Bioresource Technology 101 (2010) 8762–8771

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

1. Introduction * Corresponding author. Tel.: +57 1 2086300x234; fax: +57 1 2444711.

** Corresponding author.
E-mail addresses: DM.Martinez42@egresados.uniandes.edu.co (D. Martínez),
In view of the significant environmental contamination caused srincon@cenipalma.org (S. Rincón).
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$, United States Dollars; wt., weight basis.
 Chemicals are now regulated – for example, in the
United States by the Toxic Substances Control Act
(TSCA), in Canada by the Domestic Substances List
(DSL) or the Non-Domestic Substances List (NDSL), in
Europe by the European Inventory of Existing Com-
mercial Chemical Substances (EINECS), and in
Colombia by the Colombian Institute of Technical
Standards and Certification (ICONTEC). This, combined
with new environmental laws, chang- ing consumer
needs, the search for innovative products, and fluctu-
ating prices of raw materials, has forced manufacturing
companies to vary the formulations of their detergent
products to remove banned substances, such as
phosphates, and integrate new raw materials based on
synergy and production costs. A major outcome has
0960-8524/$ - see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.06.059
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
 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(m14350/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
Properties of the palm oil inlet stream (Firestone, 2006). 99.9 wt.% purity. This stream was recycled to the first reactor R-
101.
Stream palm oil Value
Temperature (°C) 35
Pressure (bar) 1.01 Methyl ester sulfonation
Vapor fraction 0
Molar flow (kmol/h) 14.692 The methyl ester stream obtained from the transesterification
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
PPP 1.3
only saturated compounds were desirable for methyl ester sulfona-
PLP 15.4 tion (de Groot, 1991). Therefore an intermediate separation stage
OLL 1.4 was considered to adjust the composition of the inlet stream with
PLL 7.7 only palmitate, stearate, and myristate methyl esters. Although
MLP 1.2
this unit was not included in the simulation, it was taken into ac-
OOL 3.1
POL 16.7 count when analyzing costs.
MPP 0.3
POO 18.3
Air drying
POP 22.6
SOO 2
To avoid problems caused by corrosion and acid formation,
POS 4 air moisture should be reduced. Two alternatives for air drying
PPS 0.3 were evaluated: (1) drying by contact with ethylene glycol and
SOS 0.2 (2) dry- ing by cooling of the air. In the first option, glycol was
Water 0.1
fed at the top stage in counterflow to the air in a tower to remove
Oleic acid 2.3
water. An ab- sorber model with five equilibrium stages was
*
XYZ relates to a triglyceride whose fatty acid com- used with a pres- sure of 0.5066 bar in the column. This process
position is based on ‘‘X” in the first place, ‘‘Y” in the reduced air moisture from 2.9% (molar basis) to 36 ppm. In the
second and ‘‘Z” in the third. According to this, ‘‘O”
means oleic acid, ‘‘P” means palmitic acid, ‘‘L” means
second option (see Fig. 2), air flow temperature was reduced to 1
linoleic, ‘‘M” means myristic acid, and ‘‘S” means °C (H-405) to condense the water. The air then passed to an
stearic acid. absorber tower with activated alumina (T-401) to meet air
moisture requirements (<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 SO2 (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

SO2ðgÞ 1 stage 3. The kinetic model to form the sulfonated intermediate

! SO3ðgÞ ð2Þ
þ 2ðgÞ was recently described by Torres et al. (2008a) for stearate-methyl
O2 .1 — pSO3
p Σ ester sulfonation in a second-order kinetic model (Eq. (4)).
kp 2O
1 O2 SO2
pSO p1=22Kp
r¼ ð3Þ r ¼ —kCSO CME ; r½kmol=m3 s] ð4Þ
2
22:414ð1 þ K2 pSO þ K 3 pSO Þ
2 3 3

Based on the analysis presented by Froment and Bischoff (1995)

The digestion of the product stream derived from the FFR (R-
and Kirk-Othmer (1980), the properties obtained from the SO3 501) was performed using a multitubular reactor (R-502) and
duction tower (R-402/403/404/405) are shown in Table 3. pro-
maintaining the conditions described by de Groot (1991). The reac-
tor completely transformed the sulfonated intermediates into acid-
Sulfonation and digestion sulfonated methyl esters and the remaining methyl esters were
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 1
(1996), whereas several properties of the system had been identi- Cð%SO3 Þ ¼ 100MΣ. Σ — 0:25 expð—k4 tÞ — 0167 expð—k5 tÞΣ
fied by Torres et al. (2008b). M100
ð5Þ
A 7-stage system and two heat exchangers with cooling water
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 high
temperature, affecting product color (de Groot, 1991). The kinetic
Table 3 model described by Eq. (5) was used for this reaction (Eq. (6)).
Characteristics of each tower stage for SO 2 to SO3 transformation.
Stage 1 2 3 4
T inlet (°C) 425 440 435 430 SO3H
O
T outlet (°C) 600 500 450 435 O O
O
Catalyst (V2O5) (kg) 0.7715 2.374 53.75 0.052 R + SO3 R S
Conversion (SO2to SO3 (%) 60 85 95 99
O O
 D. Martínez et al. / Bioresource Technology 101 (2010) 8762–8771 8767

Bleaching and neutralization

acid was performed in basic medium as described by Kapur et al.
The product stream from digester (R-502) went to the cyclone
(1978), using a second-order kinetic model proposed by the same
(V-501) to extract the remaining gases, while the liquid stream
author. The neutralization kinetic model used for this system cor-
continued to the bleaching and neutralization stages. The liquid
responded to a liquid phase second-order kinetic model with a
stream obtained from the cyclone (V-501) was fed to the bleaching
constant of 9033000 m3/mol s (NIST). This model was related to
CST reactor (R-503) at the conditions compiled by de Groot (1991).
the neutralization of sulfurous acid (H2SO3) and applied to all reac-
A stream of methanol and peroxide 50% (methanol as 30% of the
tions of neutralization of sulfonic acid.
total mass of the mixture entering to the reactor, and hydrogen
CH OSO H þ NaOH ! CH OSO Na þ H O ð11Þ
peroxide at 50 wt.% which was equal to 3% of the total weight of 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 ð12Þ
to a value higher than 80%. Although there was still intermediate R + NaOH R + H2 O
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

SO3H Methanol recovery

SO3H H SO Methanol was separated from the water using the distillation
2 4 OH CH OSO H ð9Þ tower T-501, and then recirculated to the bleaching stage. The
R
O 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, SO2 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 m 3/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

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

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

(2) Product Sulfates

tion were accurate and the calculations for properties and process-
ing units reliable in thermodynamic terms.

0.954 0 0
Table 8 indicates the characteristics of the methyl ester stream
obtained by the simulation of the methyl ester production process.

treatment
This stream had a composition similar to the product stream ob-
tained from similar processes (Castañeda et al., 2006) so the condi-

GasNaOH
tions and material used for this process were coherent to the

NaOH (1) Feed

selected process.

00
Based on the simulation of the methyl ester sulfonation process,

Neutralization
although it was possible to maintain the temperature below 90 °C
in most of the FFR column, as recommended by de Groot (1991), it
was not possible to do so for the final stage because the methyl es-

0.995 0 0
ter and SO3 streams were fed in countercurrent to the tower. This

NaClO Feed
also implied an increased formation of impurities, causing the

treatment
product to acquire an undesirable color. Fig. 3 compares the tem-
perature profile produced by the simulation with that proposed

Feed
by de Groot (1991).

Gas
The post-digestion sulfonation product stream was composed

Gas treatment

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-

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

Lights

0.868 0
total of 94.2 wt.%, while the disalt composition was 2 wt.%. Also,
the use of the gas treatment system reduced the mass percentage
Distillation
of SO2 from 206 ppm to 3 ppb and the SO 3 content from 277 to MP
267 ppb, while generating a stream with 3.2 wt.% sulfates in water.
MES Mixture

0.833 0
The composition of the MES salt product stream obtained from the
simulation did not really differ from real values (The Chemithon
Bleacher

Corporation, 2006), although real processes generate MES product

0.003 0
streams with 5 wt.% disalt composition. This difference can be
FFRProduct

attributed to assumptions about the pre-treatment of methyl es-

ters as only saturated compounds were used to feed sulfonation
Final

(see streams results in Table 9).

Methyl ester

Economic analysis

Methyl ester production process

3 production Feed

The price of methyl esters that made methyl ester production

Streams of the sulfonation process of methyl esters obtained from the process simulation. Table 9

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

0

(using the Aspen Icarus ® Analysis Tools). The decision was

1 1.01 28

therefore made to use the current sales cost of biodiesel in

0.019 0 0
Feed

Colombia, defined by the Colombian Ministry of Mines and Energy

Bottoms Methanol 32Air SO

at US$0.7127/kg methyl ester for 2009, because it was the value

established by authorities and rendered the process being evaluated
in this study profitable.
0.868 0
Recircula

0.255 0
Distillation
18

0.178
16 (1)FFR
Product
Water

0.921 0 0 0
Digester Product

Mass fraction (wt./total wt.)

Methyl ester Methanol Water
ion Mass flow (kg/h) Description
Stream

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
Results of the economic evaluation of the MES production process. make the process profitable – regardless of the gas purification
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
Total raw materials cost US$/year 57106175.76
price of raw materials was related to those substances that were
Total products sales US$/year 68612353.60 directly involved in the sulfonation of methyl esters to reduce air
Total operating labor and Maintenance cost US$/year 1578000.00 moisture by cooling, which was not the case with the ethylene gly-
Total utilities cost US$/year 746573.33 col technique. The variation of the IRR caused by the change in
Total operating cost US$/year 67838118.98
price of methyl esters, methanol, and peroxide ranged between
Operating labor cost US$/year 1400000.00
Maintenance cost US$/year 178000.00 12.05%, 10.71%, and 10.71%, respectively, in the case of drying by
Operating charges US$/year 350000.00 cooling. The impact of the price of ethylene glycol on the IRR
Plant overhead US$/year 789000.00 was 25.19% in the case of drying with ethylene glycol. As a result,
Subtotal operating cost US$/year 60569749.09 the methyl ester sulfonation process, using an air drying system by
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

Determination of the best air drying process
Based on the results of the Aspen Icarus Process Evaluator ®,
investment costs were lower for the drying process with ethylene
glycol (US$9174516.42) as compared with the drying process by
cooling (US$10152180.81). However, the minimum MES price to
Previous reports (The Chemithon Corporation, 2006) indicate
that, based on the costs of raw materials (US$110/ton sulfur,
US$650/ton methyl esters, US$176/ton KOH, US$192/ton metha-
nol, US$750/ton peroxide) and considering the conditions given
by the company for the sulfonation of methyl esters, the produc-
tion cost of MES was US$668.53/ton MES. Study results, given in
Table 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).
References
Aparicio, J., 2008. Metil ester sulfonado una generación nueva en surfactantes. In:
Proceedings Discussion Panel: Metil Ester Sulfonados, Una Nueva Alternativa
Surfactante Derivada Del Aceite de Palma, Cenipalma, Bogotá.
Arias, A., 2007. Los Biocombustibles en Colombia, Cenipalma. Available from:
<http://www.minagricultura.gov.co/archivos/biocombustibles_septiembre.pdf>
(accessed September 2008).
Carlson, E., 1996. Don’t gamble with physical properties for simulations. Chemical
Engineering Progress 35, 46.
Castañeda, L., Narváez, P., Rincón, S., 2006. Simulación del proceso para la obtención
de ésteres metílicos a partir de aceite de palma. Memories XXII IACCHE (CIIQ),
Argentina.
Cenipalma-Fedepalma, 2003. Estudio Prospectivo de la Oleoquímica del Aceite de
Palma en Colombia. Centro de documentación – FEDEPALMA.
Ceriani, R., Meirelles, A., 2004. Predicting vapor–liquid equilibria of fatty systems.
Fluid Phase Equilibria 215, 227–236.
Commission of the European Communities, 2004. Report from the Commission to
the European Parliament and the Council Pursuant to Article 9 of Commission
Recommendation 98/480/EC of 22 July 1998 Concerning Good Environmental
Practice for Household Laundry Detergents.
de Groot, H., 1991. Sulphonation Technology in the Detergent Industry. Kluwer
Academic Publishers.
Fangrui, M., Milford, A., 1999. Biodiesel production: a review. Bioresource
Technology 70, 1–15.
Fedepalma, 2010. Balance económico del sector palmero colombiano en 2009. El
palmicultor 456: Boletín Económico, pp. 1–8.
Firestone, D., 2006. Physical and Chemical Characteristics of Oils, Fats, and Waxes,
second ed. AOCS Press, USA.
Froment, G., Bischoff, K., 1995. Chemical Reactor Analysis and Design. John Wiley
and Sons, USA.
Ghazali, R., 2002. The effect of disalt on the biodegradability of methyl ester
sulphonates (MES). Journal of Oil Palm Research 14 (1), 45–50.
Ghazali, R., Ahmad, S., 2004. Biodegradability and ecotoxicity of palm stearin-
based methyl ester sulphonates. Journal of Oil Palm Research 16 (1), 39–44.
Hovda, 1996. Sulfonation of fatty acid esters. US Patent 5587,500.
ICIS, 2008. Chemical Prices and Chemical Industries Trends. Available from:
<http:// www.icis.com/StaticPages/a-e.htm#> (accessed December 2008).
Ismail, Z., Ahmad, S., Sanusi, J., 2002. Palm based surfactants synergy in soap
applications, Malaysian Palm Oil Board. Palm Oil Developments 37, 9–13.
Kapur, B., Solomon, J., Bluestein, B., 1978. Summary of the technology for the
manufacture of higher alpha-sulfo fatty acid esters, SD&C technical. JAOCS 55
(6), 549–557.
Kirk-Othmer, R., 1980. Encyclopedia of Chemical Technology, third ed. Wiley, New
York, 23,769.
NIST (National Institute of Standards and Technology), 2008. NIST Chemical
Kinetics Database. Available from: <http://kinetics.nist.gov/kinetics/index.jsp>
(accessed November 2008).
Okumura, O., Sakatani, T., Jaman, L., 1976. Mechanism of sulphonation of fatty acid
esters with sulfur trioxide and properties of alpha-sulfo fatty acid esters. In:
Proceedings of the Seventh CID in Moscow.
Rincón, S., Martínez, D., 2009. Análisis del potencial de las propiedades del aceite
de palma en el desarrollo de la industria. Palmas 30 (2), 1–8.
Roberts, D., Jackson, P., Saul, C., Clemett, C., Jones, K., 1988. A kinetic and
mechanistic investigation of ester sulphonation. In: Proceedings of Second
World Surfactant Congress, vol. 2, ASPA, Paris, pp. 38–41.
Satsuki, T., Umehara, K., Yoneyama, Y., 1992. Performance and physicochemical
properties of a-sulfo acid methyl esters. JAOCS 69 (7), 672–677.
Smith, G., 2008. 7th World surfactant congress examines sustainability. Inform 19
(9), 625–627.
Smith, F., Stirton, A., 1967. The alpha-sulfonation of alkyl palmitates and stearates.
Journal of the American Oil Chemist’s Society 44 (7), 405–406.
Stanley, J., 2009. The nutritional reputation of palm oil. Lipid Technology 20 (5),
112–114.
Stein, W., Baumann, H., 1975. a-Sulfonated fatty acids and esters: manufacturing
process, properties, and applications. Journal of American Oil Chemists’ Society
52, 323–329.
The Chemithon Corporation, 2006. Commercial application of the Chemithon
MES process, methyl ester sulfonates, a guide to biorenewable resources.
Biorenewable Resources 3, 7–8.
Torres, J., Días, L., Sánchez, F., 2008a. Estudio cinético de la sulfonación de ésteres
metílicos derivados de la estearina de palma. Revista Corpoica 9 (2), 88–95.
Torres, J., Suárez, O., Narváez, P., Sánchez, F., 2008b. Sulfonación de ésteres
metílicos derivados del aceite de palma. Revista Corpoica 9 (2), 77–87.
Yamada, K., Matsutani, S., 1996. Analysis of the dark colored impurities in
sulfonated fatty acid methyl esters. JAOCS 73 (1), 121–125.
Zoller, U., 2009. Handbook of Detergents, Part F: Production, Surfactant Science
Series, vol. 142. CRC Press.