OBJECTIVES To produce 60,000 MTPA of methyl esters from RBD palm kernel oil. To achieve the production of methyl esters by using homogeneous base-catalyzed transesterification method with sodium methoxide (NaOCH3) as catalyst.

1. PRODUCTION OF 60, 000 MTPA OF
OLEOCHEMICAL METHYL ESTER
FROM RBD PALM KERNEL OIL

2. WAN ADEEBAH WAN MAHMOOD
SITI IRHITH BUSHRAH NOOR MAHADI
SAJJAD KHUDHUR ABBAS
AIMAN MOHAMMED BELAL SIDAN
PRESENTED BY:

3. 1. To produce 60,000 MTPA of methyl esters
from RBD palm kernel oil.
2. To achieve the production of methyl esters
by using homogeneous base-catalyzed
transesterification method with sodium
methoxide (NaOCH3) as catalyst.
a) OBJECTIVES

4. What is methyl ester?
Methyl Ester
4
Fatty Acid Methyl Ester
(FAME)
Biodiesel
One of the Basic Oleochemicals
(Others: Fatty acids & Fatty alcohols)
Derived from
natural Oils & Fats
Plant Oils
Animal Fats
Waste Oils
Normally produced by:
• Transesterification of triglyceride (oil)
• Esterification of free fatty acid (FFA)
b) PROCESS BACKGROUND

5. Transesterification Process
5
Methoxide
A Triglyceride (Oil)Glycerol
A Methyl Ester
𝐓𝐆 + 𝟑 𝐌𝐞𝐎𝐇 ↔ 𝟑 𝐅𝐀𝐌𝐄 + 𝐆𝐋

6. Figure 1:Geographic
breakdown of global
oleochemicals market
(Weller, 2013)
Table 1:ASEAN oleochemical producers (ADI Finechem)
2013)
c) MARKET SURVEY
- supply & demand (global)

7. Novelty of Proposed
Design
D) PROCESS FLOW DIAGRAM

8. Reference Design
Source: (Costello, 2011)

9. P-101
P-102
P-103
P-104
M-101
E-101 E-102
E-103
E-104
E-105
E-106
E-112
E-107
E-110
E-111
C-101
R-101
E-114
E-113
E-115
C-105
P-112
P-109
P-110
P-113
P-111
P-107
P-105
C-104
C-103
T-101
(CE-810)
MeOH
NaOCH3
TG
Water
T-102
(CE-1214)
T-103
(CE-1618)
M-102
R-102 R-103
C-102
C-106
M-103
V-101
P-106
E-109
E-108
P-108
T-104
(Glycerol)
To waste water
treatment
To waste water
treatment
1 atm
25 °C
1 atm
25 °C
1 atm
25 °C
1 atm
25 °C
1.2 atm
25 °C
1.2 atm
25 °C
1.2 atm
25 °C
1.2 atm
25 °C
1 atm
42 °C
1 atm
32 °C
1 atm
60 °C
1 atm
120 °C
1 atm
60 °C
1 atm
120 °C
1 atm
160 °C
1 atm
160 °C
1 atm
120 °C
1 atm
160 °C
1 atm
129 °C
1 atm
60 °C
1.2 atm
60 °C
1.2 atm
160 °C
1 atm
50 °C
1 atm
50 °C
1.2 atm
50 °C
1 atm
130 °C
1 atm
130 °C
1 atm
130 °C
1 atm
25 °C
1 atm
25 °C
1 atm
25 °C
1 atm
25 °C
1 atm
176 °C
0.07 atm
176 °C
1 atm
158 °C0.25 atm
158 °C
0.25 atm
226 °C
0.45 atm
226 °C
0.25 atm
198 °C
0.07 atm
237 °C
1 atm
237 °C
1 atm
25 °C
0.5 atm
185 °C
0.7 atm
236 °C0.5 atm
236 °C
0.5 atm
25 °C
0.5 atm
59 °C
1 atm
91 °C
1.2 atm
50 °C 1 atm
50 °C
R-101
1st
Transesterification
CSTR
R-102
2nd
Transesterification
CSTR
R-103
3rd
Transesterification
CSTR
C-101
1st MeOH
Evaporator
C-102
2nd MeOH
Evaporator
V-101
ME Washing
Decanter
C-103
ME Purification
Column
C-104
CE-810 Vacuum
Column
C-105
CE-1214 and
CE-1618
Splitter
C-106
GL Purification
Column
T-101
CE-810
Storage Tank
T-102
CE-1214
Storage Tank
T-103
CE-1618
Storage Tank
T-104
GL Storage
Tank
Process Flow Diagram
9
Raw material feed
Middle/Heavy-cut Separator
Transesterification CSTRs-in-series
Glycerol Purifier
Methyl ester Purifier
Storage Tanks
Light-cut Purifier
Flash tank to recycle back
the methanol
Decanter/Wash column

10. Economic Potential 1
𝐸𝑃1 = 𝑅𝑒𝑣𝑒𝑛𝑢𝑒 − 𝑅𝑎𝑤 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝐶𝑜𝑠𝑡
= 0.0813 × 60,000,000
𝑘𝑔 𝐶𝐸810
𝑦𝑟
×
𝑅𝑀3.46
𝑘𝑔
+ 0.6416 × 60,000,000
𝑘𝑔 𝐶𝐸1214
𝑦𝑟
×
𝑅𝑀4.65
𝑘𝑔
+ 0.2771 × 60,000,000
𝑘𝑔 𝐶𝐸1618
𝑦𝑟
×
𝑅𝑀3.84
𝑘𝑔
+ 8,007,371.7200
𝑘𝑔 𝐺𝐿
𝑦𝑟
×
𝑅𝑀1.46
𝑘𝑔
− 59,542,181.6900
𝑘𝑔 𝑅𝐵𝐷𝑃𝐾𝑂
𝑦𝑟
×
𝑅𝑀2.95
𝑘𝑔
+ 8,357,937.3600
𝑘𝑔 𝑀𝑒𝑂𝐻
𝑦𝑟
×
𝑅𝑀1.08
𝑘𝑔
= 𝑅𝑀 86,743,504.21/𝑦𝑟
𝑃𝑟𝑜𝑓𝑖𝑡 𝑀𝑎𝑟𝑔𝑖𝑛 % =
𝐸𝑃1
𝑅𝑎𝑤 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝐶𝑜𝑠𝑡𝑠
× 100 %
=
𝑅𝑀 86,743,504.21/𝑦𝑟
𝑅𝑀 184,676,008.33/𝑦𝑟
× 100 %
= 46.97 %
 60,000 MTPA production
capacity of methyl ester
products is feasible (EP1>0) at
the continuous mode of
operation.
10

11. E) Process Selection

12. POSSIBLE PROCESSES FOR ME
SYNTHESIS
• Micro-emulsion
• Pyrolysis (thermal cracking)
• Transesterification

13. 1. Micro-emulsion
Process of reducing the viscosity of vegetable oil by the means of
solvent (methanol, ethanol as well as normal butanol).
Advantages:
• Clear
• Isotropic
• thermodynamically stable mixtures of a polar phase .
Disadvantages:
• Sticky
• Heavy carbon deposits when used as fuel
• Creates problems with the engine performance

14. 2. Pyrolysis
Pyrolysis is a conversion process by the means of heating with absence
of air resulting in ME
Advantages:
• Can use any type of raw material
• Gases oils/solvents and carbonized materials are produced
• Good viscosity
Disadvantages:
• Sticky
• When ME used as:
o fuel Fuel injection system experience damage
o High amount of carbon deposition
o Inacceptable combustion values in the engine

15. 3. Transesterification
Alcoholysis of triglycerides resulting in a mixture of
mono-alkyl esters and glycerol.
Advantages:
• Better separation of byproduct
• Achieve better viscosity product
Disadvantages:
• High methanol/oil ratio

16. Transesterification
Transesterification reaction
Chemical reaction of consumption of intermediate products

17. Transesterification Catalysis
• Base catalyst
• Acid catalyst
• Enzyme catalyst

18. Transesterification Catalysis
Alternative 1:
Base catalyst
PKO +methanol  methyl ester +glycerol
Advantages:
1. High reaction rate and high catalyst activity
2. Low methanol/oil ratio
3. Mild operation condition
Disadvantages:
1. Formation of soap
2. Limited free fatty acid,FFA content for oil
3. Inhibited by water

19. Alternative 2:
Acid catalyst
PKO +methanol  methyl ester +glycerol
Advantages:
1. Unlimited free fatty acid, FFA content for oil
2. Product can be easily separated
3. High conversion
Disadvantages:
1. Long reaction time
2. High methanol/ oil ratio
3. Acid has a stronger affinity for water

20. Alternative 3:
Lipase Enzyme
PKO + methanol  methyl ester +glycerol
Advantages:
1.More stable
2.Lipase can be regenerated and reused
Disadvantages:
1.Still under development
2.Very high cost of lipase enzyme
3.Unfavorable reaction yield and reaction time

21. (Cost) (Final decision)
(Alternative 1: Base catalyzed) Cheap Selected
(Alternative 2: Acid catalyzed) Medium Eliminated
(Alternative 3: Lipase enzyme) Expansive N/A

22. Catalyst & Alcohol Selection
1. Alcohol selection
• Methanol is selected instead of ethanol and
butanol.
• Shortest chain alcohol
• Low cost
2. Catalyst selection
• Sodium methoxide is selected instead of other
catalysts.
• Higher yield obtained
• Lower soap formation

23. Heterogeneous OR Homogenous
Catalytic Process
• Homogenous catalytic process is chosen
• Heterogeneous catalytic reaction is not been
explored and developed
• Less sources regarding heterogeneous catalytic
reaction
• Unexpected reaction rate and undesired side
reaction may encounter

24. • Higher ability to convert intermediate
products.
• Higher ability for shifting the reaction toward
desired product.
• Shorter reaction time.
• Lower reaction temperature.
• Reduced alcohol and catalyst used.
• Higher yield obtained.
Why Three Reactors

25. LEVEL 2 DECISION : INPUT-OUTPUT
STRUCTURE OF PROCESS FLOW SHEET
Species Boiling Point (oC) Destination Code
RBD Palm Kernel Oil
Not pertinent (Very
high)
Recycle (if X < 95%)
Methanol 64.7 Recycle
Sodium Methoxide (30wt% in
methanol)
a 93.0 Waste
Methyl Ester
CE-810
C8:0 b 193.0
Primary product
C10:
0
b 224.0
CE-1214
C12:
0
b 262.0
C14:
0
b 295.0
C16:
0
b 338.0
C18:
0
b 352.0
Table 1-1: Destination code for transesterification process
Source: a (Leonid Chemicals, n.d.); b (Graboski and McCormick, 1998)

26. Reactions
The main reaction:
The side reaction:

27. ECONOMIC POTENTIAL 2
𝐸𝑃2
𝑅𝑀
𝑦𝑟
= 𝑀𝑒𝑡ℎ𝑦𝑙 𝐸𝑠𝑡𝑒𝑟 𝑣𝑎𝑙𝑢𝑒 + 𝐺𝑙𝑦𝑐𝑒𝑟𝑜𝑙 𝑣𝑎𝑙𝑢𝑒 − 𝑅𝐵𝐷 𝑃𝐾𝑂 𝐶𝑜𝑠𝑡 − 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝐶𝑜𝑠𝑡
= 0.0813 × 60,000,000
𝑘𝑔 𝐶𝐸810
𝑦𝑟
×
𝑅𝑀3.46
𝑘𝑔
+ 0.6416 × 60,000,000
𝑘𝑔 𝐶𝐸1214
𝑦𝑟
×
𝑅𝑀4.65
𝑘𝑔
+ 0.2771 × 60,000,000
𝑘𝑔 𝐶𝐸1618
𝑦𝑟
×
𝑅𝑀3.84
𝑘𝑔
+ 8,007,371.7200
𝑘𝑔 𝐺𝐿
𝑦𝑟
×
𝑅𝑀1.46
𝑘𝑔
− 𝑚 𝑇𝐺,𝐹 ×
𝑅𝑀2.95
𝑘𝑔
− 𝑚 𝑀𝑒𝑂𝐻,𝐹 ×
𝑅𝑀1.08
𝑘𝑔
where
𝑚 𝑇𝐺,𝐹
𝑘𝑔 𝑅𝐵𝐷𝑃𝐾𝑂
𝑦𝑟
= 𝐹𝑇𝐺,𝐹
𝑘𝑔𝑚𝑜𝑙 𝑅𝐵𝐷𝑃𝐾𝑂
𝑦𝑟
×
684.8022 𝑘𝑔
𝑘𝑔𝑚𝑜𝑙
=
𝑃 𝑀𝐸
𝑌
𝑘𝑔𝑚𝑜𝑙 𝑅𝐵𝐷𝑃𝐾𝑂
𝑦𝑟
×
684.8022 𝑘𝑔
𝑘𝑔𝑚𝑜𝑙
𝑚 𝑀𝑒𝑂𝐻 ,𝐹
𝑘𝑔 𝑀𝑒𝑂𝐻
𝑦𝑟
= 𝐹 𝑀𝑒𝑂𝐻,𝐹
𝑘𝑔𝑚𝑜𝑙 𝑀𝑒𝑂𝐻
𝑦𝑟
×
32.0419 𝑘𝑔
𝑘𝑔𝑚𝑜𝑙
=
3𝑃 𝑀𝐸
𝑌
𝑘𝑔𝑚𝑜𝑙 𝑀𝑒𝑂𝐻
𝑦𝑟
×
32.0419 𝑘𝑔
𝑘𝑔𝑚𝑜𝑙
𝑃 𝑀𝐸 = 260,843.3675 𝑘𝑔𝑚𝑜𝑙/𝑦𝑟

28. LEVEL 3 DECISION- RECYCLE STRUCTURE
OF THE FLOWSHEET
Block Flow Fiagram of Recycle Structure
Figure 1-2: Block Flow Diagram of Level 3 Decision

29. Reactor
Kinetic data Values
k 0.013 𝑚𝑖𝑛−1
or 0.780 ℎ𝑟−1
Activation energy, Ea 254.5 cal/mol or 1064.81 J/mol
Temperature 60°C
Pressure 1 atm
MeOH:TG molar ratio 6:1
NaOCH3 by weight of TG 1 wt%
Table 1-4: Kinetic data (Rashid et al., 2014)
Species, 𝑖
Inlet,𝐹𝑖,0 𝑀𝑊𝑖 Density 𝜌𝑖 (60°C) 𝑣𝑖
Source for density
kgmol/hr kg/kgmol kg/m3 m3/hr
TG 10.8685 684.8022 891.2 8.3514 (Timms, 1985)
MeOH 59.7911 32.0419 755.5 2.5358
(Thermal-Fluids
Central, 2010)
NaOCH3
30%
solution
6.7976 54.0240 935.0 0.3928
See Appendix A.1.1
(BASF, 2007)
Total 77.46 𝒗 𝟎 = 11.2800
Table 1-5: Feed information

30. For isothermal reaction,
𝐹𝑇𝐺,0
−𝑟𝑇𝐺
=
𝑣0
𝑘 1 − 𝑋
where
𝑣0 = 11.28 𝑚3
/ℎ𝑟
𝑘 60°C = 0.780 ℎ𝑟−1
For adiabatic reaction,
𝐹𝑇𝐺,0
−𝑟𝑇𝐺
=
𝑣0
𝑘 1 − 𝑋
where
𝑘 ℎ𝑟−1
= 0.780 exp
1064.81
8.314
1
333.15
−
1
𝑇
𝑇 𝐾𝑒𝑙𝑣𝑖𝑛 = −6.3376𝑋 + 333.16
0
200
400
600
800
1000
1200
1400
1600
0.0 0.2 0.4 0.6 0.8 1.0
FTG,0/(-rTG)(m3)
Conversion, X
Levenspiel Plot (Isothermal)
Figure 1-3: Levenspiel Plot (Isothermal: constant k)
0
200
400
600
800
1000
1200
1400
1600
0.0 0.2 0.4 0.6 0.8 1.0
FTG,0/(-rTG)(m3)
Conversion, X
Levenspiel Plot (Adiabatic)
Figure 1-4: Levenspiel Plot (Adiabatic: k changes with temperature)

31. 31
 99% conversion
 RM73 million/yr
Highest Profit : RM75.5 million/yr
Conversion : 82%
Optimum Profit : RM73 mil/yr
Conversion : 99%
Small Gap: RM2.5 mil/yr
ECONOMIC POTENTIAL 3

32. P-101
P-102
P-103
P-104
M-101
E-101 E-102
E-103
E-104
E-105
E-106
E-112
E-107
E-110
E-111
C-101
R-101
E-114
E-113
E-115
C-105
P-112
P-109
P-110
P-113
P-111
P-107
P-105
C-104
C-103
T-101
(CE-810)
MeOH
NaOCH3
TG
Water
T-102
(CE-1214)
T-103
(CE-1618)
M-102
R-102 R-103
C-102
C-106
M-103
V-101
P-106
E-109
E-108
P-108
T-104
(Glycerol)
To waste water
treatment
To waste water
treatment
1 atm
25 °C
1 atm
25 °C
1 atm
25 °C
1 atm
25 °C
1.2 atm
25 °C
1.2 atm
25 °C
1.2 atm
25 °C
1.2 atm
25 °C
1 atm
42 °C
1 atm
32 °C
1 atm
60 °C
1 atm
120 °C
1 atm
60 °C
1 atm
120 °C
1 atm
160 °C
1 atm
160 °C
1 atm
120 °C
1 atm
160 °C
1 atm
129 °C
1 atm
60 °C
1.2 atm
60 °C
1.2 atm
160 °C
1 atm
50 °C
1 atm
50 °C
1.2 atm
50 °C
1 atm
130 °C
1 atm
130 °C
1 atm
130 °C
1 atm
25 °C
1 atm
25 °C
1 atm
25 °C
1 atm
25 °C
1 atm
176 °C
0.07 atm
176 °C
1 atm
158 °C0.25 atm
158 °C
0.25 atm
226 °C
0.45 atm
226 °C
0.25 atm
198 °C
0.07 atm
237 °C
1 atm
237 °C
1 atm
25 °C
0.5 atm
185 °C
0.7 atm
236 °C0.5 atm
236 °C
0.5 atm
25 °C
0.5 atm
59 °C
1 atm
91 °C
1.2 atm
50 °C 1 atm
50 °C
R-101
1st
Transesterification
CSTR
R-102
2nd
Transesterification
CSTR
R-103
3rd
Transesterification
CSTR
C-101
1st MeOH
Evaporator
C-102
2nd MeOH
Evaporator
V-101
ME Washing
Decanter
C-103
ME Purification
Column
C-104
CE-810 Vacuum
Column
C-105
CE-1214 and
CE-1618
Splitter
C-106
GL Purification
Column
T-101
CE-810
Storage Tank
T-102
CE-1214
Storage Tank
T-103
CE-1618
Storage Tank
T-104
GL Storage
Tank

33. M-101
M-102
E-101
R-100 E-102
C-101 C-102
M-103
E-103
E-104
V-101
E-105
E-106
C-103
E-108
C-104
E-110
C-105
C-106
E-113
P-105
P-101
P-102
P-103
P-104
P-106
P-107
P-108
E-107
P-110
E-109
P-113
E-114
E-115
E-111
E-112
P-112
P-111
P-109
2
4
3
5 6
7
MEOH
8
9 15
1011
13
14
18
22
16
20
23
25
27
28
31
33
34
37
40
42
43
45
12
1
NAOCH3
TG
WATER
17
21
24
26
32
30
41
44
46
36
39
19
35
38
29

35. Reactor
Component
Stream
6 6a 6b 7
Mass Flow (kg/hr)
TG 7,517.9522 1,611.8490 345.8258 75.1795
ME-8 29.4362 263.5800 320.0806 331.3242
ME-10 7.3485 221.3613 268.8119 278.6136
ME-12 29.0846 2,886.9164 3,505.7513 3,637.0365
ME-14 2.9385 931.7397 1,131.4660 1,174.6950
ME-16 0.4539 465.6010 565.4065 587.3475
ME-18 0.4448 1,181.3929 1,434.6344 1,490.9591
GL 0.8427 794.2666 964.5243 1,000.9215
MeOH 2,110.5902 1,281.5504 1,103.8387 1,065.8481
Water
NaOCH3 81.3248 81.3248 81.3248 81.3248
Total 9,780.4164 9,719.5819 9,721.6643 9,723.2498

36. k 0.78 hr-1
vo 11.28 m3/hr
Conv.
Number of CSTRs, n
Volume of each CSTR (m3)
x 1 2 3 4 5
0.1 2 1 1 0 0
0.4 10 4 3 2 2
0.5 14 6 4 3 2
0.7 34 12 7 5 4
0.8 58 18 10 7 5
0.9 130 31 17 11 8
0.955 307 54 26 17 12
0.99 1432 130 53 31 22

37. Component
Stream
MeOH NaOCH3 TG 3
Enthalpy Flow
kW kW kW kW
TG-8 0.00 0.00 -309.31 -309.31
TG-10 0.00 0.00 -237.91 -237.91
TG-12 0.00 0.00 -2892.25
-
2892.25
TG-14 0.00 0.00 -835.41 -835.41
TG-16 0.00 0.00 -394.70 -394.70
TG-18 0.00 0.00 -971.66 -971.66
Summarized results of streams’ enthalpy flow

38. Pump
Fluid Power
Manual Calculation Result
kW
P-101 0.008053
P-102 0.000237
P-103 0.034578
P-104 0.049475
P-105 0.007785
P-106 0.059666
P-107 0.050024
P-108 0.060870
P-109 0.016567
P-110 0.055166
P-111 0.168413
P-112 0.079416
P-113 0.054530

39. Stream
Mass Flow
Error
Theo. & Hysys
Error
Theo. &
Superpro
Manual Result Aspen Result Superpro
kg/hr kg/hr kg/hr
46 1187.1491 1231.4500 1158.579 3.60% -2.46%
30 588.4234 597.2062 608.059 1.47% 3.22%
36 4769.9296 4800.5740 4823.224 0.64% 1.1%
39 2156.0437 2171.9230 2129.760 0.73% 1.23%
Code Definition
46 Glycerol
30 ME8-10
36 ME12-14
39 ME 16-18

40. EQUIPMENT SIZING
Distillation Column Design Summary
EQUIPMENT SPECIFICATION SHEET
Equipment C-103 C-104 C-105
Material of Construction SS 304 SS 304 SS 304
Feed Trays (from top) 10 7 20
Liquid Flow Pattern Single pass Single pass Single pass
Tray spacing, lt (m) 0.6 0.6 0.6
Column diameter, Dc (m) 1.18 1.09 1.27
Column cross-sectional area, Ac (m2) 1.09 0.93 1.26
Column height, ht (m) 18.13 15.06 19.99
No. of trays 28 24 32
Provisional Plate Design
Plate thickness, tp (mm) 5 5 5
Plate area
Down comer area, Ad (m2) 0.16 0.14 0.19
Net area, An (m2) 0.93 0.79 1.07
Active area, Aa (m2) 0.76 0.65 0.88
Hole area, Ah (m2) 0.09 0.08 0.11
Hole Design
Hole diameter, dh (mm) 5 5 5
Single hole area, Ash (m2) 1.96E-05 1.96E-05 1.96E-05
Number of holes 4658 3960 5384

41. Assumptions
Optimizations
Conclusion
1. Reactors
2. Distillation column
3. Decanter
1. Operating conditions
2. Assumptions
3. Economic potential EP
4. Sizing and costing
5. Recycle
With these assumptions and
optimizations , we can produce
60,000 ton of ME per year .

42. 42