability test [2]. In his research, 0.4 μm pore size of cellulose
acetate membrane which consists of nanoparticles is used for cross-flow
filtration system [2].
Magnetic nanoparticles act as adsorbents and nano-catalysts in
wastewater treatment [1]. This is because tiny and high dispersibility
MNPs give faster and better detection when injected into contaminated
sources [1]. MNPs not just only have the same properties as
nanoparticles but also have magnetic properties. Moreover, MNPs with
30 nm diameter exhibit superparamagnetic properties, which the par-
ticles do not permanently magnetized without an external magnetic
field to support [1]. MNPs can be used to remove heavy metals, natural
OM (NOM), phosphorous, nitrogen, radionuclides, Pb2+, As3+ and
As5+ [1].
Magnetic carbon-iron oxide nanocomposites (MCIONC) had been
characterized by Singh et al. (2011) for absorption of crystal violet dye
by comparing to non-magnetic carbon [3]. In his findings, magnetic
nanocomposites have higher adsorption capacity than non-magnetic
carbon [3]. In his experiment variables’ range, the adsorption capacity
of non-magnetic carbon and the magnetic nanocomposite were 40 mg/g
and 81.7 mg/g respectively [3]. Shengxiao Zhang et al. (2013) had
proposed Thoil modified magnetite (Fe3O4) nanoparticles with silicon
dioxide (SiO2) impregnation for mercury removal [4]. Silicon dioxide
coating has protected magnetite core from oxidation and acid dissolu-
tion [4]. Modified magnetite nanoparticles that he proposed shows an
excellent result due to its high adsorption capacity, fast adsorption rate

Abbreviations: HTC, hydrothermal carbonization; MNPs, magnetic nanoparticles; SG, sugarcane bagasse; OSC, off-specification compost; GM, grape marc; ROI,
returned on investment; OM, organic matter; MCIONC, magnetic carbon-iron oxide nanocomposite
⁎
Corresponding author.
E-mail addresses: mubarak.mujawar@curtin.edu.my, mubarak.yaseen@gmail.com (N.M. Mubarak).

https://doi.org/10.1016/j.jece.2019.102932
Received 12 November 2018; Received in revised form 29 January 2019; Accepted 29 January 2019
Available online 01 February 2019
2213-3437/ © 2019 Elsevier Ltd. All rights reserved.
C.Z. Yieh et al.
and strong anti-interference [4]. Furthermore, the adsorbed mercury
can be desorbed using hydrochloric acid (HCl) solution with thiourea,
where the adsorbed mercury is reusable [4]. This is because of the in-
teraction between Thiol group mercury [4].
Magnetic nanoparticles can be synthesized by different methods
such as co-precipitation, microemulsion, thermal decomposition and
hydrothermal [5]. Co-precipitation is a simple and convenient method
to produce large amount of iron oxide magnetic nanoparticles by re-
acting base and aqueous Fe2+ and Fe3+ solution at room temperature
[5]. Nevertheless, MNPs produced are not in good shaped [5]. Micro-
emulsion is a technique to produce a thermodynamically stable iso-
tropic solution with a system consisting of water, oil and surfactant [5].
Uniform-sized of MNPs can be produced but low yield [5]. Thermal
decomposition is also one of the ways to synthesize MNPs. Mono-
disperse MNPs are formed by thermal decomposing organometallic
compounds in high-boiling organic solvents containing stabilizing sur-
factants [5]. However, this process is complicated as it requires a high
temperature and inert atmosphere [5]. Hydrothermal is another
strategy to synthesis monodisperse MNPs based on the phase transfer
and separation mechanism. Post-processing steps are required before
hydrothermal process [5]. In spite of that, hydrothermal process is re-
latively simple compared to thermal decomposition as it has shorter
reaction period and absence of inert condition [5].
In most of the recent studies, the results proved that modified
magnetite MNPs has higher adsorption capacity and stability than pure
MNPs [1]. Moreover, compared to pure MNPs, modified magnetite
MNPs are easier to separate at the end of the process [1]. This is due to
the irreversible interaction between unfunctionalized iron oxides and
metal ions [6]. On the other hand, hydroxyl and carboxyl groups are the
most common active sites for functionalized iron oxides [6]. Non-heavy
metal ions such as Mg2+ and Ca2+ strongly interact with binding sites
[6]. Thus, in order to prevent aggregate formation, modified magnetic
nanoparticles have been proposed by the researchers [6].
Carbon coated MNPs have optimal oleophilic surface properties [7].
Besides, carbon coating protects the metal core from oxidation, at the
same time not affecting magnetic properties of the core [7]. Further-
more, carbon coating has high thermal stability and low coercivity [7].
Natthanan et al. (2017) had characterized carbon coated magnetite
nanoparticles for tetracycline adsorption using sugarcane bagasse (SG)
as carbon precursor [8]. The carbon coated magnetite nanoparticles
exhibited maximum adsorption capacity of 48.35 mg/g [8]. It has good
magnetic properties and high stability [8].
Due to high market demand, this pilot study was conducted based
on the most economical and feasible approach to produce magnetite
(Fe3O4) nanoparticles. Magnetite (Fe3O4) nanoparticles are synthesized
via Hydrothermal Carbonization (HTC) process using SG as carbon
precursor followed by 400 ℃ heat treatment for tannin removal but still
retain its good magnetic property. SG was selected as carbon precursor
because it is easily available from sugar refineries.
2. Materials and method
The main feedstock chosen for this project is sugarcane bagasse, it is
fibre residue remaining after harvesting the cane stalk, with 45–50% of
moisture content, which mainly consist of cellulose, hemi cellulose,
pentosans, lignin, wax and some minerals [9]. Sugarcane bagasse is
chosen due to the ease of accessibility in south east Asia, it has been
cultivated widely in India, Thailand as well as Malaysia [10]. In addi-
tion, by comparing sugarcane waste with the palm oil waste, the usage
of sugarcane waste is not as common around the world, therefore this is
the aim of the project to utilize the uncommon waste and enhanced it
with greater usage. Over the globe, for every ton of sugarcane pro-
cessed, there will be 140 kg of bagasse, in some refinery they have
successfully generate energy by using SG [10]. Besides generating en-
ergy, sugarcane bagasse is a domestic refinery waste that is cost effec-
tive and accessible for this project. SG is considered environmental
2
Journal of Environmental Chemical Engineering 7 (2019) 102932
friendly as the heating process of sugarcane bagasse does not release
any toxic gases.
The freshly processed sugarcane bagasse contains high percentage
of moisture, therefore to be able to use in the HTC process, the bagasse
should be sun dried for at least 24 h, then ground into smaller pieces by
using a vibratory screen [11].
2.1. Project background
This project is regarding design of manufacturing magnetic nano-
particles via catalytic HTC, the production rate of magnetic nano-
particles can produce at least 5000 tonnes per year. The main feedstock
in this process is using sugarcane bagasse which it will undergoes the
first stage reaction hydrolysis of cellulose resulting in the sugar mole-
cule glucose, dehydration of glucose reacts with iron precursor through
HTC to form magnetic nanoparticles (Fe3O6@C6H2O). HTC in this
process is specifically associated with heat treatment as it is con-
siderably environmental friendly, where less carbon dioxide (CO2) is
emitted throughout the process, heat treatment aims to improve mag-
netic strength of the final product because the iron content in it was
increased by heat treatment while decreased in carbon content. Based
on experimental study conducted by Natthanan et al. the final product
consisted of both hematite (α-Fe2O3) and magnetite (Fe3O4) after ver-
ification of X-ray Powder Diffraction (XRD) results [8]. Besides, the
magnetite component did not affect by acid treatment and oxidation
whereby proven that encapsulation of carbon matric provided of great
corrosion resistance for composite, as well as the magnetic properties
studied using vibrating sample magnetometer (VSM) shown its super-
paramagnetic characteristic [8]. Heat treatment at 400 °C can remove
the organic components, so that it will not be discharged to water and
likewise, it strengthens the magnetism properties of desired final pro-
duct [8]. Furthermore, the main product produced is expected to have
up to 95% of purity with production rate of 631.313 kg/h, besides the
by-products obtained such as sodium chloride (NaCl) and sodium sul-
phate (Na2SO4) can be sold in the market as well. The design plant is
intended to operate for 330 days annually, while the remaining days are
scheduled to execute maintenance procedures. Apart from achieving
maximum production rate of the process, plant safety control system is
installed to ensure process plant is operating efficiently and safely.
Economic feasibility of this project is performed to estimate the total
revenue of the proposed plant and payback period of not more than 3
years.
2.2. Biomass waste as feedstock
A comparative study is conducted for the suitability of different
biomass types in catalytic hydrothermal carbonization (HTC) process.
Sugarcane bagasse is the most suitable biomass for carbon precursor of
catalytic HTC process in terms of economic, environment and tech-
nology. Compared to other biomass such as grape marc, off-specifica-
tion compost and rattan, it can be easily obtained with a relative low
price. SG is a byproduct from sugar refineries. An approximate of 54
million tonnes dry SG are produced from sugar refineries in the world
[12]. Grape marc is a byproduct from wine factories, but it is hard to
accessible in Malaysia, same goes to “off-specification compost” (OSC) –
a by-product of organic municipal solid waste treatment, coded by the
European Waste Catalogue as EWC 19.05.03, and rattan [13]. A sy-
nergy relationship with sugar refineries can be achieved where both
parties can gain benefits from it. Some of the sugar refineries dispose
sugarcane bagasse directly without any waste management or treat-
ment. Improper disposal of SG leads to land pollution. Since heat
treatment is involved in this proposed plant, environmental impact of
raw material heating is considered. Heating of SG does not release any
toxic gases. On the other hand, the composition of off-specification
compost is not defined as standard for every batch. Besides, heating of
off-specification compost may contribute hazardous gases emission.
C.Z. Yieh et al.
Fig. 1. Plant design work flowchart.
Due to the reasons mentioned above, sugarcane bagasse is selected as
carbon precursor for the process.
2.3. Use of catalytic reactors and autoclave
The feed material before fed into first reactor undergoes heat
treatment and grind into smaller pieces to increase the surface area
ratio to volume, which aims to increase the reaction rate and protect it
from damaging reactors. The synthesis nanoparticles is approximately
ground to 100–200 μm particles size is relatively shows high magneti-
zation as determined by present work [8]. Furthermore, with con-
trollable size of nanoparticles, it is desired to acquire finite volume of
nanoparticles as smaller size exhibit higher magnetic strength corre-
sponding to bulk material. Research of nanoparticles surface effects to
the magnetization is done beforehand which in present work, it is states
that large fractions of nanoparticles surface contributes higher mag-
netization properties [14]. In this research two types of reactors are
selected that is continuous stirred tank reactor (CSTR) (R-101 and R-
103) and autoclave (R-102). CSTR is used for its beneficial continuous
operation, offering a diverse range of engineering and temperature
controls, low operating cost and simplicity of construction whereas
autoclave is selected due to its features to capable undertake under high
pressure and temperature.
Referring to existing publish research work, synthesis of magnetic
nanoparticles can be done by incorporated various catalyst to intensify
the rate of reaction in catalytic reactor. The hydrolysis of cellulose is
takes place in the first CSTR by addition of liquid acid catalysts.
Cellulose is monomer structural components linked together to form
glucose that extracted from sugarcane bagasse, where the cellulose
polymers is first hydrolysed by sulphuric acid to break the beta-1,4-
glycosidic bonds [15]. In addition, sulphuric acid can react closer to the
linkage bonds of cellulose single unit to do the breakage. In this project
work high grade of bagasse is expected to be derived where it consists
up to 90% of cellulose. Hydrolysis of cellulose is carried out at
3
Journal of Environmental Chemical Engineering 7 (2019) 102932
temperature of 170 °C and pressure of 1.013 bar. In respect of economic
aspect and environmental concerns used water from autoclave is cir-
culated back into the first reactor, water can be used for jacket sur-
rounded CSTR for cooling usage after reaction. CSTR is selected for
reaction mixture of iron (III) chloride (FeCl3) and iron (II) sulphate
(FeSO4) with sodium hydroxide (NaOH) and cellulose hydrolysis. This
reactor is predominantly for decomposition of ferrous iron to form
ferricferrous oxide (Fe3O4) that will react with glucose to form mag-
netite hydrocar. The former reaction formed Fe3O4 is necessary to form
coating around bagasse that plays vital properties of magnetic nano-
particles. Furthermore, the magnetic strength of the coating Fe3O4 will
be heated at next reactor to yield desired magnetic hydrochar nano-
particles. Industrial autoclave (R-102) is used for HTC reaction of glu-
cose and Fe3O4. HTC is an eco-friendly route to modify carbon sources
in a closed system under mild conditions as it is comparatively release
low CO2 emissions [16]. Product’s magnetic strength can be further
improved after heating in relatively high temperature of 400 °C. The
dried glucose will undergo oxygenation with Fe3O4 to form
Fe3O4@C6H2O nanoparticles by HTC process which it is often known as
magnetic-hydrochar. Besides, industrial autoclave used in this process
is made of 316 stainless steel to prevent corrosion in prolong period due
to presence of sulphuric acid [17].
3. Pilot plant simulation
3.1. Process design and simulation
The proposed magnetite-hydrochar production plant is simulated
using Superpro Student Version 9.0 software in which the process re-
lates mostly solid-liquid phase flows. It is a continuous based project
designed to synthesis 5000 tonnes magnetite-hydrochar nanoparticles
per year in which the process is scaled up to medium-scale plant by
following a similar HTC experimental research paper published by
Natthanan et al. The synthesis of magnetic carbon composites from
C.Z. Yieh et al.
sugarcane bagasse by low temperature HTC process was successfully
developed, including simple heat treatment process to strengthen its
magnetic properties as well as its maximum adsorption capacity of
48.35 mg/g [8]. There are some assumptions made during simulation,
for example, the composition of SG is assumed to be 90% cellulose
which is obtained after chemical pre-treatment; only the main reaction
in each reactor being concerned with rate constant obtained from dif-
ferent published journals while for HTC process, the rate constant used
is referred to information of Fe3O4@TSC nanocomposites; well-mixing
and no accumulation in the equipment; pressure drops concentrate in
transferring fluids. Each equipment installed is assumed to be stationary
and adiabatic. There are two catalysts involved in simulation, which are
sulfuric acid solution and β-zeolite at r1 and r2 respectively. Since β-
zeolite is a natural catalyst, which unable to fit into simulation directly,
thus the rate constant of similar HTC process is obtained and simulated.
The processes in designing catalytic HTC plant are simplified and illu-
strated in Fig. 1. In this processing plant, there are three main reactions
involved which are listed as follows:
• Hydrolysis of Cellulose [18]:
C6 H10 O5(s) + H2 O(l) → C6 H12 O6(l)
r1 = k1 CC6 H10 O5
where k1 = 2.833 × 1017s−1Catalyst used is sulfuric acid solution.
• Iron (II, III) Oxide Formation [19]:
FeSO4(aq) + 2FeCl3(aq) + 8NaOH(aq) → Fe3 O4(s) + 6NaClaq + Na2 SO4 aq
2
+ 4H2 O(l) r2 = k2 CFeSO4 CFeCl C8
3 NaOH
where k2 = 2.5 × 1011L2mol−2atm−1s−1
• Hydrothermal Carbonization Process [20]:
C6 H12 O6(aq) → "C6 H2 O"(s) + 5H2 O(l) Fe3 O4(s) + "C6 H2 O"(s)
→ Fe3 O4 @C6 H2 O(s) r3 = k3 CC6 H2 O CFe3 O4
where k3 = 1.3167 × 10−2kgkg −1s −1Catalyst used is β − zeolite .
3.2. Conceptual process description
The overall magnetite-hydrochar nanoparticle production plant can
be categorized into several sections which are sugarcane bagasse pre-
treatment process, preparation of Fe3O4, hydrothermal carbonization
process, product and by-product purification stages. Fig. 2 shows the
conceptual design developed for a medium industrial-scale HTC plant.
First, SG enters the grinder (GR-101) for size reduction and homo-
genization before mixing up with water to reach expected mass ratio of
9:1. H2SO4 solution of 0.2 M joins the system in mixer (MX-102) for pre-
heating mixtures in s-102 to 170 °C at heat exchanger (HX-102) using
low pressurized steam. The pre-heat stream (s-103) enters a CSTR (R-
101) to undergo cellulose hydrolysis reaction to glucose while liquid
sulphuric acid acts as catalysts in this case. In a meanwhile, preparation
of Fe3O4 should be conducted simultaneously. 2 M NaOH solution, 1 M
FeSO4, and 2 M FeCl3 are fed in to storage tank with agitator (V-101)
with mass ratio of 3.8:1:1.15. Downstream a centrifugal pump (PM-
101) and butterfly valve (BFV-101) are present to avoid uncertainties in
transferring liquids from V-101 to a CSTR (R-103) to produce
4
Journal of Environmental Chemical Engineering 7 (2019) 102932
intermediate (Fe3O4) as well as valuable by-products such as NaCl and
Na2SO4. The outlet stream (s-105) of R-103 will undergo first separa-
tion process in sedimentation tank (V-102) to obtain Fe3O4 in s-107 that
requires for further reaction, while the slurry will pass through s-106
into decanter unit (V-103) to remove liquid wastewater consisting little
amount of iron precursors and NaOH, whereas the solid removal from s-
111 gets into component splitter to partially-purify the by-products.
Fe3O4 will mix with R-101 outlet stream (s-108) to further preheat
to 230 °C so as to meet the reaction condition in an industrial autoclave
(R-102) which designed to operate in pressure lower than 12 MPa. The
desired product – magnetite hydrochar (Fe3O4@C6H2O) is synthesized
in R-102 under 230 °C and 600 kPa using β-zeolite as catalysts. The
process temperatures of 215 to 235 °C are proven to have higher yield
of HTC char while increasing in temperatures and time contributes to
formation of gaseous products and produced water [21]. The operating
pressure for the autoclave should be within 10 to 50 bar for 0.5 to 8 h
depending on the biomass contents [13]. The outlet stream (s-112) of R-
102 will be transferred using conveyor belt for purification. Acetone
solution is first introduced in a rotary vacuum filtration (RVF-101) to
wash away the impurities such as remaining glucose and water on the
wet products. After that, washer (WSH-101) is built to clean acetone at
s-113 from RVF-101 using water. Moist products will pass through a
crystallizer (CR-101) to obtain uniform crystallized nanoparticles’ size
and then being transfer to the electric heater using conveyor belt to heat
up until 400 °C to remove the moisture content and increase the mag-
netic strength of the nanoparticles. According to Natthanan et al.
(2017), a simple heat treatment installed after HTC process can pro-
mote the magnetic properties of nanoparticles and likewise remove the
tannin content so that the nanoparticles can be applied in water pol-
lution purification as absorbents which results no more brown particles
appeared in water [8]. After all, the products will be transferred out of
process plant using conveyor belt and send to assigned storage using
truck (Table 1).
Since the operating condition for this plant is in higher temperature
ranging from 25 °C to 400 °C, therefore, cooler is not introduced in the
simulation while heat exchanger and heater used are suitable for bulk
solid and liquid flows. The simulated streams’ data such as temperature,
pressure, mass flowrate, and enthalpy are summarized in Table 2.
4. Results and discussion
4.1. Mass balances
Manual calculation is performed for major equipment such as re-
actors (R-101, R-102, and R-103) to evaluate the percentage difference
between manual and simulated mass flowrates, provided there are no
accumulation in reactors. Table 3 shows the percentage errors for mass
balance are below 1% which is simulated theoretically, and the use of
rate constants are validated in this case. R-102 has achieved conversion
rate of 78% in synthesis of magnetite hydrochar nanoparticles. Hy-
drochar production yield of 99.95% is simulated, as compared to hy-
drochar produced by HTC process, from OSC able to achieve 80% yield
at 180 °C and also maintain of 60% yield and above for residence time
3 h at temperature of 180–250 °C [13]. The particles size of magnetic
hydrochar produced from sugarcane by HTC process had proven by an
experimental study of which was about 10–20 nm diameter [8]. The
desired products yield of 631.314 kg/hr can meet the expected pro-
duction rate of 5000 tonnes per annum.
4.2. Energy balances
In the plant design study, all equipment requires electric energy:
Grinder, mixers, reactors, heat exchangers, pumps, decanter, crystal-
lizer, heater, and rotary vacuum filter, except for sedimentation tank
which depends on gravitational force. As electric energy demand de-
pending on the stream mass flowrate, where its specific power is
C.Z. Yieh et al. Journal of Environmental Chemical Engineering 7 (2019) 102932

Fig. 2. PFD for catalytic HTC plant.

defined as power output per mass, to compare the electrical energy
consumption with other similar process with consideration of mass
flowrate in each equipment. The major electricity consumption is
brought by RVF-101, EH-101, and CR-101 as displayed in Table 4.
In order to achieve highest production yield, HTC process parameter
was set at 230 °C and residence time of 1 h in this simulation study, as
reference to journal [8]. The rotary vacuum filter experiences highest
electricity supply of which 27.25%, followed by crystallizer as in
26.75% of total electric power demand. The grinder and mixer power
demand are 3.18 kW and 6.80 kW respectively, in which the demand
does not vary with process conditions, but dependent on mass flowrate
of biomass to be treated. The hydrochar produced from SG achieved
higher yield at 230 °C than 180 °C, where the electric power consumed
for liquid solid separator, heater and crystallizer were slightly different
due to hydrochar yield. Similarly, as reported by Lucian et al. (2017) for
hydrochar produced from grape marc (GM), the hydrochar yield and
pelletizer had reached its maximum consumption at residence time of
1 h and 220 °C [13]. The electric consumption is related to the hydro-
char flow rate entering these equipment, as well as HTC residence time
and temperature.
The thermal energy is required to heat up the treated biomass
stream before entering HTC process using heat exchanger, as well as
heat treatment towards final products to enhance its magnetic proper-
ties [8]. The manual calculation of thermal energy is focused more on

Table 1
Comparison of catalyst that can be used in hydrothermal thermal carbonization.
Types of Catalyst Catalyst Advantages Disadvantages

Alkali and Alkaline Earth Graphite • Good field emission • Few testing of applicable usage of graphite in hydrothermal thermal
Catalyst • High thermal and electrical conductivity carbonization has done [25]
• High tensile strength • Lower lifetime can be reused
Aluminosilicate minerals β-Zeolite • Thermally stable that is not highly sensitive to
temperature change
• Not applicable to all reaction, where it is only used for hydrothermal
carbonization reaction in autoclave
• Higher surface area and pore volume that allowed
better contact for reaction to takes place
• Activation reaction of catalyst is able initiated for reaction that more
than 2 hours [26].
• Natural Catalyst that does not harmful to environment
• Concentration of compound reduced relatively to
increase ash content
• Favour process that has low temperature under 270 °C
• added
Zeolite has the properties of stabilized effect when
on hydrolysis of Cellulose [26]
• Reusable for a period
Inorganic compounds KOH • More dynamic for various reaction • Large amount required where the ratio of catalyst to material is
• Large pore volume relative to the surface area commonly 5:1 [28].
• Activation condition can be accustomed to
temperature and time depending on specific reaction
• The minimum temperature pre-activation of catalytic process is 400 °C,
the optimum reaction temperature is in range of 600 °C to 900 °C [27]
[27]

5
C.Z. Yieh et al. Journal of Environmental Chemical Engineering 7 (2019) 102932

Table 2
Stream table.
Stream Name Acetone Fe3O4@C FeCl3 FeSO4 H2O H2SO4 HP Steam-2 LP Steam-2 LP Steam-3 Water

Total Mass Flowrate (kg/h) 30.0 632.8 2605.0 2267.0 35.3 13.0 8000.0 8000.0 6168.0 50.0
Temperature (°C) 25.0 400.0 25.0 25.0 25.0 25.0 242.0 100.0 208.7 25.0
Pressure (kPa) 101.325 202.650 101.325 101.325 101.325 101.325 303.975 101.325 600.000 101.325
Liq/Sol Flow (kg/h) 30.0 631.3 2605.0 2267.0 35.3 13.0 0.0 6473.6 0.0 50.0
Total Enthalpy (kWh) 0.45 10.55 60.48 58.46 1.02 0.37 6962.72 1963.07 5256.18 1.45

Stream Name S-101 S-102 S-103 S-104 S-105 S-106 S-107 S-108 S-109 S-110
Total Mass Flowrate (kg/h) 318.3 366.6 366.6 13406.0 13406.0 6960.3 6445.7 353.9 6799.6 6799.6
Temperature (°C) 25.0 28.2 170.0 25.2 25.2 25.2 25.2 170.0 31.5 230.0
Pressure (kPa) 101.325 101.325 101.325 101.325 201.225 101.325 101.325 101.325 101.325 101.325
Liq/Sol Flow (kg/h) 318.3 366.6 318.6 13406.0 13406.0 6960.3 6445.7 353.9 6799.6 808.4
Total Enthalpy (kWh) 5.85 8.16 79.74 360.92 366.41 190.55 175.86 33.19 226.05 5225.71

Stream Name LP Steam-4 LP Steam-6 Na2SO4 NaCl NaOH Recycle-1 Sugarcane BG Wastewater-1 Wastewater-2 Wastewater-3
Total Mass Flowrate (kg/h) 12.7 0.0 2525.5 1437.2 8534.0 6168.0 318.3 2997.6 1.2 77.6
Temperature (°C) 170.0 25.0 25.2 25.2 25.0 230.0 25.0 25.2 56.1 56.0
Pressure (kPa) 101.325 101.325 101.325 101.325 101.325 600.000 101.325 101.325 101.325 101.325
Liq/Sol Flow (kg/h) 0.0 0.0 2525.5 1437.2 8534.0 0.0 318.3 2997.6 0.3 77.6
Total Enthalpy (kWh) 10.57 0.00 68.42 34.51 238.81 5327.76 5.85 87.62 0.18 6.37

Stream Name S-111 S-112 S-113 S-114 S-115 S-116 S-117 S-119
Total Mass Flowrate (kg/h) 3962.7 631.6 660.3 632.8 632.8 632.8 13406.0 13406.0
Temperature (°C) 25.2 230.0 56.1 56.1 25.0 400.0 25.2 25.2
Pressure (kPa) 101.325 600 101.325 101.325 202.65 202.65 201.325 201.225
Liq/Sol Flow (kg/h) 3962.7 631.6 631.3 631.3 632.8 631.3 13406.0 13406.0
Total Enthalpy (kWh) 102.93 5.80 6.59 1.67 0.65 10.55 360.75 360.75

Table 3
Mass balance on major equipment.
Major Equipment R-101 R-102 R-103

Stream No. S-103 S-108 S-110 S-112 S-119 S-105

Component C6H10O5 H2O C6H12O6 C6H12O6 Fe3O4 Fe3O4@C6H2O H2O FeCl3 FeSO4 NaOH Fe3O4 NaCl Na2SO4 H2O
Manual Calculation (kg/h) 318.3 35.4 353.6 353.6 454.5 631.3 176.8 636.8 298.2 628.1 454.5 688.3 278.8 141.5
Superpro Simulation (kg/h) 318.3 35.3 353.7 353.7 454.5 631.3 176.8 638.1 299.0 628.1 454.5 688.3 278.8 141.5
Percentage Error (%) 0.01 0.09 0.01 0.01 0.00 0.00 0.00 0.20 0.26 0.00 0.00 0.00 0.00 0.04

Table 4
Electric Power Demand.
Biomass Temperature (°C) Time (h) Biomass inlet Electric Power (kW)
flow (kg/h)
Grinder (GR- Mixer Liquid solid separator Heater (EH- Crystallizer (CR- Pump 1 Pump 2 Totalb
101) (MIX-101) (RVF-101) 101) 101)

SG 180 1 318.3 3.18 6.80 15.36 11.07 15.25 – – 56.83

SG 230 1 318.3 3.18 6.80 15.54 11.74 15.26 – – 57.04
OSCa 220 1 2525.0 25.60 9.48 17.81 21.99 56.7 61.94 3.67 216.91
GMa 220 1 2525.0 23.91 9.29 2.95 13.08 33.52 12.98 0.67 106.04

a
Data obtained from [13].
b
The value is calculated by 10% allowance for an overall plant electric power supply of 90% efficiency.

Table 5
Energy balance on heat transfer equipment.
Major Equipment HX-101 HX-102 EH-101 PM-101 CR-101

Stream No. HP Steam-2 Recycle-1 Standard Power Standard Power Chilled Water
Manual Calculation (kJ/h) 18,118,235 13,969,146 35,652,525 1,270,995 2,888
Superpro Simulation (kJ/h) 18,003,786 256,545 41,944,146 1,815,708 2,906
Percentage Error (%) 0.63 98.16 17.65 42.86 0.62

heat or cold utilities usage equipment such as heat exchanger (HX-101,
HX-102). The manual and simulated data are listed in Table 5 which
shows large deviation in percentage errors given from 0.62% to
98.16%. Largest error of 98.16% in HX-102 might be due to over-
loaded hot stream (6000 kg/h, 230 °C, 1 atm) supply to the cold stream
(366.6 kg/h, 28 °C). Centrifugal pump (PM-101) experiences 42.86%
difference in both manual and simulated calculation because there
might be power dissipated to heat and sound energy which leads to
higher duty required in simulation. For the error percentage lower than
20%, it is considered in acceptable operation range. The thermal power
consumption for HX-101 to prepare for HTC temperatures of 180 °C and
230 °C are 4844.55 kW and 5018.06 kW respectively, where the former

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C.Z. Yieh et al. Journal of Environmental Chemical Engineering 7 (2019) 102932

has 3.46% lower of energy required. Since the production yield is more

14365.50
1306.00
significant, thus a process optimization plan is carried out to reduce
Water

90.91
Costing (RM/year)

Electricity some thermal energy cost.

1201.00 4.3. Process optimization

109.20
90.91
The objective of optimization is to minimize the utilities usage and
maximize the profit of processing plant. The chosen section to be op-
Water (kg)

timized is heat exchanger (HX-102) which requires 800 kg/h of low-

6336000
Utilities Requirement (year)

pressurized steam to preheat R-101 feed. With the recycle stream from
99.99
800

R-103 that provides sufficient energy to reach the expectation, the

operating cost of plant is estimated to be reduced by up to 90% for this
Electricity (kW)

equipment. Based on Table 6, a decrement of USD3,300 per year is

obtained after optimization whereby this amount of money is sig-
nificant to a medium processing plant for further developing purposes.
3986.0
0.5033
99.99

Apart from that, the overall utilities consumption in plant are listed in
Table 7.

4.4. Process control philosophy

Water (kg)
Utilities Requirement (first hour)

0.00

Smooth operation, safety, profit, equipment protection and en-

800
800

vironmental protection are the five main objectives for process control.
Piping and instrumentation diagram (P&ID) is developed by applying
top-down approach (Luyben algorithm) [22], which is illustrated in
Electricity (kW)

Fig. 3. Total number of control valves in this proposed plant is 18.

Hence, total number of degrees of freedom for control is 18. Legitimacy
0.5033
0.5033

of process control is checked by ensuring only one control valve for

0.00

each stream. Recycled heat management is established in this plant to

prevent propagation of thermal disturbance using cascade control
Continuous LP Steam Supply

technique. Feed inlets’ flow rate are controlled by composition para-

LP Steam Flowrate (kg/hr)

metric transmitter at the outlet stream after mixers. This is because feed
ratio must be accordingly to achieve high reaction conversion. Relief
valves and indicators (pressure and temperature) are installed for major
equipment like reactor (R-101) and autoclave (R-102) for safety pur-
poses. Pressure inside the vessels is regulated in order to prevent vessel
671.00
6168

rupture or explosion due to overpressure. Same theory is applied to

800

regulate the level inside the vessels. Ratio controller and cascade con-
trol are the advanced control configurations that applied in this plant to
Recycle LP Steam released from R-102

reduce dependence on the control valve usage and at the same time
optimize process economic.
Recycle Stream Introduced

5. Economic study of catalytic HTC plant

The main priority of the designed plant is to enable the manufacture

of products in high purity as well as to generate significant profits.
Hence, the economic study plays a vital role in identifying the profit-
Recycle-1

ability for the designed plant. In the economic study section, the cal-
culation for the capital investment, product cost and economic analysis
–

scenario is done. There are several economic assumptions made in

Initial LP Steam Preparation

order to calculate the HTC processing plant. The plant is assumed to

LP Steam Flowrate (kg/hr)

operate at a life span of 10 years, while the construction period is as-

sumed to taken up 2 years. For the annual working days, it is assumed
to be in total of 330 days while the remaining 35 days is planned to shut
down for maintenance purposes. In respect to the equipment cost, the
chemical engineering plant cost index (CEPSI) in year 2016 is used as
the reference to determine the plant cost in 2017. The prices of all the
0.00
800
800
Process optimization evaluation.

equipment is quoted from the latest market price as it is referring to the

online market or online manufacturers’ catalogue. There are two dif-
Percentage Differences (%)

ferent methods in calculating the total capital cost (TCI): Method 1 is

the percentage of delivered equipment cost method while method 2 will
be Lang Factor. The detailed explanation will be included in the fol-
Optimized Case

lowing sections.
Parameter

Base Case

5.1. Percentage of delivered equipment cost

Table 6

In the stage of the industrial plant to begin operations, large capital

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C.Z. Yieh et al. Journal of Environmental Chemical Engineering 7 (2019) 102932

Table 7
Utilities consumption summary.
Equipment HX-101 HX-102 EH-101 PM-101 CR-101 GR-101
Utility Stream HP Steam-2 Recycle-1 Standard Power Standard Power Chilled Water Standard Power

Heat Transfer Coefficient (W/m2⋅K) 200 200 – – – –

Heat Transfer Area (m2) 96.187 3.271 – – – –
Heat Duty (kJ/h) 1,8003,779.76 257,690.57 – – – –
Power (kW) 5001.05 71.58 11.6512 0.5044 0.81 3.183
Number of Unit 8 1 1 1 1 1
Total Power (kW) 40008.4 71.58 11.6512 0.5044 0.81 3.183
Equipment V-101 MX-101 MX-102 R-101 R-103 RVF-101
Utility Stream Standard Power Standard Power Standard Power Standard Power Standard Power Standard Power
Power (kW) 12.71 67.9959 3.6663 0.0111 0.0111 0.0031
Number of Unit 1 1 1 1 1 1
Total Power (kW) 12.71 67.9959 3.6663 0.0111 0.0111 0.0031

Fig. 3. P&ID for catalytic HTC plant.

is needed to make purchases and installation of the equipment. There
are two different types of cost which are known as total capital in-
vestment (TCI) and total production cost (TPC). Land and service fa-
cilities are necessary for the plant and a complete plant is supposed to
be equipped with piping and control system. Thus, the necessary
equipment and piping is known as direct plant cost which is under fixed
capital investment (FCI). The percentage of delivered equipment cost is
used to estimate each aspect under the FCI, by assuming purchased
equipment being under 100% of the cost while the other aspects taken
up the other percentage. The percentage varies for plants which involve
different phase of materials, as the chosen percentage is specifically
used by solid-liquid plant as HTC process involving liquid and solid
phase of materials throughout the process. The detailed percentage will
be included in Table 8 and Table 10.
The amount of the direct plant cost is $56,379,353. In terms of FCI,
there is another cost which is known as the indirect plant cost which
includes the cost of supervision, legal expenses, contingency and con-
tractors fee which amounts to $592,820. FCI is the sum of the direct and
indirect plant costs which contributes to a total amount of $56,972,174.
The working capital is 10% of FCI, which is $5,697,217. TCI is obtained
by adding up FCI and working capital.
5.2. Lang’s factor method
Lang’s factor is an estimation method for capital investment which
was proposed in 1947 by Hans. J Lang in Chemical Engineering
Magazine. Lang factor is widely used in industrial engineering in the
1940s. Lang Factor is a ratio of the capital investment to the cost for
major technical components. There are different factor values for dif-
ferent types of plants which are solid, solid-fluid and fluid processing
plant, since the HTC processing consists of both solid and liquid state of
materials. From the literature, the accuracy of Lang’s Factor method is

8
C.Z. Yieh et al. Journal of Environmental Chemical Engineering 7 (2019) 102932

Table 8 about ± 50% [23]. The detailed calculation will be shown in Table 9.
Summary of total capital cost. Lang Factor of FCI is 4.28 which gives a total of $45,601,615 and for
Direct costs Percent (%) USD TCI the factor is 5.03 and the amount of TCI is $2,293,761. By com-
paring both method 1 and 2, the differences are about 9.6%, roughly
Purchased equipment delivered, E 100 456,016.10 $60,000 in difference. Lang factor is believed to be less accurate as
Purchased equipment installation 39 177,846.30
there is some amount of aspects which are not taken into calculation
Instrumentation and controls (installed) 26 118,564.20
Piping (installed) 31 141,365.01
therefore it contributes to the difference of $60,000.
Electrical system (installed) 10 45,601.61
Building (including services) 29 132,244.68 5.3. Sensitivity study
Land – 55,002,184.90
Yard Improvements 12 54,721.94
In the sensitivity study, there will be three different scenarios ana-
Service facilities (installed) 55 250,808.88
Total direct plant cost 302 56,379,353.60 lysed where the results are summarized in Table 11. The changing
variables will be the raw material price, tax of the goods and the selling
Indirect Cost
Engineering and supervision 32 145,925.17 price of the product. Over the years, the prices might experience in-
Construction expenses 34 155,045.49 crement and decrement, therefore the sensitivity study is to investigate
Legal expenses 4 18,240.65 the changing variables in affecting the payback period, ROI and DCFRR
Contractor's fee 23 104,883.71 by keeping the other variables constant.
Contingency 37 168,725.97
Total indirect plant cost 130 592,820.99
5.3.1. Current financial expected outcome
Fix Capital investment (FCI)=(direct + indirect) – 56972174.6
For the base case shown in Fig. 4, all the variables as well as the
Fix Capital investment 432 56972174.6
Working Capital 10% TCI 5697217.46 prices remain at the standard in 2017. From the online market, the
Total Capital Investment – 62669392.10 latest market price of the nanoparticle cost roughly $250 per year with
rate of production for 5000 tonnes/year. The payback period for base
case is roughly around 1.3 years with a net income of $411 million per
Table 9 year. By getting the payback period of 1.3 years, this proves that the
Lang's factor summary. processing plant is feasible. The net present worth (NPW) for base case
Lang Factor method Solid-fluid plant is $298 million with a 74% of discounted cash flowrate of return
(DCFRR) and the return on investment (ROI) is 74% as well. NPW gives
FCI TCI a positive value which means that the plant gives a better return where
NPW is a measurement of profit by subtracting the present value of
Lang Factor 4.28 5.03
Purchased Equipment delivered, E 456,016.15 456,016.10 outflow of cash from the inflow of cash over a certain period. The main
Cost 1951,749.10 2,293,761.22 function of DCFRR is to determine the attractiveness of the opportunity
for investment [24]. The higher the value of the DCFRR, the more at-
tractive for the investment opportunity.
Table 10
Summary of total production cost. 5.3.2. Potential improvement in financial outcome
Manufacturing Expenses % $/ year Under the best-case scenario displayed in Fig. 5, there are several
Variable Manufacturing Cost variables which assume to experience some changes in price. The price
of raw material will be altered to 20% lower from the base case and the
Direct Production cost
Raw Material – 3.38E+07
selling price of the product experiences an increment of 20%. Ad-
Operating labour, O – 1,338,902 ditionally, the local tax which was originally 6% which is known as
Operating Supervision. S 15%O 200,835 Goods and Service tax has a decrement to 3%. All the variables have
Utilities been altered which will then contribute to the reduction in the Pro-
Electricity – 1,259,317 duction cost from $66.9 to 66.0Million. By experiencing the decrease in
Water – 616,823 cost, the revenue gain will then see an increment which is $578Million
Steam – 5,440,156
and a net profit of $554Million. The payback period has also reduced
Maintenance and repair, M 7%FCI 3,988,052
Operating Supplies, SU 15%M 598,207
from 1.3 years to 1 year, DCFRR increase to 83% from 745 and the NPW
Laboratory Charges, L 15%O 267,780 gives a total of $360Million. Generally, the best-case causes all the es-
Catalyst – 350 timation towards the positive income which generate higher profits
Subtotal 4.75E+07 compared with base case.
Fixed Manufacturing Cost
Local Tax 6%FCI 3,418,330 5.3.3. Potential breaking down in financial outcome
Insurance 0.7%FCI 398,805
Under the worst-case scenario illustrated in Fig. 6, the price of raw
Financing 5%TCI 2,848,608
Subtotal 6,665,744 material increases 20% while the local tax increases from 6% to 12%.
There is an increment in production cost which sees the total increment
Plant Overhead Charges (POC) = 50%(O + S+M)
Subtotal 2,763,894
rise to $1.6Million more than the base case. The revenue will then be
reduced if the cost increases. Subsequently, the selling price of the
Total Manufacturing Cost (MC)=VPC + FC + POC
Subtotal 56,959,020
product might be reduced by 20% compared with the price in year
2017 as well as the prices of by-products. By substituting the changing
General Expenses
variables to the base case, it leads to the total revenue of $311 Million
Administrative Expenses (AE) 20%O + S+M 552,778
Distribution & marketing expenses (DME) 11%TPC 6,265,492 which is $134Million less per annum compare with the base case.
Research and development expenses 5%TPC 2,847,951 DCFRR drops to 40% from 74% and the payback period is also affected
Subtotal 9,666,222 by the reduction of revenue, the payback period is delayed 1.5 years
Total Product Cost (TPC) =MC + GE more than the base case, even though the payback period dragged is
Subtotal 66,625,242
still within the acceptable range. This proves that the plant is feasible
even though it is under the worst scenario.

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C.Z. Yieh et al. Journal of Environmental Chemical Engineering 7 (2019) 102932

Table 11
Economic scenario study.
Case Base Worst Best

Total annual product cost ($/yr) 66,625,242.91 66,939,349.35 66,311,136.47

Total capital cost investment ($/yr) 62,669,392.09 66,939,349.35 66,311,136.47
Total annualized cost, TAC ($/yr) 129,294,635.00 133,878,698.71 132,622,272.93
Total revenue ($/yr) 4,452,949,096.20 3,117,064,367.34 5,788,833,825.06
Total Revenue include GST 4,185,772,150.43 2,181,945,057.14 5,615,168,810.31
Gross profit ($/yr) 4,119,146,907.52 2,115,005,707.78 5,548,857,673.84
Salvage ($/yr) 45,601.61 45,601.61 45,601.61
Average Depreciation ($/yr) in 10 years 5,692,657.30 5,692,657.30 5,692,657.30
Net profit ($/yr) 41,134,542.50 21,093,130.50 55,431,650.17
Net cash flow ($/yr) 46,827,199.80 26,785,787.81 61,124,307.47
Rate of Return (ROR) 7.47 4.00 9.22
Returned on investment (ROI) 74.72 40.02 92.18
Payback period (year) 1.34 2.50 1.08
Reference payback period (year) 5.32 6.80 4.80
Discount Factor 0.4865 0.6755 0.4141
Present Worth Factor 6.87 8.11 6.36
Present Worth 358,874,686.30 291,865,676.80 427,259,449.50
Net Present Worth 296,205,294.24 224,926,327.40 360,948,313.06
Discounted Cash Flow rate of Return (DCFRR) 74% 30% 83%
Cumulative Cash Position 405,602,605.90 200,918,528.70 544,931,938.20

Fig. 4. Breakeven curve of base case where raw material cost and product Fig. 6. Breakeven curve for worst case where increase in raw material cost of
market price are maintained as well as local tax of 6% introduced. 20% and product market price of 20% decrement, as well as local tax of 12%
introduced.

6. Conclusion

In this assessment, the feasibility assessment is investigated to

Fig. 5. Breakeven curve for best case where decrease in raw material cost of
20% and product market price of 20% increment, as well as local tax of 3%
introduced.
produce magnetic nanoparticles by catalytic hydrothermal carboniza-
tion (HTC). Simulation of this whole process were perform using su-
garcane bagasse as carbon precursor where β-zeolite is acted as the
catalyst to facilitate the process. The production of magnetic nano-
particles can be categorized into three processes namely pre-treatment
process, preparation of Fe3O4, hydrothermal carbonization process,
product and by-product purification stages. The economic investment
of this process plant to manufacture magnetic nanoparticles is profit-
able, it is anticipated that the annualized cost is USD $ 129,294,635
where the total revenue for base case is USD $4,452,949,096 with a
payback period of 1.3 years. This is considerable eco-friendly process as
SG, an agricultural waste is used as feedstock and hydrothermal
thermal carbonization does not emit high level of carbon dioxide
throughout the process. The major equipment used is continuous stirred
tank reactor, autoclave and crystallizer. This pilot plant study able to
achieve conversion rate of 95% and to synthesis 631.314 kg/h
Fe3O4@C6H2O. Catalyst used in HTC is β-Zeolite because it offers the
consistency of nanoparticles size at range of 10–20 nm to enhance its
relatively magnetic strength. Sensitivity analysis is performed for best

10
C.Z. Yieh et al.
case and worst cases scenario to projected future outcome which as-
sume at different condition when project is undergoing. Capital in-
vestment of the process plant is calculated corresponding to the cost for
major technical components by using Lang factor method. Economic
variables are calculated by multiply with sensitivity analysis factor,
where best case scenario total of sales is estimate increasing by 20%
which result total revenue of $578Million and worst case has
$311 Million per year. The payback period for both cases is 1.00 and
2.50 years respectively. Besides the aims to achieved maximum of
production rate, EIA and HAZOP are parts of the process design to
preserve safety of employees and minimize potential hazards dis-
charged from plant.
Conflict of interest
The authors declare no conflict of interest.
Acknowledgement
The authors would like to acknowledge Curtin University, Malaysia
for supporting this research.
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