DESIGN OF CHEMICAL

ENZYMATIC PROCESS OF
EPOXIDE
Kelompok 6:
ARDITA RIZKY PUTRI ARCANGGI (1306402293)
CLAUDIA MAYA INDRAPUTRI (1306412180)
MERIELL JADE EUGENIA TENDEAN (130644770)
TERRY MUHAMMAD OCTARYNO (1306370770)
UNIK YULIANTINA RISQI (1306370991)

Chapter 1
Background
Basic Theory
Market Anlysis
Raw Material Analysis
Plant Location

Backgroud

The imbalance of Epoxy

supply and demand
Renewable and
sustainable resource

Basic Theory

Jatropha Oil

Contain high fatty

acid
Not an edible oil
Commonly found
inIndonesia

Fatty Acid Content of Jatropha Oil

Fatty Acid

Composition ((%-weight))

Miristat Acid

0-0,1

Palmitat Acid

14,1-15,3

Stearat Acid

3,7-9,8

Oleat Acid

34,3-45,8

Linoleat Acid

29,0-44,2

Linolenat Acid

0,03

Marlina, 2014

Oleat Acid

Oleic acidis afatty acidthat occurs naturally in jatropha oil. It is an

odorless, colorless oil, although commercial samples may be yellowish

Oleic acid is a fatty acid liquid consisting mainly can be prepared by

hydrolysis of fat or fatty oil, separated by extortion.

Oleic Acids Entalphi is 39,06 J/Kg

Linoleic Acid

Linoleic acid is produced from the plant which will serve as a precursor for
the production of essential fatty acid arachidonic acid.

Essential fatty acids such as linoleic acid is one of the main components
of foods that provide a positive impact on health is a contributor to most
energy (29% or more of the total energy needed by the body).

The Entalphy of Linoleic Acid 33,6 J/Kg

CALB lipase

Lipase B fromCandida antarcticahas been shown to be an effective catalyst

for the synthesis of esters of ethylD-glucopyranoside from fatty acids larger
than octanoic acid.It has also been found to catalyze a wide variety of
organic reactions including many different regio- and enantio-selective
syntheses.

Lipases catalyze the hydrolysis of triacylglycerols into glycerol and free fatty
acids.

Epoxidation
The characteristics of the epoxide
compound is the oxirane group
formed by oxidation of olefinic
double
bonds
or
aromatic
compounds. To prevent uncontrolled
exothermic
reaction
and
to
optimize the epoxidation, the
peroxide solution is added gradually
with stirring, while maintaining the
temperature of the reaction. When
the substrate iodine number has
been reduced to the desired point,
the reaction is stopped and the
epoxidized substrate is separated
from
the
solution.
Because
epoxidation reaction is reversible
and there is a possibility of side
reaction, epoxidation endeavored
to occur at low temperatures and a
short time [Kirk-Othmer, vol.9,
251].

Usability of Epoxide

Epoxidized oil can be used directly as a plasticizer in a polymer matrix to produce a material
suitable for polyvinyl chloride (PVC), it is very important to control the viscosity of the PVC
during the manufacturing process and as a stabilizer of PVC resin to improve flexibility,
elasticity, strength and to maintain the stability of the polymer to heat and UV radiation.
Oxirane ring high reactivity causes epoxy can also be used as a feedstock for some chemicals,
such as alcohols, glycols, alkanolamine, carbonyl compounds, olefin compounds, and polymers
such as polyesters, polyurethanes and epoxy resin (Gan, 1992).

Market Analysis

Product Comparison

Our Product (ChemoEnzymes)

Competitor (Chemical)

Supply and Demand

Table 1. 3 Epoxy Resin Demand in Tooling and

Casting by Region in US$ Million

Table 1. 5 Estimated Epoxide Demand

Per Year (US$ Milion)
Year
Region
2013

Asia
Pasific

2015

2018

2020

2022

30700000 36300000 46500000 54700000 64200000

0

Indonesia 30700000 36300000 46500000 54700000 64200000

Our Plant

9210000

10890000 13950000 16410000 19260000

Production Capasity

From the table 1.5, we

calculate the epoxide demand in
US$ Million, but if we convert it to
mass using conversion factor of
epoxy resin price as 7.24 $/kg we
can get a basis of production
capacity per year:

Production Capasity
Estimated Production Capacity (Year)

Unit

2017

2018

2019

2020

Estimated Production Capacity (Year)

2021 Unit

1394817 1514771 1645042 1786515

US$

Kg

Kg/D

Ton/D

12843622

6 US$

1773981 1926543 2092226 2272157 2467563 Kg

5217.591

5.217591

5666.30

6153.60

6682.81

5.66630

6.15360

6.68281

7257.53
8 Kg/D

7.25753
8 Ton/D

2022

2023

2024

2025

2026

1940156 2107009 2288212 2484998 2698708

0

2679773 2910234 3160514 3432318 3727498

7881.68

8559.51

7.88168

8.55951

9295.63

9.29563

10095.0

10963.2

10.0950

10.9632

Production Capasity

Based on the calculation above,

we assumed that the plant will be
operating in 2017 an operated for 10
years. So the estimated production
capacity will be average at 7257,500
tonnes/ day epoxide in order to
fulfill the demand in Indonesia.

Raw Material Analysis

Intro

Jatropha
Oil

Soybean
Oil

Castor
Oil

Jatropha Oil
Table 1. 7 Fatty Acids Composition of Jatropha Oil

Fatty Acid
Oleic Acid (C 18:1
9c)
Linoleic Acid (C
18:2 6)
Linolenic Acid (C
18:3 3)
Palmitic Acid (C
16:0)
Stearic Acid (C
18:0)

Table 1. 8 Physical Characteristics

of Jatropha Oil
Physical

Characteristic

Composition (%)

Unsaturated

35-64

Flash point

Unsaturated

19-42

Unsaturated

Value

Unit

236

Density at 20 oC

g/cm3

0.9177

2-4

Viscosity at 30 oC

Mm2/s

49.15

Saturated

12-17

Pour point

-2.5

Saturated

5-10

Iodine value

G iodine/100 g oil

96.5

Characteristic

Soybean Oil
Table 1. 9 Fatty Acids Composition of Soybean Oil
Fatty Acid
Linoleic Acid (C
18:2 6)
Oleic Acid (C
18:1 9c)
Linolenic Acid
(C 18:3 3)

Characteristic

Unsaturated

Unsaturated

Unsaturated

Table 1. 10 Physical Characteristics of

Soybean Oil

Composition

Physical

(%)

Characteristic

40-57

Flash point

20-35

Value

Unit

324

Density at 20 oC

g/cm3

0.916-0.922

Viscosity at 30 oC

cp

58.5-62.2

-12 to -16

G iodine/100 g oil

129-143

5-14
Pour point

Arachic Acid
Palmitic Acid (C

Unsaturated
Saturated

0-2
7-10

Iodine value

Castor Oil
Table 1. 11 Fatty Acid Composition of Castor Oil
Fatty Acid
Oleic Acid (C 18:1
9c)
Linoleic Acid (C
18:2 6)
Linolenic Acid (C
18:3 3)
Ricinoleic Acid (C
18:1 OH)
Palmitic Acid (C
16:0)
Stearic Acid (C

Characterist
ic

Composition (%)

Unsaturated

0-6

Unsaturated

4.3-7.3

Unsaturated

0-0.5

Unsaturated

Table 1. 12 Physical Characteristics of

Castor Oil
Physical

Value

Unit

145

Density at 20 oC

g/cm3

0.959

Viscosity at 30 oC

Cp

332

2.7

G iodine/100 g oil

84.5

Characteristic
Flash point

84-94
Pour point

Saturated

0-1.3
Iodine value

Saturated

1.0-1.2

Conclusion (Jatropha)

Plant Location

Intro

Maps

Reason
Transportation
Availability of Raw Material
Utility
Land Price and Local Minimum Wage
Added Value for Local Citizen

Chapter 2
Alternative Process
Process Selection
Process Description
Block Flow Diagram
Process Flow Diagram

Alternative Process

Reaction with pre-produced peroxyacids or generated

in situ in acidic homogeneous medium
In situ epoxidation reaction generally takes place in two steps: formation
of peracetic acid and reaction of peracetic acid with the unsaturation.
Peroxyacids can be produced in situ using hydrogen peroxide. e. The process
usually requires employing an acidic catalyst and, even though traditionally
mineral acid have been used due to their lower cost, their utilization
prevents the achievement of high yields, because of the opening of the
oxirane ring during the course of the main reaction. Some studies also offer
an alternative process which use performic acid (PFA) instead of peracetic
acid (PAA), as no catalyst is needed to generate the former in situ and,
therefore, the parallel degradation reactions could be in principle
minimized. The parameter that could determine epoxide yield in this method
is temperature, degree of mixing, flow rate of hydrogen peroxide and
concentration of each compound during reaction.

Epoxidation with peroxyacids in the presence of cationic ion-exchange

resins (Amberlite IR-122, Amberlite IR 120H, KU-2x8) 33-45

In general, the side reactions that have been proposed consist of 2 parts :
the epoxy ring opening involving the formation of hydroxyl acetate or hydroxyl
groups and formation of peracids and epoxy groups. Acetic acidIR- 122
combination was found to be most effective for higher epoxide yield at shorter
reaction time.

Epoxidation over phosphotungstate heteropolyacid catalysts and in the

presence of phase-transfer catalysts (H+/WO4 -2/PO4 -3/Q+X-), QX-onium
salt

A peroxophosphotungstate (POW) based catalyst was successfully

developed by Venturello and DAloisio to perform epoxidation reaction in
a biphasic media containing an organic solvent. Because many side
reactions occur (hydrogen transfer, double bond shift, cistrans
isomerization, branching), a complex product mixture could be
obtained. During the epoxidation of FAMEs, oligomerization by-products
can be formed; the main products are dimers, trimers, and isostearic
acid. Residual tungstic acid coming from the POW catalyst could also
lead to another by-product formation, the 9,10-dihydroxystearic methyl
ester as previously described by Santacesaria et al. To keep this yield
while decreasing the amount of the oxidant (hydrogen peroxide) to an
equimolar ratio MO/H2O2, the reaction was performed with a gas ow.

Epoxidation over titanium-silicalite catalysts (Ti(IV)SiO2, Ti-MCM-41, and amorphous Ti/SiO2) 39,44-47
Titanium-grafted mesoporous silica materials showed to
be suitable catalysts for the epoxidation of unsaturated FAME
mixtures in a reaction medium that is completely free from
organic acids. They are also versatile, as they have been
used over a series of four FAME mixtures obtained from
different
vegetable
sources
exhibiting
interesting
performances. In particular, very high conversion and
selectivity values were obtained with TiMCM-41 in the
epoxidation of castor oil or soya-bean oil FAME mixtures.

Epoxidation in the presence of transition metal

complexes as catalysts (CH3ReO3 or CH3ReO2/Nb)
Metalloporphyrins have been widely investigated owing to
their relevance to biological oxidation reactions. In
particular, manganese and iron porphyrins have shown great
activity as olefin epoxidation catalysts, utilizing a variety of
oxygen sources such as iodosylbenzene, alkyl hydroperoxide,
aqueous sodium hypochlorite (NaOCl), persulfate, and O2
with a reducing cofactor. Use of inexpensive NaOCl is
especially attractive. Chiral salen-based manganese
complexes have given remarkable results in the asymmetric
epoxidation of olefins.

Epoxidation in the presence of aluminium

trioxide, obtained by a sol-gel method
Alumina synthesized by the solgel method is shown to be
an inexpensive and efficient catalyst in the epoxidation of
methyl oleate and soybean oil methyl esters with aqueous
hydrogen peroxide as oxidant. By using this method, the
aluminas show a good catalytic activity and excellent
selectivity towards the epoxides. The solgel alumina was
more efficient and when using aqueous hydrogen peroxide
could be recycled several times.

Chemoenzymatic epoxidation 28,51-55

Chemoenzymatic epoxidation is performed in the
presence of Candida antartica lipase B (CALB) which is
immobilized onto an acrylic resin (Novozym 435) or onto
silica (CALB-Silica) and another lipases as catalysts. Lipase
can catalyse the hydrolysis of triglycerides, alcoholysis,
acidolysis, esterification, interesterification and aminolysis.
Saturated or unsaturated fatty acids are transformed into
peroxyacids in the presence of hydrogen peroxide and lipase.

Process Selection

Intro

Criteria
Operating Condition Suitability
Yield of Process
Time of Enzymatic Reaction
Installed and Operations Cost
Field Experience
Manufacturing
Waste Treatment

Scoring Table
No

Criteria
Operating Condition
Sustainability

Weight

Rating

Score

Rating

Score

Rating

Score

Rating

Score

10

40

30

30

10

Yield of Process

25

75

100

75

75

Time of reaction

20

80

60

60

20

15

45

30

30

30

Installed and Operation

Cost

Field Experience

10

30

30

20

20

Manufacturing

15

15

10

10

Waste Treatment

10

10

15

10

Total

100

295

275

240

175

Rank

10

Scoring Table
No

Criteria

Operating Condition
Sustainability

Weight

Rating

Score

Rating

Score

Rating

Score

10

40

20

40

Yield of Process

25

50

100

100

Time of Reaction

20

40

20

80

15

30

45

30

Installed and Operation

Cost

Field Experience

10

20

30

20

Manufacturing

15

15

15

Waste Treatment

10

10

15

Total

100

205

240

300

Rank

10

Process Description

Process Unit
Storage Tank
Reactor
Filtration
Washing
Evaporator
Cooling
Packaging

Block Flow Diagram

Process Flow Diagram

Chapter 3
Mass Balance
Energy Balance
Mass and Energy Efficiency
Simulation of Process

Mass Balance

Overall Mass Balance

Component

Input (kg)

Output (kg)

Epoxidized Linoleic Acid

27,41585822

Epoxidized Oleic Acid

37,34807318

Hydrogen Peroxide

32,601

25,19895923

Linoleic Acid

28,818

2,881797162

Linolenic Acid

1,5815

1,581474052

Lipase

7,35

7,35

NaHCO3

1430847,2

1430847,208

Oleic Acid

39,2733

3,92732723

Palmitic Acid

12,1071

12,10706247

Stearic Acid

6,0799

6,079889134

Water

27187167,72

27187171,64

Component Mass Balance (Reactor)

P-1 / R-101
Compound

Flowrate (kg/batch)
In

Out

Linoleic Acid

28.81797176

2.882

Linolenic acid

1.58147406

1.58147406

Oleic acid

39.27327249

3.927

Palmitic acid

12.10706253

12.10706253

Stearic acid

6.079889164

6.079889164

H2O2
Lipase

32.60101
7.35

25.19896
7.35

Epoxidized Linoleic Acid

27.41586

Epoxidized Oleic Acid

37.34807

Component Mass Balance (Microfiltration)

P-2 / MF-101
Compound
Linoleic Acid

Flowrate (kg/batch)
In

Out
2.882

2.882

1.58147406

1.58147406

3.927

3.927

Palmitic acid

12.10706253

12.10706253

Stearic acid

6.079889164

6.079889164

25.19896

25.19896

7.35

7.35

Epoxidized Linoleic Acid

27.41586

27.41586

Epoxidized Oleic Acid

37.34807

37.34807

Linolenic acid
Oleic acid

H2O2
Lipase

Component Mass Balance (Washing 1)

P-3 / WSH-101
Compound

Flowrate (kg/batch)

Sodium Bicarbonate

In
1,430,847.208

Out
1,430,847.208

Linoleic Acid

2.882

2.882

Linolenic acid

1.581

1.581

Oleic acid

3.927

3.927

Palmitic acid

12.107

12.107

Stearic acid

6.080

6.080

H2O2

25.199

25.199

Lipase

7.350

7.350

Epoxidized Linoleic Acid

27.416

27.416

Epoxidized Oleic Acid

37.348

37.348

Water

27,186,176.939

27,186,176.939

Component Mass Balance (Washing 2)

P-4 / WSH-102
Compound

Flowrate (kg/batch)
In

Out

Linoleic Acid

2.882

2.882

Linolenic acid

1.581

1.581

Oleic acid

3.927

3.927

Palmitic acid

12.107

12.107

Stearic acid

6.080

6.080

H2O2

25.199

25.199

Lipase

7.350

7.350

Epoxidized Linoleic Acid

27.416

27.416

Epoxidized Oleic Acid

37.348

37.348

Water

27,186,176.939

27,186,176.939

Component Mass Balance (Evaporator)

P-5 / V-101

Flowrate (kg/batch)
Compound
In

Out

Epoxidized Linoleic Acid

22.690

22.690

Epoxidized Oleic Acid

30.910

30.910

Water

6.620

6.620

TOTAL

60.220

60.220

Component Mass Balance (Cooling)

P-6 / HX-101

Flowrate (kg/batch)
Compound
In

Out

Epoxidized Linoleic Acid

22.690

22.690

Epoxidized Oleic Acid

30.910

30.910

Water

6.620

6.620

TOTAL

60.220

60.220

Energy Balance

Overall Energy Balance

Unit Process

Input (kJ/batch)

Output (kJ/batch)

Reactor

8977.21

Evaporation Flash

8195.24

Cooling

7903.32

Total

8195.24

16880.53

Component Energy Balance (Reactor)

Content

Qin

Qout

Linoleic acid

Oleic acid
0
Hydrogen peroxide

Lipase

8977.21

Component Energy Balance

Evaporator

Content

Epoxidize
d oil

Cooler

Qin

8195.24

Qout

Content

Epoxidized
Oil

Qin

Q out

7903.32

Mass and Energy Efficiency

Energy Efficiency

The calculation of total system

efficiency is a simple and useful method
that evaluates what is produced (i.e.,
power and thermal output) compared to
what is consumed (i.e., fuel).

Mass Efficiency

So, the overall energy efficiency is

stillonly 48,55%. However, for the mass
efficiency, we calculate based on the main
raw materials mass and the main product
mass. The equation is similar to the energy
efficiency.

Simulation of Process

Chapter 4

Conclusion

Conclusion
Epoxides

demand in Indonesia is still growing

however the growth of the supply rate cannot
support it. Therefore, the solution for this problem
is by building a new epoxide plant.

The

epoxide plant that we will built is a chemoenzymatic epoxide production, because we

consider not only on fulfilling the demand but also
inventing an innovative and sustainable epoxide
plant. The estimated demand of epoxide that we
will fulfil is 7,258 tonnes/day

For

the raw material, we will use Jatropha oil

combined with hydrogen peroxide. The reaction is
supported with lipase enzyme.

Conclusion
For

the location, we choose to build the

plant in Pasuruan Industrial Estate Rungkut
Area, East of Java.

The

process is include material reaction with

enzyme as the catalyst, filtration, washing,
distillation and cooling.

The

yield of epoxidation reaction for both

linoleic acid and oleic acid are 90%.

Plant

Efficiency is 48,55% based on energy

balance and 73,72% based on mass balance.

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Thank You