hazimah ah malaysian palm oil board - official...
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Hazimah AH
Malaysian Palm Oil Board
Palm Oil Trade Fair Seminar
Marriott Karachi Hotel
Karachi, Pakistan
16-17 January 2014
PRESENTATION OUTLINE • Introduction • What are the raw materials / feedstock? • Properties / applications - Soaps - Detergents from MES (methyl ester sulphonates) - Cosmetics/Personalcare Products • Conclusion/Summary
Source: MPOB, 2013
0
200,000
400,000
600,000
800,000
1,000,000
1,200,000
1,400,000
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
0
500
1000
1500
2000
2500
3000
1998 2000 2002 2004 2006 2008 2010 2012
Capacity Oil used Export
MALAYSIAN OLEOCHEMICALS: CAPACITY, AND EXPORTS (in‘000 tonnes)
Source : MPOB, 2013
0
200000
400000
600000
800000
1000000
1998 2000 2002 2004 2006 2008 2010 2012
Acids Alcohol Methyl Ester Glycerol
Source : MPOB, 2013
0
200000
400000
600000
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
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HH Detergent
40%
Textiles Aux.10%
Personal Cares
9%
I&I6%
Oil Field5%
Others30%
70% Surfactants
Others
OLEOCHEMICALS
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 Palm Kernel Oil
Fractionated into palm olein and stearin Palm olein – food Palm stearin – nonfood / oleochemicals
Fractionated into palm kernel olein and kernel stearin Palm kernel stearin – food Palm kernel olein – nonfood / oleochemicals
Palm oil rich in C16 and C18
Palm Kernel Oil rich in C12 and C14
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
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WHAT IS SOAP?
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Saponification methyl esters
Neutralisation Fatty acids
Saponification oils/fats
NaOH (alkali)
3 RCOO- Na (soap)
+ glycerol
(oil) RCOOH
NaOH (alkali)
RCOO- Na+ (soap)
+
water
(fatty acid) RCOOCH
NaOH (alkali)
+
methanol
(ester)
RCOO- Na+ (soap)
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•Colour of soap - darker
•Combination of oils
•Good perfume retention
Saponification oils/fats
•Colour of soap - good
•Allow selection of FA
•Simple production process
•Popular in Malaysia
Neutralisation Fatty acids
•Colour of soap - best
•Simple production process
•Unpopular - methanol as by-
products
Saponification methyl esters
R, R’, R’’ PS PKO GENERAL PROPERTIES/USES C6 0.3 Irritants to eyes,
Hydrotropes, medium chain triglycerides (MCT)
C8 4.4 C10 3.7 C12 0.23 48.3 Good foaming power, good
detergency C14 1.09 15.6 C16 44.02 7.8 Good detergency C16:1 0.12 C18 4.54 2.0 Poor solubility
Good detergency, Good lubricity Poor oxidative stability
(if unsaturated)
C18:1 39.15 15.1 C18:2 10.12 2.7 C18:3 0.37 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
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1
•Palm oil/Palm kernel
oil
2 •Palm oil/Coconut oil
3 •Tallow/Coconut oil
4 •Tallow/Palm kernel oil
5 •Other oils/fats
SOME GOOD BLENDS ARE:
90PO:10PKO
80PO:20PKO
85PO:15PKO
Use by soap industry
60PS:40PKO
80PS: 20PKO 70PS:30PKO
40PS:40PO:20PKO
RBD PO 3500g RBD PKO 1500g NaOH (50%) 1920g NaCl-saturated soln
820g
EDTA (0.1%) 5g TiO2 (0.2%) 10g Perfume 48g
FORMULATION FOR SMALL SCALE PRODUCTION OF SOAP
Saponification
Distilled PO or tallow fatty acids
2000g
Distilled PK fatty acid 500g NaOH, depending on acid value (50%)
2363g
NaCl 2.5g
EDTA (0.1%) 2.5g TiO2 (0.2%) 5g Perfume 30g
NEUTRALIZATION PROCESS
PO
80, 75,
70, 60
PKO
20, 25,
30, 40
Moisture
9 -
12.5%
Total fatty
matter
(TFM)
79 - 83%
Free fatty
acid
(FFA)
1.3 - 7.0%
Glycerin
0.4 -
0.6%
Sequesteri
ng agent
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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.
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Percentage (%)
Soap noodles 86-96
Glycerol 1-6
Perfume 1-5
Colour 1-2
Additives (emollients, medicaments, anti-irritants etc)
1-5
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1. Amalgamator/mixer 2. Roll mill 3. Plodder 4. Pneumatic press mould/stamping machine
1 2 3
4
EQUIPMENT FOR OPAQUE SOAP PRODUCTION
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Mixer Mix all ingredients
1
Roll mill Thin soap – homogenize all
ingredients
2
30
Plodder Semi-finished bar
soap
3
Stamping machine
4
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
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SOAP FROM FATTY ACIDS (Neutralization)
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Fatty acids are neutralized to form soap
RCH2COOH
NaOH
RCH2COO- Na+ (Soap) + H2O
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Mixer Mould semi-finished
transparent soap
Mould for
transparent bar and
decoration soaps
EQUIPMENT & MOULD FOR TRANSPARENT SOAP PRODUCTION
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PROCESS OF MAKING TRANSPARENT SOAP
1. Neutralization of fatty acids.
Melting fatty acids
Adding NaOH Soap
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Adding glycerol, trietanolamine, surfactants and
water
Insert soap resulting from
the neutralization
Semi-finished soap
2. Blending all the ingredients.
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3. Adding colour, fragrances and pouring it into moulds.
Remelt semi-finished soap & add colour
Adding perfume
Pouring into mould
COMMERCIAL TRANSPARENT SOAP
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RM 28 (soap size = 50 g) RM 30 (soap size = 250 g)
QUALITY OF SOAPS - Starting Materials – oils/fats
Parameters Explanation on the parameter Importance
Iodine value Detect the degree of unsaturation present. Measured as g I2/100g sample.
Affect the softness, solubility and oxidative stability of soap
Acid value Detect the amount of fatty acids present Measured as mg KOH/1g sample
Reflects the quality of oils/fats. High acid value implies poor quality oils/fats
Titre Measure the solidification point of fatty acids.
Determine the hardness and foaming power of soap.
Color Color of raw material in Lovibond unit Measured using Lovibond tintometer
Determine color of soap. PO/PKO 0.1 –0.3R
Saponification value
Give an indication of the molecular weight. Measured as mg KOH needed to saponify 1g of oils/fats.
Use to calculate the amount of alkali needed to saponify the oils/fats to soap.
Saponification color value
Measure the color of the saponified oils/fats using Lovibond 5¼ inch cell
Has a direct correlation with the color of resultant soap. The higher the saponification color value the darker will be the resulting soap
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 %
Has a direct effect on the final quality of soap.
QUALITY PARAMETERS OF SOAP/SOAP NOODLES
Parameters (soap/soap noodles)
Explanation on the parameter
Importance
Water content Detect amount of water present. Measured using moisture balance and expressed as %.
Affect the cracking properties of toilet soap.
Total fatty matter
Detect amount of fatty matter soluble in pet ether, present in the soap/soap noodles. Expressed in terms of %
Reflects the quality or active ingredient present. Toilet soap has 80-85% TFM and laundry soap about 60%.
Hunter whiteness
Measure color at wavelength 475nm
Reflects the whiteness Higher value implies whiter soap
Foaming power/stability
Indicate foaming power. Measured as ml of foam from 1mg/ml solution. Vol of foam present after 5 min reflects the foaming stability.
Reflects foaming power and stability
Hardness Measured as the depth of the penetrometer needle Measured in mm.
Deeper penetration implies softer soap.
Chloride content Amount of chloride present Expressed as %
Has a direct correlation with corrosiveness
Free acid or caustic
Expressed as % of free acid or alkali present
pH of soap
Active > 85% Disalt < 6% Color < 100 Klett
Do not require phosphate for excellent detergency in hard water
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0
10
20
30
40
50
60
70
40:0 30:10 20:20 10:30 0:40
α- SME:Disalt
50556065707580859095
0 50 100 180 270 350
MES 16/18 AOS AS LAS
Detergency at Various Water Hardness
ANALYSES AND RESULTS
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
MES PERFORMANCE SUMMARY
Weight (%)
Coconut C12-C14
Palm Kernel C8-C18
Palm Stearin C16-C18
Tallow C16-C18
Soya C18
Sodium methyl ester sulphonate (-SME)
71.5
69.4
83
77.5
75.7
Disodium carboxy sulphonate (di-salt)
2.1
1.8
3.5
5.2
6.3
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 extractable
2.6
2.7
2.4
4.8
7.2
Sodium carboxylate (RCOONa)
0.2
0.2
0.3
0.3
0.5
Sodium sulphate
1.2
1.8
1.5
2.3
2.4
Sodium methyl sulphate (CH3OSO3Na)
8.0
8.4
7.2
7.7
2.5
10% pH
5.0
5.3
5.3
5.4
5.8
Klett colour, 5%active (-SME+disalt)
30
310
45
180
410
SUITABLE RAW MATERIALS FOR PRODUCTION OF MES BASED ON CHARACTERISTIC EVALUATED
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MES flakes were grounded
mixed with other dry materials & liquid additives
Powder Detergent Density: 0.7-1g/mL
Particle size: 230-1500 microns
Powder Pilot Plant (Marion Mixer) with a capacity of
120 kg/hr detergent
MES flakes were dissolved
(70-80oC)
Blend with other solid and liquid materials
(40-50oC)
Liquid Detergent
pH: 8-9
Liquid Pilot Plant with two mixing tanks with a capacity of
50 liter and 120 liter
HOW TO USE MES ?
0
10
20
30
40
50
60
70
80DETERGENCY
P5 M1 M2 M3 M4 COM P1
mineral oil sebum pigment/oil/milk pigment/oil
0
10
20
30
40
50
60
DETERGENCY
P5 M1 M2 M3 M4 COM P1
mango cocoa grass spinach curry tea
Instrument: Spectrophotometer CM-3600d (whiteness), top loading Condition: 50 ppm, 25oC, ratio wash liquor 1:18.5, dosage 0.8g/L
0
10
20
30
40
50
60
70
80
90DETERGENCY
L2 LA LE LI LJ COM L1 COM L2
mineral oil sebum pigment/oil/milk pigment/oil
05
101520253035404550
DETERGENCY
L2 LA LE LI LJ COML1
COML2
mango cocoa grass spinach curry tea
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
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Products – Sticks e.g lipsticks, lip gloss, deodorant stick Powder – loose or
compact : roughe, face and eye shadow
Emulsion – Liquid foundation, mascara etc
50
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Oleochemical Function Isopropyl palmitate Isopropyl myristate Medium Chain Triglyceride (MCT) Stearic Acid
Emollients – materials that provide lubrication on skin and prevents water evaporation from skin
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
FUNCTIONS OF OLEOCHEMICAL AND ITS DERIVATIVES IN COSMETIC PRODUCTS
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ACTIVE AGENTS IN COSMETIC PRODUCTS
Active Agent Example
Sunscreen Agent Benzophenone 3 and 4, zinc oxide
Whitening Agent Arbutin, Kojic Acid
Anti-Wrinkle Agent Anti-inflammatory Agent
Vitamin A and palm Vit E Palm Vit E (tocotrienol)
Anti-Irritant Chamomile Extract/Bisabolol
Soothing Agent Cucumber Extract
Anti-acne Tea Tree Oil
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
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SAFETY EVALUATION
SAFETY EVALUATION
PHOTOTOXICITY HYPO ALERGENICITY SKIN IRRITATION REPEATED
PATCH TEST
REPEATED APPLICATION
IN-VITRO IRRITECTION
ASSAY
OPEN PATCH TEST PATCH TEST Ocular Dermal
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EFFICACY ASSESSMENT
EFFICACY EVALUATION
MOISTURIZING SKIN LIGHTENING ANTI-WRINKLE ANTI-ACNE SKIN ELASTICITY ANTI-HAIR LOSS
ACUTE LONG TERM ANTI-DANDRUFF ANTI-CELLULITE
ANTI-CRACKED HEEL TEST
TS 48
SKIN SEBUM SKIN HYDRATION
SKIN PH
TEWL
CELL RENEWAL
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MICROBIOLOGY TEST
MICROBIOLOGY
ENUMERATION OF MICROBES
IN VITRO
ANTI-ACNE TEST MICROBIAL
CHALLENGE TEST
MINIMUM INHIBITORY
CONCENTRATION TEST
BACTERIA FUNGI PRESERVATIVE EFFICACY
WHITE COSMETIC FORMULATIONS
Ingredient Cream Lotion Milk
Water phase Deionised water Humectant preservative
75-80
2-5 0.3-0.7
80-85
2-5 0.3-0.7
80-85
2-5 0.3-0.7
Oil phase Isopropyl palmitate Stearic acid Glyceryl monostearates Mid-chain triglycerides Cetyl alcohol Triethanolamine Preservative
3-5 4-5 4-5 3-5 5-6
0.5-1 0.3-0.7
2-4 3-5 3-5 3-5 3-5
0.5-1 0.3-0.7
1-2 2-4 2-4 3-5 1-2
0.5-1 0.3-0.7
Active ingredient Perfume
qs. 0.5-1
qs. 0.5-1
qs. 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
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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.
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Basic Oleochemicals Oleo-derivatives End Products
Fatty acids
Fatty alcohols
Methyl Esters
Glycerin
Soap noodle Esters
Surfactants Amines
Dimeric Acids Metal Soap
Azelaic Resins Agrochemicals
Bio Lubricants Bio Polyols
Glycerol Derivatives
Fatty Alcohol Amide
20% of world capacity 2% of 20%
Safety, Health Environment Concern Renewable resources Non-Toxic Biodegradable Natural Green label Religious issues
PALM OIL : PERENNIAL CROP
Oil Crop Production
(million t)
% of total
production
Total area
(million ha)
% of total
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
4.09
0.75 0.5 0.37
Oil Palm Rapeseed Sunflow er Soya bean
Average Oil Yield (t/ha/year)
Source: Oil World 2010
* Combined tonnage of palm oil
and palm kernel oil
Since 1875/ commercial planting 1917
Life-long 25-30 yrs period Land need to be cleared
once
Social Equity &
People
Environment
Integrity &
Planet
Economic
Growth &
Profitability
Source: Yusof et al, 2007
SD
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