ukm - jumat salimon
DESCRIPTION
UKMTRANSCRIPT
PALM OIL CHEMISTRYPALM OIL CHEMISTRY
““OLEOCHEMICALS”OLEOCHEMICALS”
SUSTAINABLE CHEMISTRYSUSTAINABLE CHEMISTRY
Jumat Salimon
Crude oil vs. Renewable resources
productsMonomers
Cosmetics
Lubricants
fumaric acid
itaconic acid
aconitic acid
succinic acid
2,3-butanediol
1,3-propanediol
crude oil
costs?
costs?
starch
sugar
renewable resources
Vegetable Oils
OILS & FATS OILS & FATS RESOURCESRESOURCES
CONVERSION
FORMULATION
OLEOCHEMICALS PALM OILS INDUSTRY
With the development of palm oil industry in
Malaysia/Indonesia 2 types of oils become
available
Palm Oil rich in C16 and C18
Palm Kernel Oil rich in C12 and C14
TWO TYPES OF OILS/FATS FROM PALM FRUIT
OILS & FATSTRIACYLGLYCEROLS
OCH3-(CH2)n-CH2- C-O-CH2
OCH3-(CH2)X-CH=CH -(CH2)Y -CH2-C-O-CH
O CH3-(CH2)n-CH2-C-O-CH2
R-COOCH2
R’-COOCHR’’-COOCH2
COMPOSITION OF PO = TALLOW & PKO = CNO
R, R’, R’’ PO Tallow CNO PKOC6 0.2 0.3C8 8.0 4.4
C10 7.0 3.7C12 0.23 48.2 48.3C14 1.09 2.5 18.0 15.6C16 44.02 26.6 8.5 7.8C18 4.54 21.8 2.3 2.0
C18:1 39.15 42.8 5.7 15.1C18:2 10.12 2.3 2.1 2.7C18:3 0.37
GENERAL PROPERTIES OF FATTY ACIDSR, R’, R’’ PS PKO GENERAL
PROPERTIES/USESC6 0.3 Irritants to eyes,
Hydrotropes, medium chain triglycerides (MCT)
C8 4.4C10 3.7C12 0.23 48.3 Good foaming power, poor
detergencyC14 1.09 15.6C16 44.02 7.8 Good detergency, poor foamingC18 4.54 2.0 Poor solubility, Good detergency
C18:1 39.15 15.1 Good solubilityGood detergency, Good lubricity
Poor oxidative stability C18:2 10.12 2.7C18:3 0.37
GLYCEROL Good solvent, sweet taste, moisturizing
BASIC OLEOCHEMICALS(Chemicals derived from oils/fats)
H20
High T&P
R-COOCHR-COOCH22
R’-COOCHR’-COOCHR”-COOCHR”-COOCH22
CH3OH/R3OH
R-COOHR’-COOHR”-COOH ACID
HO-CH2
HO-CH HO-CH2
GLYCEROL
R-COOCH3
R’-COOCH3
R”-COOR3
ESTER MOHR-COO- K+
R’-COO- Na+
R”-COO- Mg++
SOAPS
R-CH2NH2
R’-CH2NHR1
R”-CH2-NR1R2
AMINE
R-CH2OH
R’-CH2OH R”-CH2OH
ALCOHOL
catalyst catalyst
catalystCatalystCatalyst
H2
Fatty Acid Derivatives
RNH2
O
R C N
OR Na
RO
O
OOHn
Ethoxylation
Esterification
Saponification
Amidation
Chlorination
And many more....
Amination
Reduction
(R CH2)3N(R CH 2)2NHR CH2NH2
R COOH
R CH2OH
RCOCl R O R2O
PCl3 / COCl
NH3
H2 NaOHNH3
EO
R2OHH2
HO OH
OH
O
O H
O
Epoxidation
Hydrogenation
Oxidative Cleavage Isomerisation
Polymerisation
And many more...Hydroxylation
Addition
Fatty Acid Chain - Derivatives
COOHR
H H
COOHR
CH3 CO3HO
/ H2OH+ O3
H2
I2 catalyst
Conjugation
Others30%
Oil Field5%
I&I6%
Personal Cares
9%
Textiles Aux.10%
HH Detergent
40%
70%Surfactants
Others
Surfactants: active ingredients for
FATTY ALCOHOL LINEAR ALKYL BENZENE (LAB) ALPHA OLEFIN (AO)
PETROCHEMICAL OLEOCHEMICAL
TRADITIONAL FEEDSTOCK FOR PRODUCTION OF SURFACTANTS
Linear Alkyl Benzene Sulphonates (LAS) - workhorse of detergent industry
Alpha Olefin Sulphonates (AOS)
Alpha Olefin Ether Sulfates (AES)
Fatty Alcohol Sulfates (FAS)
Fatty Alcohol Ethoxylates (FAE) #
Fatty Alcohol Ether Sulfates (FAES)
Comparative Application Characteristics of Anionic Surfactants
DETERGENCY(*)
FOAMING(*)
SOLUBILITY
SKIN COMPATIBILITY
SENSITIVITY TOH2O-HARDNESS
LAS ~ MES ~ FAS ~ FAES ~ AOS
LAS ~ AOS ~ FAES ~ FAS ~ MES
LAS > FAES > AOS > MES > FAS
MES > AOS > FAES > LAS > FAS
FAS > FAES > LAS > AOS > MES
(*) Very similar, using optimum chain length selection
Similar detergency
power
Similar foaming
power
Acceptable solution
Better skin compatibility
Lower sensitivity to water hardness
Source: Ballestra
CH3-(CH2)n-CH2-COOCH3
SO3
CHEMISTRY OF MES
CH3-(CH2)n-CH2-COOSO3CH3
SO3
CH3-(CH2)n-CH-COOSO3CH3
SO3H
SO3 / SO3
CH3-(CH2)n-CH-COOCH3
SO3H H2O2/ CH3OH
CH3-(CH2)n-CH-COOCH3
SO3H NaOH
CH3-(CH2)n-CH-COOCH3
SO3 Na
Digestion
ME
MES
Sulfonation
Digestion
Bleaching
Neutralization
Drying
METHYL ESTER
SATURATED FATTY METHYL ESTER(IODINE VALUE < 0.5)
METHYL ESTER SULFONATES (MES) (>80% ACTIVE AND <6% DISALT)
Low Hydrogenation
MES PROCESS
Good detergency especially C16 and C18 (from PO)Good tolerance to water hardnessGood synergy with soap – as soap additiveGood solubilizing powerMild and non-irritant to the skin Good biodegradation characteristics
PERFORMANCE OF MESPERFORMANCE OF MES
0102030405060708090
C12 C14 C16 C18 LAS AS
C12 C14 C16 C18 LAS AS
0102030405060708090
C12 C14 C16 C18 LAS AS
54ppm 270ppm
0102030405060708090
4 9 12 16 20 24 28
LAS MES
PALM BASED MES
Active > 85%
Disalt < 6%
Color < 100 Klett
MES can easily be transported
Palm Kleen from MES
SOAP NOODLES
PO 80, 75, 70, 60
PKO 20, 25, 30, 40H2O 9-12.5%TFM 79-83%FFA 1.3 - 7.0%GLY 0.4 - 0.6%Sesq. Present
ROSELLE SOAP
GANOZHI SOAP
PALMIANIS LOTION WITH VITAMIN E
Isopropyl MyristateOctyl StearateStearic AcidGMSnon SEMCTWaterGlycerinPreservativesRheological additivesVitamin ETriethanol Amine
PALMIANIS CREAMIsopropyl palmitateOctyl palmitateStearic acidGlycerol monostearateMCT Cetyl alcoholGlycerolPreservativeRheological additivesNeutraliser
• LIPSTICKS LIPGLOSS
• DEODORANT STICK MASCARA
• COMPACT POWDER LOOSE POWDER
• LIQUID FOUNDATION
COLOR COSMETICS
ESTERQUATS2 (RCOOH) + (HOCC-)3-N
O(R-C-O-)2-N-C-C-OH
O(R-C-O-)2-N-C-C-OH
CH3
Presence of ester bond -> biodegradable
Saturated acid - good softening - yellowing - poor rewetting Unsaturated acid - good rewetting - less yellowing - poor softening
FABRIC SOFTENER FROM ESTERQUAT
Esterquat Isopropanol Glyceryl stearate Fatty Alcohol
Ethoxylates (3EO) Dye Perfume Rheological Additive Water
OHCH3 -(CH2)7 -CH-CH-(CH2)7-COOH
OHMW 316
PALM DIHYDROXYSTEARIC ACIDSPALM DHSA
PRODUCTION OF DHSACOOH
HCO3H or CH3CO3H)
O COOH H+ H2O OH
COOH OH
9,10-dihydroxystearic acid
Palm-basedGrease
Coatedfertilizers
POLYOL / POLYURETHANE
O
OH
OHOH
Palm oil
Epoxidized palm oil
Polyol
PALM-BASED POLYURETHANE SHEETS
Lafarge Cool Roof Concept
Renewables in LubricantsEster basefluids.
Crude Oil
Vegetable Oil
Natural Fatty Acids
Formulated LubricantsEsters
Modified Fatty Acids
Acids
Alcohols
Olefins
Non-Ester Base Fluids
Additives
Biodegradable Environmental Friendly
New Generation Lubricant
Renewable
Vegetable Oil as Lubricant
• Use of vegetable oils to replace petroleum base stock oils in lubricant applications
• Current Applications
Hydraulic Fluids Rail & Flange Oils
Two-Cycle Engine Oils Wire Rope Lubricants
Bar/Chain/Penetrating Oils
Metal working/Cutting Fluids
Greases Transformer Fluid
Vegetable Oils as Lubricants
• Advantages/Performance– Excellent boundary lubrication– Good viscosity and viscosity index– High Flash Point / lower evaporative loss– Readily Biodegradable, non-toxic– Environmentally Friendly, Renewable
• Disadvantages– Poor Oxidative Stability– Poor Low Temperature Properties– Lack of a good dynamic viscosity range– Limited additive technology
New Generation Motor Oils
• Estolides– Excellent Pour Point and Oxidative Stability– Average Functionality
• Wax Esters– Excellent Oxidative Stability and Functionality– Below Average Pour Point
Making the Next Motor OilOleic Estolide + Erucamide (C22) (C18)
Pour Point: - 45oC
Oxidative stability: 2-3 times conventional oils and equal to the best synthetics
Still biodegradable
Cost: equal to the best synthetics
NH3
2004, The New Generation: Estolides
Making the Next Motor Oil:Wax ester + Hydroxy (C18-22)
OHPour Point: 2oC
Oxidative stability: 3 times conventional oils and better than
the best synthetics
Still biodegradable
Cost: mid price between synthetics and conventional
2006, Wax Esters
Oleic Acid Based Estolides LUBRICANT
Glycerol Based Lubricant
HOCH2-CHOH-CH2OH
[O]
[O]
HOOC-CO-COOH
HOOC-CO-CH2OH
TMP
TMP
FA, PO
ROH, PO
LUBRICANT
LUBRICANT
PALM OIL BASED LUBRICANT
EPO + TMP PALM BASED ESTER TMP
n-butanol iso-amyl alcohol 2-ethylhexanol
catalyst
ROHPour points -5 to -15 ºC.
CONCLUSION
Consumer preferences for natural or plant-based chemicals & materials
Reliable source of feedstock Plant-based chemicals are renewable Plant-based chemicals are environmental friendly Palm-based chemicals are sustainable
Thank you………