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Economic evaluation and production process simulation of biodiesel

production from waste cooking oil

Article  in  Current Research in Green and Sustainable Chemistry · April 2021

DOI: 10.1016/j.crgsc.2021.100091

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 Current Research in Green and Sustainable Chemistry 4 (2021) 100091

Contents lists available at ScienceDirect

Current Research in Green and Sustainable Chemistry

journal homepage: www.elsevier.com/journals/
current-research-in-green-and-sustainable-chemistry/2666-0865

Economic evaluation and production process simulation of biodiesel

production from waste cooking oil
Yanbing Liu a, Xinglin Yang a, Abdullahi Adamu b, Zongyuan Zhu a, b, *
a
School of Energy and Power, Jiangsu University of Science and Technology, No. 666 Changhui Road, Zhenjiang, Jiangsu Province, 212100, China
b
School of Engineering, Faculty of Science, Agriculture and Engineering, Newcastle University, Newcastle Upon Tyne, NE17RU, United Kingdom

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

Keywords: Waste cooking oil (WCO) is a promising feedstock for producing biodiesel, which plays a significant role in waste
Waste cooking oil resource reusing and renewable energy production. It is known that cost is the main factor restricting the large-
Biodiesel scale production of biodiesel. Therefore, the Life Cycle Cost (LCC) method was used to analyze the economic
Life cycle cost
feasibility of the biodiesel production process from WCO. Our results show that the cost of producing 1 t of WCO
Aspen plus
biodiesel is 6291.56 RMB, which is 65.28% higher than the cost of diesel. The factors influencing WCO biodiesel
production cost was further analyzed. Although WCO has a low commercial price, necessary pretreatment is
inevitable and creates additional processing cost, since WCO cannot be directly used for transesterification to
produce biodiesel. The cost of pretreatment process is relatively high, accounting for 15.60% of the total cost.
Special waste management policy should be implemented and waste cooking oil recycling technology should be
advanced, in order to make WCO biodiesel more economically competitive. Aspen Plus software was used to
simulate the production process of biodiesel from WCO, and the production process was simulated by a two-step
method. The practicability of simulation was confirmed by purity of biodiesel reaching 99.6 wt%. In the simu-
lation, processing parameters of methanol rectification tower and biodiesel rectification tower were optimized to
provide a reliable benchmark for the industrial biodiesel production from WCO.

1. Introduction simple process, etc. [11–13]. It has been used in cars [14], ships [15],
airplanes [16] and other vehicles, owing to these advantageous proper-
In recent years, the global energy consumption is booming rapidly, ties. Although the physical and chemical properties of biodiesel are
because of the continuously growing global economy and population similar to that of traditional diesel (see Table 1) [17–20], biodiesel has a
[1–3]. With China's reform and opening up policy, fossil energy con- low volatility, high viscosity and low calorific value [21]. Hence, 100%
sumption has been increasing steadily [4]. China has become the world's biodiesel is unable to be used in vehicles and it has to be blended together
second largest petroleum consumer since 2007 [5]. According to the with diesel with different percentage, ranging from 5% to 20%, for
“Statistical Review of World Energy 2020” issued by BP [6], China has practical application [22–24]. The history of biodiesel development
relatively few fossil reserves. However, Chinese annual fossil output dates back to middle 19th century. In 1853, Patrick Duffy discovered
(191.0
106 t) ranks sixth in the world, and fossil mining is greatly biodiesel. 30 years later, Rudolf Diesel [25,26] established a model using
limited. In addition, the impact of fossil fuels on the environment is peanut oil as a fuel. From then on, the interest of biodiesel production
irreversible, thus seeking alternative fuels to fossil fuels has become a began to rise globally. The global development of biodiesel is rather
vital task. Out of many, biofuels are one of the most crucial alternative rapid, reaching 20 million tons in 2012 [5], but China's biodiesel industry
green, clean and renewable energy sources [7–10]. Biodiesel has lower started late. According to the US Energy Information Administration
sulfur content and aromatic compounds content, high flash point, low report, Chinees biodiesel production in 2014 was 991 thousand metric
viscosity, environmental friendliness, wide range of raw materials, tons, which is much lower than that of Brazil and the US [27,28]. A wide

Abbreviations: C-WCO, Crude waste cooking oil; FAME, Fatty acid methyl ester; FFA, Free fatty acid; LCA, Life Cycle Assessment; LCC, Life Cycle Cost; WCO, Waste
cooking oil.
* Corresponding author. School of Energy and Power, Jiangsu University of Science and Technology, No. 666 Changhui Road, Zhenjiang, Jiangsu Province, 212100,
China.
E-mail address: [email protected] (Z. Zhu).

https://doi.org/10.1016/j.crgsc.2021.100091
Received 5 February 2021; Received in revised form 2 April 2021; Accepted 3 April 2021
Available online 8 April 2021
2666-0865/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
Y. Liu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100091

Table 1
The physical and chemical properties of biodiesel and diesel [17–20].
Items Density (g/mL) Sulfur content (wt%) Flash point ( C) Oxygen content (wt%) Viscosity(mm2/s) Calorific value (MJ/L)

Biodiesel 0.882 <0.2 >100 0 4–6 35.136

Diesel 0.834 <0.001 60 10 2–4 35.784–38.25

range of feedstock oils, including edible oil and non-edible oil, have been
used for the production of biodiesel through different methods [29]. It is
highly necessary to evaluate the energy consumption, pollutant emis-
sions and economic efficiency of the process, in order to find the suitable
feedstock oil and processing conditions for biodiesel production.
Non-edible oil is gaining growing attention, such as jatropha oil [30,
31], castor oil [32] and waste cooking oil (WCO) [33], in which WCO has
presented a promising potential, as it has a rather low commercial price
[33]. Moreover, WCO avoids competition with edible oil, and it can
address issues relating to WCO disposal, thus it is considered as a
promising feedstock oil for biodiesel production [34,35]. In our previous
study [36], Life Cycle Assessment (LCA) was applied to compare the
energy consumption and pollutants emissions of two commonly used
feedstock oil (soybean oil and WCO) for the production of biodiesel in
China. Our results showed that the production of biodiesel using WCO as
the feedstock is more competitive in terms of energy consumption and
pollutants emission control. In addition, economy is one of the key fac-
tors that determine the feasibility of biodiesel production on a large in-
dustrial scale [37,38]. On the basis of the existing research, the current
study will use the Life Cycle Cost (LCC) method to evaluate the economic
efficiency of biodiesel produced from WCO, and compare it with the
price of diesel. For the economic evaluation of WCO biodiesel, the cost of
catalyst preparation should also be taken into consideration. In the
existing studies, most researchers use homogeneous catalysts (e.g. NaOH
[39–41] and NaOCH3 [42,43]), but there are few studies about CaO
based catalysts with simple preparation process, strong basicity, and high Fig. 1. The system boundary of the LCC system for biodiesel production from
catalytic activity. Therefore, in the evaluation of WCO biodiesel in this WCO, including the inputs and outputs of the four processes.
study, CaO catalyst is selected to catalyze the transesterification to pro-
duce biodiesel. According to experiment and economic feasibility 2.2. Basic data
studies, it is highly necessary to simulate the biodiesel production process
from WCO using chemical software, so as to optimize the biodiesel Taking the production of 1 t of biodiesel as the functional unit, the
production process and its operational conditions [44]. Aspen Plus V8.4 economic analysis of WCO biodiesel is carried out. On the basis of the
was used to simulate the process of biodiesel production from WCO, and existing experiments, referring the study of Degfie et al. [48], the CaO
the technical feasibility of the simulation process is assessed based on nano-catalyst with simple preparation method and high catalytic activity
whether the purity of biodiesel can reach 99.6 wt% (ASTM standard). was selected for transesterification to prepare biodiesel from WCO. An
optimal biodiesel yield of 96% was obtained using alcohol-to-oil molar
2. Life cycle cost assessment ratio of 8 and catalyst loading of 1% (based on oil weight) at 50  C for 90
min.
LCC refers to all the costs related to the product that occur during the The transesterification reaction is shown in Scheme 1. When pre-
production of the product, and the economic model for pricing the paring 1 t of biodiesel (FAME) using WCO as the feedstock oil, 1075 kg of
product [45]. When evaluating economic feasibility of the WCO biodiesel pretreated WCO, 305.72 kg of methanol and 10.75 kg of catalyst are
production process, four processes are included, namely WCO collection, required. After collecting 1 kg of WCO and pretreatment, 0.63 kg of
WCO pretreatment, biodiesel production and product delivery. Different refined oil can be obtained for the preparation of biodiesel [4], thus 1706
resources have been involved, including labor, water, electricity, raw kg of crude WCO needs to be collected for 1075 kg of processed WCO. As
materials, equipment assets etc. [46,47]. Fig. 1 shows the system it was mentioned earlier, the biodiesel production comprises four process
boundary of the LCC of biodiesel production from WCO. stages, namely WCO collection, WCO pretreatment, biodiesel produc-
tion, and product delivery. Detailed information in each stage will be
elucidated in the following subsections.
2.1. Materials
2.2.1. WCO collection
In the process of preparing biodiesel from WCO, the price of methanol The collection of WCO is transported by a 5 t autotruck using gaso-
is referred from Northwest Port of Methanol Market, China. The price of line. This model is used to collect WCO from big cities in a factory built in
H2SO4 is from Taiyuan Kunshengda Chemical Co., Ltd. The price of the Yangtze River Delta region, and the average travel distance is 120 km
Ca(NO3)2⋅4H2O is from Nanjing Chemical Reagent Co., Ltd. The price of [49]. Furthermore, the transportation road is highway, the gasoline
ethylene glycol is from Hebei Borun Industry and Trade Technology Co., consumption of road transportation is 0.0706 L/(t⋅km), and the gasoline
Ltd. The price of NaOH is from Wujiang Shenlong Chemical Co., Ltd. The density is 0.72 g/cm3 [50]. Therefore, 1706 kg of WCO collected during
price of steam comes from Huaneng Suzhou Thermal Power Co., Ltd. The the transportation consumes 14.45 L of gasoline. The average gasoline
price of distilled water comes from Kunshan Ainault Water Treatment price is about 5.97 RMB/L according to our market survey. Manual input
Equipment Co., Ltd. is taken into account in the stage of collecting and transporting WCO,

2
Y. Liu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100091

Scheme 1. Transesterification reaction.

Scheme 2. Esterification reaction of a fatty acid with methanol [92].

including driver's wage, loading and unloading service expenses and glycol ((CH2OH)2) and 8.056 kg of sodium hydroxide (NaOH), which
other expenses incurred. According to market survey, it is found that the consumes 62 kW h of electricity [22]. The preparation of biodiesel is
driver wage in the labor market of Jiangsu Province is about 200 carried out by transesterification which mainly consumes electric energy,
RMB/day, and the loading and unloading service expenses and other and the production of 1 t of biodiesel requires 22 kW h of electricity and
expenses incurred are about 5 RMB/t and 3 RMB/t, according to previous 557 kg of steam [49]. After the transesterification, the biodiesel obtained
study [46]. The price of WCO is 224 USD/t (1499.30 RMB/t) [51,52]. contains impurities (e.g. unreacted methanol, catalyst, and by-product
glycerol), which needs to be washed away using distilled water.
2.2.2. WCO pretreatment Washing 1 t of biodiesel consumes 370 kg of distilled water [58]. The
WCO has a wide range of sources and complex compositions. The washed biodiesel needs to be dried at 120  C for 12 hours.
collected WCO contains a number of impurities and high content of free
fatty acids (FFAs). Hence, it is required to pretreat the WCO by filtration 2.2.4. Product delivery
of the impurities and deacidification of feedstock oil to reduce the acid Biodiesel is transported to the gas station on the highway by a 5 t
value [53,54]. Filtration of impurities mainly consumes water resources autotruck fueled by gasoline, and the transportation distance is 20 km.
and the deacidification process consumes electricity, methanol and Hence, 1.41 L of gasoline will be consumed to transport 1 t of biodiesel.
H2SO4 [55].
In the process of impurities filtration, screening is used repetitively, 2.3. Cost list
and then washing process is carried out. According to washing process of
the WCO in the laboratory, the ratio of washing water and untreated In the LCC evaluation of biodiesel produced from WCO, in addition to
WCO is maintained at 10:1 (wt/wt), so 1706 kg of WCO needs 17060 kg the costs involved in the above four processes, land costs and equipment
of water consumption. Pre-esterification of FFAs is performed to reduce costs should also be considered. Biodiesel industry is strongly supported
the acid value of WCO [55], which increases the yield of methyl esters. by China government, so the land occupation area is funded by the
The deacidification method of WCO is referenced from previous study government. This study does not consider the cost of land when calcu-
[55]. The esterfication reaction is given in Scheme 2. The deacidification lating the cost of WCO biodiesel. According to the economic indicators of
was performed at the condition of H2SO4 of 1.5% (based on oil weight), Tsinghua University's knowledge transfer project of biodiesel plant (solid
methanol to oil ratio of 20 wt%, and mass ratio of methanol to glycerol of acid or base catalyzed transesterification of acidified oil or waste cooking
1: 0.547 at 60  C for 2 h. In the pretreatment process of WCO, addition of oil) [46], the service life of the equipment is set to be 10 years to calculate
glycerol can esterify FFA, thereby reducing the acid value of WCO [22]. the depreciation of equipment assets. The cost of each process of bio-
Under H2SO4 catalyzed conditions, the acid value of WCO after pre- diesel production from WCO is shown in Table 2. It shows that 1 t of
treatment is relatively high, about 2 mg KOH/g, while glycerol assisted biodiesel costs 6291.56 RMB.
esterification can significantly reduce the acid value of WCO to 0.5 mg
KOH/g [56,57]. After calculation, 25.59 kg of H2SO4, 341.2 kg of
methanol, 186.64 kg of glycerol, and 32 kW h of electricity are required. 2.4. Economic result analysis
It is worth noting that the by-product of the transesterification reaction is
glycerol, which can be used in the deacidification process. It can be seen from Table 1 that the cost of WCO biodiesel is 6291.56
According to factory inspections and experiment operations, the RMB/t, and the proportion of cost in each stage is shown in Fig. 2. The
pretreatment process of WCO requires 2 human input for 1 day. Ac- cost of WCO collection process accounts for 45.42% of total cost, fol-
cording to our market survey, the local human cost is about 150 RMB per lowed by biodiesel production process, accounting for 27.99% of total
person per day. cost. WCO pretreatment cost accounts for 15.60%. Fixed equipment cost
accounts for 7.55%, and product delivery accounts for 3.44%. Com-
2.2.3. Biodiesel production mercial soybean oil [59,60], rapeseed oil [59,60], jatropha oil [61] etc.
After pretreatment process, the WCO contains sulfuric acid and a are all refined oils that can be directly used in the transesterification
large amount of moisture that need to be removed. Therefore, 20.89 kg process for biodiesel production, while WCO requires pretreatment
NaOH was used to neutralize sulfuric acid. Drying of pretreated WCO was process, thus the cost of pretreatment is classified into the cost of raw oil.
performed at 120  C for 10 hours in an oven with a power of 1200 W. Therefore, in this study, the cost of WCO is 3539.49 RMB (WCO price and
Finally, the pretreated and dried WCO is suitable for transesterification to pretreatment cost), accounting for 56.26% of the total cost. According to
produce biodiesel. the price given by the Jiangsu Oil Price Network and local gas stations,
The preparation of 10.75 kg of CaO nano-catalyst requires 45.304 kg the retail price of diesel is 6079.13 RMB/t. According to the US Energy
of calcium nitrate tetrahydrate (Ca(NO3)2⋅4H2O), 95.901 L of ethylene Information Administration [62], the retail price of diesel in February
2021 is 2.85 USD/gallon (6042.42 RMB/t), which is close to the price

3
Y. Liu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100091

Table 2 Table 3
The cost of 1 t biodiesel produced from WCO. The prices of biodiesel from different feedstocks.
Process Description Cost Feedstock Palm oil Castor oil Waste oil WCO WCO
(RMB) oil

WCO collection Purchase 1706 kg WCO 2557.80 Price 7808.87 12749.13 3413.58 6726.77 6291.56
[46,50–52] Gasoline consumption during transportation 86.27 (RMB/t)
14.45 L Reference Jegannathan Santana Marchetti Zhang this
Labor costs: drivers's wage, loading and 213.65 et al. [41] et al. [63] et al. [39] et al. study
unloading service expense and other expenses [40]
incurred

2857.72 production cost of diesel accounts for 63% of the retail price, which is
WCO pretreatment The impurity removal process consumes 17060 69.95 3806.72 RMB/t. Compared to the cost of diesel, the cost of WCO bio-
kg of water resources
diesel is 65.28% higher.
The deacidification process consumes 25.59 kg of 611.74
H2SO4, 341.2 kg of methanol, 32 kW h of The cost of WCO biodiesel mainly relates to the cost of WCO and the
electricity and 20.89 kg of NaOH production process. From our research results and the data given by the
Labor cost: 1 person 2 days 300 US Energy Information Administration, it is found that the cost of feed-
stock oil accounts for the largest proportion of the total cost. The price of
981.69 different feedstock oils has a significant influence on the cost of corre-
Biodiesel Electricity consumption includes: drying of WCO 84.96
Production and biodiesel, catalyst preparation and
sponding biodiesel product. Table 3 summarizes prices of biodiesel
transesterification process, the total consumption products derived from different feedstock oils. Among various feedstock
is 141.6 kW h oils for biodiesel production, WCO is more cost effective than other
Raw materials: 45.304 kg of Ca(NO3)2⋅4H2O, 944.65 inedible oils [41,63,64]. However, the recycling of WCO has always been
95.901 L of (CH2OH)2, 8.056 kg of NaOH and
facing challenging, for example, WCO is directly disposed into sewer or
305.72 kg of methanol
Consumption of 557 kg water vapor during 133.12 illegally refined for producing edible oil again [65]. The state has issued
transesterification specific policies and regulations for WCO management and recycling. For
370 kg of distilled water is needed to wash the 148 example, imposing fines or revoking licenses for the catering industry
biodiesel after transesterification reaction that uses refined WCO, establishing catering waste management account
Labor cost: 1 person 3 days 450
records system, strengthening WCO supervision and inspection, and
1760.73 enhancing general education to public [66]. At the same time, the state
Product delivery 1.41 L gasoline consumed during transportation 8.42 established pilot projects for WCO recycling, and constructed compre-
Labor costs: drivers’ wage, loading and 208 hensive management systems and incentive mechanisms for its recycling,
unloading service expense and other expenses transportation, and centralized processing in many provinces, cities, and
incurred
rural areas [67].
216.42
In addition to feedstock oil, the costs of WCO biodiesel are influenced
Fixed equipment Cost of fixed assets (depreciated with a 10-year 475 by the biodiesel production process, which is 27.99% of the overall pri-
life) ces. In this process, the catalyst has the greatest impact. The preparation
Total cost 6291.56 process and cost of different catalysts are very different. At present,
(1 t biodiesel)
NaOH and CaO are the most commonly used catalysts in the production
* 1 USD ¼ 6.6933 RMB (October 11, 2020 exchange rate). of biodiesel. For instance, Marchetti et al. [39] investigated the cost of
biodiesel from waste oil using a two-steps process including H2SO4 pre-
treatment of waste oil and NaOH catalyzed transesterification. The re-
sults of the study showed that the cost of waste oil biodiesel was 0.51
USD/kg (3413.58 RMB/t). It is noted that NaOH catalyst has higher re-
quirements for the feedstock oil, and the NaOH preparation process is
more complicated [68]. In contrast, CaO catalysts has a wide range of
sources (e.g. egg shell [69], snail shell [70], mussel shell [71]) and
presented strong basicity and good catalytic ability. Therefore, the
research of CaO catalysts is gaining great interest. According to the re-
sults from published studies, CaO catalysts could be very promising
catalysts for biodiesel production. Zhang et al. [40] used CaO catalyst to
catalyze transesterification of WCO that was pretreated by H2SO4. Their
results showed that the cost of WCO biodiesel was 970 USD/t (6492.50
RMB/t), and CaO catalyst accounted for 18.17% of the total cost. In our
study, the cost of CaO catalyst was only 8.32% of the total cost. It should
be noted that the physicochemical properties of such CaO catalysts may
vary depending on the original raw material and may need longer time
and additional human input for precursor preparation (i.e. separation,
cleaning) in the real industrial scenario. On the whole, the production of
biodiesel from WCO through a two-steps conversion using CaO catalyst is
an economic and effective approach to reuse waste resources and pro-
Fig. 2. The cost of producing 1 t of WCO biodiesel.
duce renewable. Life cycle cost analysis of waste resource derived CaO
catalyst for biodiesel production is not yet reported, which is worthwhile
to be investigated in the future.
from gas station that we surveyed. The retail price of diesel includes costs
of crude oil, refining, taxes and distribution marketing that account for
49%, 14%, 20% and 18% of retail price respectively. Therefore, the

4
Y. Liu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100091

3. Production process simulation wt% and 0.05 wt% [79] when using basic catalyst. However, the content
of FAA in WCO is generally high, usually higher than 2 wt% [80,81]. In
3.1. Methodology this study, the FAA percentage is assumed to be 6 wt% and is far beyond
the limit of 0.5 wt% FFA content for an oil that is suitable for trans-
Aspen Plus is a large-scale general-purpose process simulation soft- esterification process under basic catalytic condition [82,83]. Therefore,
ware integrating chemical design, dynamic simulation and other calcu- when using Aspen Plus software for process simulation, a two-step
lations. It can establish a mathematical model in the software according method is adopted. The first step uses an acid catalyst to convert FAA
to the actual production process and obtain desired results by changing in the WCO into fatty acid methyl ester (FAME), and the second step uses
the model parameters or reaction conditions. Aspen plus can perform a basic catalyst to convert the WCO into biodiesel [44]. In the process of
research and development of new technology, transformation of old simulating WCO to produce biodiesel, the stoichiometric reactor (RStoic)
equipment and the optimization of production conditions, etc., which is needs to specify the specific reaction process of the reactor. Due to the
an economic and efficient simulation method [72,73]. It has a complete complex composition of WCO, it is necessary to calculate the chemical
unit operation module, which can be used to simulate various operation formula of WCO. The elements compositions of WCO are shown in
processes from a single operation to the entire process flow. The simu- Table 5 [84]. Its main elements are C, H, O, and a small amount of N and S
lation of this study starts from a single operation unit. Functions of the elements. According to the content of each element in the WCO, the WCO
individual operating units are listed in the Table 4 [74]. Furthermore, can be abbreviated as C27H54O2 based on the C element. Thus, the
each process flow diagram is introduced in detail, especially the opti- transesterification reaction process can be defined as: C27H54O2 þ
mization of the number of stages, feed stage and reflux ratio of the 3CH3OH → C3H8O3 þ FAME. The molecular formula of C27H54O2 is drew
rectification tower. Three mathematical models that are often used for in ChemDraw 19.0 software and imported into Aspen Plus to add mo-
Aspen Plus simulation of chemical processes, including NRTL, UNIQUAC lecular structure to the database for calculation.
and UNIFAC models [75]. UNIQUAC is recommended to be used in
highly non-ideal chemical systems, which requires a highly accurate 3.2. Simulation of pretreatment process
simulation results and the calculation is not easy to converge. The UNI-
FAC model is based on molecular thermodynamics and is usually used for In the first step of the reaction process, FFA (C18H34O2) in the WCO is
the simulation that the substance has no interaction in the reaction all converted into FAME (C19H36O2) after the transesterification reactor
process and is not required to satisfy liquid-liquid equilibrium. The NRTL R-1. The reaction process is C18H34O2þCH3OH→C19H36O2þH2O, and
model is based on the principle of molecular contribution and can also be reactor module selects the stoichiometric reactor (RStoic) in Aspen Plus.
used to describe non-ideal solution processes. NRTL calculation model According to the reaction conditions reported by Boffito et al. [55], the
was chosen in the current study, because it not only satisfies the inter- simulation in this study assumes that the feed flow rate of crude oil WCO
action of reaction parameters, but also could achieve liquid-liquid equi- is 1000 kg/h, methanol is 200 kg/h, H2SO4 is 15 kg/h, and glycerol is
librium. Moreover, the calculation results are easy to be converged using 109.4 kg/h. Aspen Plus software has a HeatX heat exchanger that can
NRTL. simulate the heat exchange of two streams. The heat exchanger can ex-
The technical feasibility of the simulation process can be assessed by change heat between the exit stream in the reactor R-1 and the feedstock
whether the biodiesel quality purity can reach 99.6 wt%. Basic catalyst is oil cold stream, which can save energy. Fig. 3 shows the reaction flow
very sensitive to the FFA and water presences of feedstock oil during the chart, and results are shown in Table 6. It can be seen from the simulation
production of biodiesel. The FFA in the raw materials will react with results that the FFA content in the WCO after the esterification reactor is
basic catalyst [76,77]. The presence of water in the reaction system will very small, only 0.0002 wt%, which means almost all FFA is converted
promote the hydrolysis of triglycerides and the saponification reaction into FAME.
with the basic catalyst, and act as an emulsifier in the reaction system The stream H-1-1 entering the glycerol scrubber X-1 contains a large
[78], which in turn makes the separation and recovery of downstream amount of water and H2SO4, which need to be removed by the extraction
biodiesel more difficult. Therefore, in order to prevent these side re- module to prevent them from affecting the activity of the solid base
actions, the content of FFA and water in the raw oil must be less than 0.5 catalyst. After several simulations, the number of stages in the extraction
tower was selected as N ¼ 7. Fig. 4 shows the flowchart and Table 7
presents the simulation results. It can be seen that the content of water,
Table 4 the contents of H2SO4 and methanol in the WCO after extraction by the
Operation units description. glycerol extraction tower are rather low, which meets the requirements
Units Description This of the WCO for the transesterification reaction.
article The contents of water and H2SO4 of feedstock oil in the overhead
Mixer The mixer can mix multiple feed streams into one export M-1, stream X-1-1 are rather low after they were extracted by the glycerin
stream. M-2 scrubber X-1, thus the feedstock oil quality has reached the standard for
HeatX It is a two-stream heat exchanger, the cold feed and hot feed H-1 the transesterification. As a result, the stream X-1-1 directly enters the
exchange heat in the container, and the user does not need
second step of the transesterification reaction stage. Since the bottom
to enter the outlet temperature.
RStoic It is a stoichiometric reactor, which reacts according to the R-1, R-2
stream X-1-2 contains excessive amount of methanol, RadFrac module in
measurement relationship in the chemical reaction equation the Aspen Plus software is used to rectify and recover excessive methanol
to obtain the material balance of the reactor. from the stream. RadFrac module can perform rigorous calculations for
Extract Suitable for strict liquid-liquid extraction. X-1 rectification processes such as ordinary rectification, azeotropic rectifi-
RadFrac Strict calculations and design calculations for a single tower T-1, T-2
cation, and extractive rectification, and design and calculate the number
are suitable for ordinary distillation, extractive distillation,
reactive distillation, etc. of stages and feed stage position. Since methanol, FAME and glycerol
Sep The component separator separates the inlet stream into S-1 have different boiling points, this simulation uses a multi-stage rectifi-
multiple outlet streams based on a specified process or split cation tower to rectify and recover methanol [68]. The recovered
ratio.
Heater It can be a heater or cooler, according to the outlet H-2
temperature set by the user. It is used as a cooler in this Table 5
article. Elemental compositions of WCO.
Decanter It is suitable for the separation between two liquids. Based B-1
Elements C H O S N
on the specified process, split ratio or purity, the inlet
stream is separated into two outlet streams. Mass (%) 77.65 12.99 7.63 1.65 0.01

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Y. Liu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100091

Fig. 3. Heat exchanger, mixer and esterification reactor simulation process.

Table 6
Heat exchanger H-1 and esterification reactor R-1 simulation process.
Temperature ( C) Pressure (bar) Mass Flow (kg/hr) Mass Fraction

CH3OH H2SO4 Water C18H34O2 C19H36O2 C27H54O2

METH 25 1.013 200 1.00

H2SO4 25 1.013 15 1.00
C–WCO 25 1.013 1000 0.06 0.94
REC 44 0.40 45.745 0.9735
H-1-1 34.7 4.00 1214.97 0.1589 0.0130 0.0032 0.0002 0.0518 0.7729
R-1-1 48.5 4.00 1214.97 0.1589 0.0130 0.0032 0.0002 0.0518 0.7729

and their results showed that the pressure of the methanol rectification
tower top condenser was 20 KPa, bottom reboiler pressure was 30 KPa,
and the methanol recovery rate was higher than 94%. If atmospheric
rectification is used (110 KPa/120 KPa), the recovery rate of methanol is
only about 40%. Low recovery rate of methanol will result in difficult
separation of glycerol and biodiesel, wasting methanol resources and
increasing overall costs. Therefore, in this study, the pressure of the
condenser at the top of the methanol rectification tower T-1 is 20 KPa,
and the pressure of reboiler at the bottom of the tower is 30 KPa. Because
the reflux ratio of ordinary rectification simulation process should be
between 1.23–1.80, the intermediate value R ¼ 1.5 is selected here [22].
At the same time, number of theoretical stages N ¼ 10 is selected, and the
position of the feed stage Nf ¼ 5. The rectification flow rate of the top
product VD ¼ 43.251 kg/h. Simulation results are shown in Table 8. It can
be seen that the methanol mass fraction at the top of the methanol
rectification tower reaches 99.6%, but the temperature of the bottom
Fig. 4. Glycerol scrubber X-1 simulation process. stream is as high as 178.6  C. Since the glycerol in the bottom stream will
decompose at 150  C [85,86], it is necessary to investigate the influence
methanol is recycled back to transesterification reactor R-1, and the of the number of stages, the position of the feed stage and the reflux ratio
simulation flow chart of the methanol rectification tower T-1 is shown in on the methanol mass fraction at the top of the tower and the tempera-
Fig. 5. Zhang et al. [68] studied using NaOH catalytic process simulation, ture of the bottom stream.

Table 7
Heat exchanger H-1 and esterification reactor R-1 simulation process.
Temperature ( C) Pressure (bar) Mass Flow (kg/hr) Mass Fraction

CH3OH C3H8O3 H2SO4 Water C19H36O2 C27H54O2

GLY 25 1.013 109.4 1.00

H-1-1 34.7 4.000 1214.97 0.1598 0.0130 0.0032 0.0518 0.7729
X-1-1 45.7 2.000 1007.70 98PPM 547PPM 0.001 TRACE 0.0672 0.9328
X-1-2 52.6 4.000 319.67 0.5938 0.3422 0.0501 0.0129 102PPM 34PPB

TRACE: The content of the representative substance is very small and can be neglected; PPM: Part per million; PPB: Part per billion.

6
Y. Liu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100091

Fig. 5. Flow chart of methanol rectification and component separation.

Table 8
Simulation results of methanol rectification tower T-1.
Temperature ( C) Pressure (bar) Mass Flow (kg/hr) Mass Fraction

CH3OH C3H8O3 H2SO4 Water

X-1-2 52.6 4.00 319.67 0.5938 0.3422 0.0501 0.0129

REC 44 0.40 196.435 0.996
T-1-1 178.6 1.20 123.035 TRACE 0.8365 0.1300 0.0335

After further simulation and analysis of methanol rectification tower, top of the tower. The results are shown in Fig. 6.
equipment parameters of rectification tower T-1 were optimized by From the simulation results of the number of stages (Fig. 6 (a)), it can
investigating the influence of the number of stages, feed stage and reflux be seen the methanol mass fraction at the top of the tower gradually
ratio on the methanol mass fraction at the top of the tower. Aspen Plus increases with the number of stages increasing from 3 to 10. After the
sensitivity analysis tool was used to study the effects of the number of number of stages is greater than 7, the methanol mass fraction reaches a
stages, feed stage position and reflux ratio on the methanol content at the plateau of 99.00%, thus the number of stages is selected as 7. In addition,

Fig. 6. (a) The influence of the number of stages on methanol mass fraction; (b) the influence of the feed stage on methanol mass fraction; (c) the influence of the
reflux ratio on methanol mass fraction.

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Y. Liu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100091

the methanol mass fraction at the top of the tower gradually increases used to separate biodiesel from reaction system. West et al. [89,90] used
when the feed stage position increases from 2 to 6. When the feed stage a decanter to separate biodiesel and glycerol. Canakci et al. [91] used a
position is 3, the mass fraction gradually reaches a plateau of 99.87%, so decanter to separate the two in a small-scale experiment, and achieved
the number of feed stages is selected as 3. The common value range of good results. This study uses a solid CaO catalyst, thus the decanter unit
reflux ratio is between 1.23 and 1.80. Meanwhile, the rising reflux ratio module of a liquid-liquid phase separator B-1 is used to simulate the
will increase steam volume (V ¼ (Rþ1) ⋅D), thus tower diameter, pedal separation process of biodiesel and glycerol. The separated glycerol is
area, reboiler and condenser increase accordingly, leading to higher recovered and the biodiesel enters the rectification tower for further
equipment costs of producing biodiesel. It can be seen from Fig. 6(c) that purification to improve the quality. Fig. 7 shows the flow chart, and
a rather high methanol mass fraction is achieved (99.94%) when the simulation results are shown in Table 10.
reflux ratio is 1.4, thus the reflux ratio is selected as 1.4. According to the simulation results, almost all of the feedstock oil in
The methanol rectification tower is simulated at the condition of the stream R-1-1 is converted into FAME after passing through trans-
stages number of 7, feed stage of 3, and reflux ratio of 1.4. As a result, the esterification reactor R-1, and the temperature of the outlet stream is 55

mass fraction of methanol under this condition is 99.75%, but the tem- C. After the operation of heat exchanger, the temperature of the H-1-1
perature of bottom stream is 162.72  C. It is known that the temperature logistics outlet is reduced to 48.9  C, the stream H-1-1 then enters the
of bottom stream should be less than 150  C, as by product glycerol rectification tower T-1 for the rectification process to recover excessive
undergoes decomposition at this temperature [22]. Stages number has a methanol. According to our optimization results of the WCO pretreat-
significant impact on the temperature of bottom stream. A higher trays ment process, the number of stages of the rectification tower is initially
number leads toa higher the temperature of bottom of rectification tower. set to 4. The feed stage position is 3 and reflux ratio is 1.4. As can be seen
Therefore, under the conditions of the same feed stage position and reflux from the simulation results, the temperature of the bottom stream is
ratio, the number of stages should be reduced for debugging. Our results 138.28  C, which is lower than 150  C, and the mass fraction of methanol
show that the temperature at the bottom of the tower is 148.2  C, and the reaches almost 100%, suggesting the operating conditions are effective
mass fraction at the top of the tower is 97.35%, when the number of and reasonable. The reacted stream T-1-1 mainly contains biodiesel and
stages is 4. Under these conditions, the methanol rectification tower in glycerol, which need to be separated to obtain the biodiesel product.
Fig. 5 is simulated. The stream T-1-1 after methanol removal mainly However, the exit temperature of the stream T-1-1 is relatively high
contains H2SO4 and glycerol. H2SO4 is neutralized with stoichiometric (138.28  C), and it needs to be cooled to room temperature in the cooler
amount of CaO to achieve effective separation of glycerol and H2SO4. H-2 before the next separation process. The pressure of the decanter B-1
Whole separation process is carried out in the component separator S-1, is 101.3 kPa and the temperature is 25  C. It is gratifying that the purity
and the obtained CaSO4 can be recycled as a catalyst carrier [87] or of glycerol can reach 98.7%, thus continuous rectification and purifica-
reused as a raw material for composite materials [88]. The remaining tion are unnecessary. However, the mass fraction of biodiesel in logistics
glycerol is dried and returned to the glycerol scrubber for reuse. Fig. 5 B-1-1 is 96.8%, which requires further rectification and purification.
shows the simulation flow chart, and results are shown in Table 9. As can After passing through the rectification tower T-2, the simulation results
be seen from the simulation results, methanol has been effectively show that the mass fraction of biodiesel almost reaches 100%, which
recovered and reused. The stream S-1-1 from the component separator meets the biodiesel ASTM standard (99.6 wt%).
mainly contains glycerol, which contains a small amount of water that is
mainly from neutralization of H2SO4 and CaO. After drying, glycerol can 4. Conclusion
be used as a raw material in the X-1 reactor to reduce the acid value of the
WCO in the pretreatment process, or it can be recycled and stored. The current study applied the Life Cycle Cost (LCC) method to analyze
The flow chart and simulation results of the simulated WCO pre- the cost of producing 1 t of biodiesel from WCO. Generally speaking, it is
treatment process are given in Supplementary Information. Aspen Plus suitable to use WCO as raw material to produce biodiesel in China. The
software was used to simulate the pretreatment process of biodiesel total cost is 6291.56 RMB/t, which is 65.28% higher than the cost of
production from WCO. FFA in the raw oil is converted into FAME, which diesel. Although the purchase cost of WCO is lower than some feedstock
reduces the acid value of the raw oil, so that the WCO meets the re- oils (e.g. jatropha oil, castor oil), WCO cannot be directly used to produce
quirements of the basic catalytic transesterification process. Methanol, biodiesel due to its high contents of impurities and free fatty acids, thus it
H2SO4 and water produced from esterification were separated from the needs to be pretreated before use. Therefore, the cost of pretreatment was
feedstock oil through a glycerol scrubber, and the pretreated WCO was considered as a part of the cost of raw oil, which leads to an increase in
transferred to transesterification stage. In the simulation process, sensi- the cost of biodiesel production from WCO. Detailed cost analysis of each
tivity analysis tool of Aspen Plus software was used to optimize methanol stage of biodiesel production process shows that the cost of refining WCO
and biodiesel distillation tower to obtain the operating parameters such (WCO collection and WCO pretreatment) is relatively high, accounting
as the position of feed plate and the reflux ratio, in order to provides a for 56.26% of the total cost. Although the cost of WCO biodiesel is
benchmark for industrial production. slightly higher than that of diesel, WCO as waste resource can be effec-
tively recycled and reused.
3.3. Simulation of refined WCO process On the basis of the economic feasibility of WCO, Aspen Plus software
was used to simulate the production process of biodiesel, and large-scale
During the process of WCO pretreatment simulation, export stream X- production operation parameters were obtained, which provided a
1-1 enters the second-step refining WCO reaction process, and the raw reference for the industrial development of WCO biodiesel. A two-step
material methanol enters the stoichiometric reactor R-1 after passing method is used to simulate the production process of WCO biodiesel,
through the mixer for transesterification to produce biodiesel. Hot stream using H2SO4 as a catalyst to pretreat WCO and converting FFA into FAME
R-1-1 enters the heat exchanger H-1 to exchange heat with the pretreated that is then separated and purified. Secondly, the pretreated feedstock oil
WCO cold stream X-1-1, and then enters the rectification tower T-1 for is converted into biodiesel and by-product glycerol using CaO catalytic
rectification and recovery of excessive methanol. Bottom stream of the system. Operational conditions were investigated and optimized. Our
distillation tower enters the downstream separation and purification results showed final biodiesel product with 100% purity is obtained using
stage after passing through cooler. Homogeneous basic catalysis process number of stages in the rectification tower of 4, feed stage of 3, and reflux
often uses water washing to separate biodiesel from glycerol and remove ratio of 1.4. Meanwhile, excessive amount of methanol is recovered
liquid catalyst and most of the methanol in the biodiesel [68,85]. For the through the rectification tower T-1 after the reaction and returned to the
heterogeneous catalytic process, decanter (gravity sedimentation) can be mixer M  1 in the stream REC to continue the reaction, which realizes

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Y. Liu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100091

Table 9
Results of methanol distillation and component separation.
Temperature ( C) Pressure (bar) Mass Flow (kg/hr) Mass Fraction

CH3OH C3H8O3 H2SO4 Water CaO CaSO4

X-1-2 52.6 4.00 179.75 0.095 0.879 0.011 0.015

CaO 25 1.013 10.25 1.00
REC 44 0.40 45.745 0.9735
T-1-1 148.21 1.125 123.035 0.8365 0.1300 0.0335
S-1-1 32 1.00 110.35 0.8933 TRACE 0.1067
S-1-2 28 1.00 22.31 249PPB 405PPB 0.002 0.98

Fig. 7. Process flow chart of biodiesel production from pretreated WCO

Legend: M  1, M-2: mixer; H-1: heater; R-1: esterification reactor; T-1: methanol rectification tower; H-2: cooler; B-1: liquid-liquid separator; T-2: biodiesel recti-
fication tower.

Table 10
Simulation results of biodiesel production from WCO.
Temperature ( C) Pressure (bar) Mass Flow (kg/hr) Mass Fraction

C27H54O2 C19H36O2 CH3OH FAME C3H8O3

METH 25 1.013 305.72 1.00 0.879 0.011 0.015

X-1-1 45.7 2.000 1007.70 0.9328 0.0672 98PPM 547PPM
R-1-1 55 2.000 1307.68 862PPM 527PPM 0.174 0.742 0.084
H-1-1 48.9 2.000 1307.68 862PPM 527PPM 0.174 0.742 0.084
REC 32 1.013 178.126 1.000 796PPM 82PPM
T-1-1 28 1.00 22.31 249PPB 405PPB 0.002
H-2-1 138.28 0.700 1041.962 0.005 0.899 0.0966
GLY 28.3 1.013 80.182 0.013 331PPM 0.987
B-1-1 26.5 1.103 961.78 0.002 0.968 0.03
T-2-1 145.72 0.700 29.5 TRACE 0.091 0.909
FAME 137.65 1.013 932.28 102PPM 1.000 TRACE

reuse of methanol. Overall, according to our life cycle cost analysis and Declaration of competing interest
simulation results, WCO biodiesel production is proven to be a techni-
cally effective and economically feasible process, which provides a reli- The authors declare that they have no known competing financial
able benchmark for the industrial biodiesel production from WCO. In interests or personal relationships that could have appeared to influence
order to make the WCO biodiesel more economically favourable on a the work reported in this paper.
large industrial scale, special rectification policy should be implemented
and waste recycling practice should be undertaken. Disposal, sale and Acknowledgements
trade of WCO should be carefully regulated by government to avoid its
illegal use. We acknowledge the financial supports from Jiangsu University of
Science and Technology (1142931706) and Natural Science Foundation
CRediT authorship contribution statement of the Higher Education Institution of Jiangsu Province (20KJB480009).

Yanbing Liu: Writing – original draft, preparation, Visualization, Appendix A. Supplementary data
Writing – review & editing. Xinglin Yang: Supervision. Abdullahi
Adamu: Writing – review & editing. Zongyuan Zhu: Conceptualization, Supplementary data to this article can be found online at https://
Writing – review & editing, Supervision. doi.org/10.1016/j.crgsc.2021.100091.

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Y. Liu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100091

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