Bioresource Technology 101 (2010) 8762–8771

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Case Study

Simulation and pre-feasibility analysis of the production process of a-methyl

ester sulfonates (a-MES)
Daniel Martínez a,*, Gustavo Orozco a, Sandra Rincón b,**, Iván Gil c
a
Grupo de Diseño de Productos y Procesos, Departamento de Ingeniería Química, Universidad de Los Andes, Bogotá, Colombia
b
Corporación Centro de Investigaciones en Palma de Aceite (Cenipalma), Bogotá, Colombia
c
Grupo de Ingeniería de Sistemas de Proceso, Departamento de Ingeniería Química y Ambiental, Universidad Nacional de Colombia, Bogotá, Colombia

articleinfo abstract

Article history: a-Methyl esters sulfonates (a-MES) are anionic surfactants that are derived from biorenewable resources,
Received 11 August 2009 offering interesting environmental and chemical properties for application in the detergent industry.
Received in revised form 13 March 2010
A simulation of their production process was conducted using a commercial production process currently
Accepted 9 June 2010
used for palm oil. Results, prices of raw materials were submitted to economic analysis, and final MES
Available online 15 July 2010
price was compared with available data for linear alkyl benzene sulfonates (LAS) prices. The results for
substances properties and product streams obtained from simulation were reliable in agreement to real
Keywords:
values. It was found that increasing methyl ester national price by 20%, 50% and the equivalent to linear
Palm oil
Process simulation
alkyl benzene price, the final price of a-methyl ester sulfonates was lower than the current price of linear
Surfactant alkyl benzene sulfonates. The capital cost and payout period for a production capacity of 49,000 tons of
Transesterification surfactant per year were obtained. Results indicate that the process is economically feasible and can be
Sulfonation applied to palm oil-based industries in Colombia.
© 2010 Elsevier Ltd. All rights reserved.

1. Introduction
In view of the significant environmental contamination caused
by raw materials based on petroleum oil and the subsequent im-
pact on animal, plant, and human populations, numerous studies
have been conducted on alternative processes to obtain substitute
raw materials from renewable resources (Smith, 2008). Industrial
and household wastes, such as detergents, chloride compounds,
and pathogenic microorganisms, are major water contaminants,
particularly detergents based on alkyl benzene sulfonates, which
generate a long-lasting foam of slow biodegradability that repre-
sents a major environmental problem (Commission of the Euro-
pean Communities, 2004).
Abbreviations: C#, carbon string with # carbon; cum, cubic meters; DSL,
Domestic Substances List; EINECS, European Inventory of Existing Commercial
Substances; ICONTEC, Colombian Institute of Technical Norms and Certification;
LAS, linear alkyl benzene sulfonates; LHHW, Langmuir–Hinshelwood–Hougen–
Watson kinetics; M, sulfur trioxide to methyl ester molar ratio; M100, sulfur trioxide
to methyl ester molar ratio needed for total methyl ester conversion; ME, fatty acid
methyl ester; MES – a-MES, methyl ester sulfonates; Px, partial pressure of
component x; t, time; TSCA, Toxic Substances Control Act; USA, United States of
America; US$, United States Dollars; wt., weight basis.
* Corresponding author. Tel.: +57 1 2086300x234; fax: +57 1 2444711.
** Corresponding author.
E-mail addresses: DM.Martinez42@egresados.uniandes.edu.co (D. Martínez),
srincon@cenipalma.org (S. Rincón).
Chemicals are now regulated – for example, in the United States
by the Toxic Substances Control Act (TSCA), in Canada by the
Domestic Substances List (DSL) or the Non-Domestic Substances
List (NDSL), in Europe by the European Inventory of Existing Com-
mercial Chemical Substances (EINECS), and in Colombia by the
Colombian Institute of Technical Standards and Certification
(ICONTEC). This, combined with new environmental laws, chang-
ing consumer needs, the search for innovative products, and fluctu-
ating prices of raw materials, has forced manufacturing companies
to vary the formulations of their detergent products to remove
banned substances, such as phosphates, and integrate new raw
materials based on synergy and production costs. A major outcome
has been the improved biodegradability of products and the in-
creased income-return (Zoller, 2009).
One such raw material from a biorenewable resource that has
drawn the attention of Colombia’s industrial sector is palm oil,
which has excellent chemical properties and a growing market,
making it an attractive alternative for developing new products,
including biodiesel. Palm oil composition is characterized by
mainly oleic (C18: 1) and palmitic acid (C16: 0) derived triglycer-
ides. Furthermore it contains natural antioxidants and carotenes
which give it oxidative stability (Rincón and Martínez, 2009; Stan-
ley, 2009). Among novel palm oil-based products, a-methyl esters
sulfonates (a-MES) are anionic surfactants characterized by their
good detergency (Kapur et al., 1978), water hardness tolerance
(Satsuki et al., 1992), rapid biodegradability compared with other

0960-8524/$ - see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.06.059
 D. Martínez et al. / Bioresource Technology 101 (2010) 8762–8771
Nomenclature
Parameter Value/expression/units
R kmol SO2/kg cat h
k1 exp(12.169–5473/T (K))
K2 exp(—9.953 + 8619/T (K))
K3 exp(—71.745 + 52596/T (K))
Kp exp(—10.68 + 11300/T (K))
surfactants (Ghazali and Ahmad, 2004), and production process
advantages (Ismail et al., 2002). Palm oil production is projected
to increase as markets for products and by-products gain
importance.
In Colombia, the palm oil production of the 53 existing extrac-
tion plants, fed by produce from 360,537 ha, was estimated to be
802,310 tons in 2009, with a 7% growth compared with 2008
(Fedepalma, 2010). In 2009, the apparent consumption of palm
oil was 570,174 tons; of these, 153,496 were used in the biodiesel
market and nearly 416,678 tons in the food and soap market. Esti-
mates are that by 2010 nearly 846,000 tons will be produced, with
389,000 tons destined to biodiesel production and nearly
446,000 tons to the traditional market (Fedepalma, 2010). In addi-
tion, by 2010, 20% of the Colombian detergent market will have an
oleochemical origin (Cenipalma-Fedepalma, 2003).
Methyl ester sulfonates (MES) has been considered an alterna-
tive anionic surfactant for substances as alkyl benzene sulfonates
(LAS), fatty acid sulfates (FAS), and alkyl sulfates (AS) (Ismail
et al., 2002). Satsuki et al. (1992) found that while grease particles
dispersion in aqueous MES was more stable compared to LAS and
AS if low concentrations of surfactant were used (lower than
300 ppm), higher concentrations made that dispersion similar be-
tween all those surfactants. Also, MES is well absorbed on oil, so
Satsuki et al. (1992) found that MES micelles had better properties
than those formed from LAS or AS using concentrations between
43 and 60 wt.%. They also demonstrated that solubilization capac-
ity of MES was ever higher than LAS capacity, and for concentration
of 20 mM MES solubilization capacity was twice LAS solubilization
capacity. On the other hand, Stein and Baumann (1975) showed
that while LAS detergency was affected by water hardness, MES
detergency was independent of medium hardness. As a conse-
quence, they showed that MES detergence was maintained when
using low concentrations of the surfactant. Also, Satsuki et al.
(1992) showed that MES detergency was greater than LAS and AS
detergency when used on cotton, cotton/polyester garments at
lower surfactant concentrations (200–300 ppm), but that differ-
ence was not really significant (less than 3%) between surfactant
performances when higher concentrations were used.
Kapur et al. (1978) showed from foam high data taken from
0.1% active detergent solutions that C16 to C18 a-methyl ester sul-
fonates were moderate foamers (137 mm foam high at 0 ppm
water hardness), while C14 a-methyl ester sulfonates were high
foamers (159 mm foam high at 0 ppm water hardness). Those data
showed that those a-methyl ester sulfonates (principally C14) re-
mained moderate foamers as the water hardness increased
(159 mm foam high at 1000 ppm water hardness), while the foam
high for LAS solution decreased as the water hardness increased
(112 mm foam high at 1000 ppm water hardness).
Based on its environmental properties, Kapur et al. (1978) also
demonstrated that MES requires 3–4 days to be naturally de-
graded, while LAS needs 24 days to do it. Finally, MES biodegrad-
ability is high (94–95% of active matter in methyl blue after
30 days), not dangerous oral toxicity (2.2–3.8 g/kg weight), low
animal toxicity (low toxicity range) and good skin compatibility
8763
K 1.14 10
× 19 exp(
m 14350/T
— (K))
k4 12.10 mexp(12060/T (K)), s—1
k5 11.52 mexp(12130/T (K)), s—1
M 0.1349
M100 1.3
(Stein and Baumann, 1975; Ghazali and Ahmad, 2004). All those
properties allow low surfactant content formulations using MES,
high stability detergents and reductions in energy consumption
(20% less) (Zoller, 2009).
This study addressed the production process of a-MES, taking
into consideration reactions, technical characteristics of equip-
ment, and processing conditions. A commercially available process
was selected and implemented as part of a simulation using Aspen
Plus® v. 2006. After establishing an annual production capacity, the
Aspen Icarus Process Evaluator® and simulation results were used
to determinate the economic characteristics of this specific MES
production process and assess the technical and economical feasi-
bility of implementing the process in Colombia.
2. Methods
The production process
The process involved obtaining methyl esters from palm oil by
transesterification process with a basic catalyst. This process has
been studied extensively over recent years due to the need to pro-
duce biodiesel (Castañeda et al., 2006; Fangrui and Milford, 1999).
After production and purification, saturated methyl esters were
separated from unsaturated esters by fractionation (molecular dis-
tillation) or crystallization, or were hydrogenated based on their
primary composition of palm oil triglycerides: fatty acid derivates
with C16 (saturated) and C18 chains (unsaturated in higher pro-
portion). Unsaturated compounds were suitable for use as biodie-
sel, and saturated compounds were suitable for MES production
pending the final percentage of disalt (Aparicio, 2008; Ghazali,
2002). Hydrogenation was considered a tool to remove olefinic
groups from methyl esters. Finally, the saturated methyl esters
were sulfonated, bleached, neutralized, and dried to obtain MES.
Raw materials
Palm oil was the main raw material used to produce MES. In
Colombia, methyl esters are currently produced by palm oil-based
biodiesel plants, whose current average production capacity is
100,000 tons/year for a total installed capacity of 526,000 tons of
biodiesel/year in 2009. Other commercially available substances,
such as sulfur to generate the sulfonating agent SO 3, air, methanol,
hydrogen peroxide, sodium hydroxide, and sodium hypochlorite,
were used.
Estimation of component properties
Substances not available in the Aspen Plus® v. 2006 database
were incorporated into the program based on molecular structure
and available physical properties. In addition, the group contribu-
tion method proposed by Ceriani and Meirelles (2004) for fatty
compounds was applied to estimate critical properties and vapor
pressures of involved substances. The Carlson method (1996)
8764 D. Martínez et al. / Bioresource Technology 101 (2010) 8762–8771
was used to select thermodynamic models; the UNIFAC model was
applied to operations that mostly involved organic compounds and
the NRTL model was restricted to understanding the parameters of
interaction between substances. Finally, the program was run as a
‘‘property estimation”, and the properties obtained for the different
substances were compared with the experimental values obtained
by Castañeda et al. (2006).
Methyl ester production
To simulate the production process of methyl esters (Fig. 1), the
palm oil characteristics given in Table 1 were used as input stream:
0.1% moisture (weight basis, wt.); 2.3% free fatty acids (wt.); and a
high triglyceride content of linoleic (10.7 wt.%), palmitic
(36.3 wt.%), and oleic acid (45.4 wt.%). Carbon chains of the princi-
pal fatty acids were composed of 18 and 16 carbons, and were
unsaturated for oleic and linoleic acids.
The palm oil was pre-treated to reduce its moisture content and
the amount of free fatty acids because these products cause impu-
rities that decrease methyl ester production and limit subsequent
purification. Table 2 details the equipment, simulation models,
and conditions associated with the simulation. A deodorization
column (T-101) was used that allowed the oil to enter into contact
with the steam at 280 °C and 2 bar. This treatment decreased the
water content of palm oil to 2 ppm and that of fatty acids to
297 ppm. The outgoing steam was condensed and two types of
streams were obtained using a V-101 vessel: a water-rich stream
and an oleic acid-rich stream (98 wt.%).
Fig. 1. Methyl ester production process diagram.
After the pre-treatment, the oil was submitted to transesteri-
fication using two continuous stirred tank reactors (CSTRs) in
series. The feed of the first reactor (R-101) consisted of a mix-
ture of oil and methanol at a molar ratio of 1:6. NaOH at
0.75% oil weight was added as catalyst. The oil conversion of this
reactor was 94.5%. A V-102 vessel was then used to separate the
glycerol obtained from the transesterification reaction (heavy
phase) from the methyl esters and the remaining triglycerides
(light phase). The light phase was fed into the second transeste-
rification reactor (R-102) where the conversion of triglycerides
(oil) reached 99.7%.
The product of the second reactor (R-102) then continued onto
the methyl ester purification stage, which involved the use of a
methanol flash chamber (V-201). The overhead product stream
was sent to a methanol recovery stage (T-302). The V-201 liquid
stream, composed mainly of methyl esters and glycerol, went to
the V-202 decanter producing a glycerol-rich product stream (hea-
vy), whereas the light stream was mainly composed of methyl es-
ters and some impurities. To remove the remaining methanol from
the methyl esters, the V-202 light stream fed the V-203 flash sep-
arator where the percentage weight of methanol was reduced to
0.3%. The methanol-rich stream was sent to the same purification
stage (T-302) to reuse the methanol in the process.
The remaining NaOH catalyst of the reaction was completely
neutralized with hydrochloric acid to produce sodium chloride in
the R-201 reactor. Neutralization salts and remnants of process
impurities were removed by submitting the methyl ester-rich
stream to a 3-stage countercurrent washing with water at different
temperatures (T-201). The washed stream finally entered the flash
 D. Martínez et al. / Bioresource Technology 101 (2010) 8762–8771 8765

Table 1 99.9 wt.% purity. This stream was recycled to the first reactor R-
Properties of the palm oil inlet stream (Firestone, 2006).
101.
Stream palm oil Value

Temperature (°C) 35 Methyl ester sulfonation

Pressure (bar) 1.01
Vapor fraction 0 The methyl ester stream obtained from the transesterification
Molar flow (kmol/h) 14.692
Mass flow (kg/h) 11415.525
was used to simulate the sulfonation process (Fig. 2). As the use
Volumetric flow (cum/h) 176.327 of high iodine value feedstock (high presence of double bonded
Mass fraction (wt.%)
methyl ester) resulted in dark colored products after sulfonation,
OOO* 2.9 only saturated compounds were desirable for methyl ester sulfona-
PPP 1.3 tion (de Groot, 1991). Therefore an intermediate separation stage
PLP 15.4 was considered to adjust the composition of the inlet stream with
OLL 1.4
only palmitate, stearate, and myristate methyl esters. Although
PLL 7.7
MLP 1.2 this unit was not included in the simulation, it was taken into ac-
OOL 3.1 count when analyzing costs.
POL 16.7
MPP 0.3
Air drying
POO 18.3
POP 22.6 To avoid problems caused by corrosion and acid formation, air
SOO 2 moisture should be reduced. Two alternatives for air drying were
POS 4 evaluated: (1) drying by contact with ethylene glycol and (2) dry-
PPS 0.3
ing by cooling of the air. In the first option, glycol was fed at the top
SOS 0.2
Water 0.1
stage in counterflow to the air in a tower to remove water. An ab-
Oleic acid 2.3 sorber model with five equilibrium stages was used with a pres-
*
sure of 0.5066 bar in the column. This process reduced air
XYZ relates to a triglyceride whose fatty acid com-
position is based on ‘‘X” in the first place, ‘‘Y” in the
moisture from 2.9% (molar basis) to 36 ppm. In the second option
second and ‘‘Z” in the third. According to this, ‘‘O” (see Fig. 2), air flow temperature was reduced to 1 °C (H-405) to
means oleic acid, ‘‘P” means palmitic acid, ‘‘L” means condense the water. The air then passed to an absorber tower with
linoleic, ‘‘M” means myristic acid, and ‘‘S” means activated alumina (T-401) to meet air moisture requirements
stearic acid.
(<0.01 g water/m3) (de Groot, 1991).

evaporation stage in the V-204 unit to produce a light water-rich
stream and a bottoms stream with 99.7% methyl esters.
The glycerol-rich bottoms streams from decanters V-102 and V-
202 were mixed and neutralized (R-301), using hydrochloric acid
in the molar amount of the NaOH present to generate the cor-
responding salt. The neutralized product was sent onto distillation
(T-301), which produced a glycerol-rich bottoms stream (70.8% per
weight) and a methanol-rich light stream.
In addition, the methanol-rich light streams from units V-201
and V-203 were mixed together and passed to a rectification tower
(T-302) that generated a stream of methanol with more than
SO3 production
To keep a continuous SO 3 feed (6%/vol.) to the film reactor
(R-501) and maintain a molar ratio of 1.3:1 between SO 3 and the
methyl esters, a system with an initial sulfur burning stage (R-
401) was used to generate SO 2 (Eq. (1)). A packed bed reactor
divided into four parts (R-402/403/404/405) enabled heat exchange
and promoted SO3 formation (Eq. (2)). There were two heat
exchangers: H-402 between stages 1 and 2 and H-403 between
stages 2 and 3. The kinetic model associated with the conversion
of SO2 to SO3 (Froment and Bischoff, 1995) corresponded to that
of Langmuir–Hinshelwood–Hougen–Watson (LHHW), shown in
Eq. (3).

Table 2
Equipment description for the simulation of methyl ester production process.

Unit Description Aspen Plus ® Model Conditions

T-101 Palm oil deodorization tower RadFrac Five stages; 0.06 atm
V-101 Fatty acid recuperation decanter Decanter 1 atm; 28 °C
R-101 Transesterification reactor RCSTR 1 atm; 60 °C, t = 1.3565 h
V-102 Glycerol decanter Decanter 1 atm; 60 °C
R-102 Transesterification reactor RCSTR 1 atm; 60 °C, t = 1.683 h
V-201 Methanol evaporator Flash2 1 atm; 150 °C
V-202 Methyl ester:glycerol separator Decanter 1 atm; 150 °C
V-203 Methyl ester purification Flash2 0.49 atm; 130 °C
R-201 Methyl ester neutralization reactor RCSTR 1 atm; 28 °C, t = 0.006 s
T-201 Methyl ester washing RadFrac Three stages; T: 51–67–78 °C
V-204 Methyl ester drying Flash2 0.3 atm; 148.56 °C
R-301 Glycerol neutralization reactor RCSTR 1 atm; 28 °C, t = 17 s
T-301 Glycerol distillation column RadFrac Five stages; RR: 0.1798; 1 atm
T-302 Methanol recuperation column RadFrac 30 Stages; RR: 1.1029; 1 atm
P-101/202 Process pumps Pump 1.1 atm
H-101 Palm oil heater HeatX Type: design; oil outlet temperature: 200 °C
H-201 Transesterification product stream heater HeatX Type: design; stream outlet temperature: 150 °C
H-202/205 Flash vessels overheads coolers HeatX Type: design; stream outlet temperature: 32 °C
H-203 Methyl ester product stream cooler HeatX Type: design; stream outlet temperature: 130 °C
H-204 Methyl ester product stream heater HeatX Type: design; stream outlet temperature: 148 °C
8766 D. Martínez et al. / Bioresource Technology 101 (2010) 8762–8771

Fig. 2. Process diagram of methyl ester sulfonates production process.

SðlÞ þ O2ðgÞ ! SO2ðgÞ ð1Þ (4.3 m in height) in stage 6 and 581.5 kWh (1.1 m in height) in
1 stage 3. The kinetic model to form the sulfonated intermediate
SO2ðgÞ þ O2ðgÞ ! SO3ðgÞ ð2Þ was recently described by Torres et al. (2008a) for stearate-methyl
2
. Σ ester sulfonation in a second-order kinetic model (Eq. (4)).
kp p pSO
1— 3
2O
1 O2 SO2 pSO p1=2Kp
r¼ 2 ð3Þ r ¼ —kCSO CME ; r½kmol=m3 s] ð4Þ
2
3
22:414ð1 þ K 2pSO2 þ K 3pSO3 Þ
Based on the analysis presented by Froment and Bischoff (1995) The digestion of the product stream derived from the FFR (R-
501) was performed using a multitubular reactor (R-502) and
and Kirk-Othmer (1980), the properties obtained from the SO3 pro-
maintaining the conditions described by de Groot (1991). The reac-
duction tower (R-402/403/404/405) are shown in Table 3.
tor completely transformed the sulfonated intermediates into acid-
sulfonated methyl esters and the remaining methyl esters were
Sulfonation and digestion completely sulfonated (99.8% conversion of intermediate products
Methyl esters and SO3 (6 vol.%) streams were fed in countercur- to acid MES). The digestion kinetic model proposed by Roberts
rent to a falling film reactor (FFR) (R-501) where methyl esters et al. (1988) was based on two simultaneous pseudo first-order
reached more than 70% conversion to sulfonated intermediates. reactions and was directly related to the amount of SO 3 present
The reaction chemistry involved had previously been described in the flow as shown in Eq. (5).
by Smith and Stirton (1967), Okumura et al. (1976), and Hovda Σ. Σ Σ
(1996), whereas several properties of the system had been identi- 1
Cð%SO3 Þ ¼ 100M — 0:25 expð—k4 tÞ — 0167 expð—k5 tÞ
fied by Torres et al. (2008b). M100
A 7-stage system and two heat exchangers with cooling water ð5Þ
were established in the reactor (R-501) to remove 2907.5 kWh
The disalt formation was attributed to the reaction between
the methyl esters and the two moles of SO 3 as a result of the
Table 3 high temperature, affecting product color (de Groot, 1991). The
Characteristics of each tower stage for SO 2 to SO3 transformation. kinetic model described by Eq. (5) was used for this reaction
(Eq. (6)).
Stage 1 2 3 4

T inlet (°C) 425 440 435 430 SO3H

O
T outlet (°C) 600 500 450 435 O O
O + 2 SO3 R S ð6Þ
Catalyst (V2O5) (kg) 0.7715 2.374 53.75 0.052 R
Conversion (SO2to SO3 (%) 60 85 95 99 O O O
 D. Martínez et al. / Bioresource Technology 101 (2010) 8762–8771 8767

Bleaching and neutralization
The product stream from digester (R-502) went to the cyclone
(V-501) to extract the remaining gases, while the liquid stream
continued to the bleaching and neutralization stages. The liquid
stream obtained from the cyclone (V-501) was fed to the bleaching
CST reactor (R-503) at the conditions compiled by de Groot (1991).
A stream of methanol and peroxide 50% (methanol as 30% of the
total mass of the mixture entering to the reactor, and hydrogen
peroxide at 50 wt.% which was equal to 3% of the total weight of
acid was performed in basic medium as described by Kapur et al.
(1978), using a second-order kinetic model proposed by the same
author. The neutralization kinetic model used for this system cor-
responded to a liquid phase second-order kinetic model with a
constant of 9033000 m3/mol s (NIST). This model was related to
the neutralization of sulfurous acid (H 2SO3) and applied to all reac-
tions of neutralization of sulfonic acid.
CH OSO H þ NaOH ! CH OSO Na þ H O ð11Þ
3 3 3 3 2

the mixture) was also fed to the reactor R-503. This step reduced
the amount of impurities, mainly substances with unsaturated SO3H SO3Na
chains or OH groups in the chain (Yamada and Matsutani, 1996) O O
to a value higher than 80%. Although there was still intermediate R + NaOH R + H2 O ð12Þ

compound after the sulfonation process, it turned into a-sulfo- O O

nated methyl ester acid and SO3 thanks to its re-esterification with
methanol (Hovda, 1996).
The gas phase reaction between the SO 3 and methanol pro- Drying of MES
duced methyl sulfonic acid (Eq. (7)), preventing the formation of As much of the water and methanol present in the product
sulfuric acid between SO3 and water balance (Eq. (8)), which in stream was extracted as possible because their presence may cause
turn favored the hydrolysis of MES to a-sulfonated acids (Eq. (9)). salt hydrolysis and decrease the amount of active matter in the
product. The V-502 flash unit was accordingly used to reduce the
CH3 OH þ SO3 ! CH3 OSO3 H ð7Þ methanol mass in the product from 25.5% to 0.3 wt.% and water
content from 12.9 to 0.4 wt.%
H2O þ SO3 ! H2SO4 ð8Þ
Methanol recovery
SO3H SO3H
H SO Methanol was separated from the water using the distillation
O
2 4 OH CH OSO H ð9Þ tower T-501, and then recirculated to the bleaching stage. The
R
R + 3 3
overhead product stream was 86.8 wt.% of methanol (overhead is
O O recycled) and 97.3 wt.% of water (bottoms product).

2H2O2 ! 2H2O þ O2ðgÞ ð10Þ

To simulate this system, peroxide hydrolysis (Eq. (10)) was ta-
ken into account, using a first-order kinetic model with a constant
0.056 m3/mol s (NIST). The vapor phase was also considered, using
a second-order kinetic model, whose kinetic constant was
722640 m3/mol s for the sulfuric acid formation reaction (Eq. (8))
(NIST). The first-order expression proposed by Kapur et al. (1978)
for an acid medium was used for MES hydrolysis. Based on the
foregoing, there was 99% conversion for methanol and peroxide,
generating 0.573 kg sulfuric acid/h and 493.018 kg methyl sulfonic
acid/h.
The CSTR (R-504) was used for neutralization. Sodium hydrox-
ide 50 wt.% (1310 kg NaOH/h) was added in the stoichiometric mo-
lar amount required to neutralize both acidic substances and acid
MES in the stream (Eqs. (11) and (12)), generating MES salts.
Hydrolysis of MES salts to disalts of sulfocarboxylate or carboxylic
The treatment of effluent gases
The gas streams resulting from the sulfonation tower (R-501)
and the cyclone (V-501) continued to a purification stage to meet
environmental standards for particulates, SO 2 and SO3 gases. The
system was composed by an electroprecipitator (V-601) that ex-
tracted particulate material, mainly composed of organic sub-
stances, from the stream. The resulting gas stream passed to the
absorber tower (T-601) where the gas stream entered into contact
with a stream of NaOH 50 wt.% The absorption of SO 2 occurred by
the formation of sulfites (Na2SO3) from the reaction between NaOH
and SO2. The kinetic constant used for this reaction was
2.5292 × 1020 m3/mol s (NIST). Sulfites were finally oxidized in a
reactor (R-601) using NaClO because of the need to dispose liquid
sulfites as sulfates (reaction kinetic constant of 2408.8 m3/mol s).
Table 4 shows the models and specifications used for the simula-
tion of the methyl ester sulfonation process.

Table 4
Description of the simulation models and conditions for the methyl ester sulfonates production process.

Unit Description Model Conditions

R-401 Sulfur burner Requil 1 atm; 1129 °C

RadFrac
R-501 Sulfonation falling film reactor ABSBR Seven stages; DP = 0.4 atm; residence time: 2.916 s
R-502 Sulfonation products digester Rplug 90 °C; Residence time: 30 min; 32 tubes; 10 in. diameter
R-503 Bleaching reactor RCSTR 60 °C; 1 atm; 1.99 cum
R-504 Products neutralizer RCSTR 40 °C; 1 atm; residence time: 65 min
V-502 Product flash dryer Flash 110 °C; 1 atm
RadFrac
T-501 Methanol recovery tower Fractl 30 Stages; reflux ratio: 1.5; distillate to feed ratio: 0.54
T-601 Effluent gas scrubber RadFrac Five stages with reaction; 1 atm; no condenser nor reboiler
R-601 Sulfites to sulfates transformer Rplug Tube 1.3 m length; 0.5 m diameter
H-405 Aircooler HeatX Type: design; air outlet temperature: 2 °C
H-401 Sulfur dioxide stream cooler HeatX Type: design; stream outlet temperature: 420 °C
H-402 Sulfur dioxide to trioxide stream cooler HeatX Type: design; stream outlet temperature: 440 °C
H-403 Sulfur dioxide to trioxide stream cooler HeatX Type: design; stream outlet temperature: 435 °C
H-404 Sulfur trioxide stream cooler HeatX Type: design; stream outlet temperature: 82 °C
H-501 Digester product stream cooler HeatX Type: design; stream outlet temperature: 70 °C
8768 D. Martínez et al. / Bioresource Technology 101 (2010) 8762–8771

Economic analysis existing process’ type for methyl ester sulfonation (adjacent to
methyl ester production process).
The Aspen Icarus Process Evaluator ® and the simulation results
of both transesterification and sulfonation processes were used as 3. Results and discussion
tools to perform the economic analysis of the project. The cost of
methyl esters at which production was profitable was determined Process simulation
based on the value at which the profitability index was greater
than 1 and, as a result, the internal rate of return (IRR) was higher Mass balances
than 30% (rate of return of process). Based on the prices of raw The simulation yielded the mass balances associated with
materials (mainly methyl esters), the change of the IRR of the sul- methyl esters of the overall production process as well as the
fonation process was evaluated when the price per kg of each raw MES production process (Tables 6 and 7) for the production of
material suffered a change of US$0.1. The cost at which the produc- 49,000 tons MES/year.
tion of MES was profitable (IRR higher than 30%) was determined
based on this analysis and on program results.
Simulation results
The respective differences in terms of density and viscosity of
Location and production capacity triglycerides, as compared with experimental values, were less
Northern and eastern Colombia were determined to be the pre- than 2.4% and 0.6% (for temperatures between 25 and 100 °C),
ferred geographical locations in the country to establish a MES pro- whereas the differences for methyl esters were 5% for density
duction plant because they presented the largest area planted to oil and 0.6% for viscosity (same temperature range). These results
palm in 2009. In addition, most of Colombia’s palm oil-based bio- were based on thermodynamic models, group contribution meth-
diesel production systems are located in the northern part of the ods for properties, and several modifications of properties and
country, with an annual production capacity of approximately
100,000 tons of methyl esters (Arias, 2007). Taking into account
other factors, such as cost and ease of transportation of raw mate- Table 6
Raw material demand for methyl ester pro-
rials to the processing plant as well as price per square meter, the
duction process.
town of Ciénaga, located near the coastal city of Santa Marta in
northwestern Colombia, was determined to be the best location Substance Quantity (kg/h)
for the processing plant (average temperature of 28 °C, 1 atm. Palm oil 11415.53
atmospheric pressure, and 85% relative humidity). Steam (690 kPa) 2035
Methanol 1797.916
The maximum capacity of biodiesel plants was determined to
NaOH 103.277
be 100,000 tons biodiesel/year and, given that an intermediate Water 2042.764
treatment was required to remove unsaturated methyl esters, the HCl 94.324
capacity of the MES salt production plant was determined to be
49,000 tons/year, with the possibility of expanding its capacity to
100,000 tons/year depending on the production capacity perfor-
mance of the biodiesel plant and the treatment of methyl esters
prior to sulfonation. Table 7
Demand of raw materials for the methyl ester
sulfonation process.
Methyl ester production and sulfonation
Substance Quantity (kg/h)
The economic analysis considered cooling water, low pressure
steam, and ethylene glycol as utilities; the study period was 1 year; Air 8097.96
Glycol 11085.174
and a 20-year parameter was used to analyze investments, with a
Sulfur 664.889
30% rate of return, a 0% salvage value, and a 16% tax rate. The Methyl ester 4332.914
parameters of scale and capital costs, based on a national inflation Methanol 2681.045
of 7%, as well as prices (Table 5), were considered with a ‘probed’ Peroxide 268.105
process type for methyl ester production and an ‘adjacent to an NaOH 656.787
NaClO 1.638

Table 5
Raw material and products prices for methyl ester production and sulfonation process
(ICIS, 2008).
Table 8
Substance Price (US$/kg) Methyl ester stream obtained from the sim-
ulation of the process for production of
Limits Selected price methyl ester from palm oil in Aspen Plus ®
Raw material v. 2006.
Sulfur 0.24654–0.524 0.524
Property Value
Glycol 1.367–1.764 1.433
Methyl ester 0.8552 Molar flow (kmol/h) 34.165
Methanol 0.421 Mass flow (kg/h) 9623.959
Hydrogen peroxide 0.5401–1.1684 1.0913 Volumetric flow (cum/h) 10.589
NaOH 0.390–0.8225 0.8225
Molar fraction (mol %)
NaClO 0.2017–0.6050 0.605
Methyl oleate 35
HCl 0.3
Methyl palmitate 43.8
Palm oil 0.5
Methyl linoleate 17.1
Products Methyl myristate 0.4
Methyl ester 0.71 Methyl stearate 2.4
Glycerol 0.1 Water 0.6
MES Changeable NaCl 0.6
 D. Martínez et al. / Bioresource Technology 101 (2010) 8762–8771 8769

program calculation routes proposed by Castañeda et al. (2006). It

was therefore concluded that the values estimated by the simula-

Gas treatment
tion were accurate and the calculations for properties and process-

Sulfates

Product
ing units reliable in thermodynamic terms.

98.64

0.954

0.032
70.1
1.01
Table 8 indicates the characteristics of the methyl ester stream

0
0

0
0
0
0
0
0
0
0
0
0
obtained by the simulation of the methyl ester production process.
This stream had a composition similar to the product stream ob-

Neutralization
tained from similar processes (Castañeda et al., 2006) so the condi-

NaOH (2)
tions and material used for this process were coherent to the

1310
Feed

1.01
selected process.

0.5

0.5
28

0
0

0
0

0
0
0
0
0
0
0
0
Based on the simulation of the methyl ester sulfonation process,
although it was possible to maintain the temperature below 90 °C

Gas treatment
in most of the FFR column, as recommended by de Groot (1991), it

NaOH (1)

351.787
was not possible to do so for the final stage because the methyl es-

0.995

0.005
Feed

1.01
ter and SO3 streams were fed in countercurrent to the tower. This

28

0
0

0
0

0
0
0
0
0
0
0
0
also implied an increased formation of impurities, causing the
product to acquire an undesirable color. Fig. 3 compares the tem-

Gas treatment
perature profile produced by the simulation with that proposed
by de Groot (1991).

NaClO

1.638
Feed

1.01
The post-digestion sulfonation product stream was composed

28

0
0
0
0
0
0
0
0
0
0
0
0
0
0
of 54.9 wt.% active agent ( a-MES sodium salts), 0.3 wt.% methyl
sulfonic acid salt, 12.9 wt.% water, and a minimal amount of a-sul-

Distillation

3029.187
fo-fatty acid before drying. After drying, the active mass reached a

Lights

0.119
0.868

0.013
-75.8
1.01
total of 94.2 wt.%, while the disalt composition was 2 wt.%. Also,

MR

0
0
0
0
0

0
0
0
0
0
the use of the gas treatment system reduced the mass percentage
of SO2 from 206 ppm to 3 ppb and the SO 3 content from 277 to

3217.254
Bleacher
Mixture
267 ppb, while generating a stream with 3.2 wt.% sulfates in water.

0.833
0.083

0.083
1.01
MP

The composition of the MES salt product stream obtained from the
28

0
0
0
0
0
0

0
0
0
0
simulation did not really differ from real values (The Chemithon

6126.103
Corporation, 2006), although real processes generate MES product
Product

0.942

0.001
0.009
0.003
0.018

0.005
Final

streams with 5 wt.% disalt composition. This difference can be

MES

1.01

0.02
110

0
0
0
0
0

0
attributed to assumptions about the pre-treatment of methyl es-
ters as only saturated compounds were used to feed sulfonation
Methyl ester

(see streams results in Table 9).

4332.914
Feed

1.01
FFR

28

1
0

0
0
0
0
0
0
0
0
0
0
0
0
0
Economic analysis
SO3 production

Methyl ester production process

664.889

The price of methyl esters that made methyl ester production

Sulfur

Feed

1.01
500

process profitable (IRR > 30%) was US$0.702/kg methyl ester (using
1

0
0
0
0
0
0
0
0
0
0
0
0
0
0
Streams of the sulfonation process of methyl esters obtained from the process simulation.

the Aspen Icarus® Analysis Tools). The decision was therefore made
8097.96

to use the current sales cost of biodiesel in Colombia, defined by

0.229
0.019
Feed

1.01

the Colombian Ministry of Mines and Energy at US$0.7127/kg

Air

28

0
0

0
0
0
0
0

0
0
0
0
0
methyl ester for 2009, because it was the value established by
authorities and rendered the process being evaluated in this study
2997.987
Methanol
Recircula

profitable.
0.119
0.868

0.013
-75.8
1.01
32

0
0
0
0
0

0
0
0
0
0
Distillation
Water (1)

10518.54
Bottoms

0.001
0.549
0.129

0.003
0.255

0.005

0.034
0.012

0.012
1.01
40

0
0

0
Product

5990.6

0.822
0.178
150.2
0.61
FFR
18

0
0
0
0
0
0
0
0
0
0
0

0
Digester

5991.11
Product

0.001
0.921

0.018
Mass fraction (wt./total wt.)
1.01

0.06
16

90

0
0
0

0
0
0

0
Hydrogen peroxide 0

0
HES intermediates
Temperature (°C)

Mass flow (kg/h)

Sodium sulfate
Sulfur trioxide
Sulfur dioxide
Vapor fraction
Pressure (bar)

Methyl ester
Description

Impurities
Methanol

Acid HES

Oxygen
Stream

Water

NaOH

Disalt
Table 9

HES

Fig. 3. Temperature profile for the sulfonation reactor with a calculated stage
height of 1066 m (de Groot, 1991).
8770 D. Martínez et al. / Bioresource Technology 101 (2010) 8762–8771

Table 10 make the process profitable – regardless of the gas purification

Results of the economic evaluation of the MES production process.
stage – was lower for drying by cooling (US$1.22/kg) than for dry-
Project results summary * Units Total ing with ethylene glycol (US$3.7/kg). The greater impact of the
Total project capital cost US$ 10919025.33 price of raw materials was related to those substances that were
Total raw materials cost US$/year 57106175.76 directly involved in the sulfonation of methyl esters to reduce air
Total products sales US$/year 68612353.60 moisture by cooling, which was not the case with the ethylene gly-
Total operating labor and Maintenance cost US$/year 1578000.00
col technique. The variation of the IRR caused by the change in
Total utilities cost US$/year 746573.33
Total operating cost US$/year 67838118.98
price of methyl esters, methanol, and peroxide ranged between
Operating labor cost US$/year 1400000.00 12.05%, 10.71%, and 10.71%, respectively, in the case of drying by
Maintenance cost US$/year 178000.00 cooling. The impact of the price of ethylene glycol on the IRR
Operating charges US$/year 350000.00 was 25.19% in the case of drying with ethylene glycol. As a result,
Plant overhead US$/year 789000.00
the methyl ester sulfonation process, using an air drying system by
Subtotal operating cost US$/year 60569749.09
G and A cost 7268369.89 cooling and water condensation, was selected as a result.
*
Based on a price of US$0.8552/kg methyl ester and a price of US$1.40/kg MES.
MES production process
Previous reports (The Chemithon Corporation, 2006) indicate
that, based on the costs of raw materials (US$110/ton sulfur,
Determination of the best air drying process US$650/ton methyl esters, US$176/ton KOH, US$192/ton metha-
Based on the results of the Aspen Icarus Process Evaluator ®, nol, US$750/ton peroxide) and considering the conditions given by
investment costs were lower for the drying process with ethylene the company for the sulfonation of methyl esters, the produc- tion
glycol (US$9174516.42) as compared with the drying process by cost of MES was US$668.53/ton MES. Study results, given in Table
cooling (US$10152180.81). However, the minimum MES price to 10 and Figs. 4 and 5, show the fast growth of sales as

Fig. 4. Projected sales and operating costs of the project per year.

Fig. 5. Projected cash flow of the methyl ester sulfonates production process.
 D. Martínez et al. / Bioresource Technology 101 (2010) 8762–8771
compared with process operating costs and a short 5-year payout
period. These properties show that the process is economically
attractive and can be implemented as the income-return is positive
as of year 2 and sales are higher than operational costs as of year 3
(Fig. 4).
The analysis of the impact of the cost of raw materials on the
IRR of the project showed that the cost of methyl esters had the
greatest impact on the IRR: an average change of 21.07% in the
IRR was generated with a variation of US$0.10 in the price per kg
of methyl esters. The respective variation in the IRR caused by
the price of sulfur, peroxide–methanol ratio, NaOCl, and NaOH
was 5.36%, 18.02%, 0.1%, and 11.39%.
When analyzing the economic feasibility of the MES production
process, the decision was made to evaluate the project for three
events related to the price of methyl esters: (1) a 20% overrun com-
pared with the price provided for methyl esters (US$0.8552/kg); (2)
a 50% overrun (US$1.069/kg); and (3) a value similar to that of alkyl
benzenes, which is the raw material of linear alkyl benzene sulfo-
nates (LAS), the most currently used industrial surfactant (US$1.4/
kg). The three alternatives were used to determine the impact of
the effect of the price of methyl esters on the final price of MES
and thus compared their costs with those of other currently avail-
able surfactants. Analysis results indicated that the minimum sales
value of MES was US$1.27/kg when the price of methyl esters was
US$0.8552/kg; US$1.43/kg when the price of methyl esters was
US$1.069/kg; and US$1.66/kg when the price of methyl esters
was US$1.40/kg.
While the 2008 sales value of LAS was US$2.1/kg (Aparicio,
2008) and the MES production process was evaluated using the
2008 price of the LAS as raw material (US$1.4/kg) as the price of
methyl esters, the final cost of MES was found to be significantly
lower than the current price of LAS. This makes the selection much
more interesting if other advantages of MES, such as their biode-
gradability and hard water tolerance, are taken into account (Kapur
et al., 1978; Satsuki et al., 1992). However, because several
assumptions were made during the simulation process, simulation
errors were not quantified, and simulation data about the econom-
ics of the LAS production process were lacking, further analysis
should be conducted to support this conclusion. Nonetheless, this
evaluation evidenced that, although MES production requires more
steps to obtain a product with very good characteristics, the final
sales cost of MES is commercially competitive.
4. Conclusions
Properties of substances and characteristics of product streams
for each process indicated that pre- and post-simulation results
were reliable, enabling estimation of reliable production costs. Eco-
nomic analysis indicated that even if the cost of methyl esters was
as high as that of raw materials for LAS production, the final MES va-
lue would be significantly competitive, making MES an interesting
alternative to other commercial surfactants currently produced.
Colombian industries have the capacity to begin producing MES,
but commercially available systems are necessary to ensure high
product quality. Although investment is high, efficient recovery of
capital investments allows participation in domestic and interna-
tional markets.
Acknowledgements
The authors sincerely thank the Universidad de Los Andes
(Bogotá, Colombia), the Universidad Nacional de Colombia (Sede
8771
Bogotá), the Fondo de Fomento Palmero and Mauricio Mosquera
(Cenipalma).
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