Simulation and economic study of biodiesel

production process with supercritical methanol in

different ratios of methanol to oil

Amin Jasour1*, Milad Salem Ayegh2

1.Sahand University of Technology, Tabriz, Iran

2.Payame Noor University, Tabriz, Iran

ARTICLE INFO ABSTRACT

Article history:
Received:
Accepted:
Available online:
Key words:
Biodiesel fuel
Process simulation
Energy consumption
Economic analysis
Corresponding author:
*Amin Jasour
* examined by an economic analysis and the benefits of
E-mail address:
a_jasour98@sut.ac.ir
Increasing uncertainty about global energy production
and supply, environmental concerns due to the use of
fossil fuels, and the high price of petroleum products are
the major reasons to search for alternatives to Petro
diesel. Biodiesel fuel has become more attractive
because of its environmental benefits, due to the fact that
plants and vegetable oils and animal fats are renewable
biomass sources. In this research, five processes have
been simulated for the production of biodiesel using
waste vegetable oil and supercritical methanol by
HYSYS. We examined the amount of energy consumed
in each process and the required cost using Aspen In-
plant cost estimator. Finally, the existing processes were
each process to find the optimal process. The results
showed that biodiesel production processes with the
conversion percentages of 96 and 91 have the lowest
and highest energy consumption, respectively, and also
with increasing the amount of biodiesel produced, the
process costs increase and by performing economic
calculations, it was concluded that the process with 97
conversion percentage is an optimal process.
 1. Introduction:
The steady rise in the price of petroleum-
based fuels and environmental concerns
have increased people's attention to
alternative fuels. In addition, energy
demand has been steadily rising around
the world, raising concerns about fossil
fuel reduction, which is why biodiesel is
being considered as an alternative fuel,
because biodiesel is degradable and
they have low carbon dioxide and sulfur
and can also be implemented directly in
existing diesel engines with or without
minor modifications.[1].
Biodiesel can be produced in a variety of
ways from a wide range of feeds. These
methods include esterification, direct
mixing, micro-emulsion and pyrolysis. In
addition, biodiesel feed varies from
vegetable oils, animal fats and
microalgae oils[2].
The esterification reaction is considered
to be the most common method for
biodiesel synthesis. This reaction is
usually achieved using various
techniques such as alkaline, acidic
catalysts, etc. Recently, non-catalytic
esterification using supercritical alcohols
has become very important[2].
The origin and quality of raw materials is
the most important issue in choosing the
method of biodiesel synthesis. Currently,
vegetable oils are the best material in the
production of biodiesel. Recent research,
however, has shifted to alternative raw
materials such as waste vegetable oils
and non-edible oils, as the use of edible
oils is not economically viable due to
rising crop prices[3].
Wasted non-edible and edible oils are
significantly cheaper than vegetable oils,
which reduce the overall cost of biodiesel
production. Therefore, these oils are
known as potential biodiesel production
materials. However, high free fatty acids
and having water are the main
drawbacks of using these oils as a raw
material[4].
Production of biodiesel with
homogeneous alkaline catalysts such as
sodium hydroxide and potassium
hydroxide are the most common method
of biodiesel synthesis. However, the high
amount of fatty acids in oils, leads to side
reactions, which reduce the efficiency of
biodiesel production and make it more
difficult to separate the product. The use
of heterogeneous catalysts prevents the
side effect of soap making. However, the
presence of very small amounts of water
causes high costs for the preparation of
the catalyst and also makes the
operating conditions very difficult.
Therefore, the use of supercritical
alcohols is the best method. For the non-
catalytic production of biodiesel with
supercritical alcohols, methanol, ethanol-
1-propanol, bicarbonate, methyl tert-
butyl ether and methyl acetate can be
used[5].
West et al. (2008) designed and
simulated four biodiesel production
processes using a variety of techniques
including alkaline homogeneous
catalysts, homogeneous acidic catalysts,
heterogeneous alkaline catalysts, and
non-catalytic processes with supercritical
alcohols. They also make an economic
comparison between processes
designed to produce 8,000 tons of
biodiesel per year from non-edible oils.
Lee et al. (2011) simulated the process of
 100
98
CONVERSION(%)
96
94
92
91
90
88
86
1:03
THE STOICHIOMETRIC RATIO OF TRIOLEIN TO METHANOL
Figure 1. The rate of conversion of triolein in different ratios of methanol to triolein [1, 6]
producing biodiesel using fresh and used
oils. They reported that the use of
methanol above Critical is a more
economical method than alkaline
catalyzed processes. Hesham et al.
(2015) simulated the production process
of biodiesel with waste corn oil containing
10 wt% fatty acid and reported that this
feed can be produce 1550 tons of fuel.
Aboelazayem et al. (2018) simulated the
process of producing biodiesel with
supercritical methanol and performed a
thermal integration for the process.
In this study, due to the fact that by
increasing the amount of methanol input,
a higher conversion percentage can be
obtained from the esterification reaction,
which causing an increase in the amount
of fuel produced as well as operating
costs. Therefore, the aim is to find the
optimal economic state according to the
amount of methanol entering the
process.
2. Process simulation
2.1. Chemical components and
thermodynamic model
98
97
96
93
1:05 1:08 1:24 1:48
The process steady-state simulation was
executed by the ASPEN HYSYS
simulator version 9. Triolein (C57H98O6)
was used as a model compound to
represent oil. Waste oil was modeled as
a mixture of 94 wt% Triolein and 6 wt%
oleic acid (C18H34O2). Consequently,
methyl oleate (C19H36O2) was
considered as the product of
esterification and transesterification
reactions.
Non-random two liquid (NRTL) model
was selected as a property package due
to the presence of polar compounds.
Some interaction parameter coefficients
between components were not available
in HYSYS library. These parameters
were estimated using UNIFAC LLE
model. Since an activity coefficient-
based model such as NRTL is not
recommended to be used at pressures
greater than 1000 kPa, Peng-Robinson
equation of state (EOS) was used in
process streams and unit operators
wherever having pressures >1000 kPa.
Stream molar Ratio of Triolein to Methanol
ratio (Kmol/h) 1:3 1:5 1:8 1:24 1:48
Feed 6.577 6.577 6.577 6.577 6.577
Methanol 16.07 16.4 16.9 17.05 17.2
201 5 6.11 6.3 7.903 8.2
202 22.66 22.95 23.44 23.59 23.79
Glycerol 6.076 6.155 6.308 6.358 6.457
206 16 16.39 16.9 17.06 17.21
207 0.58 0.389 0.2176 0.1677
Stream mass fraction
Glycerol 206 Glycerol 206 Glycerol 206 Glycerol 206 Glycerol 206
Triolein 0.0001 0 0.0001 0 0 0 0 0 0 0
Methanol 0.0005 0.0001 0.0002 0 0.0002 0 0.0001 0 0.0001 0
Oleic acid 0 0.0002 0 0.0002 0 0.0002 0 0.0001 0 0.0001
Methyl Oleate 0 0.9994 0 0.9995 0 0.9996 0 0.9997 0 0.9997
Glycerol 0.9582 0.0003 0.9602 0.0003 0.9621 0.0002 0.9625 0.0002 0.9612 0.0002
Water 0.0411 0 0.0395 0 0.0377 0 0.0374 0 0.0387 0
Figure 2. The flowsheet and details of major material streams of the processes

2.2. Process design: Therefore, waste vegetable oil was

In these five processes using the
supercritical methanol method (SC-
WVO), in a constant oil inlet flow rate with
increasing the amount of methanol input
(increasing the stoichiometric ratio of oil
to methanol), the conversion
percentages of 91, 93, 96, 97, 98,
respectively, were obtained. The process
flowsheet and operating conditions for
SC-WVO process referred to those
reported by West et al. The flowsheets
and details of major material streams of
the processes are presented in Fig.2.
chosen as the raw material for SC-WVO
process. SC- WVO process basically
consisted of 4 steps: Increasing the
pressure and temperature of the inlet
feed (triolein, oleic acid and methanol) to
the conditions required for the reaction,
reaction in a plug reactor to produce
methyl oleate, Separate methanol and
return it to the beginning of the process
and Separation of the main product from
by-products (glycerin and water).
2.2.2. Increasing the pressure and
temperature of the inlet feed:

2.2.1. SC-WVO processes:

Methanol and WVO (Feed) were
As mentioned previously, a supercritical pressurized to the reaction pressure (19
process is not sensitive to the presence MPa) by P-101 and P-102, respectively.
of FFAs and water in feedstocks. Then each pressurized stream flowed
through heat exchangers (E-102 and E-
101) where the heat of reaction product
stream heated the waste oil to 211◦C and
then the methanol to 118◦C. The raw
material streams were then mixed
together in a mixer (MIX-100) and
brought to the desired temperature
(265.5◦C) by E-103.
2.2.3. Reaction in a plug reactor to
produce biodiesel:
For continuous biodiesel production, a
PFR was selected to carry out
transesterification and esterification
reactions. In this study, in both reactions,
the amount of activation energy is 79
kJ/mol and the frequency factor is 2.98
e10 per minute and the biodiesel yield is
presented in Fig.1. where the reaction
was carried out in a continuous method
using a 5.5 m in length with 3/8-in. (9.525
mm) o.d. and 0.035-in. (0.889 mm)
thickness 316SS tubing[7].
2.2.4. Separation of methanol:
A significant portion of methanol in the
reactor effluent stream can be separated
out as a vapor in a flash evaporator (V-
100) by adjusting the pressure or
temperature. Vlv-100 was used to
depressurize stream 106B from 19 to 0.2
MPa so that most of methanol
evaporates whereas the other
components remain mostly in the liquid
phase. Then, a distillation column with 4
theoretical stages was used to further
separate of methanol in stream 108. The
recovered methanol was then recycled
and mixed with the fresh methanol feed.
2.2.5. Glycerol separation:
After methanol recovery in the flash drum
and the distillation column, the bottom
stream was cooled down to 25◦C and fed
to a decanter. Two liquid phases were
formed: a glycerol-rich phase and a
methyl oleate-rich phase.
2.2.6. Biodiesel purification:
Stream 204 is mainly consisted of methyl
oleate and the balance was mostly
triolein. To satisfy the requirement of the
maximum triglyceride content in
biodiesel (≤0.20 wt%) specified in EN-
14214, further purification of stream 204
in a distillation column was necessary.
Since the normal boiling temperature of
methyl oleate is as high as 359◦C, the
pressure inside T-101 was set at as low
as 3.0–5.0 kPa in order to avoid thermal
decompositions of methyl esters. The
number of theoretical stages used was 7.
2.3. Energy consumption:
Energy consumptions of the five process
simulations were shown in Table 2.
According to the results of Table 2, it can
be seen that in the process with 91%
conversion had the highest consumption
and most of this energy consumption is
due to the existence of Tower T-100 and
the lowest energy consumption is for
processes with 93% and 96%
conversion. As the amount of methanol
increases, the energy consumption by
pumps, cooler and heaters increases,
which can also be seen in the results of
the table 2. Also, with increasing the
amount of methanol and consequently
increasing the amount of methyl oleate
and glycerin, energy consumption in
Tower T-100 also increases, but due to
 Table 1. Equipment summary for SC-WVO process
Pumps P-101 P-102
Efficiency 75% 75%
Press in (kpa) 101.3 101.3
Press out (kpa) 19000 19000
Heat exchangers E-101 E-102 E-103 E-104 E-105
Tube in (°C/kpa) 265.5/19000 140/19000 192.4/19000 82.15/101.5 167/106.5
Tube out (°C/kpa) 140/19000 124.7/19000 265.5/19000 25/101.5 25/170
Shell in (°C/kpa) 33.23/19000 32.77/19000
Shell out (°C/kpa) 211/19000 118/19000
Towers T-100 T-101
Type Distillation Distillation
Stages 4 7
Reboiler Press (kpa) 101.5 3
Condenser Press (kpa) 106.5 5
Valves Vlv-100 Vlv-101
Inlet (°C/kpa) 124.7/19000 25/170
Outlet (°C/kpa) 129/200 25/4

Table 2. Energy consumption (kw) of the five process simulation models

91% 93% 96% 97% 98%
Pumps 31.25 31.75 32.15 32.65 32.95
Heat exchangers 924.7 963.86 994.36 1036.2 1055.2
Reboiler T-100 304.9 356 371.4 430.2 443
Condenser T-100 167.6 206.1 212.3 267.5 277.5
Reboiler T-101 2044 2141 2109 2204 2140
Condenser T-101 2396 1616 1588 1738 1644
Reactor 256.6 255.5 262.6 256.3 256.3
Total 6125 5570 5569.81 5964.85 5848.95

the decrease in triolein, the amount of provides more accurate estimation.

energy consumption in Tower T-101
decreases significantly.
3. Project evaluation:
Previous studies on economic
estimations were based on the overall
factor method of Lang or bare-module
concept introduced by Guthrie. These
methods provide an approximate cost
data and have relatively poor accuracies
of estimation. We were not able to find
economic analysis of a biodiesel plant
using a software package process
evaluation in the open literature. As a
result, we have decided to use Aspen In-
Plant Cost Estimator, since it has been
used for over 30 years in commercial
plants and engineering designs, and
Aspen In-Plant Cost Estimator provides
specifications for detailed design,
estimation and economic data, allowing
quick modifications of the process
equipment and sensitivity analysis.
Table 4, gives the prices of raw materials
and chemicals used in this study. The list
of the utilities is shown in Table 3 . Since
the temperature of high-pressure
saturated steam is not sufficient to heat
up the reactant streams to reaction
temperature (265.5◦C) in SC-WVO
process, hot temperature heating oil was
used to provide heat in the process
wherever the operating temperatures
were greater than 254◦C.
 Table 3. The price of raw materials and Table 4. The price of utilities used in this
products used in this study[1] study[1]
Price($/ton) Notes Utility Price
Methanol 268.71 Chilled water 1 $/ton
WVO 530 Cooling water 0.013 $/ton
Glycerol 860 Vegetable Circulating heating water 0.04 $/ton
glycerin Steam 13.71 $/ton
Biodiesel 990 Qualified to meet Electricity 11.06 $/hr
EN-14214

Table 5. The total capital costs for the five production processes at 8000 hr/yr duration
91% 93% 96% 97% 98%
Equipment cost ($)
Pumps 893200 888600 889400 882400 881800
Heat exchangers 507600 545700 546000 555900 556300
2 phase separator 108100 108100 108100 108100 108100
3 phase separator 100500 100500 100500 100500 100500
Towers 1667600 1476100 1459000 1443700 1666900
Total equipment Cost 3277000 3119000 3103000 3090600 3313600
Installed cost ($)
Pumps 800000 795500 796300 789300 788700
Heat exchangers 97400 97800 98100 98800 99200
2 phase separator 17700 17700 17700 17700 17700
3 phase separator 17700 17700 17700 17700 17700
Towers 509600 443100 430400 419100 466000
Total installed cost 1442400 1371800 1360200 1342600 1389300
Raw materials cost 22993965 23016536 23050931 23061680 23071353
Total utilities cost 260097 269673 274888 299857 302639
Total operating cost ($/yr) 1652540 1665010 1668330 1692810 1694580
Total capital cost ($) 29625002 29442019 29457349 29487547 29771472
multiphase separators. In towers, the
3.1. Total capital investment: main cost is related to the purchase and
installation of Tower T-100, in which
Table 5, shows the total capital costs for increasing the input methanol reduces
the five production processes. the concentration of triolein, which in turn
According to the results obtained in Table reduces costs. But when triolein in the
5, among the total costs, the highest
tower is greatly reduced, costs begin to
costs are related to processes with a
rise also raw materials and all operating
conversion rate of 98, 91 and 97,
respectively, and the lowest cost is costs also increase with increasing
related to processes with a conversion methanol input.
rate of 93.
According to the results of Table 5, it can 3.2. Profitability analysis:
be seen that the costs related to the
The specified investment analysis
purchase and installation of heat
parameters are summarized in Table 6.
exchangers increase with increasing the
Table 7 shows the sales revenue of
amount of input methanol, but this
products produced in one year, and as
increase in input methanol has no effect
can be seen, as the conversion rate
on the purchase and installation of
increases, so does the sales revenue.
So, the goal was to calculate the net
profit of all 5 processes to find the optimal
process. Therefore, first according to the
results of Tables 5 and 7, the gross profit
of all 5 processes is obtained and then by
calculating the tax, the annual net profit
is also obtained. A summary of the
calculation results is presented in Table
8. According to Table 8, it can be seen
that the SC-WVO process with a
conversion rate of 97 is economically
optimal compared to the other 4
processes.

Table 6. Investment analysis for the biodiesel production processes

Name Value Unit
Facility operating parameters
Facility type Chemical processing facility
Operating mode Continuous processing
Operating hours per period 8000 Hr/year
Process fluids Liquids and Gases
Economic life of project 20 Years
Tax rate 40 %per year
Desired rate of return 15 %per year
Salvage rate 0 %of initial capital cost
Depreciation method Sum of years digits
Parameters involved in product price
Fixed costs 10 %of product production price
Overhead costs 50 %of operational worker
Administrative costs 20 %of operational worker
Distribution and marketing costs 10 %of product production price
Direct production costs
Operational worker 15 %of product production price
Direct supervision and skilled 15 %of operational worker
worker
Ancillary facilities 10 %of product production price
Laboratory 20 %of operational worker

Table 7. Revenue from the sale of products for the five production processes at 8000 hr/yr duration
91% 93% 96% 97% 98%
Biodiesel ($) 37524960 38467440 39679200 40027680 40376160
Glycerol ($) 3290016 3353312 3460640 3491600 3529440
Total income ($) 40814976 41820752 43139840 43519280 43905600

Table 8. Summary of annual net and gross profit of 5 biodiesel production processes
91% 93% 96% 97% 98%
Total income ($) 40814976 41820752 43139840 43519280 43905600
Total capital cost ($) 29625002 29442019 29457349 29487547 29771472
Gross profit ($) 11189974 12378733 13682491 14031733 14134128
Gross profit per ton of 295.21 318.58 341.45 347.05 346.57
biodiesel produced ($)
Net profit per ton of 177.13 191.15 204.87 208.23 207.94
biodiesel produced ($)
4. Conclusion:
In this study, five biodiesel production
processes were simulated, all of the
processes were feasible for producing a
high-quality biodiesel product which
meets EN 14214 standard. The energy
consumption of the processes was
investigated and it was concluded that as
the amount of methanol entering the
process increases, so does the energy
consumption.
The economic assessment of the five
processes for production of biodiesel
(8000hr/yr) was performed, based on the
process simulation models developed in
HYSYS. The assessment was done by
using Aspen In-Plant Estimator.
The results showed that with increasing
methanol inlet at constant oil flow, the
cost of purchasing and installing pumps
and heat exchangers increased, but in
distillation towers with decreasing triolein
concentration, the cost of purchasing and
installing decreases, but with a very large
decrease in triolein concentration, the
cost of purchasing and installation
increased, and finally, in order to find the
optimal process according to various
parameters, it was concluded that the
biodiesel production process with 97%
conversion rate is the optimal process.
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