PRODUCTION OF 60, 000 MTPA OF OLEOCHEMICAL METHYL ESTER FROM RBD PALM KERNEL OIL
WAN ADEEBAH WAN MAHMOOD
SITI IRHITH BUSHRAH NOOR MAHADI
SAJJAD KHUDHUR ABBAS
AIMAN MOHAMMED BELAL SIDAN
PRESENTED BY:
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
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:β’ Transesterification of triglyceride (oil)β’ Esterification of free fatty acid (FFA)
b) PROCESS BACKGROUND
Transesterification Process
5
Methoxide
A Triglyceride (Oil)Glycerol
Nucleophilic
Attack
A Methyl Ester
ππ+πππππβππ πππ+ππ
Figure 1:Geographic breakdown of global
oleochemicals market (Weller, 2013)
Table 1:ASEAN oleochemical producers (ADI Finechem) 2013)
c) MARKET SURVEY- supply & demand (global)
Novelty of Proposed Design
D) PROCESS FLOW DIAGRAM
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-105E-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-108P-108
T-104(Glycerol)
To waste water treatment
To waste water treatment
1 atm25 Β°C
1 atm25 Β°C
1 atm25 Β°C
1 atm25 Β°C
1.2 atm25 Β°C
1.2 atm25 Β°C
1.2 atm25 Β°C
1.2 atm25 Β°C
1 atm42 Β°C
1 atm32 Β°C
1 at m60 Β°C
1 at m120 Β°C
1 atm60 Β°C
1 atm120 Β°C
1 atm160 Β°C
1 atm160 Β°C
1 atm120 Β°C
1 atm160 Β°C
1 atm129 Β°C
1 atm60 Β°C
1.2 atm60 Β°C
1.2 atm160 Β°C
1 atm50 Β°C
1 atm50 Β°C
1.2 atm50 Β°C
1 atm130 Β°C
1 at m130 Β°C
1 atm130 Β°C
1 atm25 Β°C
1 atm25 Β°C
1 atm25 Β°C
1 atm25 Β°C
1 atm176 Β°C
0.07 atm176 Β°C
1 atm158 Β°C0.25 atm
158 Β°C
0.25 atm226 Β°C
0.45 atm226 Β°C
0.25 at m198 Β°C
0.07 atm237 Β°C
1 atm237 Β°C
1 atm25 Β°C
0.5 atm185 Β°C
0.7 atm236 Β°C0.5 atm
236 Β°C
0.5 atm25 Β°C
0.5 atm59 Β°C
1 atm91 Β°C
1.2 atm50 Β°C 1 atm
50 Β°C
R-1011st
Transesterification CSTR
R-1022nd
Transesterification CSTR
R-1033rd
Transesterification CSTR
C-1011st MeOH Evaporator
C-1022nd MeOH Evaporator
V-101ME Washing
Decanter
C-103ME Purification
Column
C-104CE-810 Vacuum
Column
C-105CE-1214 and
CE-1618 Splitter
C-106GL Purification
Column
T-101CE-810
Storage Tank
T-102CE-1214
Storage Tank
T-103CE-1618
Storage Tank
T-104GL Storage
Tank
Process Flow Diagram
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 1πΈπ1 = π ππ£πππ’πβ π ππ€ πππ‘πππππ πΆππ π‘
= αΊ0.0813Γ 60,000,000α»ππ πΆπΈ810π¦π Γ π π3.46ππ+αΊ0.6416Γ 60,000,000α»ππ πΆπΈ1214π¦π Γ π π4.65ππ+αΊ0.2771Γ 60,000,000α»ππ πΆπΈ1618π¦π Γ π π3.84ππ + 8,007,371.7200ππ πΊπΏπ¦πΓ π π1.46ππ ࡨ
β࡬59,542,181.6900ππ π π΅π·ππΎππ¦π Γ π π2.95ππ + 8,357,937.3600ππ ππππ»π¦πΓ π π1.08ππ ΰ΅°
= π π 86,743,504.21/π¦π
ππππππ‘ ππππππ αΊ%α»= πΈπ1π ππ€ πππ‘πππππ πΆππ π‘π Γ 100 %
= π π 86,743,504.21/π¦ππ π 184,676,008.33/π¦πΓ 100 %
= 46.97 %
60,000 MTPA production capacity of methyl ester products is feasible (EP1>0) at the continuous mode of operation.
E) Process Selection
POSSIBLE PROCESSES FOR ME SYNTHESIS
β’ Micro-emulsion β’ Pyrolysis (thermal cracking) β’ Transesterification
1. Micro-emulsion
Process of reducing the viscosity of vegetable oil by the means of solvent (methanol, ethanol as well as normal butanol).
Advantages:β’ Clearβ’ Isotropicβ’ thermodynamically stable mixtures of a polar phase .Disadvantages: β’ Stickyβ’ Heavy carbon deposits when used as fuel β’ Creates problems with the engine performance
2. Pyrolysis
Pyrolysis is a conversion process by the means of heating with absence of air resulting in ME
Advantages:β’ Can use any type of raw material β’ Gases oils/solvents and carbonized materials are producedβ’ Good viscosity Disadvantages: β’ Sticky β’ When ME used as:
o fuel Fuel injection system experience damage o High amount of carbon deposition o Inacceptable combustion values in the engine
3. Transesterification
Alcoholysis of triglycerides resulting in a mixture of mono-alkyl esters and glycerol.
Advantages:β’ Better separation of byproductβ’ Achieve better viscosity product
Disadvantages: β’ High methanol/oil ratio
Transesterification
Transesterification reaction
Chemical reaction of consumption of intermediate products
Transesterification Catalysis
β’ Base catalyst
β’ Acid catalyst
β’ Enzyme catalyst
Transesterification Catalysis Alternative 1:
Base catalystPKO +methanol methyl ester +glycerol
Advantages:1. High reaction rate and high catalyst activity2. Low methanol/oil ratio3. Mild operation condition
Disadvantages:4. Formation of soap5. Limited free fatty acid,FFA content for oil6. Inhibited by water
Alternative 2: Acid catalyst
PKO +methanol methyl ester +glycerol
Advantages:1. Unlimited free fatty acid, FFA content for oil2. Product can be easily separated3. High conversion
Disadvantages:4. Long reaction time5. High methanol/ oil ratio6. Acid has a stronger affinity for water
Alternative 3: Lipase Enzyme
PKO + methanol methyl ester +glycerol
Advantages:1.More stable2.Lipase can be regenerated and reused
Disadvantages:1.Still under development2.Very high cost of lipase enzyme3.Unfavorable reaction yield and reaction time
(Cost) (Final decision)(Alternative 1: Base catalyzed) Cheap Selected
(Alternative 2: Acid catalyzed) Medium Eliminated
(Alternative 3: Lipase enzyme) Expansive N/A
Catalyst & Alcohol Selection1. Alcohol selection
β’ Methanol is selected instead of ethanol and butanol.
β’ Shortest chain alcohol β’ Low cost
2. Catalyst selectionβ’ Sodium methoxide is selected instead of other
catalysts. β’ Higher yield obtainedβ’ Lower soap formation
Heterogeneous OR Homogenous Catalytic Process
β’ Homogenous catalytic process is chosenβ’ Heterogeneous catalytic reaction is not been
explored and developed β’ Less sources regarding heterogeneous catalytic
reaction β’ Unexpected reaction rate and undesired side
reaction may encounter
β’ Higher ability to convert intermediate products.
β’ Higher ability for shifting the reaction toward desired product.
β’ Shorter reaction time.β’ Lower reaction temperature.β’ Reduced alcohol and catalyst used.β’ Higher yield obtained.
Why Three Reactors
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 RecycleSodium Methoxide (30wt% in methanol)
a 93.0 Waste
Methyl Ester
CE-810C8:0
b 193.0
Primary product
C10:0
b 224.0
CE-1214C12:0
b 262.0C14:0
b 295.0
CE-1618
C16:0
b 338.0C18:0
b 352.0C18:1
b 349.0C18:2
b 366.0Glycerol 290.0 By-product
Table 1β1: Destination code for transesterification process
Source: a (Leonid Chemicals, n.d.); b (Graboski and McCormick, 1998)
ReactionsThe main reaction:
The side reaction:
ECONOMIC POTENTIAL 2πΈπ2 ࡬π ππ¦πΰ΅°= πππ‘βπ¦π πΈπ π‘ππ π£πππ’π+ πΊππ¦πππππ π£πππ’πβ π π΅π· ππΎπ πΆππ π‘β πππ‘βππππ πΆππ π‘
= αΊ0.0813Γ 60,000,000α»ππ πΆπΈ810π¦π Γ π π3.46ππ+αΊ0.6416Γ 60,000,000α»ππ πΆπΈ1214π¦π Γ π π4.65ππ+αΊ0.2771Γ 60,000,000α»ππ πΆπΈ1618π¦π Γ π π3.84ππ + 8,007,371.7200ππ πΊπΏπ¦πΓ π π1.46ππ ࡨβ παΆππΊ,πΉΓ π π2.95ππ β παΆππππ»,πΉΓ π π1.08ππ
where
παΆππΊ,πΉππ π π΅π·ππΎππ¦π = πΉππΊ,πΉπππππ π π΅π·ππΎππ¦π Γ 684.8022 πππππππ= πππΈπ πππππ π π΅π·ππΎππ¦π Γ 684.8022 πππππππ
παΆππππ»,πΉππ ππππ»π¦π = πΉππππ»,πΉπππππ ππππ»π¦π Γ 32.0419 πππππππ= 3πππΈπ πππππ ππππ»π¦π Γ 32.0419 πππππππ
πππΈ = 260,843.3675 πππππ/π¦π π= 3
LEVEL 3 DECISION- RECYCLE STRUCTURE OF THE FLOWSHEET
Block Flow Fiagram of Recycle Structure
Figure 1-2: Block Flow Diagram of Level 3 Decision
ReactorKinetic data Values
k or Activation energy, Ea 254.5 cal/mol or 1064.81 J/molTemperature 60Β°CPressure 1 atmMeOH:TG molar ratio 6:1NaOCH3 by weight of TG 1 wt%
Table 1β4: Kinetic data (Rashid et al., 2014)
Species, Inlet, Density (60Β°C) Source for
densitykgmol/hr kg/kgmol kg/m3 m3/hrTG 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 0.3928See Appendix A.1.1 (BASF, 2007)
Total 77.46 = 11.2800
Table 1β5: Feed information
For isothermal reaction,
where
For adiabatic reaction,
where
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00
200400600800
1000120014001600
Levenspiel Plot (Isothermal)
Conversion, X
FTG
,0/(-
rTG
) (m
3)
Figure 1β3: Levenspiel Plot (Isothermal: constant k)
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00
200400600800
1000120014001600
Levenspiel Plot (Adiabatic)
Conversion, X
FTG
,0/(-
rTG
) (m
3)
Figure 1β4: Levenspiel Plot (Adiabatic: k changes with temperature)
31
99% conversion
RM73 million/yr
Highest Profit : RM75.5 million/yrConversion : 82%
Optimum Profit : RM73 mil/yrConversion : 99%
Small Gap: RM2.5 mil/yr
ECONOMIC POTENTIAL 3
P-101
P-102
P-103
P-104
M-101
E-101 E-102
E-103
E-104
E-105E-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-108P-108
T-104(Glycerol)
To waste water treatment
To waste water treatment
1 atm25 Β°C
1 atm25 Β°C
1 atm25 Β°C
1 atm25 Β°C
1.2 atm25 Β°C
1.2 atm25 Β°C
1.2 atm25 Β°C
1.2 atm25 Β°C
1 at m42 Β°C
1 atm32 Β°C
1 at m60 Β°C
1 atm120 Β°C
1 atm60 Β°C
1 at m120 Β°C
1 atm160 Β°C
1 atm160 Β°C
1 atm120 Β°C
1 atm160 Β°C
1 atm129 Β°C
1 atm60 Β°C
1.2 atm60 Β°C
1.2 at m160 Β°C
1 atm50 Β°C
1 atm50 Β°C
1.2 at m50 Β°C
1 at m130 Β°C
1 at m130 Β°C
1 at m130 Β°C
1 atm25 Β°C
1 atm25 Β°C
1 atm25 Β°C
1 atm25 Β°C
1 at m176 Β°C
0.07 atm176 Β°C
1 atm158 Β°C0.25 atm
158 Β°C
0.25 atm226 Β°C
0.45 atm226 Β°C
0.25 atm198 Β°C
0.07 atm237 Β°C
1 atm237 Β°C
1 atm25 Β°C
0.5 at m185 Β°C
0.7 atm236 Β°C0.5 atm
236 Β°C
0.5 atm25 Β°C
0.5 atm59 Β°C
1 atm91 Β°C
1.2 atm50 Β°C 1 atm
50 Β°C
R-1011st
Transesterification CSTR
R-1022nd
Transesterification CSTR
R-1033rd
Transesterification CSTR
C-1011st MeOH Evaporator
C-1022nd MeOH Evaporator
V-101ME Washing
Decanter
C-103ME Purification
Column
C-104CE-810 Vacuum
Column
C-105CE-1214 and
CE-1618 Splitter
C-106GL Purification
Column
T-101CE-810
Storage Tank
T-102CE-1214
Storage Tank
T-103CE-1618
Storage Tank
T-104GL Storage
Tank
Process Flow Diagram
M-101
M-102E-101
R-100 E-102
C-101 C-102
M-103E-103
E-104
V-101 E-105E-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-106P-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
1822
16
20
23
2527
28
3133
34
37
40
42
43
45
12
1
NAOCH3
TG
WATER
1721
24
26
32
30
41
44
46
36
39
19
35
38
29
By Hysys Soft.
By Superpro
Reactor
ComponentStream
6 6a 6b 7Mass Flow (kg/hr)
TG 7,517.9522 1,611.8490 345.8258 75.1795ME-8 29.4362 263.5800 320.0806 331.3242ME-10 7.3485 221.3613 268.8119 278.6136ME-12 29.0846 2,886.9164 3,505.7513 3,637.0365ME-14 2.9385 931.7397 1,131.4660 1,174.6950ME-16 0.4539 465.6010 565.4065 587.3475ME-18 0.4448 1,181.3929 1,434.6344 1,490.9591GL 0.8427 794.2666 964.5243 1,000.9215MeOH 2,110.5902 1,281.5504 1,103.8387 1,065.8481Water NaOCH3 81.3248 81.3248 81.3248 81.3248Total 9,780.4164 9,719.5819 9,721.6643 9,723.2498
CSTR calculation 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 50.1 2 1 1 0 00.4 10 4 3 2 20.5 14 6 4 3 20.7 34 12 7 5 40.8 58 18 10 7 50.9 130 31 17 11 8
0.955 307 54 26 17 120.99 1432 130 53 31 22
Component
StreamMeOH NaOCH3 TG 3
Enthalpy FlowkW kW kW kW
TG-8 0.00 0.00 -309.31 -309.31TG-10 0.00 0.00 -237.91 -237.91TG-12 0.00 0.00 -2892.25 -
2892.25TG-14 0.00 0.00 -835.41 -835.41TG-16 0.00 0.00 -394.70 -394.70TG-18 0.00 0.00 -971.66 -971.66
Summarized results of streamsβ enthalpy flow
Reactor
PumpFluid Power
Manual Calculation ResultkW
P-101 0.008053P-102 0.000237P-103 0.034578P-104 0.049475P-105 0.007785P-106 0.059666P-107 0.050024P-108 0.060870P-109 0.016567P-110 0.055166P-111 0.168413P-112 0.079416P-113 0.054530
Pumps
Stream
Mass Flow
ErrorTheo. & Hysys
ErrorTheo. & 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 Definition46 Glycerol30 ME8-1036 ME12-1439 ME 16-18
Comparing
EQUIPMENT SIZING
Distillation Column Design Summary EQUIPMENT SPECIFICATION SHEET
Equipment C-103 C-104 C-105Material of Construction SS 304 SS 304 SS 304Feed Trays (from top) 10 7 20Liquid Flow Pattern Single pass Single pass Single passTray spacing, lt (m) 0.6 0.6 0.6Column diameter, Dc (m) 1.18 1.09 1.27Column cross-sectional area, Ac (m2) 1.09 0.93 1.26Column height, ht (m) 18.13 15.06 19.99No. of trays 28 24 32Provisional Plate DesignPlate thickness, tp (mm) 5 5 5Plate areaDown comer area, Ad (m2) 0.16 0.14 0.19Net area, An (m2) 0.93 0.79 1.07Active area, Aa (m2) 0.76 0.65 0.88Hole area, Ah (m2) 0.09 0.08 0.11Hole DesignHole diameter, dh (mm) 5 5 5Single hole area, Ash (m2) 1.96E-05 1.96E-05 1.96E-05Number of holes 4658 3960 5384
Assumptions
Optimizations
Conclusion
1. Reactors2. Distillation column3. Decanter
1. Operating conditions2. Assumptions3. Economic potential EP4. Sizing and costing5. Recycle
With these assumptions and optimizations , we can produce 60,000 ton of ME per year .
42