MES The Future Surfactant Rev 1 - Chemithon Enterprises The Future Surfactant Rev … · Relative Sulfonation Cost of MES and LABS MES LABS Raw Materials US$/MT T/T US$/T T/T US$/T

Copyright 2008 by The Chemithon Corp.: Used by Permission

MES – The Future Surfactant

Walter Jessup


Challenges to the Detergent Industry

Raw Material Cost IncreasesFormulating with Alternative Detergent ActivesAvailable & Sustainable Source of SupplyEnvironmental and Regulatory Concerns


Challenge to the Detergent Industry


Alternative Surfactants Require:

Adequate Volume to Supply the IndustryEquivalent Surfactant PropertiesDeveloped Processing TechnologyDeveloped Formulation TechnologyLower Cost


The Case for MES

Methyl Ester Sulfonates (MES)Methyl Ester Raw Material Widely Available – renewable natural oilsTrans-esterification of fatty acids with Methanol followed by refining and hydrogenation – all known technologiesSulfonation Process Available that can be adapted to Existing Sulfonation PlantsExcellent Surfactant Properties


Advantages of MESDerived from renewable oil resources

Natural fats and oilsSupply of palm oil steadily increasingME Cost per ton historically has been less than LAB (subject to changing market conditions)

High detergency and calcium ion stabilityLess MES for equivalent washing powerGood co-active


Advantages of MES

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


Cost Compare MES & LABS

February, 2006Relative Sulfonation Cost of MES and LABS

MES LABS

Raw Materials US$/MT T/T US$/T T/T US$/T

Sulfur 110 0.11 $12.10 0.102 $11.22LAB 1475 -- -- 0.721 $1,063.48ME 650 0.775 $503.75 -- --NaOH 220 0.158 $34.76 0.26 $57.20MeOH 150 0.08 $12.00 -- --H2O2 260 0.06 $15.60 -- --Na2SO4 100 0.02 $2.00 -- --N2 75 0.035 $2.63 -- --Total Raw Materials $582.84 $1,131.90

UtilitiesElectricity US$102/MWH 0.209 MWH $21.32 0.180 MWH $18.36Steam 8.70/MT 2.05 T $17.84 0.14 $1.22Cooling Water 21.74/KT 0.055 KT $1.20 0.055KT $1.20Total Utilities $40.35 $20.77

Total Cost Excluding Labor, Capital & OH $623.18 $1,152.67


Cost Compare MES & LABS

August, 2008Relative Sulfonation Cost of MES and LABS

MES LABS

Raw Materials US$/MT T/T US$/T T/T US$/T

Sulfur 475 0.11 52.25 0.102 48.45LAB 1800 -- -- 0.721 1297.8ME 1250 0.775 968.75 -- --NaOH 650 0.158 102.7 0.26 169MeOH 550 0.08 44 -- --H2O2 700 0.06 42 -- --Na2SO4 400 0.02 8 -- --N2 75 0.035 2.625 -- --Total Raw Materials $1,220.33 $1,515.25

UtilitiesElectricity US$102/MWH 0.209 MWH 21.318 0.180 MWH 18.36Steam 8.70/MT 2.05 T 17.835 0.14 1.218Cooling Water 21.74/KT 0.055 KT 1.1957 0.055KT 1.1957Total Utilities $40.35 $20.77

Total Cost Excluding Labor, Capital & OH $1,260.67 $1,536.02


ME Feedstocks

From Variety of Animal and Vegetable OilsPart of Normal Synthesis Route to Fatty Alcohols, Ethoxy Alcohols and Bio-DieselEnjoys Natural Economic Advantage


ME Feedstocks

Fats or Oils

Low Pressure Hydrogenation

Esterification& Purification

High Pressure Hydrogenation Ethoxylation

Methylesters

Fatty Alcohols Ethoxy Alcohols


Vegetable Oils~71 MillionMetric Tons

Animal Oils~29 MillionMetric Tons

Total NaturalFats and Oils~100 MillionMetric Tons

Animal Feeds~8 Million

Metric Tons

Oleochemical Uses~12 MillionMetric Tons

Food~80 MillionMetric Tons

Industrial Uses~20 MillionMetric Tons

Approximate Production and Use of Natural Fats and Oils


MES Surfactant Uses

Liquid Household Cleaners (C12 to C14)Dishwash, Fine Fabrics, Hard Surfaces

Personal Care (C12 to C14)Shampoos, Bubble Bath, Liquid Hand Soaps, Bar Soap

Laundry Powders and BarsC1416 used by LionC1618 used by Henkel and others

Industrial Surfactants


Detergency Vs. Hardness

50

60

70

80

90

100

0 100 200 300

Water Hardness (ppm CaCO3)

Det

erge

ncy

(%)

C1618 MES C1618 AOS C1215 AS LAS

Surfactant Concentration

210 ppm


Detergency Vs. Concentration

30

50

70

90

0 100 200 300 400

Concentration of Surfactant (ppm)

Det

erge

ncy

(%)

C1416 MES LAS C12 AS

Water Hardness 54 ppm


Why Isn’t MES in Widespread Use?

Traditional Process Technology Has Been Inadequate

Poor color compared to other anionicsPoor yield of MES from feedstockOnly low active aqueous paste products

More complex to manufacture compared to other anionics


Why Isn’t MES in Widespread Use

Feed Stock AvailabilityME production and refining Price and supply of natural oils

Product FormulationMES is hydrolytically unstable at high pHRequires formulation techniques specific to MES

Competition from Bio-fuels for Feedstock


Making High Quality MES

ColorMESA digestion step causes color darker than typical anionicsMES requires bleaching to achieve acceptable final color

Di-SaltUndesirable by-product – sulfonated soapCan be a major componentConversion to MES


Methods to Improve Color in MES

Feed StockLowest cost method to improve product qualityR&B OilLower Iodine Value

FractionationHydrogenation


Methods to Improve Color in MES

SulfonationGood Mole Ratio ControlColor Inhibitor

Bleaching – Required for Consumer Products

Sodium Hypochlorite – Unacceptable byproductsHydrogen Peroxide – Safety Issues but Required for an Acceptable Product


Bleaching Methods

Neutral BleachingLess EffectiveRequires Extended Times - Large Storage Vessels

Acid BleachingFast and Best Product ColorRequires Special Materials of Construction


Di-Salt in MES

Di-Salt is Sulfonated SoapTwo Sources in MES Manufacture

R-CH-C-OCH3 (II)

R-CH-C-ONa (III)

O

SO3Na

R-CH-(C-OCH3):SO3 (I)O

SO3H

+3 NaOH +2 H2O + CH3OSO3Na

O

SO3Na

R-CH-C-ONa (III)

O

SO3Na

+ H2O + CH3OH + H2ONaOH


Detergency of Di-Salt

Water C12MES

C12Disalt

C14MES

C14Disalt

C16MES

C16Disalt

C18MES

C18Disalt

010203040506070

% D

eter

genc

y

Water C12MES

C12Disalt

C14MES

C14Disalt

C16MES

C16Disalt

C18MES

C18Disalt75 ppm Mg++


Impact of Di-Salt

Poorer Surfactant PropertiesMES has 50% higher detergencyMES has similar surface tension at 1/10 conc.

Poor Cold and Hard Water PropertiesDi-salt has much higher Kraft pointsDi-salt precipitates even in soft water

Di-Salt is a Yield LossBlends of di-salt / MES similar toSoap / MES – at much higher cost


Formulation with MES

Form of Product Critical for MESMES 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%


Need MES in Dry Form

Dry Neural Paste to Remove MethanolLaundry Powder Formulations

Agglomerate / blend to final productDetergent Bar Formulation

Co-mix molten or powder dry MESCo-extrude / form final product

Liquid Formulations – Dilute to Desired Concentration


Challenges of MES Production

High SO3:ME mole ratios and high temperatures for high yields

Resulting dark MESA requires bleachingDi-salt an undesirable by-productStricter formulation requirements for shelf-stable productSafety Issues

Peroxides and MethanolOrganic Peroxides


Meeting the ChallengesBest Practice MES process

MeOH re-esterification w/ H2O2 acid bleaching

Critical parametersLow residual oil, low colorMinimal di-saltNeutral dried product


Best Practice MES Process

Uses Conventional Air/SO3 Film SulfonationSpecial Acid DigesterRe-Esterfication with MethanolAcid Bleaching with 50% H2O2Drying of Neutral MESMonitoring Equipment for O2Peroxide Control in Off-streams


Acid Bleaching MES Process Flow Diagram

SulfurSupply

AirSupply

OptionalSO3

AbsorberEffluent GasTreatment

SulfonationReactor Acid DigestionSO3 Gas

Generator

OrganicRaw

Material

NeutralizingAgent

Product

Bleaching

Neutralization

Product DryingTTD

Methanol Recovery

H2O2

Methanol


MES Sulfonation Chemistry

Formation of adduct(II) from methyl ester (I):

Sulfonation of adduct(I) to sulfonated adduct(III):

Elimination of SO3 to form MESA(IV):

------> R-CH-C-OCH3 (IV)O

SO3H

R-CH-(C-OCH3):SO3 (III)O

SO3H

+ SO3

+ SO3 ------>R-CH2-(C-OCH3):SO3 (II)O

R-CH-(C-OCH3):SO3 (III)O

SO3H

R-CH2-C-OCH3 (I)O

R-CH2-(C-OCH3):SO3 (II)O

+ SO3 <------>


By-product Sulfonation Chemistry

Dimethyl sulfate (trace)CH3OSO3H + CH3OH ----> CH3OSO2OCH3 + H2O

Dimethyl etherCH3OSO2OCH3 + CH3OH ---> CH3OSO3H + CH3OCH3

Reduction of SO3 to SO2, and Oxidation of the alkyl chain:

Sulfonation to form Color Bodies

SO3 + + SO2 + H2O--->R-C-C-C-C-C-R' R-C-C-C=C-C-R'


Effect of SO3 Mole Ratio on MESA Color and Free Oil

% E

xtra

ctab

le O

il

35

350000

5

10

15

20

25

30

0 5000 10000 15000 20000 25000 30000

Color, 5% Klett

MR=1.1, T=70°C MR=1.1, T=80°C MR=1.1, T= 90°CMR=1.3, T = 70°C MR = 1.3, T = 80°C MR = 1.3, T = 90°CMR = 1.5, 70°C MR = 1.5, 80°C MR = 1.5, 90°C


Effect of Mole Ratio & Digestion Temperature on Extractable Oil

468

1012141618

% E

xtra

ctab

le O

il

Mole Ratio

Low

High Low

High

Digest Temperature


Effect of Mole Ratio & Digestion Temperature on Color

4,000

8,000

12,000

16,000

20,000

Col

or (5

% K

lett)

Low

HighMole Ratio Low

High

Digest Temp


Effect of Digestion Time & Temperature on Extractable Oil

81012141618202224

% E

xtra

ctab

le O

il

Low

Digest Time

High Low

High

Digest Temp


Effect of Digestion Time and Temperature on MESA Color

2,000

4,000

6,000

8,000

10,000

12,000

Col

or (5

% K

lett)

Digest Time

Low

HighDigest Temp

Low

High


Reaction of sulfonated adduct (III) to MESA (IV)

Reaction with SO2 to form Sulfuric AcidDecomposition of Hydrogen Peroxide2 H2O2 O2 + 2 H2O

Epoxidation with Hydrolysis of unsaturates

Hydrolysis of MESA to Di-Acid

Bleaching Chemistry

R-C=C + H2O2O HO OH

R-C - C-R + H2O R-C - C-R

R-CH-C-OH (VI)O

SO3H

R-CH-C-OCH3 (IV)O

SO3H

+ H2O + CH3OH

R-CH-C-OCH3 (IV)O

SO3HR-CH-(C-OCH3):SO3 (III)

O

SO3H+ CH3OSO3H+ CH3OH


Development of Acid/MESA Bleaching Technology

Developmental GoalsEliminate halogen bleachingDecrease sensitivity to feedstockReduce extremely long bleaching timesReduce di-salt level in product

Technical Problems for Aggressive BleachingH2O2 decomposed at higher temperaturesHighly viscous sulfonic acid during bleachingHydrolysis to di-acid was favored as bleaching became more aggressive


Aggressive Bleaching Technology

Alcohol Addition was IncreasedDecreased viscositySuppressed hydrolysis

Non-Metallic or Low-iron Corrosion Resistant alloys

Reduced decomposition of hydrogen peroxideHigher temperature operation possible

Optimum Operating Conditions were DeterminedPart of an Integrated MES Process


Effect of Temp in Metallic Systems

0

1000

2000

3000

4000

5000

0 20 40 60

Bleaching Time (min)

5% K

lett

colo

r

T= 65 CT= 72 CT= 80 C


Non-Metallic Bleaching of MES

Bleaching Rate Very Temperature SensitiveH2O2 Decomposition Same at Higher Temperature

0

500

1000

1500

2000

0 50 100

150

200

Time (min)

5% K

lett

70ºC90ºC

10

100

1000

10000

%H2O2 remaining

5% K

lett

70 ºC90 ºC

100% 50% 0%75% 25%


Minimizing Di-Salt

816

2432

40

2733

3944

50

456789

1011

% Yield to Di-Salt

Methanol Addition (%)

H2O2 Conc. (%)

C1618 MES


Minimizing Neutral Color

3745

5361

6977

7582

8996

0200400600800

1000120014001600

Color (5% Klett)

BleachTime (min)

BleacherTemp (°C)

C1618 MES


Minimizing Unreacted Oil

1.11.2

1.31.4

1.570

7580

8590

468

1012141618

% Extractable Oil

Mole Ratio

Digest Temp (C)


Bleaching & Neut. Effect on Oil

Acid DigesterBleacher Loop

BleacherDigester Neutralized

Volatile Oil

Non-Volatile Oil

Total Oil0%

1%

2%

3%

4%

5%

6%

7%

wt.%

(AM

B)


Iodine Value Needed with Aggressive Bleaching

Only IV is Shown, but Hydroxy Groups Should Have an Equivalent EffectIodine Values Above Two Will Produce Inferior MES

Oil levels become excessive at reasonable SO3 mole ratioLarge H2O2 requirement increases di-salt

IVs Below Two Produce Good Quality MESIVs Below One Produce Excellent MES


Neutralization ChemistryMESA neutralization

MESA:SO3 adduct neutralization to form Di-Salt

Hydrolysis of MES

R-CH-C-OCH3 (VII)O

SO3Na

R-CH-C-OCH3 (IV)O

SO3H+ NaOH + H2O

OR-CH-(C-OCH3):SO3 (III)

SO3H+3 NaOH +2 H2O + CH3OSO3NaR-CH-C-ONa (V)

SO3Na

O

R-CH-C-ONa (V)

O

SO3Na

R-CH-C-OCH3 (IV)

O

SO3H

+2 NaOH + H2O + CH3OH


MES Hydrolytic Stability

MES is prone to hydrolysis at high and low pH

Concern in Neutralization is high point temperatures and pH

Hydrolysis data for C1214 SASME from Stein and Baumann, JAOCS, September, 1975

0123456

1 2 3 4 5 6 7 8 9 10 11

pH

% H

ydro

lysi

s / h

r

20 C40 C60 C

80 C


Product CharacteristicsFlake has excellent characteristics

Non-clumping in storage at 5% moistureExcellent flowabilityNon-dusting

Formed Flake can be ground as needed


MES Drying: Residual Water

1519

2327

31Feed Rateof SASME

(Kg/hr)16

0

140

120

1008060

Inlet FeedTemperature (°C)

012345678

% ResidualH2O


Minimizing Residual Methanol

1519

2327

31

16014012010080600.10

0.30

0.50

0.70

0.90

% ResidualMethanol

Feed Rateof SASME

(Kg/hr)

Inlet FeedTemperature (°C)


Pilot Plant ME Sulfonation Tests

Over 25 different ME feeds sulfonatedChemithon MES pilot plant, Seattle U.S.A

Will present the results for five ME’sAll products stripped or driedIncludes low quality, low cost, unsaturated ME’s

Cheap source of surfactant

Building a product database for a wide variety of feedstocks


Methyl Ester ComparisonPalm Palm

Coconut Kernel Stearin Tallow SoyaC12-C14 C8-C18 C16-C18 C16-C18 C18

Molecular weight 222 227 279 287 295Iodine value (cg iodine/g ME) 0.1 1.4 0.3 0.1 1.1Carboxylic Acid (wt%) 0.1 0.2 n/a 0.1 1.0Acid value (mg KOH/g ME) 0.2 0.5 0.4 3.8 0.4Saponification no. (mg KOH/g ME) 252 240 n/a n/a n/aFreeze Point (C) 0 18 26 31 33Moisture (wt%) 0.03 0.03 0.02 0.04 0.01Carbon chain length (wt%)<C10 0.0 5.2 0.0 0.0 0.0C10 0.0 4.4 0.0 0.0 0.0C12 71.5 51.0 0.2 0.0 0.0C14 28.0 15.1 1.5 3.1 0.0C16 0.6 7.2 65.4 31.6 10.4C17 0.0 0.0 0.0 1.2 0.0C18 0.0 17.2 32.2 63.6 89.6>C18 0.0 0.0 0.7 1.8 0.0


Methyl Ester Carbon-Chain Length

C8 C10 C12 C14 C16 C18 C20

CoconutPalm Kernel

Palm StearinTallow

Soya

0255075

100

Wei

ght %


Dried MES Product Quality

Wt%SoyaC18

Sodium methyl ester sulfonate (α-MES) 71.5 69.4 83.0 77.5 75.7

Disodium carboxy sulfonate (di-salt) 2.1 1.8 3.5 5.2 6.3

Methanol (CH3OH) 0.48 0.60 0.07 0.00 0.03

Hydrogen peroxide (H2O2) 0.10 0.04 0.13 0.15 0.05

Water (H2O) 14.0 15.2 2.3 2.9 1.4

Petroleum ether extractables (PEX) 2.6 2.7 2.4 4.8 7.2

Sodium carboxylate (RCOONa) 0.2 0.2 0.3 0.3 0.5

Sodium sulfate (Na2SO4) 1.2 1.8 1.5 2.3 2.4

Sodium methyl sulfate (CH3OSO3Na) 8.0 8.4 7.2 7.7 2.5

10% pH 5.0 5.3 5.3 5.4 5.8

Klett color, 5% active (α-MES + di-salt) 30 310 45 180 410

CoconutC12-C14

Palm KernelC8-C18

Palm Stearin

C16-C18TallowC16-18


MES Product Specifications

Color of MES:< 100 (5% Klett) usually

is adequate, < 20 is possible

Extractable Oils in MES:

< 4 ± 1% AMBVolatile Oils in MES:

< 2 ± 1% AMB

By-product Di-Salt: Less than 6% AMB

Actives concentration:

25% to 85% (alcohol free)

Residual Alcohol to Required spec.


MES Dried Product

Palm

KernelC8-c18

Palm StearinC16-C18

SoyaC18 Tallow

C16-C18

CoconutC12-C14

Palm KernelC8-C18

Palm StearinC16-C18

SoyaC18

TallowC16-C18


MES Product


MES Product Quality

MES Active (%): 88.7%Disalt (100% AI basis): 5.6%Color (5% Klett): 18PEE (100% AI basis): 2.00Water (%): 2.3%Methanol (%): < 0.1%


MES Dryers and Chilled Belt


MES Profitability

Savings est. ~US$275/MT vs. LABS

Potential Annual Savings US$11,000,000 for a 40,000MT/y plant


Conclusion

MES is a Viable Alternative SurfactantStill Show Lower Cost than LABS>100 Million MT/y Produced in North AmericaProven Process TechnologySuccessful Use in Detergent Market

Documents

MES The Future Surfactant Rev 1 - Chemithon Enterprises The Future Surfactant Rev … · Relative Sulfonation Cost of MES and LABS MES LABS Raw Materials US$/MT T/T US$/T T/T US$/T