The use of coconut oil as a surfactant has several advantages, among others, are renewable (renewable resources), cleaner

(cleaner) and more pure than using petrochemical-based raw materials. Surfactant is a molecule that also has a hydrophilic
group and a lipophilic group that can unite a mixture consisting of water and oil. Surfactant is surface active agent.
Surfactant molecule has a polar part that likes water (hydrophilic) and non-polar parts like the oil / fat (lipophilic).
Along with the increasing awareness of health and good environment, easily degraded surfactant demand and also
increasing plant-based (Holmberg, 2001). Thus it is necessary to study to obtain a surfactant that has these two criteria
are derived from renewable raw materials (renewable) and degrading in nature so it is acceptable ecologically. One
surfactant which meets both these criteria are surfactants diethanolamide.

Methyl ester sulfonate (MES) is an anionic surfactant made through sulfonation process using raw materials from
vegetable oils such as coconut, palm or jatropha seed. Excellence MES compared with a surfactant made from petroleum
is that it can be updated, more environmentally friendly because it is easily degraded by bacteria, has the ability lathering
good, good tolerance to water hardness, synergize well with soap (as additives soap), solubility in good water, gentle and
non-irritating to the skin, as well as having a good biodegradation characteristics (Hui, 1996). MES widely applied for
hygiene products and detergents and is used to process petroleum recovery. This is due to the surfactant has both
hydrophobic and hydrophilic groups were able to lower the interfacial tension of oil - water so that Terje oil-bath in the
rock pores can produksikan. Coconut oil is a vegetable oil that can Diman MES faatkan for raw materials. The largest
component of coconut oil is lauric acid (C12). According Swern (1979), the length of the molecule is critical to balance
the needs of both hydrophilic and lipophilic groups. If the hydrophobic chain is too long, there will be an imbalance of
the affinity for the oil group is larger when compared to the water group. This is demonstrated by the limited solubility in
water. In general, the length of the chain
best for the surfactant is a fatty acid with a carbon atom 10-118.

In general, the process of the production of methyl ester sulfonate comprising the steps of sulfonation, bleaching stage
and neutralization stage. Sulfonation process generally involves reacting sufonasi agent with oils, fatty acids or fatty acid
esters. Sulfonation agent that can be used is SO 3, H 2 SO 4, SO 3 .h 2 SO 4, NaHSO 3, or 3 H. ClSO Important factors
that must be considered at this stage of the sulfonation process include concentration, reaction temperature, and time
reactions (Foster, 1996).
Sulfonation agent widely used in the sulfonation reaction is sulfuric acid (H 2 SO 4) and oleum (SO 3 · H 2 SO 4). In the
process of sulfonation required H 2 SO 4 in large quantities or excess that occurs sulfonation reaction to completion.
According to de Groot (1991), water as byproducts generated in the process of sulfonation
using H 2 SO 4 was able to slow down or even inhibit the sulfonation reaction, so that the necessary arrangements
sulfonation old, and the concentration of H 2 SO 4 to produce optimal MES. This research
aims to determine the concentration of H 2 SO 4 and the duration of sulfonation best of the characteristics of MES, make
surfactant diethanolamide of virgin coconut oil (VCO) with the amidation, assessing the effect of the mole ratio of
pereaktan methyl ester: diethanolamine against surfactant produced, and assess the effect of weight percent the catalyst
of the surfactant produced.

METHOD
This study is divided into two main stages, namely the reaction process of making the MES and analysis of reaction
products. MES-making process comprises reaction of sulfonation process ME with H 2 SO 4, purification by methanol,
and neutralization with NaOH. The materials used for the manufacture of methyl ester is VCO and methanol with a
catalyst H 2 SO 4, while the materials used for the amidation process is the methyl ester of the VCO and diethanolamine
with NaOH catalyst. The tools used in this study is a three-neck flask, turning cooler, magnetic stirrer, heater, water bath,
stative and clamps.
The tools used in the study of equipment for making the MES and equipment for sample analysis. Tools for creating MES
consists of a suite of tools sulfonation or sulfonation apparatus (consisting of pumpkin three neck 500 ml, thermometer,
hot plate which is equipped with a magnetic stirrer, a motor stirrer, and condenser), analytical balance, watch glass,
measuring cup 100 ml, measuring cups 10 ml erlenmeyer flask, centrifuged and the pH meter.

Coconut oil (VCO) by 200 ml, is reacted with methanol 100 ml were mixed with H 2 SO 4 (4% by weight solution) in a
batch reactor (three neck flask) equipped with a water bath, the mixture is stirred with a magnetic stirrer, scale stirring at
magnetic stirrer 9 (transesterification). This reaction is carried out at a temperature of 60 ° C for 2 hours. After the
transesterification process is complete, the methyl esters were separated from glycerol by using a separating funnel pH
neutralized using NaOH, warm distilled water was added to the methyl esters that the remainder of methanol, glycerol,
and other impurities separated from the methyl ester. Lastly, Na 2 SO 4 anhydrous added to the methyl ester remaining
so that water can be absorbed. Na 2 SO 4 and then separated from the methyl ester by filtration. Then analyzed ester
numbers initially. Methyl esters are obtained and used in the process of amidation to obtain methyl ester In the amidation,
methyl esters are reacted with diethanolamine to weight ratio pereaktan diethanolamine: methyl ester varied (1: 1, 1:25:
1, 1.5: 1, 1.75: 1 and 2 : 1) and the addition of NaOH catalyst, the catalyst concentration was varied (0.25%, 0.5%, 0.75%,
1%, 2%). Reaction transactions are carried out at a temperature of 160 ° C for 3 hours, the catalyst used is sodium
hydroxide (NaOH). The reaction takes place in the three-neck flask equipped with a water bath, the mixture is stirred with
a magnetic stirring strirrer scale on the magnetic stirrer 9. formed diethanolamide analyzed residual ester numbers. Methyl
esters from palm oil-based material made by a process of transesterification. Transesterification reaction carried out at a
temperature of 55-60 ° C for 1 hour by adding a methoxide solution with a concentration of 3.5 grams per 1000 ml of
coconut oil, and oil and methanol volume ratio is 10: 1. Flow diagram of the process of making methyl esters of coconut
oil can be seen in Figure 1.
Equipment for sample analysis is tensiometer du Nuoy, analytical balance, pycnometer and refractometer. Treatment
arranged in a factorial (3 x 3) in the group randomized design with three replications Complete. The first factor is the
concentration of H 2 SO 4 with 3 levels, namely 70% (K1), 80% (K2), and 90% (K3). The second factor is the long
sulfonation with 3 levels: 30 minutes (L1), 60 minutes (L2) and 90 minutes (L3). Similarity variety tested with Bartlett
and kemenambahan data is tested by Tukey's test. Data were analyzed by analysis of variance to obtain variance estimators
error and significance test to determine whether there is a difference between treatments. The data can then be tested
further by using test ebih Significant Difference (LSD) at the 5% significance level. Phase of the study began with the
manufacture of methyl ester.

Transesterification Methanol 100 ml

VCO NaOH 3.5g
T: 60 ° C, t: 60 min

ME

The resulting methyl esters made methyl ester sulfonate. MES-making process through several stages of the sulfonation,
refining, and counteraction. Sulfonation reaction between the methyl ester with reactant H 2 SO 4 is the main stage of the
process of making an MES. Methyl ester of coconut oil is heated at a temperature of 50-55 ° C was added dengani H 2
SO 4 with a concentration of 70%, 80%, and 90% and the ratio of 1: 1.4 (Mira, 2004) is reacted in a three-neck flask with
a long berkondensor reaction of 30 minutes, 60 minutes and 90 minutes. After the purification process is carried out by
using 40% methanol and H 2 O 2 1% for the bleaching process with menggunakn a temperature of 55 ° C for 0.5 h and
then performed the final process which is a process of neutralization with NaOH 20% at 50 ° C for 0 , 5 hours. Based on
analysis of MES products produced include the stability of the emulsion (modified ASTMD 1436, 2001), using surface
tension duNouy (Zajic and Seffens, 1984), the specific gravity test and test the acid number (AOAC, 1995). MES
production process flow diagram of waste cooking oil methyl ester can be seen in Figure 2. Observations were made to
get the value of the acid number, surface tension, emulsion stability and density.
 methyl Ester

H2SO4 Sulfonation

MES

Methanol
40% Purification

Residue Sparation

MES

NaOH 20% neutralization

Pure MES

Figure 2. Flowchart of the research on the effect of H2SO4 on production of MES from coconut oil

acid number
A total of 10-20 grams of material was weighed in a 50 ml Erlenmeyer 200 ml.Ditambahkan neutral alcohol 95%, then
heated for 10 minutes in a water bath while stirring. This solution is titrated with 0.1 N KOH indicators Phenolptalein 1%
solution in alcohol, until just look pink. After that counted the number of milligrams of KOH required to neutralize the
free fatty acids in 1 gram of material (AOAC, 1995).

Surface tension
Test method for determining the surface tension of the surfactant solution is done by using a tensiometer Du-Nuoy. The
solution used is distilled water and surfactant solution as much as 10%. Equipment and containers used must be clean.
The position of the tool set so that the horizontal with water pass and put in a safe place. The solution was put into a glass
sample and placed in a holder (platform) on the tensiometer. The temperature of the liquid on the sample is measured and
recorded. The next ring of platinum immersed in the sample (circular ring immersed 3-5 mm below the surface of the
liquid). Disetpada tensiometer vernier scale zero position and guide the needle should be in line coincides with the line
on the glass. Furthermore, the platform is slowly lowered, and at the same time the right scope rotated until the proper
fluid film breaking. At this time do the reading scale. Tests carried out at least two repetitions. Then compared to the value
of surface tension between before and after the added surfactant.

emulsion stability
The stability of the emulsion is measured between the water with toluene. Toluene with water mixed with a ratio of 6: 4.
The mixture was then shaken for 5 minutes using a vortex mixer. Emulsion separation between toluene in water is
measured by the length of separation between phases. The concentration of surfactant added is 1 ml. The duration of
separation between phases before it is added after the surfactant compared with added surfactant

Specific gravity
Density determination procedures were analyzed using AOAC procedure 1995. Measurement of specific gravity
performed by using a pycnometer. Pycnometer cleaned with distilled water, then put into an oven at 105 OC for 2 hours.
Measurement is done at room temperature 20 o C. pycnometer is weighed, and materials incorporated into the pycnometer
sam-pies filled, then closed, and the rest of the material that comes out wiped with a tissue. After the pycnometer
containing material weighed.
RESULTS
Effect of H2SO4 concentration and Old Sulfonation on Surface Tension of Coconut Oil Methyl Ester Sulfonate

The test results characteristics of coconut oil methyl ester obtained values are (Table 1).
Table 1. charateristic of MES from coconut oil
\
Specsi unit Result of
measurement
Sour Number Mg KOH / g .0559
iodine
Number g / 100 g 3.1096

The test results MES characteristic coconut oil showed a decrease in surface tension values ranged from 27.55 dyne / cm
to 32.35 dyne / cm. Values are the smallest surface tension at a concentration of 80% H2SO4 and long sulfonation 60
minutes at 27, 55 dyne / cm (Figure 3). Results of analysis of variance showed that the concentration of H2SO4 significant
long while sulfonation and their interaction was not significantly different to the value of surface tension.

Figure 3. Effect of H2SO4 concentration level and sulfonation time on the surface tension of the MES.
The results showed that high concentrations of H2SO4 which would cause the value of MES increased surface tension.
Dizziness-katan is suspected surface tension due to increased reaction time and concentration led to an increase in
hydrolysis which are not as lowering the surface tension.

Hidayati (2006) states that the sulfonation reaction time will lead to increased product oxidation process and
the formation of by-products, namely disalt which reduce the effects of MES employment in lowering the
surface tension.
The research result Abdu et al. (2006) showed the best conditions of the process of formation of the MES of CPO reactions
occur in longer treatment 90 minutes from H2SO4 concentration of 80% with the abi-pared to lower the surface tension
of 37.93%. In research Son et al. (2006) obtained the best results in the production of MES in process conditions
sulfonation temperature 65oC H2SO4 concentration of 80% using the methyl ester of palm kernel yield per surface of the
voltage value by 32.80%.

Effect of H2SO4 concentration and Old Sulfonation of the Emulsion Stability Coconut Oil Methyl Ester Sulfonate

Results of testing the effect of H2SO4 concentration and long-tration sulfonation of the methyl ester sulfonate emulsion
stability of oil ranged from 57.464 to 100%. The best stability results occur in the treatment with 80% H2SO4
concentration and the duration of sulfonation 60 minutes (Figure 4). Results of analysis of variance showed that the
concentration of H2SO4 and long sulfonation as well as their interaction significantly affect the stability of the emulsion
MES.

Figure 4. Effect of H2SO4 concentration on the level and sulfonation time on emulsion stability of
MES
The results showed that the longer the time sufonasi occur, then decrease-kan emulsion stability value.
Emulsion stability is inversely proportional to the value of surface tension. Impairment will surface tension
and thus increasing the stability of the emulsion. The results showed that increasing the length of time the
reaction will increase the surface tension resulting in decreased stability of the emulsion. While the research
results Abdu et al. (2006) on the treatment of H2SO4 concentration and reaction time of 90 minutes using the
methyl ester of palm oil emulsion stability at 62.50% and the results of research Son et al. (2006) on the
treatment of H2SO4 concentration and reaction temperature 65oC-nakan menggu raw material methyl ester
from palm oil yield of 63.32% emulsion stability.

Fluid emulsion occurs when two mixed and one pitch-dispersion fluid into the other fluid. Addition of a surfactant in an
emulsion system aims thus increasing the stability of the dispersion phases by reducing the interfacial tension. The
surfactant that acts as an emulsifier to form a thin layer that will envelop emulsified particles and prevent the particles
recombine with particles like (William and Simons, 1992). The addition of the surfactant can menstabil-kan an emulsion
for me-nurunkan surfactant surface tension gradually. A decrease in surface tension will gradually runkan menu-free
energy required for the formation of emulsions become increasingly minimal. This means that the emulsion will be stable
when done penam-surfactant materials that serve to lower the free energy of formation of emulsions as much as possible.
The lower the free energy of formation of emulsions the emulsion will be more easily formed. Ter-finished emulsion
stability when the system can retain-kan droplets dispersed phase, ie when the merger between the droplets can be
prevented by the energy barrier large enough (Sutria et al., 2006).

Effect of H2SO4 concentration and Old Sulfonation against Acid Methyl Ester Sulfonate Numbers Coconut Oil

Results of testing the chemical properties of the acid number of coconut oil methyl ester obtained value of 0.3786 mg
KOH / g - 2.0617 mg KOH / g. Results of analysis of variance showed that the concentration of H2SO4 and long
sulfonation as well as their interaction significantly affect the acid number of MES.

Figure 5. Effect of H2SO4 concentration level and sulfonation time on acid number of MES
Increasing the temperature and duration of sulfonation lead to increased formation of peroxides and
hidroperok-sida. Hydroperoxide in the oxidation process will decompose to form aldehydes, ketones, acids,
alcohols, and hydrocarbons (Ketaren, 1986). The results of this decomposition menyebab-right MES acid
number increase with old palm oil sulfonation increases.
Rival research results (2004) showed the same pattern that the longer the reaction will increase the
acid number. Edison (2008) reports to the effect that the sulfonation reaction time by using Na-bisulfite as a
reactant will increase the longer the acid number where the sulfonation reaction will cause the establishmen-
tukan sulfate and side reactions such as acid - short-chain acids such as aldehydes and ketones. In further
degradation will produce establishmen-tukan sulphurous acid that causes an increase in acid number (Moreno
et al., 1988; Hu and Tuvell, 1988; Dunn, 2002).

Effect of H2SO4 concentration and Old Sulfonation against Gravity Coconut Oil Methyl Ester
Sulfonate

The results showed the value of the density ranged from 0.8675 to 0.875 g / ml. The highest specific
gravity value contained in the sample with 80% H2SO4 concentration treatment and sulfonation time 60
minutes (Figure 6). Results of analysis of variance showed that the concentration of H2SO4 and long
sulfonation as well as their interaction did not significantly affect the density of MES.

Figure 6. Effect of H2SO4 concentration level and sulfonation time on specific gravity of MES
The results showed that the higher concentration of H2SO4to 80% will increase the specific gravity
value of MES. Oil specific gravity value is often associated with weight fraction of the components contained
 therein. The higher levels of the heavy fraction of an oil then the density or higher density. Increasing
concentrations of H2SO4 over 80% and over 60 minutes long sulfonation lead to an increase in the
establishmen-tukan peroxide and hydroperoxide. Hydroperoxide in the oxidation process will decompose
memben-tuk aldehydes, ketones, acids, alcohols, and hydrocarbons (Ketaren, 1986). Kom-Ponen formed in
this oil has a lower molecular weight, so that the specific gravity of the oil produced is also low. Edison
research results (2008) reported that the sulfonation reaction time of 4.5 hours using a Na-bisulfite as a
reactant and a reaction temperature of 100 ° C using raw materials of castor oil methyl ester gives the best
results against a specific gravity value that is equal to 1.0021.
Effect of mole ratio of reactants to the reaction conversion

7
3
7
2
7
conversion

1
catalyst weight
7 NaOH 1%
0
(%)

6
9
6
0 1 1:2 1. 1.752
the mole ratio (diethanolamine:
methyl ester)

Figure 1. Effect of conversion of the reactant mole Comparison (diethanolamine: methyl ester)
Based on the chart the experimental results, it can be seen that the larger the
mole ratio of reactants then converting the resulting higher. Converting the mole
ratio of methyl ester and diethanolamine 1: 1 conversion of 63.34% and then
increased at a mole ratio of 1: 1.25 by 70.8%.
For a mole ratio of 1: 1.5 conversion amounted to 71.06%, while the mole ratio of methyl
ester
: Diethanolamine 1: 1.75 at 71.3% conversion. Highest conversion resulting in a
mole ratio methyl ester: diethanolamine%; 1: 2 which has a conversion of 71.4%.
This is because a mole ratio of reactants will affect the shift reaction results
when viewed in terms of balance. The use of mole one created excess reactants then
the reaction will be shifted to the right so diethanolamide produced also increases.
(Hilyati et al, 2004)
Judging from the mechanism of the methyl ester amidation reaction with diethanolamine with
NaOH catalyst
RCOOCH3 + NaOH → RCOONa + CH 3 OH ......................... (1)
RCOONa + NH (C2H4OH) 2 → RCON (C2H4OH) 2 + NaOH ...... ...
(2)
RCOOCH3 + NaOH + NH (C2H4OH) 2 → RCON (C2H4OH) 2 + CH 3 OH + NaOH
methyl ester catalytic diethanolamine diethanolamide methanol catalytic
The second reaction is the reaction between RCOONa with diethanolamine
(NH (C2H4OH) 2). This is the main reaction of formation diethanolamide.
Diethanolamine ionized and then react with RCOONa. The following reaction
mechanism:
RCOONa → RCO + +
NaO- NH (C2H4OH)
-
2
→ N (C2H4OH) 2 + H +
RCO + + N (C2H4OH) 2 → RCON (C2H4OH) 2 NaO- + H + → NaOH
RCOONa + NH (C2H4OH) 2 → RCON (C2H4OH) 2 + NaOH
In this second reaction can be evaluated that the use of excess diethanolamine
(excess) will affect the formation of diethanolamide. The reaction for the formation
of diethanolamide are:
RCO + + N (C2H4OH) 2 → RCON (C2H4OH) 2
In the amidation process, it is very important that you use excess
diethanolamine (excess) during the reaction process. We need at least a mole ratio
between diethanolamine: methyl ester is 1.1: 1, the higher the mole ratio the better
the running process ( "Process for the preparation of amides", US Patent, 1986).
Maugard, et al. (1998) investigated changes in the composition of the products along
the reaction and find if the mole ratio is made excess methyl esters, then most of the
products that are formed are esters. Decreased fatty acid methyl esters in accordance
with the formation of amides and esters at the start of the reaction. At the beginning
of reaction, the amide or ester has been formed, and after 3 hours of ester formed to
change into ester amide.

Influence wt% NaOH catalyst to a reaction conversion

71.
5
71
70.
5
conversion

70 mole ratio
69. methyl ester:
5 diethanolamine 1:
(%)

1.25
69
68.
5
68
66.
5 0 0. 1 1. 2 2.
5 Wt% NaOH catalyst
5 5
 Graph 2. Effect of conversion of the catalyst wt% NaOH

From the graph it can be seen that the greater the weight percent of the
catalyst will be greater conversions. From the graph shows that for 0:25% weight
percent catalyst obtained conversions by 67.1%. At 0.5% by weight of the catalyst
conversion obtained was 68.9%. Conversions increased at 0.75% by weight of the
catalyst conversion of 69.7%.
Conversion reach the maximum point on the weight of the catalyst 1%
conversion that generated 70.9% and to 2% by weight catalyst obtained conversions
by 70.8%. The variable weight percent of the catalyst between 1% to 2% conversion
decreased by about 0.1%. This decline is not a significant decrease.
NaOH catalyst is a homogeneous catalyst. That catalyst has the same phase
with the reactants. The function of the NaOH catalyst is to break the bond in methyl
ester in order to facilitate the course of the reaction and the resulting diethanolamide
also more than running without a catalytic reaction process ( "Process for the
preparation of amides", US Patent, 1986).
If the concentration of the catalyst is too low, then it's likely course of the
reaction is also increasingly sluggish due to the ability of the catalyst to break the
bond in methyl ester to react with diethanolamine is also reduced (Lukmanul Hakim,
2005).
Strongly alkaline NaOH and easily ionized. Thus providing an advantage in
the reaction process, Na + ions will bind ester into RCOONa which will react with
diethanolamine.
Diethanolamide forming reaction occurs in a second reaction in which RCO
+ ions react 2with ions N (C2H4OH) - forming diethanolamide.
RCO + + N (C2H4OH)
2 - → RCON (C2H4OH) 2
RCO + here is the result of the termination of the methyl ester bonds by NaOH
catalyst. RCOONa forming ionized into RCO + and NaO-. RCO + plays a role in
the formation of dietanoamida.
The greater the concentration of the catalyst, a methyl ester will be more
easily disconnected so RCO + will be more easily formed and diethanolamide
produced will be greater. Ion OH- ions will bind methyl form methanol, which is a
byproduct of this amidation process. NaOH will be re-formed at the end of the
amidation reaction.
CONCLUSION
 The results of the MES manufacturing of raw material methyl ester of minyakkelapa shows
that the conditions process Best sulfonation contained in the con - sentrasi H 2SO4 80% and
reaction time 60 minutes. Characteristics of the resulting best MES exhibit 2surface tension
values, ie 27.55 ne dy / cm up, emulsion stability 100%, a specific gravity of 0.875 g / ml and
the value of the acid number 1.584 mg KOH / g.The influence of the process variables mole ratio is
greater amidation mole ratio between diethanolamine: methyl ester, then converting the resulting higher. This is
consistent with the formation reaction involving ion diethanolamide N (C2H4OH) - derived from the ionization
diethanolamine. Conversions that if the terms of the efficient use of reactant then the best is in comparison
dietanilamina: methyl ester 1.25: 1. The variable weight of the catalyst, it can be concluded that the greater the
weight of the catalyst, the conversion of the resulting higher. Best Conversion namely on the weight of the catalyst
1%. This influence can be observed from reactions involving the formation diethanolamide RCO + ions derived
from the termination of the methyl ester bonds by NaOH