Presented to

CESIO - 2008CESIO 2008

Methyl Ester Sulfonate The Next Generation Surfactant

Linear Alkylbenzene SulfonateHistorically the workhorse anionic surfactantGood surfactant properties, but…

Cost of raw material is increasing Petroleum derived, non-renewableRecent environmental concerns about biodegradation of production of aromatics

Search for ReplacementsAlternative surfactants require

Developed processing technology Equivalent surfactant propertiesAdequate volume to supply the industryDeveloped formulation technologyLower cost

Methyl Ester Sulfonates (MES)

One New Surfactant That Can Meet These Conditions

Methyl Ester Sulfonates (MES)Inexpensive raw materialGood surfactant propertiesProcess available that can be used in existing sulfonation plants

Methyl Ester SulfonatesDerived from renewable resources

Natural fats and oilsSupply of palm oil steadily increasingCurrent price for ME is about US$1200/MT

High detergency and calcium ion stabilityLess MES for equivalent washing powerGood blending partner with soap, LAS

Attractive biological propertiesLow toxicityBiodegrades similar to FAS and soapBiodegrades quicker than LAS

Chemithon MES Process is Versatile

Chemithon MES process uses either lower or higher MW ME feedsChemithon MES process uses higher iodine value feeds thus saving hydrogenation costs

MES Product SpecificationsColor of MES:< 100 (5% Klett) usually is

adequate, <10 is possible

Extractable oils in MES: Includes some

byproducts, <4±1% AMB

Volatile oils in MES:Mostly methyl ester, <2±1% AMB

By-product di-salt: Less than 6% AMB

Actives concentration: 25% to 85% (alcohol-free)

Undetectable residual peroxidesResidual alcohol to required specification

ME Carbon Chain Determines MES Quality

Lower molecular weight (shorter carbon chain length) ME is easier to processLower molecular weight ME gives lower disalt and colorLaundry applications require higher molecular weight MEOnly acid bleaching gives low disalt and low color long chain MES

Need MES in Dry FormLaundry powder formulations

Use MES in dry formAgglomerate / blend to final product

Detergent bar formulationCo-mix molten or powder dry MESCo-extrude / form final product

Liquid formulations – dilute to desired concentration

BioDiesel Changes EverythingBioDiesel is Methyl EsterHuge worldwide increase in BioDiesel productionHuge potential increase in ME availability

Palm-Based BioDieselNeed to separate C16

C16 has low IV numberMost double bonds on C18 fractionC16 fraction IV before hydrogenation ~5

Easy to hydrogenate to make sulfonation quality ME

C16 MES Product QualityActive/disalt ratio: 17/1MES total active: 88.7%Disalt (100% AI basis): 5.6%Color (5% Klett): 10 to 20PEE (100% AI basis): 2.00Water (%): 2.3%Methanol (%): <0.1%

MES in Commercial DetergentsAnalysis of commercial laundry powder

Safeway Select Ultra II23.5% MES40 wash loads/box US$0.125 per load

Sun Liquid Detergent4% MES4% non-ionic

MES Used In Commercial Product

Continuous Air/SO3 Sulfonation

SulfurSupply

AirSupply

OptionalSO3

AbsorberEffluent GasTreatment

SulfonationReactor

AcidDigestion

SO3 GasGenerator

OrganicRaw

Material

NeutralizingAgent

Product

Bleaching

Neutralization

ProductDrying

TTD

Methanol Recovery

H2O2

Methanol

Methyl Ester Acid Bleach System

CWS

METHYL ESTER ACIDFROM SULFONATOR

METHANOL

TICTE

Steam

BLEACHED ACIDTO NEUTRALIZER

CWR

CWS

CWR

TICTE

CWS

TICTE

Steam

CWR

HYDROGENPEROXIDE

Steam

POST-DIGESTER/HEAT EXCHANGER

POST-BLEACHING DIGESTER/HEAT

EXCHANGER

RECYCLE HEATEXCHANGER

RECYCLEPUMP

Dry Detergent Active Manufacturing

RAWMATERIAL

FEED

FILMREACTOR

SO GAS3

PROCESSWATER

CAUSTIC HIGH ACTIVE NEUTRALIZER

CONDENSATE

VAPORDISCHARGE

DRYPRODUCT

TURBO TUBEDRYER/

STRIPPER

STEAM

CONDENSATE

VACUUMSYSTEM

C16 MES Product

Drying of MES with Spray TowersForm of product critical for MES

MES hydrolytically unstableWill hydrolyze rapidly if formulation is aqueous and basic

Example – spray drying

Time InitialAfter Spray

DryAfter 1 month

After 2 months

Di-Salt 4.40% 33% 89% 98%Takashi Imamura, et al., French Patent 2,571,368, “Method forthe Preparation of Salts of Alpha-Sulfonated Fatty Acid Esters”

An Alternative to Spray DryingTurbo Tube™ Dryer System

CONDENSATE

VAPORDISCHARGE

TE TIC

DRY PRODUCT

TURBO TUBEDRYER/

STRIPPER

PRE-HEATER FLASH

TANK

PT

PIC

STEAM

PLODDER

CWR

CWS

FROM PASTESURGE TANK

CONDENSATE

VACUUMSYSTEM

PT

PIC

Turbo Tube® Dryer System Advantages

Lower capital and operating costsNo product degradation during processingCompact, self cleaning & energy efficientNo moving partsNo fire explosion hazardsNo plume or particle emissionsEnhances spray tower and agglomerator capacities and efficienciesAnd more…

ConclusionMES is a desirable alternative surfactant

Demonstrated processing technologyLower cost productionHundreds of thousands of metric tons have been produced and used in detergent formulationsSuccessful in detergent market for the last 5 yearsAdequate availabilityNew Chemithon MES plants coming on stream