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………