Hazimah AH

Malaysian Palm Oil Board

Palm Oil Trade Fair Seminar

Marriott Karachi Hotel
Karachi, Pakistan
16-17 January 2014 1
 PRESENTATION OUTLINE
• Introduction
• What are the raw materials / feedstock?
• Properties / applications
- Soaps
- Detergents from MES (methyl ester
sulphonates)
- Cosmetics/Personalcare Products
• Conclusion/Summary
 1,400,000

1,200,000

1,000,000

800,000

600,000

400,000

200,000

0
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013
CPO 115,144 123,187 94,029 84,027 103,681 116,913 148,912 135,881 147,309 125,177 155,834 131,943 103,112 186,117
PPO 368,706 418,842 457,390 531,488 553,924 619,961 714,396 657,815 762,390 796,619 655,347 787,190 875,462 1,251,890
CPKO 516,584 520,230 591,227 653,570 736,290 735,478 718,412 767,448 886,737 914,408 876,581 858,420 782,469 754,475
PPKO 285,310 251,168 280,660 308,203 309,776 382,750 416,538 424,432 358,267 428,413 472,698 411,779 540,397 519,270

Source: MPOB, 2013

 MALAYSIAN OLEOCHEMICALS: CAPACITY,
AND EXPORTS (in‘000 tonnes)

3000
2500
2000
1500
1000
500
0
1998 2000 2002 2004 2006 2008 2010 2012

Capacity Oil used Export

Source : MPOB, 2013

1000000

800000

600000

400000

200000

0
1998 2000 2002 2004 2006 2008 2010 2012

Acids Alcohol Methyl Ester Glycerol

Source : MPOB, 2013

 600000

400000

200000

0
1999 2001 2003 2005 2007 2009 2011 2013

Soap noodles

Source : MPOB, 2013

 Chemicals derived from plant and animal fats
 Analogous to petrochemicals derived from
petroleum
 Formed by various chemical reactions oe by
enzymatic reactions
 Common reactions – hydrolysis, esterification,
transesterification and saponification
 Basic oleochemicals – fatty acids, fatty alcoholes,
fatty methyl ester, fatty amines and glycerine
 Soaps
 OLEOCHEMICALS

Others
70%
Surfactants

Others
30% HH
Detergent
Oil Field 40%
5%

Textiles
Personal Aux.
I&I 10%
6% Cares
9%
9
Source: www.apag.org/oleo/rm.htm
 Interchangeable
 Many raw materials
 No such parallels exist in
petrochemicals
 Natural are replenishable
since they can be grown
(or reared for animals)
 Supply assured
 Some are by-products of
other industries
MAIN RAW MATERIALS
C16 - C18 Fatty acids
•Developed countries rely on soya, corn,
sunflower, rapeseed, tallow and lard
C12 - C14 (lauric oils)
•All rely on SEA – Malaysia, Indonesia,
Philippines
Source of
C16 C18

Source of
C12 C14
 Palm oil rich in
Palm oil Palm Kernel Oil
C16 and C18

Fractionated into Fractionated into

palm olein and palm kernel olein and
stearin kernel stearin
Palm olein – food Palm kernel stearin –
Palm stearin – food
nonfood / Palm kernel olein –
oleochemicals nonfood /
oleochemicals
Palm Kernel Oil rich
in C12 and C14
WHAT IS SOAP?
Oldest cleaning agent.
Most important anionic surfactant.
Known as sodium salt of fatty acid.
Type of soaps
Sodium soap: toilet soap, laundry soap, specialty
soap
Metallic soap: animal feeds, stabilizer, pigment
improvers etc.
Potassium soap: liquid soap
14
 Saponification Neutralisation Saponification
oils/fats Fatty acids methyl esters

RCOOH (fatty acid) RCOOCH (ester)

(oil)

NaOH (alkali) NaOH (alkali)

NaOH (alkali)
RCOO- Na+ (soap) RCOO- Na+ (soap)
+ +
3 RCOO-Na (soap)
+ water methanol
glycerol
15
 • Colour of soap - darker
Saponification
• Combination of oils
oils/fats • Good perfume retention

• Colour of soap - good

Neutralisation • Allow selection of FA
Fatty acids • Simple production process
• Popular in Malaysia

• Colour of soap - best

Saponification • Simple production process
methyl esters • Unpopular - methanol as by-
products

16
R, R’, R’’ PS PKO GENERAL PROPERTIES/USES
C6 0.3 Irritants to eyes,
C8 4.4 Hydrotropes, medium chain
triglycerides (MCT)
C10 3.7
C12 0.23 48.3 Good foaming power, good
C14 1.09 15.6 detergency

C16 44.02 7.8 Good detergency

C16:1 0.12
C18 4.54 2.0 Poor solubility
C18:1 39.15 15.1 Good detergency, Good lubricity
C18:2 10.12 2.7 Poor oxidative stability
C18:3 0.37 (if unsaturated)

GLYCEROL Good solvent, sweet taste,

moisturizing
R, R’, R’’ PO PS Tallow CNO PKO

C6 0.2 0.3
C8 8.0 4.4
C10 7.0 3.7
C12 0.23 0.3 48.2 48.3
C14 1.09 1.3 2.5 18.0 15.6
C16 44.02 55.0 26.6 8.5 7.8
C16:1 0.12
C18 4.54 5.1 21.8 2.3 2.0
C18:1 39.15 29.5 42.8 5.7 15.1
C18:2 10.12 7.4 2.3 2.1 2.7
C18:3 0.37 -
OTHERS 0.38 0.7 4.0 0.2
 TRADITIONAL RAW MATERIALS –
 Tallow –source for C16C18 fatty acids
 Coconut – source for C12C14 fatty acids

PROPERTIES OF TOILET OR LAUNDRY SOAPS

Directly related to Fatty acid composition (FAC)
Long chain/saturated – good detergency but poor
solubility
Long chain/unsaturated – soft soap, poor in oxidative
stability
Medium chains- less detergency, good solubility and
good foaming
 IDEAL SOAP
Good detergency Good solubility

Good foaming power Medium hardness

Stable to oxidation Therefore

Feedstock – usually a
mixture of oils/fats

**The preferred choice now

PO – for tallow
PKO – for coconut
 •Palm oil/Palm kernel
1
oil
2 •Palm oil/Coconut oil

3
•Tallow/Coconut oil

4
•Tallow/Palm kernel oil

5
•Other oils/fats

21
SOME GOOD BLENDS ARE:

90PO:10PKO
Use by
80PO:20PKO
soap
85PO:15PKO industry

60PS:40PKO 40PS:40PO:20PKO

80PS: 20PKO
70PS:30PKO
FORMULATION FOR SMALL SCALE
PRODUCTION OF SOAP
Saponification
RBD PO 3500g
RBD PKO 1500g
NaOH (50%) 1920g
NaCl-saturated 820g
soln
EDTA (0.1%) 5g
TiO2 (0.2%) 10g
Perfume 48g
NEUTRALIZATION PROCESS
Distilled PO or tallow 2000g
fatty acids
Distilled PK fatty acid 500g
NaOH, depending on 2363g
acid value (50%)
NaCl 2.5g
EDTA (0.1%) 2.5g
TiO2 (0.2%) 5g
Perfume 30g
 PO
80, 75,
70, 60 PKO
Sequesteri 20, 25,
ng agent
30, 40

Glycerin Moisture
0.4 - 9-
0.6% 12.5%
Free fatty Total fatty
acid matter
(FFA) (TFM)
1.3 - 7.0% 79 - 83% 25
Specialty soaps - contain special
additives for specific functionality
(1- 5%)
Process similar to toilet soaps
Categories of additives:
emollients, humectant,
moisturiser, medicaments,
anti-irritants etc.

26
 Percentage
(%)
Soap noodles 86-96
Glycerol 1-6
Perfume 1-5
Colour 1-2
Additives (emollients, 1-5
medicaments, anti-irritants etc)

27
 EQUIPMENT FOR OPAQUE SOAP
PRODUCTION

1 2 3

1. Amalgamator/mixer
2. Roll mill
3. Plodder
4. Pneumatic press mould/stamping mach
4
28
1

Mixer Mix all ingredients

Thin soap – homogenize all

Roll mill
ingredients

29
3

Plodder
Semi-finished bar
soap
4
30

Stamping machine
 Percentage
(%)
Fatty acids 16-20
Sodium hydroxide 2-8
Glycerol 20-25
Triethanolamine 10-15
Surfactants 4-8
Water 30-35
pH adjuster 1-5
Additives 1-5
Colour 1-2
Perfume 1-2
31
 SOAP FROM FATTY ACIDS
(Neutralization)

RCH2COOH
NaOH Fatty acids are
neutralized to form
RCH2COO- Na+ soap
(Soap)
+
H2O

32
 EQUIPMENT & MOULD FOR
TRANSPARENT SOAP PRODUCTION

Mould for
Mould semi-finished
Mixer transparent bar and
transparent soap
decoration soaps

33
PROCESS OF MAKING TRANSPARENT
SOAP

1. Neutralization of fatty
acids.
Melting fatty
Adding NaOH Soap
acids

34
2. Blending all the ingredients.

Adding glycerol, Insert soap

trietanolamine, resulting from Semi-finished
surfactants and the soap
water neutralization

35
3. Adding colour, fragrances and pouring it into
moulds.

Remelt semi-
Adding Pouring into
finished soap
perfume mould
& add colour

36
COMMERCIAL TRANSPARENT SOAP

RM 28 (soap size = 50 g) RM 30 (soap size = 250 g)

37
 QUALITY OF SOAPS -
Starting Materials – oils/fats
Parameters Explanation on the parameter
Iodine value Detect the degree of
unsaturation present.
Measured as g I2/100g sample.
Acid value Detect the amount of fatty acids
present
Measured as mg KOH/1g
sample
Titre Measure the solidification point
of fatty acids.
Color Color of raw material in
Lovibond unit
Measured using Lovibond
tintometer
Importance
Affect the softness,
solubility and oxidative
stability of soap
Reflects the quality of
oils/fats. High acid value
implies poor quality
oils/fats
Determine the hardness
and foaming power of
soap.
Determine color of
soap.
PO/PKO 0.1 –0.3R
Saponification Give an indication of the
value molecular weight.
Measured as mg KOH needed
to saponify 1g of oils/fats.
Saponification Measure the color of the
color value saponified oils/fats using
Lovibond 5¼ inch cell
FAC Determine the fatty acids
composition of oils/fats.
The amount of a particular
type of fatty acid present in
the oils/fats is expressed in
terms of %
Use to calculate the
amount of alkali
needed to saponify the
oils/fats to soap.
Has a direct
correlation with the
color of resultant
soap. The higher the
saponification color
value the darker will
be the resulting soap
Has a direct effect on
the final quality of
soap.
 QUALITY PARAMETERS OF
SOAP/SOAP NOODLES
Parameters Explanation on the
(soap/soap parameter
noodles)
Water content Detect amount of water
present. Measured using
moisture balance and
expressed as %.
Total fatty Detect amount of fatty
matter matter soluble in pet ether,
present in the soap/soap
noodles.
Expressed in terms of %
Hunter Measure color at
whiteness wavelength 475nm
Importance
Affect the cracking
properties of toilet
soap.
Reflects the quality or
active ingredient
present.
Toilet soap has 80-85%
TFM and laundry soap
about 60%.
Reflects the whiteness
Higher value implies
whiter soap
Foaming Indicate foaming power. Reflects foaming
power/stability Measured as ml of foam power and stability
from 1mg/ml solution.
Vol of foam present after 5
min reflects the foaming
stability.

Hardness Measured as the depth of Deeper penetration

the penetrometer needle implies softer soap.
Measured in mm.

Chloride content Amount of chloride Has a direct

present correlation with
Expressed as % corrosiveness

Free acid or Expressed as % of free pH of soap

caustic acid or alkali present
  Do not require phosphate
for excellent detergency in
hard water

Active > 85%

Disalt < 6%
Color < 100 Klett
 ANALYSES AND RESULTS
Detergency at Various Water Hardness
95
90
85
80
75
70
65
60
55
50
0 50 100 180 270 350
MES 16/18 AOS AS LAS

70
60
50
40
30
20
10
0
40:0 30:10 20:20 10:30 0:40

α- SME:Disalt
43
 MES PERFORMANCE SUMMARY

Good detergency especially in hard water and

without phosphate
Good tolerance to water hardness
Good synergy with soap – as soap additive
Good solubilizing power
Mild and non-irritant to the skin
Good biodegradation characteristics
 SUITABLE RAW MATERIALS FOR PRODUCTION OF
MES BASED ON CHARACTERISTIC EVALUATED

Weight (%) Coconut Palm Kernel Palm Stearin Tallow C16- Soya
C12-C14 C8-C18 C16-C18 C18 C18

Sodium methyl ester

sulphonate (-SME) 71.5 69.4 83 77.5 75.7

Disodium carboxy 2.1 1.8 3.5 5.2 6.3

sulphonate (di-salt)

Methanol 0.48 0.60 0.07 0.00 0.03

Hydrogen peroxide 0.10 0.04 0.13 0.15 0.05

Water 14.0 15.2 2.3 2.9 1.4

Petroleum ether 2.6 2.7 2.4 4.8 7.2

extractable

Sodium carboxylate 0.2 0.2 0.3 0.3 0.5

(RCOONa)

Sodium sulphate 1.2 1.8 1.5 2.3 2.4

Sodium methyl sulphate 8.0 8.4 7.2 7.7 2.5

(CH3OSO3Na)

10% pH 5.0 5.3 5.3 5.4 5.8

Klett colour, 30 310 45 180 410

5%active (-SME+disalt)
 HOW TO USE MES ?

MES flakes
MES flakes were dissolved
were grounded (70-80oC)

Blend with
mixed with
other solid and
other dry materials
liquid materials
& liquid additives (40-50oC)

Powder Detergent
Density: 0.7-1g/mL Liquid Detergent
Particle size: pH: 8-9
230-1500 microns

Powder Pilot Plant Liquid Pilot Plant with two

(Marion Mixer) with a capacity of mixing tanks with a capacity of
120 kg/hr detergent 50 liter and 120 liter
46
 mineral oil sebum pigment/oil/milk pigment/oil

80

70

60
DETERGENCY

50

40

30

20

10

0
P5 M1 M2 M3 M4 COM P1

mango cocoa grass spinach curry tea

60

50
DETERGENCY

40

30

20

10

0
P5 M1 M2 M3 M4 COM P1

Instrument: Spectrophotometer CM-3600d (whiteness), top loading

Condition: 50 ppm, 25oC, ratio wash liquor 1:18.5, dosage 0.8g/L
 mineral oil sebum pigment/oil/milk pigment/oil

90
80
70
DETERGENCY

60
50
40
30
20
10
0
L2 LA LE LI LJ COM L1 COM L2

mango cocoa grass spinach curry tea

50
45
40
35
DETERGENCY

30
25
20
15
10
5
0
L2 LA LE LI LJ COM COM
L1 L2
Instrument: Spectrophotometer CM-3600d (whiteness), top loading
Condition: 50 ppm, 25oC, ratio wash liquor 1:18.5, dosage 1.62g/L
 Multiple Products
– Milk, Lotion, Cream, Gel

 Skin Care Products (with

functionality)
– Anti-aging, skin
whitening, Sunscreen etc.

 Hair Care Products

– Shampoo, Conditioner

49
 Products
– Sticks e.g lipsticks, lip
gloss, deodorant stick
 Powder – loose or
compact : roughe, face
and eye shadow
 Emulsion
– Liquid foundation, mascara
etc

50
 FUNCTIONS OF OLEOCHEMICAL AND ITS
DERIVATIVES IN COSMETIC PRODUCTS

Oleochemical Function
Isopropyl palmitate Emollients – materials that provide
Isopropyl myristate lubrication on skin and prevents water
Medium Chain Triglyceride (MCT) evaporation from skin
Stearic Acid

Glycerine Moisturizing Agent – improve the skin

hydration

Glycerol Monostearate Emulsifier – enable the emulsification of

oil and water

Stearyl Alcohol, Cetyl Alcohol Rheological Agents – improves the

viscosity of an emulsion
51
 ACTIVE AGENTS IN COSMETIC PRODUCTS

Active Agent Example

Sunscreen Agent Benzophenone 3 and 4, zinc

oxide
Whitening Agent Arbutin, Kojic Acid
Anti-Wrinkle Agent Vitamin A and palm Vit E
Anti-inflammatory Agent Palm Vit E (tocotrienol)
Anti-Irritant Chamomile Extract/Bisabolol
Soothing Agent Cucumber Extract

Anti-acne Tea Tree Oil

52
Formulation
◦ White Cosmetics: Cream, Lotion, Gel
◦ Color Cosmetics: Lipstick, Compact Powder, Foundation
◦ Soap: Herbal & Transparent Soap

Stability Studies
◦ Stability studies at -5oC (Freeze/thaw cycles), room temperature &
450C (3 months)
◦ Parameters: Particle Size, Liquid Crytalline Structure, Viscosity etc.

Product Performance
◦ pH (5.5-7)
◦ Viscosity measurement by Brookfield Viscometer
◦ Rheological measurement using Rheometer.
◦ Cleaning power etc.

Safety/Efficacy/Microbiology Assessment
53
 SAFETY EVALUATION

SAFETY
EVALUATION

REPEATED IN-VITRO
HYPO REPEATED
PHOTOTOXICITY SKIN IRRITATION APPLICATION IRRITECTION
ALERGENICITY PATCH TEST
ASSAY

OPEN
PATCH TEST
PATCH TEST Ocular Dermal

54
 EFFICACY ASSESSMENT

EFFICACY
EVALUATION

ANTI-CRACKED
HEEL TEST
TS 48

SKIN ELASTICITY
MOISTURIZING SKIN LIGHTENING ANTI-WRINKLE ANTI-ACNE ANTI-HAIR LOSS

SKIN SEBUM
ANTI-CELLULITE
ACUTE LONG TERM SKIN HYDRATION CELL RENEWAL ANTI-DANDRUFF
SKIN PH

TEWL

55
 MICROBIOLOGY TEST

MICROBIOLOGY

MINIMUM
ENUMERATION IN VITRO MICROBIAL INHIBITORY
OF MICROBES ANTI-ACNE TEST CHALLENGE TEST CONCENTRATION
TEST

PRESERVATIVE
BACTERIA FUNGI
EFFICACY

56
 WHITE COSMETIC
FORMULATIONS
Ingredient Cream Lotion Milk
Water phase
Deionised water 75-80 80-85 80-85
Humectant 2-5 2-5 2-5
preservative 0.3-0.7 0.3-0.7 0.3-0.7
Oil phase
Isopropyl palmitate 3-5 2-4 1-2
Stearic acid 4-5 3-5 2-4
Glyceryl 4-5 3-5 2-4
monostearates 3-5 3-5 3-5
Mid-chain 5-6 3-5 1-2
triglycerides 0.5-1 0.5-1 0.5-1
Cetyl alcohol 0.3-0.7 0.3-0.7 0.3-0.7
Triethanolamine
Preservative
Active ingredient qs. qs. qs.
Perfume 0.5-1 0.5-1 0.5-1
Note: qs. means quantity not specified
Ingredient Composition (%)
Waxes 8-23
Ozokerite 3-10
Cetyl alcohol 2-5
Anhydrous lanolin 5-15
Castor oil 30-50
RBD palm kernel oil 10-20
Mid-chain triglycerides 10-20
Isopropyl myristate 2-5
Pigments 2-10
Antioxidant 0.1-0.3
Preservative 0.1-0.2
Perfume/flavour 0.1-2
Raw materials are from natural resources

Environmentally Friendly

Consistent & Abundant Supply

Halal

Natural pro Vitamin A, Vitamin E (Tocopherol &

Tocotrienol), Co-enzim Q10 – abundant in palm oil.

59
 Basic Oleochemicals Oleo-derivatives End Products

Soap noodle Esters

Fatty acids

Surfactants Amines

Dimeric Acids Metal Soap

Fatty alcohols

Azelaic Resins Agrochemicals

Methyl Esters Bio Lubricants Bio Polyols

Glycerol Fatty Alcohol

Derivatives Amide

Glycerin

20% of world
capacity 2% of 20% 61
 Safety, Health
 Environment Concern
 Renewable resources
 Non-Toxic
 Biodegradable
 Natural
 Green label
 Religious issues
 PALM OIL : PERENNIAL CROP
Average Oil Yield (t/ha/year)
 Since 1875/ commercial
planting 1917 4.09

 Life-long 25-30 yrs period

 Land need to be cleared
once 0.75 0.5 0.37

Source: Oil World 2010

* Combined tonnage of palm oil Oil Palm Rapeseed Sunflow er Soya bean
and palm kernel oil

Oil Crop Production % of total Total area % of total

(million t) production (million ha) Area
Oil palm 52.30* 38.2 12.8 5.5
Soya bean 38.06 27.8 102.7 44.3
Rapeseed 23.27 17.0 31.1 13.4
Sunflower 11.64 8.5 23.4 10.1
 Social Equity &
People

SD
Economic Environment
Growth & Integrity &
Profitability Planet

Source: Yusof et al, 2007

65
hazimah@mpob.gov.my

66