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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