Volatile Oil Production

Natural Product Technology

VOLATILE OIL PRODUCTION
▪ Steam distillation
▪ Water-Steam distillation
▪ Distillation-Maceration
▪ Empyreumatic (or destructive) distillation
▪ Pressing
▪ Extraction with solvent
▪ Extraction with supercritic gas
▪ Enfleurage
Steam Distillation
▪Do not let water in the tank dry (insufficient amount
of water may cause overheating and charring,
formation “off notes” or frequently called “still
notes”. The cause is Maillard reaction, Strecker
degradation, pyrolitic degradation).
▪Always mixed to avoid sedimentation and
overheated. Cinnamon powder will sediment
releasing mucilago , increase viscosity and
charring.
▪Volatile oil in ester form may hydrolyzed, aldehyde
easily oxidized and polymerized..
▪Oxygenated component may partially soluble in
water and difficult to separate.
▪Usually production in small scale, good product
may mixed with poor quality product.
▪Practician consider process as an art and not
oriented at optimization (from quality or quantity
aspect).
Historical Background
▪ Distillation was first recorded in the valley of Indus River in pakistan 5000 years
ago (approximately 3000 BC)
▪ It was thought in Arabia 1000 years ago. May be due to cultural exchange and not
reinvention by Arabian.
Principles in Distillation

▪ TD-1 : Energy (hot) can not be created or destroyed in a system with constant
mass.
▪ TD II : Hot can not be transferred from colder to hotter system by a continuous
spontaneous process.
Related Principles
▪Boyle Law : Gas volume reversely correspond to
pressure
V ~ 1/p
▪Charles Law: gas Volume ~ T absolute at
constant P
V~T
▪Avogadro : The same gas volume will contain
the same number of molecule at the same P and
T.
1 mol = 22,4 L at 1 Atm
Latent Heat
▪ Change from liquid to vapor needs energy supplied as a heat. If the heat is not
replaced, the liquid is cooling.
▪ The heat is called latent heat for evaporation.
Latent heat
▪ Heat absorbed or released as the result of a phase change is called
latent heat. There is no temperature change during a phase change,
thus there is no change in the kinetic energy of the particles in the
material. The energy released comes from the potential energy
stored in the bonds between the particles.
▪ exothermic (warming processes)
▪ condensation
▪ warmer in the shower
▪ steam radiators
▪ freezing
▪ orange growers use ice to stop oranges from freezing
▪ deposition
▪ snowy days are warmer than clear days in the winter
▪ endothermic (cooling processes)
▪ evaporation / boiling
▪ sweat
▪ alcohol is "cool"
▪ melting
▪ melting ice in drinks
▪ sublimation
▪ cooling with dry ice
▪ Q = mL
Scattered thoughts
▪ Under extreme conditions of heat and exercise, an individual may
sweat more than a liter of liquid per hour.

▪ The interior of roasted meat can never reach temperatures higher than the
boiling point of water until all the water is cooked out of it, at which point it
would resemble shoe leather. The outside is quickly dried out, and can reach
the temperature of the surrounding cooking medium.

▪ Cocoa butter is unique among the fats in that it is very regular in composition;
whereas most other fats are actually mixtures. This gives it a very definite
point; unlike butter, which softens gradually. As it melts in your mouth, it
absorbs latent heat. This makes chocolate bars taste "cool". Cocoa butter is
remarkably uniform in composition and structure: only three fatty acids in the
majority of its triglycerides, with the same one occupying the middle position.
Pure cocoa butter is quite brittle up to about 34 ℃ (93 ℉), at which point it
melts quite quickly.
Vapor Pressure
▪ At controlled temperature, constant volume, vapor and liquid are in balance.
Pressure produced is vapor pressure.
▪ If the temperature increases the pressure will also increase.
▪ In saturated vapor balance
▪ V increase, T constant, mol vapor increase, accompanied with a slight
cooling due to latent evaporation heat, and the pressure decrease.
▪ If all liquid become vapor:
▪ T increase, molecule is not longer balance, the vapor become
superheated, T> BP, contact with humid, evaporate, saturation and T
decrease.
In an open system
▪ Liquid continuously evaporate, only little part condensate
and the balance vapor-liquid does not take place.
▪ During evaporation, cooling takes place.
▪ The speed of evaporation remain constant if T and P
constant.
▪ Liquid is heated, P increase reaching vapor pressure=
atmospheric pressure (the atmosphere is only filled with the
vapor).
 Unit of Energy

▪ Heat 🡪 Energy
▪ Unit : 1 calorie (1oC/g)
BTU (British Thermal Unit, 1 pound 1oF}
BOILER and Its CAPACITY
▪ In general boiler will produce 1.6 kg steam at 100oC per
kwh.
▪ 1 g water 1oC 🡪 1 calori = 4,2 Joule
1 Watt = 1 Joule/second
▪ 540 kcal evaporation of 1 kg water in one second.
▪ need 4,2 x 540 kJoule/second= 2268 kWatt
1 second = 1 kg
1 hour = 60 x 60 second
= 3600 kg/hour needs 2268 kw
per-kwh = 3600/2268 = 1,6 kg
▪ Boiler usually produces 1,6 kg steam per kwh at 100oC.
Boiler
Boiler
Using Linalool Data

o o
C K 1/T P(mm Hg) Log p

79,8 352,8 2,84. 10-3 10 1,0000

93,8 366,8 2,73.10-3 20 1,3010

109,9 382,9 2,61.10-3 40 1,6020

 Heat Latent of Oil Component

-2,3 R d (log p)
L=
d (1/T)
▪ L = molar heat latent in cal/gram.mol
▪ R = a gas constant (1,987 cal/K/mol)
▪ T = oK
▪ p = vapor pressure by linalool
d (log p) = -(1,6020 – 1,0000) = -2617
d(1/T) (2,84-2,61)10-3

L = -2,3 x 1,987 x -2613 = 11959,95 cal

M = 154

L = 11959,95 cal/154 g = 77,66 cal/gram

▪ Bp of oil >> water
▪ Immiscible mixture will boil if the total pressure = 1 atm (bar)
▪ At 99,5oC pA linalool 27,8 mm
▪ Water :760 – 27,8 = 732,2 mm
▪ Bp of Linalool = 198oC Bp water = 100oC.
▪ Mixture will boil at 99,5oC
▪This is the reason why oil can be isolated
with steam distillation at T lower than Bp of
each oil component.
▪Mixture boils will absorb energy in the form
of latent evaporation heat. To keep boiling
heat must be continuously supplied.
▪Ex : x gram linalool = x/154 mol
y gram water = y/18 mol
▪ Mol fraction of linalool = mol linalool
mol linalool + water

▪ Dalton Law Ptotal = PA + PB + PC

▪ Linalool immiscible with water, so :
P total = Plinalool + P water
▪ Plinalool = weight linalool x Ptotal
Mlinalool x total mol in the mixture
▪ Weight of linalool = Plinalool x M linalool x total mol.
P total
Weight of linalool = P linalool x M linalool
Weight of water Pwater x M water
Temp. Vap P linalool Vap P P total Ratio vap. Linalool :
water Pres. water
66,5 5 200,5 205,5 1 : 40,1 1 : 4,68

79,8 10 354,0 364,0 1 : 35,4 1 : 4,14

93,8 20 598,5 618,5 1 : 29 1 : 3,49

99,5 27,5 732,2 760,0 1 : 26,3 1 ; 3,07

▪In every 3,07 kg water distillate there will be
1 kg of linalool.

▪More Simple formula derivation is as follows:

▪ Ptotal = PA + PB
▪ mol A = pA/P total mol B = pB/p total
▪ mol A/mol B = p A/p B
▪ (wa/MA) /(wB/MB) = pA/pB

▪ wA/wB = pA MA
pB MB
▪Example for application
▪ If you have a boiler 2 kwh (1 kwh produce 1,6 kg steam per-hour
or approximately 2000 L steam per-hour with pressure 1 atm).
How long will you need to distill 1 ton of crude drug containing 2
% of oil with the major component having M 212 and vapor
pressure at 100oC 9 mm Hg.
THE ENFLEURAGE PROCESS
▪ Cold Enfleurage (Enfleurage a froid)
▪ Hot Enfleurage (Enfleurage a chaud)
Cold Enfleurage
▪ Fat:
▪ Mixture of lard-beef tallow (2:1) for cold
▪ Mixture of lard-beef tallow (1:1) for hot.

▪ Method
▪ Fat is smeared on both side of glass plates.
▪ Make many furrows (holes) to expand surface area.
▪ Keep in a wooden rack, then put the flower above the fat.
▪ Contact period between 24-27 hours.
▪ The flower is then replaced with the fresh one. (up to 30x)
▪ Extraction results 🡪 pomade
▪ Ratio of weight fat-flower 🡪 flower value
▪ Number of treatment🡪 as the number
▪ Pomade No 30 mean treated for 30 times.
Recovery of Oil from Pomade
▪ Fat is blended in ethanol
▪ Further recovery can be performed by distillation or extraction with petroleum
ether.
Hot Enfleurage
▪ Fat can be mixed with olive oil, parafine or wax.
▪ Temperature 50-70oC.
▪ Weight of flower 5-10 x fat.
QUALITY ASSESMENT

▪Sensory :
▪ By olfactory expert (taster)
▪ Taster can be trained and achieved after years of tedious experiences,
but systematic training olfactory.
▪ Oil is smeared on a strip, after few moments experience taster will
identify: source, age, major component, purity.
▪ Inhale and after 1, 2 and 6 hours and after overnight and 18 hors
compared with original marker.
▪Physics :
▪ Water content
▪ Density
▪ Optical rotation
▪ Refractive index
▪ Evaporation residue
▪ Melting point and solidifying point
▪ Solubility in ethanol.
▪Chemistry
▪ Aldehyde, acid number, esther number, carbonyl
number, phenol number.
Instrumentation
▪ Column chromatography, TLC, GLC, MPLC, SFC, Size exclusion
chromatography
▪ UV-Vis
▪ IR
▪ MS
▪ NMR

GLC and GLC-MS is the most informative method to evaluate

volatile oil. More component can be detected using this system.
GLC-MS provide information on mass spectra of each peak of
the chromatogram
Region Importer (%) Exporter (%)
E.U 42,8 16,3
USA 17,3 16,1
Japan 7,9 1,2
Hong Kong 5,9 16,1
Switzerland 5,0 2,2
Canada 2,8 0,9
Brazil 1,6 18,7
Philipines 1,3
South Korea 1,2
Singapore 1,2 1,5
Mexico 1,0 1,0
India 1,0 3,2
Indonesia 0,5 4,4
China 18,6
Argentina 2,1
Paraguay 1,5
Haiti 1,3
Turkey 1,1
Morocco 1,1
Ex USSR 1,0
Argentina 2,1
Paraguay 1,5
Haiti 1,3
Turkey 1,1
Morocco 1,1
Ex USSR 1,0
Price List of Oil (2009)
▪ Clove bud Indonesian €17-20/kg, 1-5 ton lots, Indian €35/kg
▪ Clove stem Indonesian €8-10/kg, 2-5 ton lots, India €18/kg
▪ Clove leaf Indonesian €5-6/kg, 2-5 ton lots, Indonesian €5/kg container cif,
Madagascar €6/kg spot, India €15/kg 1 kg lots
▪ Cinnamon bark Sri Lankan 60/65% €155-230/kg
▪ Cinnamon leaf Sri Lankan light €10-12/kg
▪ Cassia bark China €15/kg forward
▪ Black pepper Sri Lankan €60-70/kg, Indian €80/kg
Price of Oil, ESSENTIAL OILS AND OLEORESINS
MARKET NEWS SERVICE (MNS), QUARTERLY EDITION, 2009)
▪ Nutmeg Indonesian €48/kg spot
▪ Indonesian €60-70/kg 1 kg lots
▪ Sri Lanka €60/kg
▪ Ginger Chinese €20-25/kg ton lots
▪ Indian €80/kg
▪ Sri Lankan €130-140/kg
▪ Indonesia (from fresh ginger) €90/kg
▪ Pimento leaf Jamaican €75-90/kg ton lots
▪ Pimento berry Jamaican €145-160/kg
▪ Cardamom Guatemala €165-220/kg
Indonesian VO (Kusnandar & CO, 2015)
▪ World market 4 billion USD growth 5% annually.
▪ 300 types of oil, Indonesia 40 types.
▪ 80 % Indonesian oil is exported.
▪ Demand > 1,000 ton per-year.
▪ Clove leaf/stem, lemmongrass, patchouli, eucalyptus.
▪ Terpentin > 10.000 tons/year.
World demand
▪ Clove oil demand 5.000-6.000 tons/year.
▪ Lemon grass 2000 tons/year
▪ Patchouli 1299-1500 tons/year.
▪ Turpentin 10.000 tons/year.
▪ Nutmeg 400 tons/year (Indonesia 350 tons)
▪ Vetiver 100 tons/year (Indonesia 30 tons)
▪ Australia started massive planting sandalwood.
Essential Oils Market Size, Share & Trends Analysis Report By Application (Food
& Beverages, Spa & Relaxation), By Product (Orange, Peppermint), By Sales
Channel, And Segment Forecasts, 2020 - 2027

Orange
Commint
Peppermint
Eucalyptus
Cedarwood
Citronella
Lemon
Clove
DMO
Lime
(2016-2027)
References
▪ Tuley De Silva K (1995) A Manual On The Essential Oil Industry, UNIDO, Vienna,
Austria.