HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY

MASTER THESIS
Study on the process of purifying cinnamaldehyde from cinnamon cassia oil by
using an advanced distillation method

PHAN NGOC QUANG

Chemical Engineering

Supervisor: Dr. Nguyen Trung Dung
School of Chemical Engineering

Signature of supervisor

Hanoi, 08/2022


TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI

LUẬN VĂN THẠC SĨ
Nghiên cứu quá trình tinh chế Cinnamaldehyde từ tinh dầu quế bằng hệ thống
chưng luyện tiên tiến

PHAN NGỌC QUANG

Ngành: Kỹ thuật Hóa học

Giảng viên hướng dẫn: TS. Nguyễn Trung Dũng
Viện: Kỹ thuật Hóa học

Hà Nội, 08/2022


CỘNG HÒA XÃ HỘI CHỦ NGHĨA VIỆT NAM
Độc lập – Tự do – Hạnh phúc

BẢN XÁC NHẬN CHỈNH SỬA LUẬN VĂN THẠC SĨ
Họ và tên tác giả luận văn: PHAN NGỌC QUANG
Đề tài luận văn : Nghiên cứu quá trình tinh chế Cinnamaldehyde từ tinh dầu quế
bằng hệ thống chưng luyện tiên tiến
Chuyên ngành: Kỹ thuật hóa học
Số hiệu học viên: 20202763M
Tác giả, người hướng dẫn khoa học và Hội đồng chấm luận văn xác nhận tác giả đã
sửa chữa, bổ sung luận văn theo biên bản họp Hội đồng ngày 27/08/2022 với các nội
dung sau:
-

Bổ sung các kết quả nghiên cứu đã có ở Việt Nam và trên thế giới trong phần
tổng quan
Bổ sung phần hồi lưu ở Hình 3.4
Thay thế tỷ số QB/F bằng QB/P trong phần 3.5.

Ngày
Giảng viên hướng dẫn

tháng

năm

Tác giả luận văn


CHỦ TỊCH HỘI ĐỒNG


ĐỀ TÀI LUẬN VĂN
Nghiên cứu quá trình tinh chế Cinnamaldehyde từ tinh dầu quế bằng hệ thống
chưng luyện tiên tiến

Giảng viên hướng dẫn
Ký và ghi rõ họ tên


ACKNOWLEDGEMENT
First of all, I really appreciate my family that is my biggest motivation, for giving
me the best to study and practice so far.
Secondly, I would like to express my deep appreciation to my supervisor Dr.
Nguyen Trung Dung, for pursuing my Master’s study at the School of Chemical
Engineering, Hanoi University of Science and Technology, giving me a great
chance to intern at the National Polytechnic Institute of Toulouse and many
precious contributions to complete this thesis. Because of my thesis defense, he
had to delay his work. One more time I really appreciate him.
I also would like to give precious thanks to Dr. Ta Hong Duc, who is a crucial
person in my career path. He always believed, motivated, directed, and gave me
many great opportunities to achieve my expectations. Besides, he encouraged me
to take part in related programs, seminars, and outside programs to improve my
horizon. One more time, I really appreciate his help on my path.
I also really appreciate Dr. Cao Hong Ha, who helped directly me a lot from first
technics to making experiments and scientific ideas for my research from the first
days when I began to approach the topic of my research in the laboratory.
Especially, I am really grateful for his perfect suggestions which help me improve

significantly my knowledge a lot. One more time, I would like to sincerely thank
his help during all of my working time in the laboratory. No matter where I go or
do anything in the future, I still want to be taught by him. Besides that, I would
like to thank Thầy Hiệp, who guided me in testing samples in my part-time job.
I would like to express my sincere thanks to Dr. Phung Lan Huong, Assoc. Prof.
Dr. Chu Manh Hung, Assoc. Prof. Dr. Nguyen Dac Trung, Assoc. Prof. Dr. Dinh
Van Hai, Ms. Tran Vu Huong Tra, and Ms. Trinh Thi Thuy Linh for not only
giving me a valuable opportunity to study in France but also helping me
wholeheartedly home country’s priority in the stressful time of the covid
pandemic.
I would like to thank lecturers in the Department of Chemical Process Equipment
for their teaching, giving me contributions, and always creating the best conditions
for students to improve.
I also really appreciate Prof. Michel Meyer, who gave me a perfect opportunity to
work at LGC, INP-Toulouse, and supported me with great scientific ideas. That is
a duration of a memorable time in my life with Dr. Benoit Mizzi who helped a lot
in my work.
I would like to thank MSc. Pham Duc Chinh always advised and supported me
anytime. In addition to being a lot of help came from my colleague Juan Bulle who
is a good teammate. We have a memorable duration of time when working
together.


I really appreciate Mr. Jean Louis Guy – “Thầy chủ nhà”, chị Linh, anh Bản, chị
Ngân for their help during my working time in Toulouse. I am really happy and
lucky when I met them with a memorable time in Toulouse, France.
I also would like to warmly thank anh Nguyễn Chiêm Dương Thanh and my
friends Trương Khánh Duyên, Lại Văn Duy, Bùi Văn Trường, Lê Công Tuấn who
helped me in difficult time and other students in laboratory: Hảo, Mai, Ngọc,
Thạch Mai – Máy hóa K62 and Cơng, Trọng – Hóa lý.

Last but not least, I would like to thank Prof. Michel Meyer’s scholarship and
Vallet scholarship 2021 and 2022 which are gratefully acknowledged.
A memorable journey closed to open the next journey with new interesting things.
Thanks and regards!!!


SUMMARY
The cinnamon tree is widely distributed throughout tropical and sub-tropical areas.
It is widely used as herbal medicine. Vietnam is the world's third largest producer
of cinnamon oil. Cinnamon oil contains cinnamaldehyde (80-90%wt), eugenol,
cinnamic acid, etc. Therefore, it can be used to produce high purity
Cinnamaldehyde (99%wt) via high-vacuum batch distillation (1–30mmHg).
However, the disadvantages of the process are the relatively long separation time,
the high energy consumption, and the loss of a large amount of Cinnamaldehyde
into the light and middle cut-of components.
Two continuous columns were used to purify Cinnamaldehyde from Cinnamon
cassia oil. The NRTL thermodynamic model is used to calculate and simulate the
process. The preliminary configurations of columns were obtained by using the
FUGK method, which is calculated by the DSTWU model in Aspen plus V10. The
Radfrac model was used for the rigorous simulation. The heat integration was
performed when the vapor stream temperature in the second column was greater
than the reboiler temperature in the first column by at least 10oC. The purity of
Cinnamaldehyde was 0.99 mass fraction and the recovery ratio was 98.60% in all
of the cases. When P1=10mmHg, P2=20mmHg, heat integration was applied for
process and QB,total,min =1326 cal/s.
Process intensification technology, which is one of the most significant advances
in chemical engineering today, offers the potential for development in the chemical
industry. A divided wall column is an excellent illustration of a method for process
intensification. The optimal configurations of DWC are N1=6, N2=14, N3=2, N4=6,
N5=14, N6=7 with heat duty is 1219 cal/s at P=10mmHg.

Four different random packings (M-50, M-80, O-80, S-80) were characterized by
HETP values when using mixture of n-Hexane and Cyclohexance at differrent
concentrations. The results showed that O-80 is the minimum HETP value in four
type of packings. Therefore, the applications of these packings in the industry are
feasible.


CONTENTS
ACKNOWLEDGEMENT ....................................................................................... ii
SUMMARY ........................................................................................................... iv
LIST OF FIGURES ................................................................................................ iii
LIST OF TABLES ...................................................................................................v
LIST OF SYMBOLS AND ABBREVIATIONS .................................................... vi
INTRODUCTION ....................................................................................................1
CHAPTER 1. LITERATURE REVIEW ...................................................................2
1.1.

Overview of Cinnamaldehyde .....................................................................2

1.1.1.

Introduction of Cinnamaldehyde ...........................................................2

1.1.2.

Application of Cinnamaldehyde ............................................................3

1.1.3.

Preparation of Cinnamaldehyde ............................................................4


1.2.

Overview of Cinnamon Cassia Oil ..............................................................5

1.2.1.

Origin and distribution in nature ...........................................................6

1.2.2. Demand, production, benefits of using, and value of cinnamon cassia
oil………………………………………………………………………...……...7
1.3.

Cinnamaldehyde purification technologies from Cinnamon Cassia Oil......10

1.3.1.

Batch distillation model ......................................................................10

1.3.2.

Continuous distillation model .............................................................11

1.3.3.

Divided wall column model ................................................................13

1.4.

Conclusion chapter 1 .................................................................................19


CHAPTER 2. METHOD OF STUDY ....................................................................20
2.1. Determination of the thermodynamic model .................................................20
2.2. Simulation method .......................................................................................20
2.2.1. Methodology of the continuous distillation column ................................20
2.2.2. Methodology of Divided wall column ....................................................21
2.3. Pinch technology ..........................................................................................37
2.4. Method to evaluate the product quality .........................................................38
2.4.1. Determine the refractive index of the products .......................................38
2.4.2. Gas Chromatography..............................................................................39
i


CHAPTER 3. RESULTS AND DISCUSSION .......................................................40
3.1. Material characteristics .................................................................................40
3.2. Choosing the best thermodynamic model .....................................................40
3.2.1. Experimental data ..................................................................................40
3.2.2. Simulation data ......................................................................................40
3.3. Continuous distillation..................................................................................44
3.3.1. Shortcut calculation ................................................................................44
3.3.2. Rigorous simulation ...............................................................................45
3.4. Divided wall column ....................................................................................52
3.4.1. Initial parameters for simulation .............................................................52
3.4.2. Sensibility analysis of Divided wall column ...........................................53
3.5. Comparison of three distillation models: batch column, continuous column
and DWC ............................................................................................................55
3.6. Determination of the HETP of the various random packing ..........................56
3.6.1. Material of the packing...........................................................................56
3.6.2. Distillation pilot plant.............................................................................57
3.6.3. HETP calculation ...................................................................................59

CHAPTER 4. CONCLUSION AND OUTLOOK ...................................................62
4.1. Conclusion ...................................................................................................62
4.2. Outlook ........................................................................................................62
APPENDIX ............................................................................................................63
REFERENCES .......................................................................................................67

ii


LIST OF FIGURES
Figure 1.1. Cinnamaldehyde .....................................................................................2
Figure 1.2. Global Cinnamic Aldehyde Market, by the application (%) [1]...............3
Figure 1.3. Crude cinnamon Cassia Oil ....................................................................5
Figure 1.4. Cinnamon tree ........................................................................................5
Figure 1.5. Supply of cinnamon oil ...........................................................................6
Figure 1.6. Importers of cinnamon cassia oil ............................................................8
Figure 1.7. Batch disstillation column.....................................................................11
Figure 1.8. Conventional arrangements for separating three components mixture
a)direct, b)indirect, c)sloppy sequences ..................................................................14
Figure 1.9. Fully thermally coupled distillation column (Petlyuk column) ..............15
Figure 1.10. HIDiC disstilation column ..................................................................15
Figure 1.11. Divided wall column...........................................................................16
Figure 1.12. Seperation for ternary mixture in the divided wall column ..................16
Figure 1.13. Energy is lost separating the middle component B in the conventional
arrangement ............................................................................................................17

Figure 2.1. (a) DSTWU and (b) RADFRAC models in Aspen plus V10 ................21
Figure 2.2. Petlyuk column configuration ...............................................................22
Figure 2.3. (a) Divided wall column; (b) Thermally coupled distillation .................24
Figure 2.4. Simplified model design of divided wall column ..................................25

Figure 2.5. The detailed structure and operating variables of a divided wall column
...............................................................................................................................33
Figure 2.6. Types and position of dividing wall in the DWC system .......................35
Figure 2.7. A procedure for the design of a divided wall column ............................36
Figure 2.8. Schematic of pinch technology .............................................................37
Figure 2.9. Refraction of a light ray ........................................................................38
Figure 2.10. Diagram of a gas chromatography ......................................................39

Figure 3.1. x,y-T diagram for the BA-CA system at 10kPa .....................................41
Figure 3.2. x,y-T diagram for the BA-CA system at 20kPa .....................................42
Figure 3.3. x,y-T diagram for the BA-CA system at 30k.........................................43
Figure 3.4. Block flow diagram (BFD) of purification process ...............................44
Figure 3.5. Plot of the relationship between P1, P2 and QB1, QB2, QB,total ..................47
Figure 3.6. Plot of TW1 and TD2 ...............................................................................47
Figure 3.7. Graph of the relationship between P2-QB2 and comparison TW1-TD2 ......49
Figure 3.8. Plot of TW1 at P1=10mmHg and TD2 at P2=15-100mmHg ......................49
Figure 3.9. Flowsheet of energy integration for two columns with case P1=10mmHg,
P2=20mmHg ...........................................................................................................49
iii


Figure 3.10. Plot of the relationship between P2 and QB2 ........................................50
Figure 3.11. Plot of TW1 at P1=10mmHg and TD2 at P2=5-9mmHg ..........................51
Figure 3.12. Plot of the comparison of cases with the minimum QB,total values in
cases 1,2,3 ..............................................................................................................51

iv


LIST OF TABLES

Table 1.1. Two types of cinnamon cassia oil.............................................................5
Table 2.1. Relationship between feed quality and internal flowrates .......................33
Table 3.1. Five main components in CCO ..............................................................40
Table 3.2. Experimental VLE data and calculated results by the different models in
Aspen Plus for binary system of BA-CA at 10 kPa .................................................41
Table 3.3. Experimental VLE data and calculated results by the different models in
Aspen Plus for binary system of BA-CA at 20 kPa .................................................42
Table 3.4. Experimental VLE data and calculated results by the different models in
Aspen Plus for the binary system of BA-CA at 30 kPa ...........................................43
Table 3.5. Short-cut calculation and rigorous simulation results in two columns at
P1=P2=10-100mmHg ..............................................................................................46
Table 3.6. Short-cut calculation and rigorous simulation results in two columns at
P1=10mmHg, P2=15-100mmHg..............................................................................48
Table 3.7. Short-cut calculation and rigorous simulation results in two columns at
P1=10mmHg, P2=5-9mmHg ...................................................................................50
Table 3.8. Specification for short-cut calculation by DWC .....................................52
Table 3.9. Comparison of three distillation models .................................................55
Table 3.10. Technical data of packaging materials ..................................................57
Table 3.11. HETPm evaluations .............................................................................61

v


LIST OF SYMBOLS AND ABBREVIATIONS
CA

Cinnamaldehyde

BA


Benzaldehyde

CH

Cinnamyl Alcohol

CCO

Cinnamon Cassia Oil

HI

Heat Integration

BFD

Block Flow Diagram

VLE

Vapor – Liquid Equilibrium

NRTL

Non-Random Two-Liquid Model

HK

Heavy Key


LK

Light Key

HETP

Height Equivalent to a Theoretical Plate

HTU

Height of Transfer Unit

QB1

Heat duty of the first column

QB2

Heat duty of the second column

QB,total

Total heat duty of the first and second column

∆T

Temperature difference between two streams D2
and W1

vi



INTRODUCTION
Nowadays, natural productions play an important role in the quality of food and
beverages. Among them, Cinnamaldehyde (CA) is of commercial importance for
flavor, being the main component in Cinnamon Cassia Oil (CCO), which is commonly
used in pharmaceutical, food, and beverages industries because of its merits [1, 2, 3].
In order to obtain natural Cinnamaldehyde with higher purity, purification of CA from
CCO is one of the best ways.
Distillation is the most often used separation method in the chemical industry [4]
whereas batch distillation is the most commonly used method to purify essential oil.
Typically, CA is produced from CCO by a high-vacuum batch distillation process [5,
6]. For the batch distillation, the multicomponent mixture can be separated by a single
column and its flexible operation [7], but according to the previous study, with CCO
mixture, the disadvantages of the batch column is a large amount of CA loss, long
separation time and high energy consumption [6]. Besides, distillation is an energyintensive process, so the problem of reducing energy consumption during distillation
is of economic significance [8].
In this thesis, the relationship between pressure and heat duty of columns was
investigated and a solution was proposed to save energy by using two continuous
columns system to purify CA from CCO. In which, choosing a highly reliable
thermodynamic model is the most important for designing and simulation the
distillation column. The short-cut method was used to calculate the preliminary
structure of the columns. The rigorous simulations are performed to determine the
heat duty of the column and find the minimum value of total heat duty. Heat
integration is carried out to optimize the distillation process. The pressures of columns
were investigated in the range of 5-100 mmHg.
Another model of distillation is Divided wall column (DWC) is used to simulate in
the purification the CA from CCO. The objective of this work was to obtain CA 99%
mass fraction in the final product which was done by Aspen plus software. The
purpose of thesis is to obtain the optimal configurations of two models distillation

columns: continuous and DWC model.

1


CHAPTER 1. LITERATURE REVIEW
1.1. Overview of Cinnamaldehyde
1.1.1. Introduction of Cinnamaldehyde
Cinnamaldehyde (CA) is an organic compound with the formula C6H5CH=CHCHO.
Occurring naturally as predominantly the trans (E) isomer, it gives cinnamon its flavor
and odor. Figure 1.1 shows the natural cinnamic aldehyde is a pale yellow colored
organic compound that is widely used in liquid form.
A yellow oily liquid more viscous than water, cinnamaldehyde smells strongly of
cinnamon. Concentrated cinnamaldehyde is a skin irritant, and the chemical is toxic
in large doses, but no agencies suspect the compound is a carcinogen or poses a longterm health hazard. Most cinnamaldehyde is excreted in urine as cinnamic acid, an
oxidized form of cinnamaldehyde.
Both aromatic and an aldehyde, cinnamaldehyde has a mono-substituted benzene ring.
A conjugated double bond (alkene) makes geometry of the compound planar.
Cinnamaldehyde is technically trans-cinnamaldehyde because the terminal carbonyl
is on the opposite side of the aromatic ring over the rigid double bond.
Global Natural Cinnamic Aldehyde Market is expected to grow at a CAGR of 4.17%
during the forecast period and is expected to reach US$ 1326.54Mn by 2027. The
report covers an in-depth analysis of COVID 19 pandemic impact on the Global
Natural Cinnamic Aldehyde Market by region and on the key player revenue affected
till July 2020 and expected short-term and long-term impact on the market. It finds
significant applications in the perfume, food & beverages, metal & mining industries
[1].

Figure 1.1. Cinnamaldehyde


2


1.1.2. Application of Cinnamaldehyde

Figure 1.2. Global Cinnamic Aldehyde Market, by the application (%) [1]
❖ An antimicrobial agent
Cinnamaldehyde exhibits antimicrobial activity. The antimicrobial nature of
Cinnamaldehyde was proved by a study conducted at the University of Illinois,
Chicago. It had been found that Cinnamaldehyde prevents above 50% of bacterial
growth in the oral cavity. It is especially effective for preventing the growth of bacteria
and other pathogens in the tongue.
According to a study titled “Antimicrobial Activities of Cinnamon Oil and
Cinnamaldehyde from the Chinese Medicinal Herb Cinnamomum cassia Blume”
published in The American Journal of Chinese medicine, Cinnamaldehyde effectively
inhibits the growth of various segregates of bacteria including gram-positive and
gram-negative bacteria, fungi including yeasts, filamentous mold and dermatophytes.
Thus, Cinnamaldehyde possesses anti-bacterial and antifungal properties.
❖ As perfume additive
Cinnamic aldehyde has a good fragrance holding effect. It is used as the raw material
in perfumes to make the aroma of the main spices more fragrant.
For example, adding edible Cinnamic aldehyde in soap essence can make essences of
hyacinth, Cape jasmine, jasmine, lily of the valley, rose and so on. These essences are
widely used in soaps, laundry powder and shampoo.
In food, Cinnamic aldehyde can be used to make fruit essences such as apple and
cherry essences, which can be used in candy, ice cream, beverage, gum, cake and
tobacco.
❖ As a flavoring agent

3



Cinnamaldehyde is mainly added to foods and medicines to enhance its quality in
terms of aroma and taste. It is used as a flavoring agent in liquid refreshments, ice
creams, chewing gums, and candy. It is also used in perfumes to recreate the magic
of fruity and interesting fragrance ranges.
1.1.3. Preparation of Cinnamaldehyde
A technique to synthesize cinnamaldehyde was published in 1884. Several methods
of synthesis are now known, but cinnamaldehyde is most economically obtained from
the steam distillation of the oil of cinnamon bark. The compound can be prepared
from related compounds like cinnamyl alcohol, (the alcohol form of cinnamaldehyde),
but the first synthesis from unrelated compounds was the aldol condensation of
benzaldehyde and acetaldehyde.
Several methods of laboratory synthesis exist, but cinnamaldehyde is most
economically obtained from the steam distillation of the oil of cinnamon bark. The
compound can be prepared from related compounds such as cinnamyl alcohol (the
alcohol form of cinnamaldehyde) but the first synthesis from unrelated compounds
was the aldol condensation of benzaldehyde and acetaldehyde. This process was
patented by Henry Richmond on November 7, 1950.
CA occurs widely, and closely related compounds give rise to lignin. All such
compounds are biosynthesized starting from phenylalanine, which undergoes
conversion.
The biosynthesis of cinnamaldehyde begins with deamination of L-phenylalanine into
cinnamic acid by the action of phenylalanine ammonia lyase (PAL). PAL catalyzes
this reaction by a non-oxidative deamination. This deamination relies on the MIO
prosthetic group of PAL. PAL gives rise to trans-cinnamic acid. In the second step, 4coumarate–CoA ligase (4CL) converts cinnamic acid to cinnamoyl-CoA by an acid–
thiol ligation. 4CL uses ATP to catalyze the formation of cinnamoyl-CoA.[12] 4CL
effects this reaction in two steps. 4CL forms a hydroxycinnamate–AMP anhydride,
followed by a nucleophile attack on the carbonyl of the acyl adenylate. Finally,
Cinnamoyl-CoA is reduced by NADPH catalyzed by CCR (cinnamoyl-CoA

reductase) to form cinnamaldehyde.
In the plant, these compounds may have evolved to ward off hungry herbivores and
help defend against pathogenic fungi and bacteria. Investigation of cinnamaldehyde’s
bioactive properties have found it to be an effective insecticide – specifically against
mosquito larvae – and an effective repellent to ward off adult mosquitoes. Although
there’s not enough evidence at present to state any specific health benefits with
confidence, there’s some suggestion it can prevent formation of Tau protein tangles,
so may have a role to play in preventing or treating Alzheimer’s disease. It’s being
investigated for its role in metabolic health and obesity, as it seems to interact with
4


adipose tissue. Cinnamaldehyde can also kill certain bacteria outright, while it inhibits
the growth of others and prevents them from forming a biofilm.
1.2. Overview of Cinnamon Cassia Oil
Cinnamon is a perennial woody plant that can grow up to 15m tall in an adult tree,
and up to 40cm in diameter at chest height 1.3m in Figure 1.4. Cinnamon has simple
leaves growing apart or close to the opposite, leaves with 2 base veins extending to
the tip of the leaf. Cinnamon has green ovate foliyear-round, and natural pruning is
poor in Figure 1.3. All parts of cinnamon contain essential oils, especially in the bark
which can reach 3 - 4% dry weight. Self-inflorescences grow at the tips of branches,
small white or yellowish flowers. There are two types of cinnamon cassia oil with the
different properties are showed in Table 1.1.

Figure 1.3. Crude cinnamon Cassia Oil

Figure 1.4. Cinnamon tree
Table 1.1. Two types of cinnamon cassia oil
Made from
Aroma

Color
Taste

Bark Cassia Oil
Tree bark
Strong, robust
Clear yellow to deep reddishbrown
More expensive
5

Leaf Cassia oil
Tree leaf
Mild scent and musky aroma
Lighter in color, often
brownish-yellow
Cheaper


1.2.1. Origin and distribution in nature
1.2.1.1. Distribution of cinnamon cassia oil in the world
In the world, cinnamon is naturally distributed and cultivated as a commodity in some
Asian and African countries such as Sri Lanka, Madagascar, Indonesia, China and
Vietnam. In countries with cinnamon, the cinnamon tree is only distributed in a certain
locality, where the climate, soil and topographic characteristics are suitable for it.
Outside the ecological zone, cinnamon will not grow and develop well.

Figure 1.5. Supply of cinnamon oil
The world’s greatest exporter of cinnamon is Vietnam. It is widely renowned for the
cassia cinnamon essential oil made from Saigon cinnamon, which has a richer flavor
and perfume than cassia cinnamon farmed in China. Vietnamese Cassia cinnamon

essential oil has a golden or dark-brown hue, and its perfume is similar to that of
Vietnamese cinnamon. Its flavor is sweet, woodsy, and just a touch peppery.
Aldehyde cinnamic acid, which makes up roughly 80–95% of the whole composition,
is the primary component in Cassia cinnamon oil. Consequently, one of the
advantages of Vietnamese Cassia cinnamon essential oil over Chinese Cassia
cinnamon oil is its distinctive scent, which is frequently acknowledged to have a really
fantastic flavor. And it’s clear from that why Vietnamese Cassia cinnamon essential
oil is pricier than Chinese one.
1.2.1.2. Distribution of cinnamon in Vietnam
In our country, natural cinnamon trees grow mixed in humid tropical natural forests,
from North to South. However, up to now, natural cinnamon has disappeared and
instead is a domesticated cinnamon tree. For a long time, our country has formed 4
6


cinnamon growing regions, each with its own natural nuances in terms of ethnicity
and benefits from cinnamon.
The major cinnamon growing areas in Vietnam (by area) are in the following order:
- Cinnamon Yen Bai: Cinnamomum cassia
Yen Bai cinnamon area has the largest area, up to 60,000 hectares. Que Yen Bai is
concentrated in Van Yen, Van Chan, Van Ban and Tran Yen districts of Yen Bai
province. The characteristics of Yen Bai cinnamon area are divided and dangerous
mountain forests, located in the East and Southeast of Hoang Lien Son range, with an
absolute height of about 300 - 700m; the average annual temperature is 22.7oC; the
average annual rainfall is over 2,000mm; average humidity is 84%. The soil develops
on sandstone, schist with thick, moist, humus-rich and well-drained soil.
- Cinnamon Quang Nam, Quang Ngai: Cinnamomum cassia
The districts of Tra Mi (Quang Nam province) and Tra Bong (Quang Ngai province)
are located to the East of the Truong Son range, with an area of up to 17,700 hectares
of cinnamon growing. Tra Mi and Tra Bong cinnamon areas have an altitude of about

400 - 500 m; average annual temperature 22oC; average rainfall is 2300 mm/year;
average humidity is 85%. Soil developed with parent rocks, sandstone or sandstone
with thick, moist, well-drained soil layer.
- Que Thanh Hoa, Nghe An: Cinnamomum Loureirii
Que Phong, Quy Chau (Nghe An province) and Thuong Xuan, Ngoc Lac (Thanh Hoa
province) districts are a contiguous region located to the east of Truong Son mountain
range, with latitude from 19o - 20o north, with planted area. cinnamon about 12,200
ha. Here, average pond level is about 300 - 700 m; average temperature 23.1oC;
average rainfall is over 2000 mm/year; average humidity is 85%. Plants in the area
are diverse and abundant, Que Thanh and Que Quy here are considered the best in the
country because of their high quality and essential oil content.
- Quang Ninh cinnamon: Cinnamomum cassia
Hai Ninh, Ha Coi, Dam Hoa, Tien Yen and Binh Lieu districts (Quang Ninh province)
are hilly areas close together in the Northeast arc extending to the sea, with an area of
about 6,800 hectares of cinnamon growing. Due to the terrain blocking the wind, the
rainfall is very high, about 2,300 mm/year; altitude is about 200-400m; average annual
temperature is 23oC.
1.2.2. Demand, production, benefits of using and value of cinnamon cassia oil
1.2.2.1.
World demand

7


Cinnamon products in our country have been traded for a long time. The formation of
the cinnamon market from small to large today is due to the increasing demand for
cinnamon in the world market. But cinnamon is only suitable for growing in some
parts of the world, so the market for cinnamon is even more exciting.
The cinnamon production market is valued at 0.23 million tons, based on 2018
production volume, and is expected to reach a volume of 0.25 million tons by 2024,

witnessing a growth rate of 2.21% in the forecast period 2019 - 2024. In which the
fastest and largest growing market is Asia - Pacific.

Figure 1.6. Importers of cinnamon cassia oil
Figure 1.6 indecated that the importers of cinnamon cassia oil while Malaysia: In
2020, Malaysia imports $196.3M worth of cassia cinnamon essential oil in total. This
figure has been decreasing since 2017, reaching $164.5M in 2019, then rising again
until now. Even though it only accounts for 6.5% of total annual import, Malaysia is
still the number one importer of this product. If you are looking for a client to sell
cassia cinnamon essential oil, you should try to find one in Malaysia.
Netherlands: With $180.9M import volume of cassia cinnamon essential oil in 2020,
Netherlands is the world’s second largest importer of Cassia oil. Since 2017,
Netherlands’ import of cassia cinnamon essential oil has been constantly increasing.
Therefore, it can be expected that this country will take over Malaysia and become
the biggest consumer of Cassia oil.
Italy: Italy is the country with the biggest growth in the period from 2019 to 2020, at
a stunning 92.18% increase from $81M to $156M. This growth can mark a milestone
for the cassia cinnamon essential oil market of Italy.
8


1.2.2.2.

Benefits of using Cinnamon Cassia Oil

Cinnamon Cassia Oil has many amazing benefits related to health, mostly because of
its chemical components. Some of the most popular advantages are:
❖ Treats diarrhea
Everyone knows what diarrhea is, and if you have ever got it, you would also know
how bad and annoying it is. Luckily, now you know that Cassia cinnamon essential

oil can treat this illness.
❖ Improves circulation
By enhancing blood flow throughout the body, cassia cinnamon oil makes sure that
you get enough oxygen and minerals to thrive. The benefits of cassia cinnamon oil
include increased blood circulation, a warming sensation throughout the body, pain
relief, a reduction in disease-causing inflammation, and stimulation of urine, which
helps the body rid itself of pollutants.
On the other hand, cinnamon cassia oil can aid in the prevention of these two
potentially fatal illnesses by improving circulation, which lowers the risk of heart
attack and stroke.
❖ Relieves arthritis
According to estimates, 67 million Americans from 18 years old above will have
arthritis by 2030, which is characterized by stiff, painful, difficult-to-move joints and
bones. As pain and swelling in the joints are common indications of arthritis, cassia
oil’s anti-inflammatory qualities help to naturally lessen these symptoms.
❖ Antidepressant
It has been studied that cinnamic aldehyde, the iconic substance of Cassia cinnamon
essential oil, can reduce stress. That is why Cassia cinnamon essential oil is frequently
used for vaporizing. By inhaling some of the oil, your nerves can be relieved a lot,
leaving the body with a cozy and peaceful sensation.
❖ Boost immune system
Even minor, Cassia cinnamon essential oil does have an impact of boosting your
immune system. In addition to acting as a febrifuge and antibacterial, cassia oil also
has antiviral and antimicrobial properties. This therapeutic oil guards against bacterial
activity and infections in the urethra, colon, kidneys, and urinary tract.
There are still some more benefits like fighting bacterias, treating diabetes, or even
working as a bug repellent.
1.2.2.3.

Economic value of cinnamon

9


Yen Bai is the province with the largest cinnamon area in the North of Vietnam,
concentrated in the districts of Van Yen, Tran Yen, Van Chan, Yen Binh and Luc
Yen. Currently, cinnamon has become one of the main crops, bringing high economic
value to Yen Bai people. The goal is to strive that by 2020, the province will plant
19,500 hectares of new cinnamon, the area of cinnamon trees in the province is 76,000
hectares with a bark output of 20,000tons and 600tons of essential oil. Each year, there
are 2 harvests of cinnamon, the first crop of the year (March-May) and the end-year
crop (from August to October). In 2017, the selling price of cinnamon was stable at a
high level, dried cinnamon bark sold for an average price of 30,000 - 40,000VND/kg,
cinnamon leaves 2 - 3 thousand VND/kg, cinnamon stems of 15cm or more sold for
1.5 - 1.8 million VND/m3, cinnamon essential oil from 500 to 600 thousand VND/kg.
According to the current selling price with the above output of cinnamon in 2020, it
will then bring income to people in the province more than 1 trillion VND/year.
According to the Department of Agriculture and Rural Development of Yen Bai
province, the whole province has over 60,000 hectares of cinnamon, earning more
than 800 billion VND each year, most of which is concentrated in Van Yen district
with an area of over 40,000hectares. The district has become the largest commodity
cinnamon growing area in the country today, each year the district exports about 9,000
tons of dried cinnamon sticks of all kinds, earning 500 billion VND.
1.3. Cinnamaldehyde purification technologies from Cinnamon Cassia Oil
1.3.1. Batch distillation model
Batch distillation is widely used for separation processes in pharmaceutical,
biochemical, and chemical industries. As the study of Zhong Chan-yong et al a
process for preparing CA from CCO by using vacuum distilltion and molecular
distilaltion was investigated. The purity and yield of the final product were 98.66%
and 84.68%, respectively. The purity and yield reach 99.5% and 85.63% respectively
after molecular distillation [2].

One of the main advantages of batch distillation in Figure 1.7 is the possibility
separating a multicomponent mixture into high purity of products in only one
distillation column. CA or trans-cinnamaldehyde is contained in the leaves, bark,
twigs and stalks of the cinnamon, and it is the major component of cassia oil (> 75%
mass). The high purity cinnamic aldehyde (greater than 99% mass) can be obtained
from cinnamomum cassia oil by the high vacuum batch distillation. However,
disadvantages of this process are the relatively long separation time which means that
the energy consumption must be correspondingly large, and the loss of a large amount
of CA into the light and middle cut-of components. To overcome the disadvantages,
both the structure of batch distillation column and the reflux ratio policy for the
operation must be optimized. The optimization problems related to distillation are

10


often maximizing distillate amount, minimizing operating time, and maximizing the
techno-economical profit.

Figure 1.7. Batch disstillation column
1.3.2. Continuous distillation model
Until now, there is no study about the purifycation of CA from CCO by continuous
distillation while it is an ongoing separation process in which a liquid mixture of two
or more miscible components is continuously fed into the process and physically
separated into two or more products by preferentially boiling the more volatile (lower
boiling point) components out of the mixture.
Large-scale, continuous distillation is commonly used in the chemical process
industries where large quantities of liquids have to be distilled, as in petroleum
refining, natural gas processing, the liquid fraction of gases such hydrogen, oxygen,
nitrogen, and helium, and the other low temperature processing.
Industrial distillation is typically performed in large, vertical cylindrical columns

referred to as distillation columns or fractionators with diameters ranging from about
65 centimetres to 11 metres and heights ranging from about 6 metres to 60 metres or
more [2].
The principle for continuous distillation is the same as for normal distillation: when a
liquid mixture is heated so that it boils, the composition of the vapor above the liquid
differs from the liquid composition. If this vapor is then separated and condensed into
a liquid, it becomes richer in the lower boiling point components of the original
mixture.

11


This is what happens in a continuous distillation column. A mixture is heated up, and
routed into the distillation column. On entering the column, the feed starts flowing
down but part of it, the components with lower boiling points, vaporizes and rises.
However, as it rises, it cools and while part of it continues up as vapor, some of it
enriched in the less volatile component begins to descend again
A feed stream into two fractions, an overhead distillate product and a bottoms product.
The "lightest" products (those with the lowest boiling point or highest volatility) exit
from the top of the columns and the "heaviest" products (the bottoms, those with the
highest boiling point) exit from the bottom of the column. The overhead stream may
be cooled and condensed using a water-cooled or air-cooled condenser. The bottoms
reboiler may be a steam-heated or hot oil-heated heat exchanger, or even a gas or oilfired furnace.
In a continuous distillation, the system is kept in a steady state or approximate steady
state. Steady state means that quantities related to the process do not change as time
passes during operation. Such constant quantities include feed input rate, output
stream rates, heating and cooling rates, reflux ratio, and temperatures, pressures, and
compositions at every point (location). Unless the process is disturbed due to changes
in feed, heating, ambient temperature, or condensing, steady state is normally
maintained. This is also the main attraction of continuous distillation, apart from the

minimum amount of (easily instrumentable) surveillance; if the feed rate and feed
composition are kept constant, product rate and quality are also constant. Even when
a variation in conditions occurs, modern process control methods are commonly able
to gradually return the continuous process to another steady state again.
Since a continuous distillation unit is fed constantly with a feed mixture and not filled
all at once like a batch distillation, a continuous distillation unit does not need a sizable
distillation pot, vessel, or reservoir for a batch fill. Instead, the mixture can be fed
directly into the column, where the actual separation occurs. The height of the feed
point along the column can vary on the situation and is designed so as to provide
optimal results.
The design of a distillation column depends upon the composition and the thermal
condition of the feed as well as the composition of the desired products. The McCabeThiele method and the Fenske equation may be used to design a simple binary
distillation column.
To design a column for the distillation of a multi-component feed to provide more
than two product distillates computerized simulation models may be used for the
design as well as for the subsequent online operation of the column.

12