353446_ASS1

(1)

Group 33

Production of Synthetic

Va

Van

niill

llin

in fr

from

om Clove Leaf Oil

Clove Leaf Oil

Ahlan

(2)

(3)

INTRODUCTION

(4)

““

Vanillin is one of the most popular

flavouring ag

flavouring agents

ents in

in food industry

food industry

and its wide range of application

also spreads to the fields of

perfu

perfumery

mery and

and pharma

pharmaceuti

ceutical

cal

intermediates.

(5)

Vanillin Market Segmentation

(6)

Natural Vanillin from

vanilla beans

takes a lot of time, labor and

land leading to less sustainable

product with high cost.

(7)

Alternative ideas of vanillin

manufacturing

CLOVE

LEAF OIL

LIGNIN

GUAIACOL

(8)

“

So far, Indonesia is known as the

world's largest producer of clove oil

which controls

63%

of the world

(9)

Asia Pacific (39.7%) of the total revenue in 2016

followed by Europe (27.33% )

(Grand View Research, 2017).

(10)

Global Vanillin Demand

Year

Demands (tons)

2016

14,264

2017

15,148.37

2018

16,087.57

2019

17,085

2020

18,144.27

2021

19,269.21

2022

20,463.90

2023

21,732.66

2024

23,080.09

2025

24,511.05

According to Grand Market

Research 2017,

global vanillin demand

expected growth rate is

6.2%

from 2016 to 2025

(11)

Global Vanillin Supply

Vanillin Industries

Supply Ability

Simagchem corp.

5000 ton/year

Shanghai Fuxin Fine Chemical Co., Ltd.

360 ton/year

Guangzhou Yahe Food Ingredients Co., Ltd.

1100 ton/year

Shanghai Yancui Import and Export Co., Ltd.

3000 ton/year

Anhui Eastmark International Trading Co., Ltd.

10000 ton/year

(12)

950 tons/year

(2.88 tons/day)

(13)

PLANT LOCATION

(14)

Jl. Raya Modern Industri, Barengkok, Kawasan Industri Cikande, Serang, Banten 42185

(coordinate: -6.1832544, 106.3171502).

(15)

Plant Location Considerations

Raw Material Distribution

Clove leaf oil

– PT Global Muda Tridharma, Tangerang

Additional material

– PT Asahimas Chemical, South Jakarta

Product Distribution

◉

Near Jl. Tol Tangerang-Merak

◉

Near Pelabuhan Merak

◉

75% of Indonesian food and

beverage industries

Water Accesibility

Process water is supplied by

PT Sarana Tirta Rejeki for the

whole Kawasan Industri

Cikande

Land Price and Local Min. Wage

◉

Started from Rp1,500,000.00/



(lower

than other Jabodetabek)

◉

Minimum wages Rp3,542,713.5 (lower

(16)

PROCESS

SELECTION

(17)

Clove Leaf Oil to Vanillin

General Process

Eugenol

(18)

Process Selection of Eugenol

Isolation Method

Clove

Leaf Oil

Phenolic Compounds

(largest component).

Contains 80-85% Eugenol

Non-Phenolic Compounds.

Num. Criteria Percentage FD CE

R S R S 1 Suitability for raw material 20% 3 0.6 5 1.0 2 Production Capacity 20% 5 1.0 4 0.8 3 Process Time 10% 3 0.3 5 0.5 4 Human Skill Requirement 5% 1 0.05 4 0.2 5 Installation 10% 2 0.2 4 0.4 6 Capital Investment &Ops. Cost 20% 2 0.4 3 0.6 7 Environmental Risk 15% 1 0.15 4 0.6

Total 100% 2.7 4.1

Rank ₂ ₁

•

Fractional distillation is also highly

efficient

•

Chemical extraction have shorter time

reaction

•

Fractional distillation is expensive;

large structures, heavy duty materials,

specialize machinery with staff to be

fully trained

•

Dangerous

for

people

because

(19)

Num. Criteria Percentage AB TM R S R S 1 Reaction time 30% 3 0.9 4 1.2 2 Reactant concentration 30% 2 0.6 4 1.2 3 Difficulty 15% 3 0.45 4 0.6 4 Phase 10% 2 0.2 4 0.4 5 Hazardous 15% 2 0.3 4 0.6 Total 100% 2.45 4.0 Rank ₂ ₁

Strong solutions of alkaline base at very high

temperatures (140-190

o

_{C) which are very long}

(5-7 hours) can result in overheating and

decomposition

The advantages of metal catalyst:

1. high eugenol conversion rates

2. the process is easier because there is no

thickening of the reactants during the

reaction

3. efficient because the amount of reactants

added is relatively small

4. low hazardous effluent after reaction

(Sharma et al., 2006).

Several factors :

•

the type of catalyst, solvent

•

temperature

•

molar ratio (catalyst concentration)

•

the presence of water

(20)

“

Num. Criteria Percentage NB KMnO4 H2O2 R S R S R S 1 Conversion 20% 3 0.6 2 0.4 4 0.8 2 Concentration 20% 2 0.4 3 0.6 3 0.6 3 Purity 30% 3 0.9 2 0.6 3 0.9 4 Price 30% 3 0.9 2 0.6 1 0.3 Total 100% 2.8 2.2 2.6 Rank 1 3 2

o

Nitrobenzene (130

o

C, 3 hours) produce

53.8% (conventional), 86.10%

(microwaves)

o

KMnO

4

with18-crown ether-6 catalyst

produce 22.9%.

o

H

2

O

2

oxidizer with

methyltrioxorhenium (MTO) catalyst

produce 64-75% at lower temperature

(60

O

_{C), shorter time (2 hours). But}

high prices of MTO and it availability.

Several factors :

1. the type of oxidizer, catalyst

2. temperature

3.oxidizer mole ratio with isoeugenol

4.reaction time

(21)

PROCESS

DESCRIPTION

(22)

Vanillin From Clove Oil Production Process

◉

High efficiency in

mass and heat

transfer

The plant runs in continuous mode

◉

Large production capacity:

977 tons/yr (>500 tons/yr

according to Walas (1988))

◉

The process takes

many procedures

(>20 unit operations)

◉

Reduces the

required volume of

reactors

(23)

Sections of Vanillin Production

1

Eugenol

from Clove

Oil Isolation

2

Eugenol

Isomerisation

3

Isoeugenol

Oxidation

4

Vanillin

Purification

(24)

Vanillin

Purification

(25)

Eugenol Isolation Section

1. Salts formation

2. Excess clove oil

removal

3. Neutralization

4. Eugenol from

by-products

separation

Acid-base extraction method

(26)

Eugenol Isolation Section

◉

Salt is formed by the

reaction of NaOH 4% and

eugenol

◉

Oil and NaOH ratio is 1:5

1. Salts Formation

Continuous Stirred Tank Reactor (CSTR)

Parameter Value Temperature 45o_C

Pressure 1 atm Conversion 85% Total Reaction Time 0.5 h

(27)

Eugenol Isolation Section

1. Salts Formation

Continuous Stirred Tank Reactor (CSTR)

Component

Mass Comp.

(%wt)

Na-eugenolat

16.25 Excess clove

oil

8.14 Sodium

Hydroxide

0.47 Water

75.13

Product Stream:

Component

Mass Comp.

(%wt)

Clove oil

100 Feed Stream 1:

Component

Mass Comp.

(%wt)

Sodium

Hydroxide

4%

Water

96 Feed Stream 2:

(28)

Eugenol Isolation Section

◉

Employs a high rotational speed to separate

components of different densities

2. Excess Clove Oil Removal

Centrifuge Decanter

Component

Density at

20

o

_{C (g/mL)}

Mass Comp.

(%wt)

Clove Oil

1.04

26.74 Water

0.99

73.26 Component

Density at

20

o

_{C (g/mL)}

Mass Comp.

(%wt)

Na-Eugenolat

2.028

23.38 Sodium

Hydroxide

2.13

0.67 Water

0.99

75.95

Bottom Product Stream:

Component

Mass Comp.

(%wt)

Na-eugenolat

16.25 Excess clove

oil

8.14 Sodium

Hydroxide

0.47 Water

75 13

Feed Stream:

(29)

Eugenol Isolation Section

◉

Strong acid addition (HCl

8%) to obtain eugenol from

Na-eugenolat

3. Neutralization

_{Continuous Stirred Tank}

Reactor (CSTR)

Na-Eugenolat Eugenol

(30)

Eugenol Isolation Section

3. Neutralization

Component

Mass Comp.

(%wt)

Eugenol

10.81 Na-eugenolat

3.32 Sodium

Chloride

4.41 Sodium

Hydroxide

0.16 Water

81.30 Product Stream:

Continuous Stirred Tank

Reactor (CSTR)

Component Mass Comp._(%wt) Na-Eugenolat 23.38 Sodium Hydroxide 0.67

Water 75.95

Feed Stream 1:

Component Mass Comp._(%wt)

HCl 8

(31)

Eugenol Isolation Section

◉

Employs a high rotational

speed to separate

components of different

densities

4. Eugenol from by-products separation

Centrifuge Decanter

Component

Density at

20

o

_{C (g/mL)}

Mass Comp.

(%wt)

Eugenol

1.046

21.82 Water

0.99

78.18 Component

Density at

20

o

_{C (g/mL)}

Mass Comp.

(%wt)

Na-Eugenolat

2.028

6.59 Sodium

Hydroxide

2.13

0.32 Sodium

Chloride

2.16

8.74

(32)

Eugenol Isomerisation

Section

◉

Employs the catalyst

of rhodium(III) chloride

dissolved in ethanolic

solution (99.9%).

Parameter Value Temperature 150o_C Pressure 1 atm Rate constant 3,6087 h-1

Total Reaction Time 5 h

Operation Data

(33)

Eugenol Isomerisation

Section

Component Mass Comp. (%wt) Water 92.55 Ethanol 7.44 Bottom Product Stream: Component Mass Comp.

(%wt) Eugenol 0.007 Isoeugenol 99.993

Isoeugenol Oxidation

Section

Procedures:

1. K-isoeugenolat

formation

2. Oxidation

3. Neutralization

(35)

Isoeugenol Oxidation

Section

Operation Data

1. K-isoeugenolat Formation

Parameter Value Temperature 36.43o_C Pressure 1 atm Conversion 90% Total Reaction Time 0.5 h

Continuous Stirred Tank

Reactor (CSTR)

(36)

Isoeugenol Oxidation

Section

1. K-isoeugenolat Formation

Continuous Stirred Tank

Reactor (CSTR)

Feed Stream 1:

Component Mass Comp. (%wt) Eugenol 0.007 Isoeugenol 99.993

Feed Stream 2:

Component Mass Comp. (%wt)

KOH 76

Water 24

Component Mass Comp. (%wt) Isoeugenol 5 K-eugenolat 0.004 K-isoeugenolat 56.21 KOH 21.86 Water 16.87 Product Stream:

(37)

Isoeugenol Oxidation

Section

Operation Data

2. Oxidation

Parameter Value Temperature 130o_C Pressure 1 atm Rate constant 5.29 h-1

Total Reaction Time 3 h

Continuous Stirred Tank

Reactor (CSTR)

◉

The reaction proceeds with the

present of nitrobenzene as

oxidator. DMSO acts as

solvent of nitrobenzene with

the ratio of 2:1

(38)

Isoeugenol Oxidation

Section

2. Oxidation

Continuous Stirred Tank

Reactor (CSTR)

Feed Stream 1:

Component Mass Comp. (%wt) Isoeugenol 5.04 K-eugenolat 0.004 K-isoeugenolat 56.21 KOH 21.86 Water 16.87

Component Mass Comp. (%wt) DMSO 66.67

Feed Stream 2:

Component Mass Comp. (%wt) Acetaldehyde 25.73 Water 74.27 Product Stream 1:

Component Mass Comp. (%wt) Azobenzene 12.62 DMSO 39.28 Isoeugenol 2.26 K-eugenolat 0.002 K-isoeugenolat 11.12 K-vanilat 13.24 KOH 9.80 Product Stream 2:

(39)

Isoeugenol Oxidation

Section

Operation Data

3. Neutralization

Continuous Stirred Tank

Reactor (CSTR)

◉

K-vanilat salt is reacted with

HCl 25% to obtain vanillin

_Parameter _Value

Temperature 36.43o_C

Pressure 1 atm Conversion 90% Total Reaction Time 1 h

(40)

Isoeugenol Oxidation

Section

3. Neutralization

_{Continuous Stirred Tank}

Reactor (CSTR)

Feed Stream 1: Feed Stream 1: C Coommppoonneenntt MMaasss s CCoommpp. (. (%%wwtt)) Azobenzene Azobenzene 12.6212.62 D DMMSSO O 3399..2288 IIssooeeuuggeennool l 22..2266 K K--eeuuggeennoollaat t 00..000022 K K--iissooeeuuggeennoollaat t 1111..1122 K K--vvaanniillaat t 1133..2244 K KOOH H 99..8800 N Niittrroobbeennzzeenne e 1111..6677 _C_Co_om_mp_po_on_ne_en_ntt _M_Ma_as_ss_{s C}_Co_om_mp_{p. (}_{. (%}_%w_wtt)) H HCCll 2255 Feed Stream 2: Feed Stream 2: Component

Component Mass Comp.Mass Comp. (%wt) (%wt) Azobenzene Azobenzene 9.209.20 D DMMSSO O 2288..6622 IIssooeeuuggeennool l 11..6655 H HCCl l 00..9955 K K--eeuuggeennoollaat t 00..000011 K K--iissooeeuuggeennoollaat t 88..1100 K K--vvaanniillaat t 00..9966 K KCCl l 1144..2222 N Niittrroobbeennzzeenne e 88..55 V Vaanniilllliin n 77..4444 W Waatteer r 2200..3355 Product Stream: Product Stream:

(41)

Procedures:

1.

1. Extraction

Extraction

2.

2. Sodium Bisulfite

Sodium Bisulfite

Addition and

Neutralization

3.

3. Re-extraction

Re-extraction

4.

4. Spray Drying

Spray Drying

Vanillin Purification Section

(42)

1. Extraction

Vanillin Purification Section

◉

Diethylether acts as organic

solvent to extract vanillin from

dissolved mixture of oxidation

by-product

◉

Diethylether is volatile

compound and has low boilling

point (35

oo

_C)

__

_{separated with}

evaporation

(43)

1. Extraction

Vanillin Purification Section

Component Mass Comp. (%wt) Azobenzene 9.20 DMSO 28.62 Isoeugenol 1.65 HCl 0.95 K-eugenolat 0.001 K-isoeugenolat 8.10 K-vanilat 0.96 KCl 14.22 Nitrobenzene 8.5 Vanillin 7.44 Feed Stream 1:

Component Mass Comp. (%wt) Feed Stream 2:

Component Mass Comp. (%wt) Diethylether 9.20 Isoeugenol 28.62 Vanillin 1.65 Water 0.95 Top Product

(44)

2. Sodium Bisulfite Addition and

Neutralization

Vanillin Purification Section

◉

NaHSO

₃

extracts vanillin

dissolved in diethylether to

form vanillin-bisulfite

Operation Data

Parameter Value Temperature 30o_C Pressure 1 atm Conversion 100% Total Reaction Time 1.5 h

(45)

2. Sodium Bisulfite Addition and

Neutralization

Vanillin Purification Section

Component Mass Comp. (%wt) Diethylether 9.20 Isoeugenol 28.62 Vanillin 1.65 Water 0.95 Feed Stream 1:

Component Mass Comp. (%wt)

NaHSO₃ 100

Feed Stream 2:

Component Mass Comp. (%wt) Diethylether 21.22 Isoeugenol 3.22 NaHSO3 11.27 Vanillin-bisulfite 24.49 Water 39.79 Form as bottom product in centrifuge Product Stream Recovery with evaporation and condensation

(46)

2. Sodium Bisulfite Addition and

Neutralization

Vanillin Purification Section

◉

Neutralization with 96% sulfuric acid to separate

vanillin from vanillin-bisulfite

Operation Data

Vanillin-bisulfite + H

₂

SO

₄ 

Vanillin + Na

₂

SO

₄

+ SO

₂

+ H

₂

O

Component Mass Comp.

(%wt) NaHSO₃ 9.36 Sulfuric acid 11

Vanillin 43.45 Water 36.18

(47)

3. Re-extraction

Vanillin Purification Section

Component Mass Comp. (%wt) NaHSO₃ 9.36 Sulfuric acid 11 Vanillin 43.45 Water 36.18

Feed Stream

◉

Re-extraction of vanillin with diethylether

◉

Followed by centrifugation to remove bottom

product, and evaporation to remove the solvent

(48)

3. Spray drying

Vanillin Purification Section

◉

Vanillin is dried to form vaillin powder

Operation Data

Parameter Value Heating Agent Steam

Temperature 152o_C

Evaporation Rate 100 (kg/h)/m3 Component Mass Comp.

(%wt) Vanillin Powder 100

(49)

BLOCK FLOW DIAGRAM (BFD)

PFD of Vanilin from Clove Leaf Oil

(50)

BFD of Vanilin from Clove Leaf Oil

(51)

PROCESS FLOW DIAGRAM (PFD) CONT’D

(52)

MASS & ENERGY

BALANCE

(53)

Overall

Mass Balance

Overall Mass Balance

Components Input Output

kg/year kg/h kg/year kg/h Acetaldehyde 0 0 162.254 0.02048662 Azobenzene 0 0 671.168 0.08474343 Diethyl Ether 792000 100 792 0.1 Diethylether-Vanillin 0 0 DMSO 2376000 300 2088235 263.666035 Clove Oil 1980000 250 741731 93.652904 Ethyl Alcohol 593406 74.925 305202 38.5356061 Eugenol 0 0 HCl 748440 94.5 69535 8.77967172 Isoeugenol 0 0 120275 15.1862374 K-eugenolat 0 0 97 0.01224747 K-isoeugenolat 0 0 591141 74.6390152 K-vanilat 0 0 70403 8.88926768 KCl 0 0 1037245 130.965278 KOH 896861 113.24003 0 0 Na-eugenolat 0 0 315785 39.8718434 NaHSO3 792000 100 420761 53.1263889 Nitrobenzene 1188000 150 620392 78.3323232 Sodium Chloride 0 0 418784 52.8767677 Sodium Hydroxide 285120 36 14964 1.88939394 Sulfur Dioxide 0 0 252164 31.8388889 Sulfuric Acid 633600 80 247542 31.255303

For more details, click

(54)

Overall

Energy Balance

Overall Energy Balance

Machines Input Output

Per year Per hour Per year Per hour Reactor I (P-7 / R -101) 75739.212 9.563031818 75111.192 9.483736364 Decanter Centrifugation I (P-14 / DC-101) -93888.99 -11.85467045 -93155.7423 -11.76208867

StorageI(P-16/V-106) 0 0 0 0

Reactor II (P-9 / R-102) 97112.00959 12.26161737 113018.8661 14.27005885 Decanter Centrifugation II (P-25 / DC-102) -113018.8661 -14.27005885 -112390.3509 -14.19070087 Reactor III / Kinetic (P-10 / R-103) 314035.0498 39.65089013 134980.2999 17.04296716 Condenser I (P-15 / HX-104) -130866.335 -16.52352714 -275957.2716-34.84308985 StorageII(P-18/V-105) 0 0 0 0 Cooler I (P-3 / HX-101) -8443.648162 -1.066117192 -8443.648162 -1.066117192 Reactor IV (P-11 / R-104) 7044.25474 0.889426104 7328.320631 0.925293009 Reactor V / Kinetic (P-1 / R-108) 114232.4087 14.42328392 109696.4516 13.85056207 Cooler II (P-12 / HX-102) -92868.88568 -11.7258694 -92868.88568 -11.7258694 Reactor VI (P-13 / R-105) 16260.32101 2.053070835 141419.5162 17.85599951 Blending Tank I (P-4 / V-103) 48.23686921 0.006090514 7001.373345 0.884011786 Decanter Centrifugation III (P-8 / DC-103) -30372.2404 -3.834878839 -30076.47515 -3.797534741 Reactor VII (P-19 / R-106) 11701.8567 1.477507159 10851.08012 1.370085873 Decanter Centrifugation IV (P-5 / DC-104) -10851.08012 -1.370085873 -10780.24064 -1.361141495 Evaporator I (P-20 / EV-101) 5222.594056 0.659418441 3790.093792 0.478547196 Condenser II (P-2 / HX-103) -3265.704 -0.412336364 -4772.952-0.602645455 Reactor VIII (P-17 / R-107) 15578.47983 1.966979776 21281.07815 2.687004816 Blending Tank II (P-21 / V-108) 26003.05584 3.283214121 20429.82514 2.579523376 Decanter Centrifugation V (P-6 / DC-105) -20429.82514 -2.579523376 -20604.89534 -2.6016282 Evaporator II (P-22 / EV-102) 8603.65848 1.086320515 7191.106049 0.907967935 Condenser III (P-23 / HX-105) -3265.704 -0.412336364 -3181.968-0.401763636

For more details, click BIO33_NME

REPORT_ASSIGNMENT1. xlsx

(55)

Mass & Energy Efficiency

Calculation

◉

Efficiency power plant can be calculated with the equation

shown below:

η =

Energy in

Energy out

◉

The calculation of total system efficiency is a simple and

useful method that evaluates what is produced compared to

what is consumed.

 =

184309.8591

(56)

Product Conversion

Efficiency

Product conversion efficiency can be calculated

in below:

 =



 



_{ }

x 100%

 =

 /

 /

x 100%

 = 80%

(57)

Product Yield

Product yield based on reactant (clove oil) can

be calculated as:



_{   }

=

123.364015 /ℎ

250 /ℎ

 100%

= 49.34%

(58)

Energy Consumption of Unit

Product

  =

  

  

  =

184309.8591 /ℎ

123.364015 /ℎ

= 1494.0326





 

(59)

CONCLUSIONS

(60)

1. The ideas of substitute vanillin sources is because natural vanillin from vanilla bean is very

laborious to cultivate, has long production periods and very e xpensive comparatively to synthetic

counterpart.

2. Clove leaf oil is chosen as main raw material considering the fact of its availability and

potentiality in Indonesia.

3. Kawasan Industri Cikande, Banten, is chosen as vanillin plant location with minimum wages in

Rp 3,542,713.50.

4. Based on the market analysis, the production capacity of

writer’s

_{vanillin plant is about 950}

ton/year or 2.88 ton/day by fulfilling 5% of global market share.

5. The production of vanillin are divided into 4 section including eugenol isolation, isomerization,

oxidation, and purification.

6. Continuous process is selected due to high production capacity to meet the global vanillin

demand and long purification procedure to have 100% purity of vanillin powder.

7. Purification of vanillin requires extraction and re-extraction method using diethylether as

waterimmiscible organic solvent.

8. The production capacity in this vanillin plant is 977 tons/year which is higher than the vanillin

demand.

(61)