Sie sind auf Seite 1von 11

Energy Conversion and Management 153 (2017) 493–503

Contents lists available at ScienceDirect

Energy Conversion and Management


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

Process design of biodiesel production: Hybridization of ester-and MARK


transesterification in a single reactive distillation
Nattawat Petchsoongsakula, Kanokwan Ngaosuwanb, Worapon Kiatkittipongc, Farid Aiouached,

Suttichai Assabumrungrata,
a
Center of Excellence in Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok
10330, Thailand
b
Chemical Engineering Division, Engineering Faculty, Rajamangala University of Technology Krungthep, Bangkok 10120, Thailand
c
Department of Chemical Engineering, Faculty of Engineering and Industrial Technology, Silpakorn University, Nakhon Pathom 73000, Thailand
d
Engineering Department, Lancaster University, United Kingdom

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

Keywords: A novel hybridization of esterification and transesterification processes in a single reactive distillation column
Transesterification was proposed for biodiesel production from waste cooking oil. Continuous process operation was designed in a
Esterification single reactive distillation column using two different types of heterogeneous catalyst. Amberlyst-15 was loaded
Hybridized reactive distillation on the top of reactive section to eliminate free fatty acid via esterification and CaO/Al2O3 was loaded at the
Biodiesel
lower section for biodiesel synthesis via transesterification. Suitable design parameters and operating conditions
Waste cooking oil
were determined by process simulation using commercial Aspen Plus program. The hybridized process via re-
active distillation could reduce the number of equipment, methanol to oil in feed and energy consumption
compared to the conventional alkaline catalyzed process and the process of two reactive distillation columns in
series (packing with Amberlyst-15 and CaO/Al2O3). Net specific energy requirement was achieved to the lower
value as 216 kWhr/kmol biodiesel (or 197 kWhr/kmol biodiesel with allocation to 98% purity of glycerol by-
product). This value is lower than that from the conventional process and also the two reactive distillation
columns in series of 665 and 224 kWhr/kmol biodiesel, respectively. Moreover, increasing pressure in the hy-
bridized column from 1 to 3 bar decreased the number of reactive stage from 24 stages (4 esterification and 20
transesterification) to 8 stages (3 esterification and 5 transesterification). Several feedstocks with different FFA
content can be operated in this hybridization ester- and transesterification column within the 8 reactive stages
with flexible of number of catalyst packing stage (acid and alkali catalysts) under column pressure of 3 bar.

1. Introduction the most competitive method for producing higher quality of biodiesels
[4–6]. Biodiesel is defined as a mono alkyl ester of a fatty acid that is
The demand for fossil resources in all sectors such as transportation, produced from vegetable oils or animal fats, reacting with short chain
power production and various industries is steadily increasing. For in- alcohol such as methanol [7].
stance, it is anticipated that consumption of petroleum in the USA, a However, production of biofuels from human nutrition sources can
reference country for worldwide demand and consumption of fossil cause a food crisis. Consequently, using non-edible oil or waste cooking
fuels, will rise from 84.4 to 116 million barrels per day in 2030 [1,2]. oil as feedstock for biodiesel production such as algae oil [8–10], mi-
Energy from fossil resources will therefore remain the main contributor croalgae [11–15], jatropha oil [16] and grease oil [17] are of interest.
to various pollutions, including CO2 emissions and global warming Moreover, the use of waste edible oil as feedstocks can reduce biodiesel
consequences [3]. Because of the environmental concern, the explora- production costs by 60–90% [18–20]. However, water and free fatty
tion and development of alternative energies for sustainable develop- acid (FFA) content in the waste cooking oil have a negative influence on
ments, are therefore very crucial in term of energy security. the transesterification rate [21,22]. Hydrolysis of triglyceride can also
Vegetable oil can be used as liquid fuel by different modification take place in the presence of heat and water, resulting in an increase of
methods such as dilution, thermal cracking (pyrolysis), transester- percentage of FFA in the oil [23]. Therefore, in order to produce eco-
ification, and microemulsification. However, transesterification is so far nomical biodiesel, the amount of FFA and water must be eliminated or


Corresponding author.
E-mail address: Suttichai.A@chula.ac.th (S. Assabumrungrat).

http://dx.doi.org/10.1016/j.enconman.2017.10.013
Received 27 June 2017; Received in revised form 21 September 2017; Accepted 5 October 2017
0196-8904/ © 2017 Elsevier Ltd. All rights reserved.
N. Petchsoongsakul et al. Energy Conversion and Management 153 (2017) 493–503

reduced before transesterification. The conventional technology (using process [39]. Kesic et al. [40] reported that CaO catalyst has a long
continuous reactor) was found not compatible with FFA content oils catalyst lifetime and could maintain activity even after being reused.
threshold value of about 0.5 wt% [24]. Otherwise, alternative ap- Moreover, Liu et al. [41] has confirmed by their experimental results
proaches e.g. sub- and supercritical methanol [25] or superheated that CaO can be repeatedly used for 20 cycles for transesterification of
methanol technology is suggested [26,27]. soybean oil and methanol. However, it should be noted that the time
Reactive distillation (RD) is a process that includes a chemical re- stream of catalysts was not included in the simulation since the process
action and a distillation, occurring simultaneously in single equipment. was assumed to run under steady state operation.
A variety of reactions with homogenous catalyst or heterogeneous The performance of processes was determined by observing the
catalyst or without catalyst have been tested via the RD process, mainly yield and purity of biodiesel. A standard purity of biodiesel or fatty acid
driven by advantages such as, a continuous removal of product from methyl ester (FAME) of 96.5 wt% was used as criteria of performance.
reaction zone for shifting the chemical equilibrium limitation, a de- The yield of biodiesel is defined by Eq. (1):
crease in capital costs by using a single reaction-separation unit, re-
FMethyl oleate
duction in complexity of the piping and instrumentation design, re- Biodiesel yield, % = × 100%
sulting in suitable heat integration and utilities utilizations. RD design (3 × FTriolein,initial ) + FOleic acid,initial (1)
has been currently cited for biodiesel production by esterification where FMethyl oleate is the molar flow rate of methyl oleate in product
[28,29] and transesterification [30,31]. Recently, Pérez-Cisneros et al. stream, FTriolein,initial and FOleic acid,initial are molar flow rate of triolein
[32] proposed an integration of two heterogeneous RD processes for and oleic acid in feed stream, respectively.
biodiesel production. FFA in the feed was pretreated by esterification in
the first RD and a decanter was employed to separate non-converted
triglycerides before being sent to the second RD for transesterification. 3. Results and discussion
The process design, however, was carried out solely for one reaction
(i.e. esterification or transesterification) per column of RD. 3.1. Kinetic data validation
The aim of this work is to hybridize the esterification and transes-
terification processes into a single RD column for biodiesel production. Model validations of kinetic parameters of the reaction catalyzed by
The concept of this RD design consists of an upper section for the sodium hydroxide as homogeneous base catalyst [42] and CaO/Al2O3
pretreatment of waste cooking oil to eliminate FFA and a lower section as solid base catalyst [43], which were performed in a batch reactor, are
for conversion of triglyceride into biodiesel. shown in Fig. 1(a) and (b), respectively. The results for both kinetic
data were in good agreement with the experimental data as shown
2. Methodology herein.
The kinetic data for esterification pretreatment step by using
In this work, Dortmund modified UNIFAC model [33] was selected Amberlyst-15 catalyst were validated by using the work of Steinigeweg
to predict vapor-liquid equilibrium (VLE) and liquid-liquid equilibrium and Gmehling [29], who employed this catalyst for the RD process. The
(LLE). VLE of mixtures of methanol-biodiesel and methanol-glycerol validation results in terms of FFA conversion as a function of reflux
systems, and LLE of mixtures of water-biodiesel, methanol-biodiesel- ratio are provided in Fig. 2. The results of our simulation show close
glycerol, and methanol-water-biodiesel systems have been experimen- trends of conversion along with the reflux ratio with the maximum
tally investigated by Kuramochi et al. [34]. They reported that the deviation of less than 10% than aforementioned work [29]. It should be
Dortmund modified UNIFAC model was the most suitable for prediction noted that the pseudo-homogeneous kinetic model did not fit well the
of the physical equilirbia properties of various mixtures associated with experimental data, especially at values of low reflux ratio. Moreover,
the design of biodiesel processes. the swelling parameter of Amberlyst-15 data (as present in Langmuir-
Steady state process simulation has been performed with Aspen Hinshelwood model) could not be included in the kinetic model that
Plus® version 8.0. The continuous stirred tank reactor (CSTR) model was implemented in the RADFRAC model, which is a ready-to-use and
was employed for the conventional process. The RADFRAC model has compatible with the RADFRAC model, was therefore not applied in this
been extensively used in the design of RD columns. RADFRAC relies on study. It is worth to note that the comparison among three process
an equilibrium stage model and is capable to deal with ideal and non- configurations (conventional process, integrated two RDs in series and
ideal vapor-liquid equilibrium (VLE) and vapor-liquid (I)-liquid (II) hybridized RD which will be mentioned later), waste cooking oil con-
equilibrium (VLLE). Note that although thermodynamic model used in taining 6% FFA was employed as a feedstock. With low FFA content, the
the previous works for the prediction of VLE were accurate enough for amount of produced water via esterification was not significant, and
esterification [35] and transesterification [36] in reactive distillation at therefore the effect of water adsorption on Amberlyst 15 can be negli-
atmospheric pressure, at pressure higher than atmosphere, however, gible and pseudo-homogeneous kinetic models were effectively em-
mixtures containing glycerol, FAME, methanol and water lead to the ployed in the calculations. However for high FFA content ca. 80–100%
presence of a second liquid phase, and therefore, a VLLE should be which will be considered in the hybridized RD, the effect of water in-
taken into account (as can be illustrated in Fig. S1(a)–(c)). Therefore, a hibition should be taken into account which will be discussed later.
VLLE model was implemented in the simulations of this study. More-
over, the RADFRAC model does not require the need to set details about 3.2. Conventional process for biodiesel production
the packing and the size of the column, leading to assumed preliminary
values of stage efficiency [30]. Oleic acid and triolein were used as a The conventional process of biodiesel production by using waste
model compound of FFA and triglyceride, respectively. Amberlyst-15 cooking oil is presented in Fig. 3(a) esterification and acid removal and
was chosen to catalyze esterification of FFA as it was demonstrated to (b) transesterification, water washing, methanol recovery, glycerol
produce high yield of biodiesel [32]. Pal et al. [37] reported that this purification and biodiesel purification. [44] A molar flow of waste
catalyst has a long life time, is widely used in important industrial cooking oil (6% FFA content) was preheated (E-111) to 60 °C before
processes and is also cost-effective. Boz et al. [38] also reported that feeding the pretreatment reactor (R-111) in order to eliminate FFA by
this catalyst did not deteriorate after reuse at least for three cycles of 9 h esterification. The fresh methanol was mixed with the sulfuric acid
reaction time each at laboratory scale. (H2SO4) before feeding to R-111 reactor. All FFA was converted to
Calcium oxide supported on alumina (CaO/Al2O3) was selected to FAME and the exit stream (stream-7) was cooled before feeding to the
catalyze transesterification of triglyceride. This catalyst was demon- glycerol washing column (T-110) to remove the catalyst and some
strated to offer an economic merit for biodiesel production by the RD water from the triglyceride. The washing stream was fed into

494
N. Petchsoongsakul et al. Energy Conversion and Management 153 (2017) 493–503

Fig. 1. Model validations of (a) kinetic model catalyzed by sodium


hydroxide in batch reactor (data adapted from Noureddini and Zhu
[42], T = 50 °C, methanol to oil = 6:1 at atmospheric pressure) and
(b) kinetic model catalyzed by CaO/Al2O3 in batch reactor (data
adapted from Pasupulety et al. [43], T = 150 °C, methanol to oil =
9:1 at pressure = 1 bar).

distillation column (T-111) to recover unreacted methanol and further distillation column (T-132) for purification of glycerol. Crude glycerol
recycle back to the reactor. Sodium hydroxide (NaOH), as homo- (i.e. composition higher than 85%) can be achieved in T-132 with the
geneous catalyst in the alkali catalyzed transesterification unit, was reflux ratio of 1.0. However, the standard of technical grade glycerol for
mixed with the fresh methanol (Methanol-2 or stream-15) and fed to washing column was preferred (i.e. composition higher than 92%) [44].
transesterification reactor (R-121). Meanwhile, the pretreated oil In order to obtain technical grade glycerol, a high reflux ratio (i.e.
stream was preheated (E-121) to 60 °C before feeding the reactor. In R- higher than 2.0) was required and hence energy consumption of T-132
121, 97% of triglyceride was converted to FAME. After completing the was increased from 31 to 48 kW. As summarized in Table 1, under this
reaction, product stream was fed to distillation column (T-121) with the design condition, the purity and yield of biodiesel were 99.97% and
optimal reflux ratio of 1.0 to recover the unreacted methanol 99.70%, respectively. Glycerol purity was 85.01% (with a low reflux,
(Fig. 3(a)). The overhead stream, mainly of unreacted methanol, was i.e. value of 1.0) and 92.01% (with a reflux of 2.0) which could meet
recycled back to the reactor while the bottom stream of mainly bio- the specifications of the crude and the technical grade glycerol, re-
diesel, glycerol and catalyst was processed by water washing in the spectively.
purification unit (T-133) with the optimal reflux ratio of 1.0 to reach a Since the technical grade of glycerol could be obtained as a valuable
high-quality biodiesel product conforming to ASTM/EN specification by-product, the allocation of this energy consumption to glycerol
(i.e. composition greater than 97%). The bottom effluent stream should be taken into account. Based on this allocation (by mass) to
(stream-21) was sent to the neutralization column (T-131) to remove glycerol production, energy requirement is attributed to 605 kWhr/
catalyst by adding phosphoric acid (H3PO4), and to produce sodium kmol biodiesel productions. In order to compare with the real experi-
phosphate (Na3PO4). Sodium phosphate as solid material was then re- mental or commercial data, the energy requirement in the transester-
moved by filtration. The filtrate (76% glycerol) was fed to the ification process ((Fig. 3(b)), including transesterification, water

495
N. Petchsoongsakul et al. Energy Conversion and Management 153 (2017) 493–503

Fig. 2. Model validation of kinetic data using Amberlyst-15 in term of


free fatty acid conversion as a function of reflux ratio using packing of
Katapak-SP.

(a) Part 1: Esterification and acid removal

(b) Part 2: Transesterification, water washing, methanol recovery, glycerol purification and biodiesel purification
Fig. 3. Simplified conventional processes for biodiesel production using waste cooking oil as feedstock. (a) Part 1 and (b) Part 2.

496
N. Petchsoongsakul et al. Energy Conversion and Management 153 (2017) 493–503

Table 1 3.3. An integrated unit of two reactive distillation columns for biodiesel
Performance comparison of different biodiesel production processes. production
Conventional Integrated Hybridization
process two RDs of RD An integrated process by two RD columns for the esterification and
the transesterification has been proposed (Fig. 4) [32]. Fresh methanol
Overall methanol to oil feed 8:1 6.5:1 4:1 and waste cooking oil (containing 6% FFA) was fed in the first RD (T-
molar ratio
211) with molar ratio of 2.5:1. T-211 was loaded with Amberlyst-15 as
Biodiesel purity, wt% 99.70 97.49 97.61
Overall biodiesel yield, % 99.97 98.32 99.87 solid catalyst for esterification. In order to eliminate FFA to less than
Heat exchanger duty, kW 0.5 wt%, the configuration design for reactive distillations was shown
Preheat or cool-down heat (E-111) 21 24 22 in Table 2. The result indicated that 3 reactive stages are required.
exchanger Methanol and water were vaporized out at top column while trigly-
(E-112) 12
ceride and FAME (from esterification) were retrieved from the bottom
(E-121) −36
(E-122) 46 of this column. Triglycerides were separated by using decanter (D-211)
Reactor heat duty, kW before proceeding to next RD column for transesterification. Methanol
Pretreatment reactor 21 (stream-7) and triglyceride (stream-6) were fed to the second stage of
Neutralization reactor 20 – –
the second RD column (T-221) which was loaded with alkali solid
Transesterification reactor −24
Distillation column duty, kW catalyst (CaO/Al2O3). In this column, 18 reactive stages and a reflux
Methanol recovery −407/385.5 – – ratio of 1.0 were used to obtain a good separation and high biodiesel
Biodiesel purification −568/523.8 – – production. Unreacted methanol was vaporized in overhead stream
Reactive distillation (stream-8) while downstream, mainly FAME and glycerol, was pro-
column, kW
cessed by the decanter (D-221) to separate glycerol and reached a final
Column-1 – −127/213 −138/229
Column-2 – −112/187 – biodiesel product, adhering to ASTM/EN specification. Glycerol ob-
Total reactive distillation tained from the decanter is marginal on crude glycerol specification
column, kW (84.6%). Purification of glycerol to technical grade could be achieved
Make up glycerol usage, kg/ 110 – –
with further glycerol distillation.
hr
Make up water usage, kg/hr 11 – –
This process can produce high purity biodiesel by using hetero-
Make up acid usage, kg/hr 9.8 – – geneous catalyst system for both reactions, thus, the number of oper-
Glycerol purity before 76.78 84.61 87.44 ating equipment unit was reduced (no requirement of catalyst separa-
purified, wt% tion). However, this process required at least two RD columns (T-211
Glycerol purity after purified,
for esterification and T-221 for transesterification) to produce biodiesel
wt%
Low reflux ratio 85.01 96.80 96.38 from waste cooking oil. Under the optimal condition, biodiesel yield of
High reflux ratio 92.01 – – 98.3% with purity of 97.5% was achieved with energy consumption of
Energy requirement for 224 kWhr/kmol of biodiesels. The energy consumption is higher than
glycerol purified, kW
the value reported Pérez-Cisneros [32] (138 kWhr/kmol) who em-
Low reflux ratio −26/30 −4/10 −4/10
High reflux ratio −34/48 – –
ployed Amberlyst-15 and MgO catalyst in esterification and transes-
Total net specific energy 665 224 216 terification. This might be due to CaO/Al2O3 catalyst that exhibited
requirement (kWhr/kmol slower kinetic rate than MgO and was driven by less surface basic sites
biodiesel) in the former catalyst, resulting in requirement of higher number of
Total net specific energy 605 216 197
reactive stages [46].
requirement allocates
with technical grade As summarized in Table 1, the conventional process was very en-
glycerol production ergy intensive due to energy consumption of the distillation column for
(kWhr/kmol biodiesel) the purification and the recovery processing. An integration of two RD
Number of unit operation columns would reduce the number of unit operations along with sig-
Reactor 3 – –
Reactive distillation – 2 1
nificantly low energy consumption.
column
Distillation column 4 – – 3.4. Hybridization of esterification and transesterification in a single
Decanter – 1 1 reactive distillation column for biodiesel production
Extraction column 2 – –
Total number of unit 9 3 2
operation The hybridization of esterification and transesterification in a single
RD was proposed as shown in Fig. 5. The upper section of column was
packed with Amberlyst-15 for esterification. After FFA content (6% FFA
washing, methanol recovery, glycerol purification and biodiesel pur- content) was reduced, the resulting reactants flow down to the lower
ification unit, was calculated as 393 kWhr/kmol biodiesel which is in a section which was packed with CaO/Al2O3 for transesterification. Me-
good agreement to the energy consumption for biodiesel production via thanol and waste cooking oil were co-fed at the second stage. In order to
transesterification process of 360 kWhr/kmol biodiesel reported by meet the specification of biodiesel standard, the RD configuration with
Smith et al. [45]. minimum stage requirement was determined as shown in Table 2.
Despite the reduction of raw material cost by using waste cooking The suitable RD configuration to produce biodiesel by hybridized
oil, the process was found complex, necessitating a large number of RD using Amberlyst-15 and CaO/Al2O3 catalyst consist of 24 reactive
operating units. This is because of the addition of a pretreatment unit to stages (4 stages for the esterification and 20 stages for the transester-
remove FFA, separation of catalyst out from the system (neutralization ification). Reflux ratio did not affect product purity and yield, leading
unit), and purification of biodiesel and glycerol. RD process was chosen such low reflux ratio to be considered sufficient. This was due to large
as alternative option to reduce the number of unit operation as dis- difference in the boiling temperatures between overhead products,
cussed in the next section. mainly methanol and water (methanol: 69 °C, water: 100 °C) and other
components of the reaction mixture (glycerol: 290 °C, methyl oleate
biodiesel: 351 °C, oleic acid: 360 °C, triolein: 554 °C).
The optimum condition was found to be 4:1 of methanol to oil molar

497
N. Petchsoongsakul et al. Energy Conversion and Management 153 (2017) 493–503

Fig. 4. An integrated reactive distillation for biodiesel production (dashed frame represents optional distillation column to obtain technical grade glycerol).

Table 2
Details of simulation design for integrated and hybridized reactive distillation processes.

Parameter Integrated two RDs Hybridization of RD

Esterification column (T-211) Transesterification column (T-221) Column pressure 1 bar Column pressure 3 bar

Column diameter (m) 0.24 0.96 0.82 0.30


Column height (m) 3.00 12.00 15.60 6.00
Number of reactive stage 3 18 24 8
Catalyst loading Acid catalyst 2.5 wt%a Alkali catalyst 3 wt%b Acid 2.5 wt%a and alkali catalyst 3 wt%b
Biodiesel production rate (kg/h) 1000 1000

a
Steinigeweg and Gmehling [29].
b
Pasupulety et al. [43].

feed ratio, reflux ratio of 0.1 and reboiler heat duty of 216 kWhr/kmol column of 3 bar would provide higher biodiesel yield than that operated
biodiesel. at normal pressure. The effect of operating pressure for biodiesel pro-
The downstream product from the RD column, mainly FAME and duction on the number of stage in the single hybridization ester-
glycerol, was fed into the purification step using only decanter (D-311) transesterification RD were therefore investigated. To elucidate the
to separate biodiesel from glycerol. In comparison with the two RD influence of column pressure on the reaction performance, the extent of
columns in series, the hybridized RD column can reduce methanol feed reaction was plotted as shown in Fig. 6.
ratio and consume lower energy requirement as illustrated in Table 1. Our finding suggests that an increase in the column pressures not
It can be concluded that the hybridization of esterification and only enhances the rate of transesterification but also improves the rate
transesterification in a single RD to produce biodiesel from waste of esterification, owing to promoted miscibility of triglycerides and FFA
cooking oil is a very promising process. It exhibits several advantages in methanol at high temperatures and pressures. The polarity of me-
over conventional process and two RD columns in series e.g. lower thanol increases at high pressure and temperature, resulting in accel-
amount of methanol to oil ratio and reduced process steps to obtain eration of the reaction rate [48]. Moreover, it was found that increasing
high purity biodiesel and glycerol, resulting in lower number of unit the operating pressure would provide the highest biodiesel production
operation and energy consumption. Therefore, the next section will because the highest temperature profile (i.e. bottom temperature was
provide the optimum operating parameters to produce biodiesel in the 173, 184, 205 and 247 °C under pressure column 1, 2, 3 and 4 bar,
single hybridization of ester-transesterification RD column. respectively) along the column was obtained and also would pressurize
more methanol in liquid phase. This led to higher reaction rate than
that obtained at atmospheric pressure. However, the optimum column
3.4.1. Hybrid ester- and transesterification RD process under pressurized pressure should be set no more than 3 bar since no significant difference
condition in biodiesel yield was found at column pressure of 4 bar (as shown in
Gaurav et al. [47] revealed that the process design for biodiesel Fig. 6). The required number of stages for esterification and
production via transesterification using RD column at high pressure

498
N. Petchsoongsakul et al. Energy Conversion and Management 153 (2017) 493–503

Fig. 5. Hybridization of ester-and transesterification in a single reactive distillation for biodiesel production (dashed frame represents optional distillation column to obtain technical
grade glycerol).

loading and the sizing of RDs are summarized in Table 2.

3.4.2. Effects of rectifying and stripping stages


Other configurations and operating parameters were fixed while the
number of stages in rectifying and stripping sections was varied to
determine the suitable operating conditions. It was found that this
hybridization would not require more rectifying and stripping stages to
provide more separation of each component from the main product,
due to their relevant relative volatilities (result is not shown).

3.4.3. Effects of reflux ratio and reboiler duty


Fig. 7 shows the purity of biodiesel (bottom stream), biodiesel yield
and reboiler heat duty with different reflux ratio. Total feed flow rate,
methanol to oil molar ratio and specification of biodiesel yield (i.e.
composition higher than 97%) were fixed while reflux ratio was varied
from 0.1 to 3. The results show that the purity and the yield of biodiesel
did not change when reflux ratio was increased from 0.1 to 3, at me-
Fig. 6. Reaction rate profiles with in the reactive distillation column using methanol to oil thanol to oil feed ratio of 4:1. However, increasing the reflux ratio led to
ratio of 4:1 and reflux ratio 0.1 for waste cooking oil with 6% FFA.
higher energy consumption due to more amount of methanol being
refluxed back into the column, requiring thus more duties for the
Table 3 condenser and the reboiler duty to condense and vaporize, respectively.
Required number of stages for achieving biodiesel yield greater than 97% at different It was found that a value of reflux ratio of 0.1 was enough to produce
column pressures.
high purity biodiesel but was not enough to reach a purity of biodiesel
Column pressure [bar] 1 2 3 4
that is conform to the standard. This is due to large differences in the
boiling temperature between methanol and other component of the
Total number of stagesa 26 18 10 10 reaction mixture as mentioned earlier. Low reflux ratio was enough for
Esterification stages 4 4 3 3 catalytic distillation to produce biodiesel via transesterification as re-
Transesterification stages 20 12 5 5
ported by others researcher [30,47].
a
Total number of stage = reactive stage + rectifying stage + stripping stage.
3.4.4. Effects of methanol excess, reactive stages and methanol feed
transesterification under different operating pressures are summarized location
in Table 3. Lower number of stages for esterification and transester- Effects of number of reactive stages and methanol excess on bio-
ification are required at high operating pressure. The amount of catalyst diesel yield, biodiesel purity and reboiler duty requirement are shown

499
N. Petchsoongsakul et al. Energy Conversion and Management 153 (2017) 493–503

Fig. 7. Yield of biodiesel, purity of biodiesel and reboiler duty of


reactive distillation at various molar reflux ratio by using methanol
to oil ratio of 4:1 under column pressure of 3 bar.

in Fig. 8(a)–(c), respectively. In the case of 6% FFA in oil feed, a number contacting area of methanol to drive forward reaction in the reactive
of three esterification stages was found enough to diminish FFA even zone. However, reboiler duty was increased too due to additional en-
with no methanol excess; therefore, the number of reactive stages in ergy consumed to heat methanol and the nature of endothermic reac-
this hybridization RD would be a function of the transesterification tion in the reactive section. The optimal conditions for hybridization RD
stage when a number of three stages of esterification was fixed. Bio- with 6%FFA were found to be 8 reactive stages (3 for esterification and
diesel yield and purity increased significantly by increasing the number 5 for transesterification), 22% methanol excess and reboiler duty of
of reactive stages or using higher methanol excess, owing to more 141 kWhr/kmol of biodiesel.

Fig. 8. Yield of biodiesel (a), purity of biodiesel (b) and reboiler duty of reactive distillation (c) at various reactive stages by using different methanol to oil ratio under column pressure of
3 bar.

500
N. Petchsoongsakul et al. Energy Conversion and Management 153 (2017) 493–503

Fig. 9. Yield and purity of biodiesel at various methanol feed location


by fixed oil feed stage at first stage of reaction zone and under column
pressure of 3 bar.

Fig. 9 shows effect of methanol feed location on biodiesel yield and packing of acid and base catalysts could be adjusted, depending on free
purity. Waste cooking oil, as heavier reactant, was fed at the first of fatty acid content in waste cooking oil feed, to obtain a biodiesel of high
reactive stage (2nd stage). Methanol, as a lighter reactant, was fed at the yield and purities of biodiesel. However, as mentioned earlier, in case of
last reactive stage (9th stage), agreeing with typical design of RD. The high FFA content ca. 80–100% of hybridized RD, the effect of water
result of feed location for the hybridized RD column was in agreement inhibition should not be neglected. The recalculation was performed by
with the reactive distillation catalyzed by heterogeneous catalyst for a decreasing rate of reaction of pseudo-homogeneous kinetic model ap-
single reaction of esterification and transesterification [30,32]. Finally, prox. 30% (to fit with experimental data of low reflux ratio in Fig. 2)
impact of the free fatty acid on the design column will be discussed in and the calculation results show that 4 reactive stages (instead of 3
the following section. reactive stages as shown in Table 4) are recommended to ensure the
complete conversion of FFA.
3.4.5. Effect of FFA content in feedstock Note that our simulation results were based on a design that relied
Amount of FFA content is typically function of the source of feed- on the equilibrium model between the phases along with reaction ki-
stocks. Therefore, effect of FFA content must be considered to de- netics. It simplified the anticipated challenging calculations of the non-
termine the suitable operating condition for this hybridized RD column. equilibrium model that would have required detailed physical proper-
Moreover, if the number of stage for esterification was not sufficient to ties, prediction of missing mass and heat transfer characteristics and
eliminate all amount of FFA, biodiesel production rate would be de- extended computational time. It is a typical approach to obtain a pre-
creased because of side reactions (i.e. saponification). It is illustrated in liminary design. In order to design real column for actual plant, a more
Table 4 for six cases; 0 (Pure TG), 20, 40, 60, 80 and 100% (pure FFA). complex model taking into account more realistic phenomena such as
Table 4 summarizes the requirement for the number of reactive non-equilibrium with mass transfer limitation, and other issues such as
stages and operating conditions to obtain design specifications for dif- dynamic controllability need to be taken into account.
ferent FFA content in the feedstock. It can be concluded that the ad-
vantage of hybridization of ester-and transesterification RD is reflected 4. Conclusion
by a flexible design of biodiesel production from different feedstocks
(various FFA contents). The requirement of maximum number of re- The hybridization of ester- and transesterification for biodiesel
active stages was found not exceeding eight reactive stages (i.e. three production in a single reactive distillation column was investigated in
stages for esterification and five stages for transesterification) to meet this study. Heterogeneous catalysts, Amberlyst-15 was loaded at the
FFA composition (ca. 20%FFA). The requirements for number of stages upper part of the reactive section to eliminate free fatty acid (via es-
and energy could be reduced, depending on feed composition as shown terification), while CaO/Al2O3 was loaded at the lower part for bio-
in Table 4. This implied a column to be fabricated with ten total stages; diesel synthesis (via transesterification). The hybridized RD column not
one stripping stage, one rectifying stage and eight reactive stages. The only combined the step of esterification pretreatment,

Table 4
Number of required reactive stage and operating conditions for achieving design specification for different free fatty acid contents.

Oil specification Number of required reactive stage Methanol excess (%) Energy requirement, kWhr/kmol biodiesel

Esterification Transesterification

Pure TG – 5 33 117
FFA 20% 3 5 24 144
FFA 40% 3 4 19 138
FFA 60% 3 3 16 132
FFA 80% 3 3 14 136
Pure FFA 3 – 0 124

501
N. Petchsoongsakul et al. Energy Conversion and Management 153 (2017) 493–503

transesterification and separation/purification of the products into a apenergy.2012.03.027.


[15] Huang G, Chen F, Wei D, Zhang X, Chen G. Biodiesel production by microalgal
single RD but also improved the biodiesel yield with lower methanol in biotechnology. Appl Energy 2010;87:38–46. http://dx.doi.org/10.1016/j.apenergy.
feed, hence lower energy requirement compared to the conventional 2009.06.016.
alkaline catalyzed process, or even with the process of two RD columns [16] Ganapathy T, Murugesan K, Gakkhar RP. Performance optimization of Jatropha
biodiesel engine model using Taguchi approach. Appl Energy 2009;86:2476–86.
in series. The suitable design of the hybridized RD column consisted of http://dx.doi.org/10.1016/j.apenergy.2009.02.008.
4 stages of esterification and 20 stages of transesterification with op- [17] Montefrio MJ, Xinwen T, Obbard JP. Recovery and pre-treatment of fats, oil and
timum condition of 4:1 of methanol to oil molar feed ratio and reflux grease from grease interceptors for biodiesel production. Appl Energy
2010;87:3155–61. http://dx.doi.org/10.1016/j.apenergy.2010.04.011.
ratio of 0.1. The net energy requirement for the hybridized RD, cata- [18] Marchetti JM, Miguel VU, Errazu AF. Techno-economic study of different alter-
lyzed by Amberlyst 15 and CaO/Al2O3, reached a value of s 216 kWhr/ natives for biodiesel production. Fuel Process Technol 2008;89:740–8. http://dx.
kmol biodiesel (or 197 kWhr/kmol biodiesel with an allocated purity of doi.org/10.1016/j.fuproc.2008.01.007.
[19] Mansir N, Taufiq-Yap YH, Rashid U, Lokman IM. Investigation of heterogeneous
98 wt% to glycerol by-product). Moreover, increasing the operating
solid acid catalyst performance on low grade feedstocks for biodiesel production: a
pressure of the hybridized column from 1 to 3 bar decreased the review. Energy Convers Manage 2017;141:171–82. http://dx.doi.org/10.1016/j.
number of reactive stages from 24 stages to 8 stages. Effect of FFA enconman.2016.07.037.
content in feed has shown that a maximum number of 8 stages was [20] Nurfitri I, Maniam GP, Hindryawati N, Yusoff MM, Ganesan S. Potential of feed-
stock and catalysts from waste in biodiesel preparation: a review. Energy Convers
enough to cope with all FFA contents. By adjusting the ratio of acid Manage 2013;74:395–402. http://dx.doi.org/10.1016/j.enconman.2013.04.042.
catalyst and base catalyst packed stage, the design eliminated FFA for [21] Jacobson K, Gopinath R, Meher LC, Dalai AK. Solid acid catalyzed biodiesel pro-
different feedstock, and thus reached high values of yield and purity of duction from waste cooking oil. Appl Catal B Environ 2008;85:86–91. http://dx.doi.
org/10.1016/j.apcatb.2008.07.005.
biodiesel. [22] Utlu Z. Evaluation of biodiesel fuel obtained from waste cooking oil, energy sources.
Part A Recover Util Environ Eff 2007;29:1295–304. http://dx.doi.org/10.1080/
Acknowledgements 00908310500434564.
[23] Marmesat S, Rodrigues E, Velasco J, Dobarganes C. Quality of used frying fats and
oils: comparison of rapid tests based on chemical and physical oil properties. Int J
This work was financially supported by the Thailand Research Fund Food Sci Technol 2007;8.
(DPG5880003). Department of Chemical Engineering, Faculty of [24] Demirbas A. Biodiesel from waste cooking oil via base-catalytic and supercritical
methanol transesterification. Energy Convers Manage 2009;50:923–7. http://dx.
Engineering, Chulalongkorn University would like to acknowledge The
doi.org/10.1016/j.enconman.2008.12.023.
Institutional Research Grant (The Thailand Research Fund), IRG [25] Laosiripojana N, Kiatkittipong W, Sutthisripok W, Assabumrungrat S. Synthesis of
5780014, and Chulalongkorn University, Contract No. methyl esters from relevant palm products in near-critical methanol with modified-
zirconia catalysts. Biores Technol 2010;101:8416–23. http://dx.doi.org/10.1016/j.
RES_57_411_21_076.
biortech.2010.05.076.
[26] Ang GT, Tan KT, Lee KT, Mohamed AR. Biodiesel production via injection of su-
Appendix A. Supplementary material perheated methanol technology at atmospheric pressure. Energy Convers Manage
2014;87:1231–8. http://dx.doi.org/10.1016/j.enconman.2014.02.037.
[27] Ang GT, Tan KT, Lee KT, Mohamed AR. Kinetic studies of sea mango (Cerbera
Supplementary data associated with this article can be found, in the odollam) oil for biodiesel production via injection of superheated methanol vapour
online version, at http://dx.doi.org/10.1016/j.enconman.2017.10.013. technology. Energy Convers Manage 2015;105:1213–22. http://dx.doi.org/10.
1016/j.enconman.2015.08.076.
[28] Dimian AC, Bildea CS, Omota F, Kiss AA. Innovative process for fatty acid esters by
References dual reactive distillation. Comput Chem Eng 2009;33:743–50. http://dx.doi.org/
10.1016/j.compchemeng.2008.09.020.
[1] E. Department, Energy Department www.energy.gov (n.d.). [29] Steinigeweg S, Gmehling J. Esterification of a fatty acid by reactive distillation. Ind
[2] B.R. Inc., Bioengineering Resource www.brienergy.com (n.d.). Eng Chem Res 2003;42:3612–9. http://dx.doi.org/10.1021/ie020925i.
[3] Maceiras R, Rodrı́guez M, Cancela A, Urréjola S, Sánchez A. Macroalgae: raw ma- [30] Boon-anuwat N, Kiatkittipong W, Aiouache F, Assabumrungrat S. Process design of
terial for biodiesel production. Appl Energy 2011;88:3318–23. http://dx.doi.org/ continuous biodiesel production by reactive distillation: comparison between
10.1016/j.apenergy.2010.11.027. homogeneous and heterogeneous catalysts. Chem Eng Process Process Intensif
[4] Lian S, Li H, Tang J, Tong D, Hu C. Integration of extraction and transesterification 2015;92:33–44. http://dx.doi.org/10.1016/j.cep.2015.03.025.
of lipid from jatropha seeds for the production of biodiesel. Appl Energy [31] Prasertsit K, Mueanmas C, Tongurai C. Transesterification of palm oil with me-
2012;98:540–7. http://dx.doi.org/10.1016/j.apenergy.2012.04.029. thanol in a reactive distillation column. Chem Eng Process Process Intensif
[5] Yusuf NNAN, Kamarudin SK, Yaakub Z. Overview on the current trends in biodiesel 2013;70:21–6. http://dx.doi.org/10.1016/j.cep.2013.05.011.
production. Energy Convers Manage 2011;52:2741–51. http://dx.doi.org/10.1016/ [32] Pérez-Cisneros ES, Mena-Espino X, Rodríguez-López V, Sales-Cruz M, Viveros-
j.enconman.2010.12.004. García T, Lobo-Oehmichen R. An integrated reactive distillation process for bio-
[6] Knothe G, Razon LF. Biodiesel fuels. Prog Energy Combust Sci 2017;58:36–59. diesel production. Comput Chem Eng 2016;91:233–46. http://dx.doi.org/10.1016/
http://dx.doi.org/10.1016/j.pecs.2016.08.001. j.compchemeng.2016.01.008.
[7] Miladinovi MR, Stamenkovi OS, Bankovi PT, Milutinovi Nikoli AD, Jovanovi DM, [33] Lohmann J, Joh R, Gmehling J. From UNIFAC to Modified UNIFAC (Dortmund). Ind
Veljkovi VB. Modeling and optimization of sunflower oil methanolysis over quick- Eng Chem Res 2001;40:957–64. http://dx.doi.org/10.1021/ie0005710.
lime bits in a packed bed tubular reactor using the response surface methodology. [34] Kuramochi H, Maeda K, Kato S, Osako M, Nakamura K, Sakai S. Application of
Energy Convers Manage 2016;130:25–33. doi: http://dx.doi.org/10.1016/j. UNIFAC models for prediction of vapor–liquid and liquid–liquid equilibria relevant
enconman.2016.10.020. to separation and purification processes of crude biodiesel fuel. Fuel
[8] Karatay SE, Dönmez G. Microbial oil production from thermophile cyanobacteria 2009;88:1472–7. http://dx.doi.org/10.1016/j.fuel.2009.01.017.
for biodiesel production. Appl Energy 2011;88:3632–5. http://dx.doi.org/10.1016/ [35] Banchero M, Gozzelino G. Nb2O5-catalyzed kinetics of fatty acids esterification for
j.apenergy.2011.04.010. reactive distillation process simulation. Chem Eng Res Des 2015;100:292–301.
[9] Rasoul-Amini S, Montazeri-Najafabady N, Mobasher MA, Hoseini-Alhashemi S, http://dx.doi.org/10.1016/j.cherd.2015.05.043.
Ghasemi Y. Chlorella sp.: A new strain with highly saturated fatty acids for biodiesel [36] Xiao Y, Li H, Xiao G, Gao L, Pan X. Simulation of the catalytic reactive distillation
production in bubble-column photobioreactor. Appl Energy 2011;88:3354–6. process for biodiesel production via transesterification, ICMREE 2013 – Proc. 2013
http://dx.doi.org/10.1016/j.apenergy.2010.12.040. Int. Conf. Mater. Renew. Energy Environ. 2013;1:196–9. http://dx.doi.org/10.
[10] Chisti Y, Yan J. Energy from algae: current status and future trends: algal biofuels–a 1109/ICMREE.2013.6893646.
status report. Appl Energy 2011;88:3277–9. http://dx.doi.org/10.1016/j.apenergy. [37] Pal R, Sarkar T, Khasnobis S. Amberlyst-15 in organic synthesis. Arkivoc
2011.04.038. 2012;2012:570–609. http://dx.doi.org/10.3998/ark.5550190.0013.114.
[11] Abou-Shanab RAI, Hwang J-H, Cho Y, Min B, Jeon B-H. Characterization of mi- [38] Boz N, Degirmenbasi N, Kalyon DM. Esterification and transesterification of waste
croalgal species isolated from fresh water bodies as a potential source for biodiesel cooking oil over Amberlyst 15 and modified Amberlyst 15 catalysts. Appl Catal B
production. Appl Energy 2011;88:3300–6. http://dx.doi.org/10.1016/j.apenergy. Environ 2015;165:723–30. http://dx.doi.org/10.1016/j.apcatb.2014.10.079.
2011.01.060. [39] Jaeger WK, Egelkraut TM. Biofuel economics in a setting of multiple objectives and
[12] Gao C, Zhai Y, Ding Y, Wu Q. Application of sweet sorghum for biodiesel production unintended consequences. Renew Sustain Energy Rev 2011;15:4320–33. http://dx.
by heterotrophic microalga Chlorella protothecoides. Appl Energy 2010;87:756–61. doi.org/10.1016/j.rser.2011.07.118.
http://dx.doi.org/10.1016/j.apenergy.2009.09.006. [40] Kesic Z, Lukic I, Zdujic M, Mojovic L, Skala D. Calcium oxide based catalysts for
[13] Lam MK, Lee KT. Potential of using organic fertilizer to cultivate Chlorella vulgaris biodiesel production: a review. Chem Ind Chem Eng Q 2016;22. http://dx.doi.org/
for biodiesel production. Appl Energy 2012;94:303–8. http://dx.doi.org/10.1016/j. 10.2298/CICEQ160203010K. 10-10.
apenergy.2012.01.075. [41] Liu X, He H, Wang Y, Zhu S, Piao X. Transesterification of soybean oil to biodiesel
[14] Sánchez Á, Maceiras R, Cancela Á, Pérez A. Culture aspects of Isochrysis galbana for using CaO as a solid base catalyst. Fuel 2008;87:216–21. http://dx.doi.org/10.
biodiesel production. Appl Energy 2013;101:192–7. http://dx.doi.org/10.1016/j. 1016/j.fuel.2007.04.013.

502
N. Petchsoongsakul et al. Energy Conversion and Management 153 (2017) 493–503

[42] Noureddini H, Zhu D. Kinetics of transesterification of soybean oil. J Am Oil Chem [46] Moradi G, Davoodbeygi Y, Mohadesi M, Hosseini S. Kinetics of transesterification
Soc 1997;74:1457–63. reaction using CAO/AL2O3 catalyst synthesized by sol-gel method. Can J Chem Eng
[43] Pasupulety N, Gunda K, Liu Y, Rempel GL, Ng FTT. Production of biodiesel from 2015;93:819–24. http://dx.doi.org/10.1002/cjce.22158.
soybean oil on CaO/Al2O3 solid base catalysts. Appl Catal A Gen [47] Gaurav A, Leite ML, Ng FTT, Rempel GL. Transesterification of triglyceride to fatty
2013;452:189–202. http://dx.doi.org/10.1016/j.apcata.2012.10.006. acid alkyl esters (biodiesel): comparison of utility requirements and capital costs
[44] Zhang Y, Dubé MA, McLean DD, Kates M. Biodiesel production from waste cooking between reaction separation and catalytic distillation configurations. Energy Fuels
oil: 1. Process design and technological assessment. Biores Technol 2003;89:1–16. 2013;27:6847–57. http://dx.doi.org/10.1021/ef401790n.
http://dx.doi.org/10.1016/S0960-8524(03)00040-3. [48] Glišić S, Lukic I, Skala D. Biodiesel synthesis at high pressure and temperature:
[45] Smith EG, Janzen HH, Newlands NK. Energy balances of biodiesel production from analysis of energy consumption on industrial scale. Biores Technol
soybean and canola in Canada. Can J Plant Sci 2007;87:793–801. http://dx.doi. 2009;100:6347–54. http://dx.doi.org/10.1016/j.biortech.2009.07.024.
org/10.4141/CJPS06067.

503

Das könnte Ihnen auch gefallen