DRY-ANIONIC SURFACTANTSA valuable tool for the detergent industry

by

I. Adami (R&D Dept.)

BALLESTRA S.p.A.

Contents:Contents:

• SULPHONATES and THEIR IMPORTANCEin the SURFACTANTS SCENARIO

• SULPHONATES PRODUCTION TECHNOLOGY

• DRY-ANIONIC SURFACTANTS PRODUCTION

• USE and ADVANTAGES of DRY-ANIONIC SURFACTANTS

• ECONOMICAL CONSIDERATIONS

ANIONIC SURFACTANTS

are the most widely used

ACTIVE COMPONENTS

because of their

Wide spectrum of applicability Wide range of industrially available types Consolidated manufacturing technology Proven overall performances Chemical compatibility with other detergent components

ANIONIC SURFACTANTS

SULPHONATES

LABS : Linear-Alkyl-Benzene-Sulphonate

FAS : Fatty-Alcohol-Sulphates

FAES : Fatty-Alcohol-Ethoxy-Sulphates

AOS : Alpha-Olefins-Sulphonates

MES : Methylester-Sulphonate

SURFACTANTS USE SURFACTANTS USE in in

HOUSEHOLD and PERSONAL CARE PRODUCTSHOUSEHOLD and PERSONAL CARE PRODUCTS

57%

40%

2% 1%

ANIONICS

NON IONICS

CATIONICS

AMPHOTERICS

ANIONIC SURFACTANTS USE ANIONIC SURFACTANTS USE in in

HOUSEHOLD and PERSONAL CARE PRODUCTSHOUSEHOLD and PERSONAL CARE PRODUCTS

0

200

400

600

800

1000

1200

W. Europe USA Japan

MESAOSFASFAESLABS

KTY

Comparative Application Characteristics Comparative Application Characteristics of main Anionic Surfactantsof main Anionic Surfactants

DETERGENCY(*)

FOAMING(*)

SOLUBILITY

SKIN COMPATIBILITY

SENSITIVITY toH2O-HARDNESS

LABS ~ MES ~ FAS ~ FAES ~ AOS

LABS ~ AOS ~ FAES ~ FAS ~ MES

LABS > FAES > AOS > MES > FAS

MES > AOS > FAES > LABS > FAS

FAS > FAES > LABS > AOS > MES

(*) Very similar, using optimum chain length selection

SURFACTANT SELECTIONSURFACTANT SELECTION

Performance

Price

Physical shape& characteristics

SULPHONATESSULPHONATES

PRODUCTION TECHNOLOGY

FEEDSTOCK FOR SULPHONATION PROCESSFEEDSTOCK FOR SULPHONATION PROCESS(Key Parameters for Quality Processing)(Key Parameters for Quality Processing)

FEEDSTOCK PARAMETER TYPICAL FIGURES

Linear Alkylbenzene

- (High) Sulphonability- (Controlled) 2-Phenyl-Isomers Content

- (Low) Moisture- (Low) Bromine Number- (Constant) Distillation Range

98.5 - 99.0 (%)15 - 20 (%) (via HF-Alkylation)25 - 35 (%) (via AlCl3-Alkylation)0.01 - 0.02 (%)0.01 - 0.02 (gr Br2/100 gr)275 - 305 (°C)

Fatty Alcohols(Natural & Synthetic)

- (Low) Unsulphatable- (Low) Moisture- (Low) Iodine Number

0.3 - 0.5 (%)0.01 - 0.05 (%)0.05 - 0.10 (gr J2/100 gr)

Fatty Alcohol Ethoxylates(Natural & Synthetic)

- (Low) PEG content- (Low) Moisture content- (Negligible) EO content

0.5 (%) max.0.01 - 0.05 (%)2 ppm max.

Alpha-Olefins

- (Low) Moisture- (Low) Internal Olefins- (Low) Branched Olefins- (High) Alpha-Isomers Content- (Constant) Distillation Range

0.05 - 0.10 (%)0.5 - 2.0 (%)1.0 - 4.0 (%)94 - 98.5 (%)(depending on cut)

Fatty AcidMethylesters

- (Low) Iodine Number- (Low) Acid Value- (Low) Moisture- (Low) Glycerides Content

0.01 - 0.3 (gr J2/100 gr)0.1 - 0.5 (mg KOH/g)0.05 - 0.1 (%)0.05 - 0.1 (%)

Sulphur AIRDRYING

HEATRECOVERY

OrganicR.M.

SULPHURPRE-TREATMENT

SULPHURMELTING &

DOSING

SULPHURBURNING

SO2 / SO3PRODUCTION

SULPHONATION&

SULPHATION

AGEING &STABILIZING

LABFAFAEAOME

EXHAUST GASTREATMENT

SULPHITESOXIDATION

^atm

NEUTRALIZATION

ProcessH2O

RE-ESTERIFICATIONCaustic

Soda

BLEACHINGHYDROLYSIS

LABSO3HMESpaste

AOSpaste

DEAERATION&

STRIPPING

LABSpaste

FASpasteFAES

paste

SulphonationSulphonation ProcessProcess

SulphonationSulphonation and Neutralization Plantand Neutralization Plant

ANIONIC QUALITY SPECS.ANIONIC QUALITY SPECS.

PRODUCT AM (%) Na2 SO4(on 100% AM)

F.O.(on 100% AM)

°Klett Color(on 5% AM sol.)

LABSO3 H 97.5 - 97.7 0.5 - 0.6 ()0.8 - 1.0 10 - 20FAS (12-14 nat.) 70 - 75 0.8 - 1.20.8 - 1.0 5 - 10FAS (13-15 synt.) 70 - 73 0.9 - 1.31.0 - 1.2 15 - 25FAS (16-18 nat.) 68 - 70 1.2 - 1.71.5 - 1.8 35 - 50AES-2EO (*) 70 - 73 0.6 - 1.10.5 - 1.0 3 - 10AES-3EO (**) 70 - 73 0.6 - 1.00.8 - 1.0 5 - 15AOS (14-16/14-18) 70 - 75 1.0 - 1.51.0 - 1.6 25 - 40MES (12-14/16-18) 68 - 70 (***) 1.5 - 1.80.8 - 1.5 40 - 50 (****)() : As H2 SO4 content(*) : 1,4 Dioxane content of max. 30 ppm (on AM basis) with FO = 2% max. (on AM)(**) : 1,4 Dioxane content of max. 30 ppm (on AM basis) with FO = 2,5% max. (on AM)(***) : Di-salt content = 5% max. (on tot. AM)(****) : Color figures after bleaching

ANIONIC SURFACTANTS PHYSICAL SPECIFICATIONSANIONIC SURFACTANTS PHYSICAL SPECIFICATIONS

PRODUCT SHAPE

LABSO3H

LABSO3Na

FAS

Liquid

Liquid

LiquidPaste

FAES LiquidPaste

AOS LiquidPaste

MES LiquidPaste

VISCOSITY(mPa.s)

300 - 500

2000 - 5000

500 - 6005000 - 10.000

300 - 5005000 - 8000300 - 500

7000 - 12.000800 - 1500

5000 - 10.000

ACTIVECONTENT (%)

96,5

50 - 60

27 - 3070 - 72

2770 - 7235 - 38

7035 - 3865 - 68

SULPHONATES PRODUCTION ENERGY DEMAND and YIELDSULPHONATES PRODUCTION ENERGY DEMAND and YIELD

LABSO3 H

LABS

FAS (12-14)

FAS (16-18)

AES-2EO

AES-3EO

AOS (14-18)

MES (16-18)

Production Index

10050

Energy Demand

0250500

(Kw)

DRYDRY--ANIONIC SURFACTANTSANIONIC SURFACTANTS

PRODUCTION

SULPHONATES DRYINGSULPHONATES DRYING

LABS

FAES

FAS

AOS

MES

YES

NO

SULPHONATES DRYINGSULPHONATES DRYING

to generate products characterised by:

Optimised chemical specification (i.e.: low content of unsulphonated matter, inorganic sulphate and low color)

Regular and stable physical shape

Easy handling, storage and re-using

DryDry--Anionic Surfactants Production StepsAnionic Surfactants Production Steps

ANIONIC SURFACTANT

PASTE (70% AM)

FLASHPRE-CONCENTRATION DRYING COOLING and

FLAKING

PHYSICAL SHAPE MODIFICATION

POWDER NEEDLES GRANULES

: FLASH-PRECONCENTRATOR

: SCRAPED FILM DRYER

: ROLL-FLAKER

DRY-FLAKES

CW

STE

AM

CW

W ET SCRUBBING

VACUUM PUMP

HYDRO LYSISNEUTRALIZATION

ACID

H2O/NaOH

FAS/MESPRE HEATING

AOS

SULPHONIC

ANIONIC SURFACTANT DRYING UNITANIONIC SURFACTANT DRYING UNIT

SURFACTANS UPGRADING

DRYING PHYSICAL SHAPEMODIFICATION

FLAKES > POWDER > NEEDLES > GRANULES

PROCESSING DEMAND

Product Shape Processing DemandProduct Shape Processing Demand

DRY SURFACTANT FLAKESDRY SURFACTANT FLAKES

MILLINGMILLING

BLENDINGBLENDING

CLASSIFYINGCLASSIFYING

EXTRUSIONEXTRUSION

COOLING&

CUTTING

COOLING&

CUTTING

DRYINGDRYING

PULVERIZINGPULVERIZING

GRANULATIONGRANULATION

CONDITIONINGCONDITIONING

COATINGCOATING

SIEVINGSIEVING

DRY SURFACTANTPOWDER

DRY SURFACTANTPOWDER

DRY SURFACTANTNEEDLES

DRY SURFACTANTNEEDLES DRY SURFACTANT

GRANULESDRY SURFACTANT

GRANULES

SIEVING &CLASSIFYINGSIEVING &

CLASSIFYING

SOLID/LIQUIDADDITIVES

SOLID/LIQUIDADDITIVES

SOLID/LIQUIDADDITIVES

SOLID/LIQUIDADDITIVES

Surfactants Shape Modification ProcessesSurfactants Shape Modification Processes

DRY SURFACTANTS PHYSICAL CHARACTERISTICSDRY SURFACTANTS PHYSICAL CHARACTERISTICS

POWDER NEEDLES GRANULES

BD = 500 - 550 BD = 450 - 500 BD = 450 - 700

Particle size = 100 - 1000 Diameter = 0,7 - 1,5 mm Particle size = 500 - 1500

DFR

80 Length = 5 - 15 mm DFR =

120

DRY-ANIONIC SURFACTANTS

GLYCOL

GLYCOL

DRY POWDER

NITROGEN

ATM

DRY FLAKES

: COOLING BATTERY

: DEDUSTING AND COOLING FAN

: DEDUSTING FILTER

: CENTRIFUGAL MILL

DRYDRY--ANIONIC POWDER PRODUCTIONANIONIC POWDER PRODUCTION

DRY-FLAKES

DRY NEEDLES

COOLINGFLUID

CONDITIONED AIR

: PNEUMATIC TRANSPORT FAN

: EXTRUDER AND CUTTER

: PNEUMATIC TRANSPORT FILTER

DRYDRY--NEEDLES PRODUCTIONNEEDLES PRODUCTION

COARSES

FINES

DRY-GRANULES

NITROGEN

: GRANULATOR

: CLASSIFIER

: COARSES/FINES RECOVERY SYSTEM

: MILL

AIR

DRY-FLAKES

DRYDRY--GRANULES PRODUCTIONGRANULES PRODUCTION

DRYDRY--ANIONIC SURFACTANTSANIONIC SURFACTANTS

USES and ADVANTAGES

DRYDRY--SULPHONATESSULPHONATES allow to produce formulated detergents by:

• Simple Plant Configuration

• Low Energy-demanding equipment

• Reduced production cost

Main applications of DRY ANIONIC SURFACTANTSMain applications of DRY ANIONIC SURFACTANTS

XX = Good/Suitable = Possible ApplicationX - = Not Used/Not Suitable

SURFACTANTTYPE

POWDERS

HD LD DW

LIQUIDS

HD LD DW

SYNDET BARS

HD LD

FAS

AOS

MES

X

XX

XX

XX

X

-

-

-

-

-

X

X

X

-

X

XX

-

-

X

X

X

-

-X

THERMOSENSITIVECOMPONENTS

AGGLOMERATEDDETERGENT

(COARSE)

PERFUME

LIGHT-SILICATE

LIQUID BINDER

HOT AIR

LABS

FFA

NI

ADDIT.

STPP/ZEOLITENa2CO3Na2SO4

: HIGH-SHEAR AGGLOMERATOR

: FLUIDIZED BED CONDITIONER

: 1st AIR FILTER and DUST RECOVERY

: POST-AGGLOMERATOR

: FINAL MIXER/SIEVE

: 2nd AIR FILTER and DUST RECOVERY

COLD AIR

FAS

AOS

MES

POWDERDRY

POWDER

NONNON--TOWER DETERGENT PRODUCTION PLANTTOWER DETERGENT PRODUCTION PLANT

DRYDRY--SULPHONATES in POWDER FORMSULPHONATES in POWDER FORM

are the optimum “tool” to obtain:

- Extension of the total Active Matter content

- Improvement of the product bulk density control

- Increase of the formulation flexibility

- Reduction of the overall process energy input

FAS AOS MES

Active (%)Additional

Energy Demand(%)

Active (%)Additional

Energy Demand(%)

Active (%)Additional

Energy Demand(%)

30 ± 35 35 - 38 35

70 - 75 (70 - 75) (65 - 70)

>90 + 38-40 >90 + 23-25 >90 + 34-36

>92 + 50-55 >94 + 34-36 >90 + 50-52

>90 + 65-68 - - - -

>85 + 70-72 - - - -

Surfactantcommercial

shape

LIQUID

PASTE

DRY-FLAKES

DRY-POWDER

DRY-NEEDLES

DRY-GRANULES

SURFACTANT UPGRADING ENERGY DEMANDSURFACTANT UPGRADING ENERGY DEMAND

200100 150

Liquid/Paste

Dry-granules

Dry-needles

Dry-powder

(%) + Product Added Value

DRYDRY--FAS ADDED VALUEFAS ADDED VALUE

DRYDRY--ANIONIC SURFACTANTSANIONIC SURFACTANTS

• ADVANTAGES for MANUFACTURERS

- Workable in processes where liquid Surfactant cannot be used- Increased range of product formulations and relevant performance- Easiness in handling and dosing

• ADVANTAGES for MANUFACTURERS

- Easy and safe production process- Add value to the production- Easy storage, handling and transportation- Increased production range/variety- Offer additional marketing opportunities

DETERGENT

SURFACTANT

MANUFACTURING PROCESSESMANUFACTURING PROCESSES

INCREASED USE OF DRYDRY--ANIONIC SURFACTANTSANIONIC SURFACTANTS

DISPLAY OF THE CAPABILITY OF THE

SURFACTANTS & DETERGENTS INDUSTRYSURFACTANTS & DETERGENTS INDUSTRY

to developLESS ENERGYLESS ENERGY--INTENSIVEINTENSIVE

MORE EFFICIENTMORE EFFICIENT

OPTIMIZATION OF

DETERGENT MANUFACTURING TECHNOLOGYDETERGENT MANUFACTURING TECHNOLOGY