353446_ASS1

Group 33 Production of Synthetic Van Vanillin llin from from Clove Leaf Oil  Ahlan Fauzi. Khusnul Layli Putri. Muhammad Muhammad Akbar. Reysa Anggraini. Sauria Karina

1

INTRODUCTION

Vanillin is one of the most popular  flavouring agents agents in food in food industry and its wide range of application also spreads to the fields of perfumery perfumery and pharmaceuti pharmaceutical cal intermediates.

“

Vanillin Market Segmentation

Ph.D. Dissertation of Biological and Chemical Engineering in Universidade do Porto

Natural Vanillin from vanilla beans takes a lot of time, labor and land leading to less sustainable product with high cost.

Alternative ideas of vanillin manufacturing 

CLOVE LEAF OIL

GUAIACOL

LIGNIN

So far, Indonesia is known as the world's largest producer of clove oil

63%

which controls of the world market (Rizal and Djazuli, 2006)

“

 Asia Pacific (39.7%) of the total revenue in 2016 followed by Europe (27.33% ) (Grand View Research, 2017).

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

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 

A.M Food Chemical (Jinan) Co., Ltd.

1000 ton/year 

950 tons/year (2.88 tons/day) Based on 5% market share target from global demand.

2

PLANT LOCATION

 Jl. Raya Modern Industri, Barengkok, Kawasan Industri Cikande, Serang, Banten 42185 (coordinate: -6.1832544, 106.3171502).

Plant Location Considerations Raw Material Distribution

Product Distribution

Water Accesibility

Clove leaf oil

◉

Near Jl. Tol Tangerang-Merak

 – PT Global Muda Tridharma, Tangerang

◉

Near Pelabuhan Merak

 Additional material

◉

75% of Indonesian food and beverage industries

Process water is supplied by PT Sarana Tirta Rejeki for the whole Kawasan Industri Cikande

 – PT Asahimas Chemical, South Jakarta

Land Price and Local Min. Wage ◉

Started from Rp1,500,000.00/ (lower than other Jabodetabek)

◉

Minimum wages Rp3,542,713.5 (lower than Bekasi and Karawang)

3

PROCESS SELECTION

Clove Leaf Oil to Vanillin General Process

Eugenol Isolation

Isomerization

Oxidation

Purification

Process Selection of Eugenol Isolation Method •

•

•

•

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 potentially explosion

Num.

Clove Leaf Oil

Phenolic Compounds (largest component). Contains 80-85% Eugenol Non-Phenolic Compounds.

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 Rank 

100%

2.7

4.1

2

1

Catalyst Selection in Eugenol Isomerization Several factors : the type of catalyst, solvent  temperature molar ratio (catalyst concentration) the presence of water • • • •

Strong solutions of alkaline base at very high temperatures (140-190oC) 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).

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 Rank 

100%

2.45

4.0

2

1

Oxidizer Selection in Isougenol Oxidation Several factors : 1. the type of oxidizer, catalyst  2. temperature 3.oxidizer mole ratio with isoeugenol 4.reaction time o

o

o

Nitrobenzene (130oC, 3 hours) produce 53.8% (conventional), 86.10% (microwaves) KMnO4 with18-crown ether-6 catalyst produce 22.9%. H2O2 oxidizer with methyltrioxorhenium (MTO) catalyst produce 64-75% at lower temperature (60OC), shorter time (2 hours). But high prices of MTO and it availability.

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 Rank

“

100%

2.8 1

2.2

2.6

3

2

4

PROCESS DESCRIPTION

Vanillin From Clove Oil Production Process The plant runs in continuous mode ◉

Large production capacity: 977 tons/yr (>500 tons/yr according to Walas (1988))

◉

Reduces the required volume of reactors

◉

◉

The process takes many procedures (>20 unit operations)

High efficiency in mass and heat transfer 

Sections of Vanillin Production

        1

Eugenol

        2

        4

        3

from Clove

Eugenol

Oil Isolation

Isomerisation

Isoeugenol Oxidation

 Vanillin Purification

Vanillin From Clove Oil Production Process

 Vanillin Purification

Eugenol Isolation Section  Acid-base extraction method 

1. 2.

Salts formation

3. 4.

Neutralization

Excess clove oil removal Eugenol from byproducts separation

Eugenol Isolation Section Continuous Stirred Tank Reactor (CSTR)

1. Salts Formation ◉

◉

Salt is formed by the reaction of NaOH 4% and eugenol Oil and NaOH ratio is 1:5 Operation Data Parameter

Value

Temperature

45oC

Pressure

1 atm

Conversion

85%

Total Reaction Time

0.5 h

Eugenol Isolation Section Continuous Stirred Tank Reactor (CSTR)

1. Salts Formation

Product Stream:

Feed Stream 1:

Component

Mass Comp. (%wt)

Component

Mass Comp. (%wt)

Naeugenolat

16.25

Clove oil

100

Excess clove oil

8.14

Sodium Hydroxide

0.47

Water

75.13

Feed Stream 2: Component

Mass Comp. (%wt)

Sodium Hydroxide

4%

Water

96

Eugenol Isolation Section Top Product Stream:

2. Excess Clove Oil Removal ◉

Employs a high rotational speed to separate components of different densities Feed Stream:

Component

Mass Comp. (%wt)

Centrifuge Decanter

Component

Density at 20oC (g/mL)

Mass Comp. (%wt)

Clove Oil

1.04

26.74

Water

0.99

73.26

Component

Density at 20oC (g/mL)

Mass Comp. (%wt)

Bottom Product Stream:

Naeugenolat

16.25

Excess clove oil

8.14

Na-Eugenolat

2.028

23.38

Sodium Hydroxide

0.47

Sodium Hydroxide

2.13

0.67

Water

75 13

Water

0.99

75.95

Eugenol Isolation Section 3. Neutralization ◉

Strong acid addition (HCl 8%) to obtain eugenol from Na-eugenolat

Na-Eugenolat

Eugenol

Continuous Stirred Tank Reactor (CSTR)

Operation Data Parameter

Value

Temperature

45oC

Pressure

1 atm

Conversion

90%

Total Reaction Time

0.5 h

Eugenol Isolation Section 3. Neutralization Continuous Stirred Tank Reactor (CSTR)

Feed Stream 1:

Product Stream:

Component

Mass Comp. (%wt)

Component

Mass Comp. (%wt)

Na-Eugenolat

23.38

Eugenol

10.81

Sodium Hydroxide

0.67

Na-eugenolat

3.32 4.41

75.95

Sodium Chloride Sodium Hydroxide

0.16

Water

81.30

Water

Feed Stream 2: Component

Mass Comp. (%wt)

HCl

8

Eugenol Isolation Section 4. Eugenol from by-products separation ◉

Employs a high rotational speed to separate components of different densities

Centrifuge Decanter

Top Product Stream:

Component

Density at 20oC (g/mL)

Mass Comp. (%wt)

Eugenol

1.046

21.82

Water

0.99

78.18

Bottom Product Stream:

Component

Density at 20oC (g/mL)

Mass Comp. (%wt)

Na-Eugenolat

2.028

6.59

Sodium Hydroxide

2.13

0.32

Sodium Chloride

2.16

8.74

Eugenol Isomerisation Section ◉

Employs the catalyst of rhodium(III) chloride dissolved in ethanolic solution (99.9%).

Operation Data

Eugenol

Isoeugenol

Parameter

Value

Temperature

150oC

Pressure

1 atm

Rate constant

3,6087 h-1

Total Reaction Time

5h

Eugenol Isomerisation Section Feed Stream 1:

Top Product Stream:

Component

Mass Comp. (%wt)

Component

Mass Comp. (%wt)

Eugenol

92.55

Water

92.55

Water

7.44

Ethanol

7.44

Feed Stream 2:

Bottom Product Stream:

Component

Mass Comp. (%wt)

Component

Mass Comp. (%wt)

Ethanol

92.99

Eugenol

0.007

Water

0.1

Isoeugenol

99.993

Isoeugenol Oxidation Section Procedures:

1.

K-isoeugenolat formation

2. 3.

Oxidation Neutralization

Isoeugenol Oxidation Section 1. K-isoeugenolat Formation

Continuous Stirred Tank Reactor (CSTR)

Operation Data Parameter

Value

Temperature

36.43oC

Pressure

1 atm

Conversion

90%

Total Reaction Time

0.5 h

Isoeugenol Oxidation Section 1. K-isoeugenolat Formation

Continuous Stirred Tank Reactor (CSTR) Product Stream:

Feed Stream 1: Component

Mass Comp. (%wt)

Component

Mass Comp. (%wt)

Eugenol

0.007

Isoeugenol

5

Isoeugenol

99.993

K-eugenolat

0.004

K-isoeugenolat

56.21

KOH

21.86

Water

16.87

Feed Stream 2: Component

Mass Comp. (%wt)

KOH

76

Water

24

Isoeugenol Oxidation Section Continuous Stirred Tank 2. Oxidation ◉

The reaction proceeds with the present of nitrobenzene as oxidator. DMSO acts as solvent of nitrobenzene with the ratio of 2:1

+

Reactor (CSTR) Operation Data Parameter

Value

Temperature

130oC

Pressure

1 atm

Rate constant

5.29 h-1

Total Reaction Time

3h

Product Stream 1:

Isoeugenol Oxidation Section 2. Oxidation Continuous Stirred Tank Feed Stream 1: Component

Mass Comp. (%wt)

Isoeugenol

5.04

K-eugenolat

Reactor (CSTR)

Component

Mass Comp. (%wt)

 Acetaldehyde

25.73

Water

74.27

Product Stream 2: Component

Mass Comp. (%wt)

0.004

 Azobenzene

12.62

K-isoeugenolat

56.21

DMSO

39.28

KOH

21.86

Isoeugenol

2.26

Water

16.87

K-eugenolat

0.002

K-isoeugenolat

11.12

K-vanilat

13.24

KOH

9.80

Feed Stream 2: Component

Mass Comp. (%wt)

DMSO

66.67

Isoeugenol Oxidation Section 3. Neutralization ◉

K-vanilat salt is reacted with HCl 25% to obtain vanillin

Continuous Stirred Tank Reactor (CSTR)

Operation Data Parameter

Value

Temperature

36.43oC

Pressure

1 atm

Conversion

90%

Total Reaction Time

1h

Product Stream:

Isoeugenol Oxidation Section 3. Neutralization

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

W ater

20.35

Continuous Stirred Tank Reactor (CSTR)

Feed 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

Nitrobenzene

11.67

Feed Stream 2: Component

Mass Comp. (% (%wt)

HCl

25

Vanillin Purification Section Procedures:

1. 2. 3. 4.

Extraction Sodium Bisulfite  Addition and Neutralization Re-extraction Spray Drying

Vanillin Purification Section 1. Extraction ◉

Diethylether acts as organic solvent to extract vanillin from dissolved mixture of oxidation by-product

◉

Diethylether is volatile compound and has low boilling point (35oC)  separated with evaporation

Top Product

Vanillin Purification Section Feed Stream 1:

1. Extraction

Component

Mass Comp. (%wt)

Diethylether

9.20

Isoeugenol

28.62

Component

Mass Comp. (%wt)

 Azobenzene

9.20

Vanillin

1.65

DMSO

28.62

Water

0.95

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 2: Component

Mass Comp. (%wt)

Operation Data

Vanillin Purification Section 2. Sodium Bisulfite Addition and Neutralization ◉

NaHSO3 extracts vanillin dissolved in diethylether to form vanillin-bisulfite

Parameter

Value

Temperature

30oC

Pressure

1 atm

Conversion

100%

Total Reaction Time

1.5 h

Product Stream

Vanillin Purification Section 2. Sodium Bisulfite Addition and Neutralization Feed Stream 1: Component

Mass Comp. (%wt)

Diethylether

9.20

Isoeugenol

28.62

Vanillin

1.65

Water

0.95

Feed Stream 2: Component

Mass Comp. (%wt)

NaHSO3

100

Recovery with evaporation and condensation

Component

Mass Comp. (%wt)

Diethylether

21.22

Isoeugenol

3.22

NaHSO3 Form as bottom product in centrifuge

 

11.27

Vanillin-bisulfite

24.49

Water

39.79

Operation Data

Vanillin Purification Section 2. Sodium Bisulfite Addition and Neutralization ◉

Neutralization with 96% sulfuric acid to separate vanillin from vanillin-bisulfite

Vanillin-bisulfite + H2SO4  Vanillin + Na2SO4 + SO2 + H2O

Bottom Product Stream Mass Comp. (%wt)

Component NaHSO3

 

9.36

Sulfuric acid

11

Vanillin

43.45

Water

36.18

Parameter

Value

Temperature

40oC

Pressure

1 atm

Conversion

100%

Total Reaction Time

1.5 h

Vanillin Purification Section 3. Re-extraction ◉

Re-extraction of vanillin with diethylether 

◉

Followed by centrifugation to remove bottom product, and evaporation to remove the solvent

Feed Stream Mass Comp. (%wt)

Component NaHSO3

 

9.36

Sulfuric acid

11

Vanillin

43.45

Water

36.18

bottom product

Vanillin Purification Section Operation Data

3. Spray drying ◉

Parameter

Vanillin is dried to form vaillin powder 

Component

Mass Comp. (%wt)

Vanillin Powder

100

Heating Agent

Value  

Steam

Temperature

152oC

Evaporation Rate

100 (kg/h)/m3

BLOCK FLOW DIAGRAM (BFD)

PFD of Vanilin from Clove Leaf Oil

PROCESS FLOW DIAGRAM (PFD)

BFD of Vanilin from Clove Leaf Oil

PROCESS FLOW DIAGRAM (PFD) CONT’D Stream Information

5

MASS & ENERGY BALANCE

Components  Acetaldehyde  Azobenzene Diethyl Ether Diethylether-Vanillin DMSO Clove Oil Ethyl Alcohol Eugenol HCl Isoeugenol K-eugenolat K-isoeugenolat K-vanilat KCl KOH Na-eugenolat NaHSO3 Nitrobenzene Sodium Chloride For more details, click Sodium Hydroxide BIO33_NME REPORT_ASSIGNMENT1.xlsx Sulfur Dioxide Sulfuric Acid

Overall Mass Balance

Overall Mass Balance Input kg/year kg/h 0 0 0 0 792000 100 0 2376000 300 1980000 250 593406 74.925 0 748440 94.5 0 0 0 0 0 0 0 0 0 0 896861 113.24003 0 0 792000 100 1188000 150 0 0 285120 36 0 0 633600 80

Output   kg/year kg/h 162.254 0.02048662 671.168 0.08474343 792 0.1 0 2088235 263.666035 741731 93.652904 305202 38.5356061 0 69535 8.77967172 120275 15.1862374 97 0.01224747 591141 74.6390152 70403 8.88926768 1037245 130.965278 0 0 315785 39.8718434 420761 53.1263889 620392 78.3323232 418784 52.8767677 14964 1.88939394 252164 31.8388889 247542 31.255303

Overall Energy Balance 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 Storage I (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 Storage II (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 -2.6016282 Decanter Centrifugation V (P-6 / DC-105) -20429.82514 -2.579523376 20604.89534 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 Machines

Overall Energy Balance

For more details, click BIO33_NME REPORT_ASSIGNMENT1. xlsx

Mass & Energy Efficiency Calculation ◉

Efficiency power plant can be calculated with the equation shown below: Energy in  η = 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 =   100% = 138300.429% 133.2268559

Product Conversion Efficiency

Product conversion efficiency can be calculated in below: =

 

=

   /  /

x 100%

x 100%

 = 80%

Product Yield

Product yield based on reactant (clove oil) can be calculated as:     =

123.364015 /ℎ 250 /ℎ

= 49.34%

 100%

Energy Consumption of Unit Product 

  =

  

   184309.8591 /ℎ   = 123.364015 /ℎ  = 1494.0326   

4

CONCLUSIONS

1.

2. 3. 4. 5. 6. 7. 8.

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. Clove leaf oil is chosen as main raw material considering the fact of its availability and  potentiality in Indonesia. Kawasan Industri Cikande, Banten, is chosen as vanillin plant location with minimum wages in Rp 3,542,713.50. 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. The production of vanillin are divided into 4 section including eugenol isolation, isomerization, oxidation, and purification. 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. Purification of vanillin requires extraction and re-extraction method using diethylether as waterimmiscible organic solvent. The production capacity in this vanillin plant is 977 tons/year which is higher than the vanillin demand.

Thank You