HYDROLYSIS ME80 LAB TRIAL

BACKGROUND AND OBJECTIVE

Esterification process of short chain fatty acid (C8 and C10) to methyl ester (ME80) has been applied
in Ecogreen. However, it is known that the price of fatty acid 80 is higher than ME80 and Ecogreen has
a high demand, but also, low stock on the fatty acid. In order to meet the demand, fatty acid 80 is going
to be produced by hydrolysis of ME80 to fatty acid 80. Hydrolysis reaction follows the equation below:

R-COOCH3 + H2O ↔ R-COOH + CH3OH

Previous trials have proven that the hydrolysis reaction can be done by using resin-based catalyst at a
relatively low temperature and pressure. This trial aims to determine the best resin-based catalysts for
further study.

TRIAL PROCEDURE
The trial is done by using ME80 from EOB1 as feedstock. Compared resins were supplied from
PUROLITE, namely CT 275, CT 169, and CT 482. Feed and resin were mixed together and heated to
128 deg C before demin water was added slowly until the mixture temperature remained constant at
125 deg C. Addition of water was stopped until the water reached mol ratio 5:1 to methyl ester and the
trial was ended. The configuration of the trial equipment can be seen in Picture 1.

Picture 1. Hydrolysis trial equipment configuration

In the trials, there was a two-phase distillate which consists of methanol-water lower phase and fatty
acid-methyl ester upper phase. As stated in the previous trial, returning the fatty acid-methyl ester
carryover can increase the product yield. This was achieved by letting the distillate upper phase
overflowed back to the flask before the lower phase was drained.

Picture 2. Two-phase distillate

The final product was analyzed for acid value (AV), saponification value (SV), and GC to measure the
best resin performance.

TRIAL RESULTS
There was total of nine batches of trial with each resin had three batches. The product of each batch can
be seen in Picture 4, Picture 5, and Picture 6.

Batch #1
The first batch used CT 275 resin for the catalyst. 400 g of ME80 was mixed with 80 g of resin (20% of
ME80's mass) and then heated to 128 deg C. Nitrogen was flushed to the mixture, in order to help
water and methanol vapor getting out of the mixture, with maximum flow 100 to lessen the carryover
of methyl ester and fatty acid. However, at 106 deg C, there was a lot of froth from the mixture and
bumping nearly occurred. The heating was stopped to let the froth disappeared before the trial restarted.
Heating continued from 103 deg C but the froth continued to build up, thus the heating was stopped
again. It is believed that there was water already in the mixture because the resin that was used is a wet
resin, therefore the froth was so much. The water was quite a lot because it needed to be drained before
demin water was added. The trial was restarted again at 100 deg C and heated to 128 deg C gradually
with 5 deg C step and it was held 10-30 minutes in each step. After the mixture temperature reached
128 deg C, demin water was added slowly until the temperature remained constant in 125 deg C. Trial
was ended when 210 mL of water was added (mol ratio 5:1 to methyl ester). The product had AV and
SV of 262 and 348 respectively.
 Picture 3. Froth built up in the flask and almost reached the necks

Batch #2
The second batch was done with similar condition with the previous batch and the resin was reused.
Heating was done to 128 deg C and this time the froth was lesser than the previous batch because some
of the water had been removed in the previous batch, hence there was no need for stopping the heating.
Demin water was added slowly after the mixture temperature reached 128 deg C. Trial was ended after
210 mL of water was added to the mixture. The product had AV and SV of 242 and 363 respectively.

Batch #3
The third batch used the resin again (reused two times) with the same operating condition as before.
The froth was lesser than the previous batch so there was no problem with the heating and demin water
was added like before. The product had AV and SV of 246 and 348 respectively.

Batch #4
The fourth batch used fresh CT 169 resin. The water content of the resin was lower than the first resin
(CT 275) because there was less froth than in the first batch and the first drain of water occurred 9
minutes after demin water was added. The product had AV and SV of 258 and 344 respectively.

Batch #5
The fifth batch reused the CT 169 resin from before. There was no problem with froth and trial can be
run as planned. The product had AV and SV of 253 and 368 respectively.

Batch #6
The sixth batch used the same resin from the previous batch and it ran normally. The product had AV
and SV of 245 and 349 respectively.

Batch #7
The seventh batch used fresh CT 482 resin. This time the froth is not much but the first drain occurred
5 minutes after the addition of demin water, meaning that the water content in this resin was higher
than the second resin (CT 169) but lower than the first resin (CT 275). There was no problem in the
run. The product had AV and SV of 263 and 348 respectively.

Batch #8
The eighth batch reused the resin from before with the same operating condition with previous batches.
The product had AV and SV of 260 and 366 respectively.

Batch #9
The ninth batch reused CT 482 resin the second time. The product had AV and SV of 264 and 348
respectively.

Picture 4. (From left to right) Product of Batch #1, Batch #2, and Batch #3
 Picture 5. (From left to right) Product of Batch #4, Batch #5, and Batch #6

Picture 6. (From left to right) Product of Batch #7, Batch #8, and Batch#9

From previous trials, the performance of resin can be determined by the degree of hydrolysis, which
follows the equation below:

The result summary and the product compositions can be seen in Table 1 and Table 2 below.
 Table 1. Result summary

Table 2. Product compositions

From Table 1, it can be seen that the highest degree of hydrolysis was achieved in Batch #9. Similar
results were achieved in Batch #1, Batch #4, and Batch #7. If the fresh resins were compared, the best
resin would be the third resin (CT 482). The decrease of the degree of hydrolysis when resins were
reused could be caused by removal of resin's water content from the previous batches. In general, the
best result of degree of hydrolysis was achieved when CT 482 resin was used.

From Table 2, the highest desired product (fatty acid C8 and C10) was achieved in Batch #1, with the
total AC80 composition is 76.13%. However, the total of AC80 continued to decrease with further
reuse of the resin. The lowest product composition reduce gradient was resulted from the use of CT 482
resin, with the total AC80 composition in Batch #7, Batch #8, and Batch #9 are 70.71%, 70.20%, and
70.51% respectively. This means CT 482 resin can be reused in hydrolysis reaction more than the other
two resins without major performance decrease.

Froth was formed because of water vapor trapped in the bottom of the mixture trying to move upward.
If the froth builds up so much, it can cause bumping. The first resin formed the most froth when trials
were done, followed by the second and the third resin. Looking from the conditions and the results, it
can be concluded that the best resin in this trial is the CT 482 resin.

CONCLUSION AND SUGGESTION

1. Hydrolysis of methyl ester to fatty acid can be achieved by using resin-based catalyst. In this
trial, the best resin for the catalyst is PUROLITE CT 482 resin.
2. In this trial, conversion of methyl ester to fatty acid was not yet reached 100%. The next trial
can be done until the conversion reached 100%.
3. Ways to separate the fatty acid products can be studied in further.