Applications of BasicApplications of Basic Oleochemicals

PIPOC November 2009 PIPOC - November 2009 Kuala Lumpur Convention Centre

- Eva Suyenty -- Eva Suyenty -

Petrochemicals vs Oleochemicals

PetrochemicalsSynthetic oil PetrochemicalsSynthetic oil

Animal fat

Oleochemicals

Vegetable oil

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Oleochemicals

Fatty AlcoholR (CH ) OHR-(CH2)n-OH

Fatty AcidR-(CH2)n-COOH

Methyl EsterR-(CH2)n-COOCH3Basic

OlBasicOlOleoOleo

GlycerinC3H5(OH)3

Fatty AmineR3-N

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Oleochemicals in Daily Life

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Fatty Acid

ApplicationApplication

Direct Derivative

• Rubber • Cosmetic & toiletry

Direct Derivative

• Rubber • Cosmetic & toiletry• Rubber • Textile• Lubricants• Metal working

• Cosmetic & toiletry • Slipping agents• Softener• Biocides

• Rubber • Textile• Lubricants• Metal working

• Cosmetic & toiletry • Slipping agents• Softener• Biocides

• Crayon & pencils• Candles• Ore flotation• Personal care

• Food processing• Synlubes• Paints & coating• Elastomer

• Crayon & pencils• Candles• Ore flotation• Personal care

• Food processing• Synlubes• Paints & coating• Elastomer• Personal care • Elastomer• Personal care • Elastomer

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Fatty Acid – Direct Use (1)

RubberVulcanizing additives in dry rubber compoundingVulcanizing additives in dry rubber compounding processDispersing agent for carbon black & conferring plasticity to the rubberplasticity to the rubberVulcanization is promoted with fatty soaps of zinc formed in-situHydrogenated tallow fatty acids & stearic acid (1-5 parts/100 parts rubber)

LubricantsM t lli ( f d/i it ) thi k iMetallic soaps (preformed/in-situ) thickening agents in greaseHydrogenated castor oil fatty acids, stearic acid, 12 hydroxy stearic acid etc

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12-hydroxy stearic acid, etc

Fatty Acid – Direct Use (2)

Metal workingRolling oils 2 4% fatty acidRolling oils 2-4% fatty acidCutting oils 2-15% fatty acidCommon acids: oleic, stearic, TOFA

Ore flotationAnionic collectorsCommon acids: TOFA and oleic acidCommon acids: TOFA and oleic acid

Personal careStearic acid give firmness in shaving bars, ingredient in creams and lotionsTallow, stearic, and myristic acid ingredients in sha ing cream

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shaving cream

Fatty Acid – Direct Use (3)

Crayon & pencils

Crayons fatty acids (stearic and tallow fatty acids) incorporated into petroleum waxpencils acids) incorporated into petroleum waxFatty acids firm the crayon tip, disperse the pigment in the waxSoft crayons up to 40% of fatty acidsSoft crayons up to 40% of fatty acidsColored pencils 10-15% of fatty acids fill up the porosity of the core

Candles Fatty acids opacifier, melting rate controller, and give hardness of the taper Stearic, palmitic-rich stearic acid, hydrogenated , p , y gtallow fatty acidsStearic acid gives fine luster and non-greasy feelUsage: from a few percent to 100%

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Fatty Acid – Derivative (1)

Cosmetic & toiletry

Amine soaps, calcium and magnesium salts of fatty acids alkanolamides betaine imidazolinium etc& toiletry acids, alkanolamides, betaine, imidazolinium, etcHair care, oral hygiene products, deodorants, bath products, etcLevel of usage: 0.5 – 50% or moreLevel of usage: 0.5 50% or more

Softener Amido amine, imidazolinium, quaternary ammonium, amido amine quatsamido amine quatsHydrogenated tallow (long chain acid)Environmental issues ester quats (biodegradable surfactants))

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Fatty Acid – Derivative (2)

Biocides Quaternary ammonium compounds (replacing chloro & h l d )& phenol compounds)Swimming pool sanitizers, fungicides, preservatives in cosmetic & pharmaceuticals, etc

Food processing

Esters-mono and diglycerides, propylene glycol stearates, sorbitan esters, etcEmulsifiers dispensing agents thickeners stabilizersEmulsifiers, dispensing agents, thickeners, stabilizers

Paints & coatings

Glycerides, purified fatty acids, or derivatives (imidazolines)coatings derivatives (imidazolines)Film-forming surfaces, thickeners, pigment dispersion agents, biocides

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Fatty Acid – Derivative (3)

Slip agentFatty acid soaps LDPE and PP productionFatty acid soaps LDPE and PP productionC18-C22 primary amides approved by US FDA for food wrappings

Elastomers5 – 7%w fatty acid soaps emulsifiers in the production of Styrene-Butadiene Rubber (SBR)production of Styrene Butadiene Rubber (SBR)Nitrile rubber production hydrogenated tallow, stearic acid, oleic acid, low linoleic TOFA

Synthetic lubricantsDiesters & polyesters of short chain acids synlube base fluids

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base fluids

Fatty Acid – Derivative (4)

Fire f

Glycerol Mono Oleate (GMO) fire retardant ffighting hydraulic fluid

Paper Calcium Stearate lubricant coated paper

Specialty surfactant

Coco-range fatty acid anionic surfactant synthesis (acyl isethionates, acyl sarcosinates, acyl taurates)

Plastics N,N Ethylene Bis Stearamide (EBS) Acrylonitrile-Butadiene-Styrene (ABS) and Polyvynil Chloride y ( ) y y(PVC) resins as internal lubricant improves polymer flow during injection molding

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New Trend in Fatty Acid Application

Convert to fatty alcoholyFatty Acid Methyl Ester Fatty AlcoholFatty Acid + Fatty Alcohol Wax Ester Fatty Alcohol

Convert to biodieselFatty Acid + Methanol Biodiesel

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Fatty Acids Applications

14%

18%

30%

Plastic

Intermediate

Soap & detergent

6%

6%

6%

Paper

Lubricant & grease

Coating & resin

2%

5%

6%

Food & feed

Personal care

Rubber

5%

2%

Various

Candle

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Source: The Changing World of Oleochemicals, Wolfgang Rupilius and Salmiah Ahmad

Methyl Ester

Current applications of methyl esters:pp yManufacture of fatty alcoholsBiodieselL b i tLubricantsCosmeticProduction of ‘superamides’Production of superamidesProduction of imidazolines and betainesPreparing antibiotics formulations

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Potential Future Application (1)

Production of Methyl Ester SulfonateRaw material: palm stearin, C16 ME from Europe’s biodiesel Alternative ester sulphonates to substitute Linear Alkyl Sulphonate (LAS)Flotation agent in mining defatting agent in leather industriesFlotation agent in mining, defatting agent in leather industries

Production of Methyl Ester EthoxylatesHave different foaming and solubility from alcohol ethoxylatesHave different foaming and solubility from alcohol ethoxylatesTotal production cost should be lower than alcohol ethoxylatesLarge price difference between unsaturated alcohol and unsaturated methyl ester attractive technologyLimitation: less hydrolytic stability of the ester bond

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Potential Future Application (2)Production of Sucrose Polyester (SPE)

No calorie and no cholesterol fat substitutesHave potential application in food industry

Production of monoglycerides for food industrySalad oil is already being produced in Israel by methyl ester interchange process

Production of fatty acid cyanamide soapsProduction of fatty acid cyanamide soapsExcellent detergency for all-purpose liquid cleaners (particularly C12-C14, C12-C18, and C16-C18 ranges

Production of monoglycerides for industrial productsGlycerolysis of methyl esters (40, 60, and 90% monoglycerides)L b i d l ifi f i il i di

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Lubricants and emulsifiers for cutting oils, grinding or polishing pastes

Fatty AlcoholMost important market household detergent (C12 and higher)

Derivatives

(Generally for detergent-surfactant)

Direct Uses

95%

5%

Alcohol Ether Sulfate (AES)C iti l h l f t tAlcohol Ethoxylates (AE)

Alcohol Sulfate (AS) Composition as alcohol surfactant:

AES, AE, AS75%

Linear Alkyl Benzene Sulfonate (LABS)

interchangeability

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Linear Alkyl Benzene Sulfonate (LABS)Alkyl Phenol Ethoxylates (APE)

Others25%

Fatty Alcohol – Detergent Applications

Applications of alcohol-based ppsurfactants:

Heavy duty washing powdersHeavy and light duty washing liquidsHeavy and light duty washing liquidsFabric softenerPersonal care Auxiliaries for the processing of textiles and leatherPetroleum drilling and processingPetroleum drilling and processing

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Fatty Alcohol – Non-detergent Applications

Compound Application

Free alcohol Foam depressants, rolling oil, solvent, lubricants, evaporation control agent, pharmaceutical

Fatty esterThiodipropionate esters

preparationEmollients, plasticizersAntioxidantsThiodipropionate esters

Alkyl polyglucosides Sulfosuccinates estersP l th l t t

AntioxidantsPersonal care, food productsHousehold cleaners, wetting agentL b i ti il l ti iPolymethacrylate esters

Alkyl phosphatesLubricating oils, plasticizers Cosmetic emulsifiers, textile auxiliaries

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Fatty Alcohol Derivatives

22.0%

35.7%

AE

AES

3.1%

14.8%

Quaternary ammonium

AS

1.1%

1.3%

2.5%

APG

Amine oxide

Methacrylate esters

19.5%

1.1%

Others

APG

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Source: Internal

Fatty Alcohol Applications

7%

11%

48%

Flavor & Fragrance

Antioxidant

Detergent & Cleaner

4%

4%

7%

Food

Petroleum

Personal Care

2%

3%

3%

Polymer Emulsion

Fabric Softener

Agriculture

9%

2%

Others

Textile

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Source: Internal

Fatty Amine

Organic compound with nitrogen as the key atom

Primary Amine Secondary Amine Tertiary Amine

Applications:> 75% fabric softener actives (e.g. DHTDMAC)< 25% directly consumed in certain applications

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Primary AminesProduction of quaternary ammonium compounds and amphoterics via tertiary amine

Long chain primary amines & their salts:Rubber mold release agentsPrevent nicking in granular and blended fertilizersg g

Short chain amines:LarvicidesFly repellentsFly repellents

Blends of various lengths amines & their salts:Cationic collectors in ore flotation

Amine ethoxylates (2-50 EO):Corrosion inhibitorsEmulsifiers for textile spinning oils

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p gEmulsifier for agricultural herbicide

Secondary Amines

Chemical intermediaries difatty dimethyl ammonium salts y y(fabric softener actives)

Do not have any direct market

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Tertiary Amines

CHR CH2RR N

CH3

CH3

R CH2 NCH2R

CH3R

RR N

Symmetrical Asymmetrical AsymmetricalSymmetricalTrialkylamine

AsymmetricalDialkylmonomethylamine

AsymmetricalAlkyldimethylamine

The largest market share

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Tertiary Amine ApplicationsProduction of quaternary ammonium compounds and amine oxides

Use of dimethylalkylamine:manufacture of quaternary ammonium compounds for biocidesmanufacture of quaternary ammonium compounds for biocides, textile chemicals and oilfield chemicals, amine oxides, betaines, catalyst in polyurethane foam synthesis

Use of methyldialkylamine:softener, conditioner for shampoo, cosmetics, agricultural wetting agents

Use of trialkylamine:cationic collector in ore flotation

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Glycerin

Polyol with more than 2000 applications :

water-solubleodorlesscolorlesscolorlesshas certain sweetnessabsorbs and retains waterhas a capacity to dissolve flavors and dyeshas plasticizer and antioxidant propertiesnontoxic and easily biodegradableo o c a d eas y b odeg adab e

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Application of Glycerin (1)

FoodsSolvent for preparation of concentrated flavor extracts from natural productsTexture improver and emulsifier in ice-creamC diti f i f d t ftConditioner for wine gums, fondants, soft creamsEmulsifiers in bread production (glycerol esters of acetic and tartaric acids)

CosmeticsEmulsifier, moisturizer, and conditioning agentC l ti t th t d d t lCreams, lotions, tooth pastes and dental mouthwashes, and skin & hair care products

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Application of Glycerin (2)

Pharmaceuticals Cough syrup, expectorant, ointmentsMild laxative in suppositoriesSoftener in gelatin capsulesGlycerol trinitrate treatment for heart disease

Plastics resins Production of phthalic and maleic alkyd resinsPlastics, resins, and cellophane

Production of phthalic and maleic alkyd resinsMoisturizer and plasticizer in cellulose filmsPolyether polyols of glycerol are polymerized with diisocyanates to form flexible or rigid y gpolyurethane foams

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Application of Glycerin (3)

Tobacco Solvent, humidifier, and plasticizer , , pin tobaccoGlycerol triacetate (triacetin) softener for cigarette filters

Others Hydraulic fluid formulationsInks and printing colors to prolong the self-lifeHumidifier, plasticizer, and lubricant in paper industry

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Glycerin’s Future Application (1)

Propylene Traditionally produced by propylene oxide glycol hydration

Has similar properties with EG, but less toxicColorless, odorless, tastelessH h t t ti i t i iHas humectant properties moisturizer in medicines, cosmetics, toothpastes, foods, and tobacco productsHas antibacterial properties hand sanitizersHas antibacterial properties hand sanitizers, antibacterial lotions, etc

E i hl h d i T diti ll th i d f id ti fEpichlorohydrin Traditionally synthesized from epoxidation of allyl chlorideAs building block in the manufacture of epoxy resins elastomers and synthetic glycerol

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resins, elastomers, and synthetic glycerol

Glycerin’s Future Application (2)

Acrolein Lab scale reaction of potassium bisulfate ith l i d h d ti f l i t 280 oCwith glycerin, dehydration of glycerin at 280 oC

Preparation of acrylic acid, polyester resin, polyurethane, propylene glycol, acrylonitrile

Renewable fuel & H2 production

Renewable fuel by cracking process to hydrocarbonHydrogen by reforming processHydrogen by reforming process

Eicosapentaenoic id (EPA)

Common source: fish oil, microalgae, human b t ilkacid (EPA);

omega-3 fatty acid

breast milkCan be synthesized from crude glycerin by enzymatic process using Pythium irregulare(new research at Virginia Polytechnic Institute)

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(new research at Virginia Polytechnic Institute)

Glycerine Applications

13%

37%

Alkyd resin

Soap, cosmetic, pharm.

11%

12%

Polyurethanes

Food

3%

9%

Explosive

Tobacco

15%Others

Source: The Changing World of Oleochemicals Wolfgang Rupilius and Salmiah Ahmad

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Source: The Changing World of Oleochemicals, Wolfgang Rupilius and Salmiah Ahmad

www ecogreenoleo comwww.ecogreenoleo.com

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T i K ih

h k

Terima Kasih

Thank You

谢谢

どうもありがとうございます36