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:• Transesterification of triglyceride (oil)• Esterification of free fatty acid (FFA)

b) PROCESS BACKGROUND

Transesterification Process

5

Methoxide

A Triglyceride (Oil)Glycerol

Nucleophilic

Attack

A Methyl Ester

𝐓𝐆+𝟑𝐌𝐞𝐎𝐇↔𝟑𝐅𝐀𝐌𝐄+𝐆𝐋

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 °C

1 atm25 °C

1 atm25 °C

1 atm25 °C

1.2 atm25 °C

1.2 atm25 °C

1.2 atm25 °C

1.2 atm25 °C

1 atm42 °C

1 atm32 °C

1 at m60 °C

1 at m120 °C

1 atm60 °C

1 atm120 °C

1 atm160 °C

1 atm160 °C

1 atm120 °C

1 atm160 °C

1 atm129 °C

1 atm60 °C

1.2 atm60 °C

1.2 atm160 °C

1 atm50 °C

1 atm50 °C

1.2 atm50 °C

1 atm130 °C

1 at m130 °C

1 atm130 °C

1 atm25 °C

1 atm25 °C

1 atm25 °C

1 atm25 °C

1 atm176 °C

0.07 atm176 °C

1 atm158 °C0.25 atm

158 °C

0.25 atm226 °C

0.45 atm226 °C

0.25 at m198 °C

0.07 atm237 °C

1 atm237 °C

1 atm25 °C

0.5 atm185 °C

0.7 atm236 °C0.5 atm

236 °C

0.5 atm25 °C

0.5 atm59 °C

1 atm91 °C

1.2 atm50 °C 1 atm

50 °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 1𝐸𝑃1 = 𝑅𝑒𝑣𝑒𝑛𝑢𝑒− 𝑅𝑎𝑤 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝐶𝑜𝑠𝑡

= ሺ0.0813× 60,000,000ሻ𝑘𝑔 𝐶𝐸810𝑦𝑟 × 𝑅𝑀3.46𝑘𝑔+ሺ0.6416× 60,000,000ሻ𝑘𝑔 𝐶𝐸1214𝑦𝑟 × 𝑅𝑀4.65𝑘𝑔+ሺ0.2771× 60,000,000ሻ𝑘𝑔 𝐶𝐸1618𝑦𝑟 × 𝑅𝑀3.84𝑘𝑔 + 8,007,371.7200𝑘𝑔 𝐺𝐿𝑦𝑟× 𝑅𝑀1.46𝑘𝑔 ൨

−൬59,542,181.6900𝑘𝑔 𝑅𝐵𝐷𝑃𝐾𝑂𝑦𝑟 × 𝑅𝑀2.95𝑘𝑔 + 8,357,937.3600𝑘𝑔 𝑀𝑒𝑂𝐻𝑦𝑟× 𝑅𝑀1.08𝑘𝑔 ൰

= 𝑅𝑀 86,743,504.21/𝑦𝑟

𝑃𝑟𝑜𝑓𝑖𝑡 𝑀𝑎𝑟𝑔𝑖𝑛 ሺ%ሻ= 𝐸𝑃1𝑅𝑎𝑤 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝐶𝑜𝑠𝑡𝑠× 100 %

= 𝑅𝑀 86,743,504.21/𝑦𝑟𝑅𝑀 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.

E) Process Selection

POSSIBLE PROCESSES FOR ME SYNTHESIS

• Micro-emulsion • Pyrolysis (thermal cracking) • 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:• Clear• Isotropic• thermodynamically stable mixtures of a polar phase .Disadvantages: • Sticky• Heavy carbon deposits when used as fuel • 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:• 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

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

Transesterification

Transesterification reaction

Chemical reaction of consumption of intermediate products

Transesterification Catalysis

• Base catalyst

• Acid catalyst

• 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

• 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

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

• 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

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 1‑1: Destination code for transesterification process

Source: a (Leonid Chemicals, n.d.); b (Graboski and McCormick, 1998)

ReactionsThe main reaction:

The side reaction:

ECONOMIC POTENTIAL 2𝐸𝑃2 ൬𝑅𝑀𝑦𝑟൰= 𝑀𝑒𝑡ℎ𝑦𝑙 𝐸𝑠𝑡𝑒𝑟 𝑣𝑎𝑙𝑢𝑒+ 𝐺𝑙𝑦𝑐𝑒𝑟𝑜𝑙 𝑣𝑎𝑙𝑢𝑒− 𝑅𝐵𝐷 𝑃𝐾𝑂 𝐶𝑜𝑠𝑡− 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝐶𝑜𝑠𝑡

= ሺ0.0813× 60,000,000ሻ𝑘𝑔 𝐶𝐸810𝑦𝑟 × 𝑅𝑀3.46𝑘𝑔+ሺ0.6416× 60,000,000ሻ𝑘𝑔 𝐶𝐸1214𝑦𝑟 × 𝑅𝑀4.65𝑘𝑔+ሺ0.2771× 60,000,000ሻ𝑘𝑔 𝐶𝐸1618𝑦𝑟 × 𝑅𝑀3.84𝑘𝑔 + 8,007,371.7200𝑘𝑔 𝐺𝐿𝑦𝑟× 𝑅𝑀1.46𝑘𝑔 ൨− 𝑚ሶ𝑇𝐺,𝐹× 𝑅𝑀2.95𝑘𝑔 − 𝑚ሶ𝑀𝑒𝑂𝐻,𝐹× 𝑅𝑀1.08𝑘𝑔

where

𝑚ሶ𝑇𝐺,𝐹𝑘𝑔 𝑅𝐵𝐷𝑃𝐾𝑂𝑦𝑟 = 𝐹𝑇𝐺,𝐹𝑘𝑔𝑚𝑜𝑙 𝑅𝐵𝐷𝑃𝐾𝑂𝑦𝑟 × 684.8022 𝑘𝑔𝑘𝑔𝑚𝑜𝑙= 𝑃𝑀𝐸𝑌 𝑘𝑔𝑚𝑜𝑙 𝑅𝐵𝐷𝑃𝐾𝑂𝑦𝑟 × 684.8022 𝑘𝑔𝑘𝑔𝑚𝑜𝑙

𝑚ሶ𝑀𝑒𝑂𝐻,𝐹𝑘𝑔 𝑀𝑒𝑂𝐻𝑦𝑟 = 𝐹𝑀𝑒𝑂𝐻,𝐹𝑘𝑔𝑚𝑜𝑙 𝑀𝑒𝑂𝐻𝑦𝑟 × 32.0419 𝑘𝑔𝑘𝑔𝑚𝑜𝑙= 3𝑃𝑀𝐸𝑌 𝑘𝑔𝑚𝑜𝑙 𝑀𝑒𝑂𝐻𝑦𝑟 × 32.0419 𝑘𝑔𝑘𝑔𝑚𝑜𝑙

𝑃𝑀𝐸 = 260,843.3675 𝑘𝑔𝑚𝑜𝑙/𝑦𝑟 𝑌= 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 60°CPressure 1 atmMeOH:TG molar ratio 6:1NaOCH3 by weight of TG 1 wt%

Table 1‑4: Kinetic data (Rashid et al., 2014)

Species, Inlet, Density (60°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 1‑5: 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 1‑3: 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 1‑4: 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 °C

1 atm25 °C

1 atm25 °C

1 atm25 °C

1.2 atm25 °C

1.2 atm25 °C

1.2 atm25 °C

1.2 atm25 °C

1 at m42 °C

1 atm32 °C

1 at m60 °C

1 atm120 °C

1 atm60 °C

1 at m120 °C

1 atm160 °C

1 atm160 °C

1 atm120 °C

1 atm160 °C

1 atm129 °C

1 atm60 °C

1.2 atm60 °C

1.2 at m160 °C

1 atm50 °C

1 atm50 °C

1.2 at m50 °C

1 at m130 °C

1 at m130 °C

1 at m130 °C

1 atm25 °C

1 atm25 °C

1 atm25 °C

1 atm25 °C

1 at m176 °C

0.07 atm176 °C

1 atm158 °C0.25 atm

158 °C

0.25 atm226 °C

0.45 atm226 °C

0.25 atm198 °C

0.07 atm237 °C

1 atm237 °C

1 atm25 °C

0.5 at m185 °C

0.7 atm236 °C0.5 atm

236 °C

0.5 atm25 °C

0.5 atm59 °C

1 atm91 °C

1.2 atm50 °C 1 atm

50 °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 streams’ 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