intech-sulfonation sulfation processing technology for anionic surfactant manufacture

7/30/2019 InTech-Sulfonation Sulfation Processing Technology for Anionic Surfactant Manufacture

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Sulfonation/Sulfation ProcessingTechnology for Anionic Surfactant Manufacture

JessAlfonsoTorresOrtega

UniversidaddeLaSalleColombia

1. IntroductionIn 2008, global production of surfactants was 13 million metric tons reaching aturnover ofUS$24,33 million at 2009, which means an increment of 2%from the previous year. Moreover, it is projected a strong growth ca. 2,8%annually till 2012 and between 3,5 4% thereafter (Resnik et al., 2010).Sulfonation plants are scattered around the globe inproduction units withcapacitiesvarying from3.000 to50.000 tons/year,mainlyofanionicsurfactants.At least800sulfonationplantsareestimatedtobecurrently inoperationaroundthe World. However,about20%oftheglobalproduction (2.500.000tons/yearofsulfonated anionic surfactants) is concentrated in the United States, WesternEuropeandJapan(AcmiteMarketIntelligence, 2010).

Anionic surfactants are the key component in a detergent formulation. Amolecule ofanionic surfactant is composed of a lipophilic oil soluble tail(typically an organic molecule C12-C14) and a hydrophilic water soluble

head (such as SO3). Mixtures of organic molecules, either form non-renewable resources, such as crude oil or fromrenewablesources,suchasvegetableoils,arecurrentlyusedasrawmaterialsforhouseholddetergents.Thecleaning process performed by anionic surfactants (active detergents) isdescribed in the following way (de Groot,1991):

i. Wettingofthesubstrateanddirtduetoreductionofsurface

tension;ii. Remotion of dirt fromsubstrate;iii. Retaining the dirt in a stable solution orsuspension.

Sulfonationisthetermthatidentifiesanelectrophilicchemicalreactionwhereasulfonic group SO3H is incorporated into a molecule with the capacity todonate electrons.The product of this chemical reaction is recognized assulfonic acid if the electron donormolecule is a carbon. Sulfuric anhydridereacts easily with delocalized electronic densities as those present inaromatics groups or alkenes in general.These reactions produce avariety of

products, including derivate polysulfones. On the other hand, the sulfatingprocess involvesthe incorporationof theSO3Hmolecules toanoxygenatom inanorganicmolecule to form COS bonds and the sulfate group (Figure 1). Sulfatesacids can beeasily hydrolyzed, and for this reason an immediate neutralization is required


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after the sulfate group is formed (Foster, 1997). Although sulfonation andsulfating processes areemployedindustriallytoobtainawiderangeofproductsfromhairdyestopesticidesand

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270 Advances in Chemical Engineering

organic intermediates, their main applications are in the production of anionicsurfactants(Foster,2004).

Fig.1.Functionalgroups: (a)sulfonateSO3Hand (b) sulfateOSO3H

2. Main anionic surfactants

2.1 Linear alkyl benzene sulfonate (LABS)

Linear alkylbenzene is the most common organic feedstock employee in thedetergentindustry(Figure2).LABSoflowmolecularweight(230245)layinthecategory of anionic surfactants most used in all ranges of householddetergent formulations. Dishwashing liquids are prepared from LABS of lowmolecularweight incombinationwithotheranionicsurfactant as Lauryl EtherSulfate (LES) promoting high detergency, foam stability, degreasingcapacity, and high stability in hard water (Zhu et al., 1998). Common

concentrations of active detergents in liquid products are: LABS 10-15%(30%), Primaryalcoholsulfate/LES3-5%(10%),wherevalues inbracketsarethemaximumforconcentratedproducts (Table 1). LABS of high molecular weight(245-260) are the anionic surfactants more used in all ranges of householddetergents formulation, but especially in heavy duty laundry products,sometimes in combination with nonionics alcohol sulfates from tallow andsoaps(Mungray&Kumar,2009).

Fig. 2. Sulfonation of alkylbenzene (adapted fromFoster,1997)

Heavypowdersdetergents(nosoapy) Highfoam Lowfoam

LABS,highmolecularweight(245-260) 2030% 510%

TallowAlcoholSulfate(TAS) 25 %

Nonionics 25 %

Tallowsoap 25 %

Table1.Heavypowdersdetergentsusedinallrangesofhouseholddetergentsformulation


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(deGroot,1991)

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Sulfonation/Sulfation Processing Technology for Anionic Surfactant Manufacture 271

2.2 Primary alcohol sulfates (PAS)

PAS are categorized in different groups regarding the number carbon thatcompose them:The socalled lauryl alcohol sulfates C12-C14, the tallowalcoholsulfates (TAS) C16-C18, and the broader cut C10-C18 alcohol sulfate comprisingcoconut fatty alcohol sulfates.The broad cut (C10-C18) alcohol sulfates presentscost/performance equilibrium in terms of detergency, solubility and foamingproperties. This product can partially or totally substitute other anionicsurfactants either in liquid or powder detergent formulations with adequatebiodegradability and low defatting action, which is important for humantissue and delicate natural or synthetic fibers.The narrow cut (C12-C14) alcoholsulfatesfindtheirmainapplication in a wide range of personal care productssuch as shampoos, bubble bath products, tooth pastes, dishwashing liquid,delicate products for laundry wash.The C16-C18 alcohol sulfates (tallow) areused as sodium salts in the formulation of heavy dutylaundry products forhand and machine washing.Their detergency power is up to 10%higherthan

LABS in a wide range of detergent formulations (de Groot, 1991). Furthermore,TASshowscontrolled foam,which is importantmainlyathightemperatures,stillkeepingtheadvantageofsoftness inthewashofsensitivenaturalandsyntheticfibers (Rosen, 2005).The physical detergency and biodegradability of primaryalcohols can be affected by thecarbon chain length distribution. Therefore,each new supply may require testing to determine whether the desiredproperties inthechosenapplicationcanbeachieved.Themechanismforalcoholsulfationisthoughttobesimilartothatforlinear alkylbenzenesulfonationwithH=150kJ/mol(Figure3).

Fig. 3. Mechanism of alcohol sulfation (adapted fromRoberts,1998)

2.3 Alcohol ether sulfates (AES)

Primary alcohol ethoxylates are made by the addition of ethylene oxide to aprimaryalcohol in the presence of an alkaline catalyst (Boskamp & Houghton,

1996). The addition of the second ethylene oxide molecule to the alcohol iskinetically favored in comparison with the addition of the first ethylene oxide;hencetheproductofethoxylationcontainsadistributionofethyleneoxidechainlengths attached to the alcohol along with the starting alcohol itself.Consequently the physical, detergency and biodegradation characteristics areaffected notonlybythecarbonchainlengthdistributionasisthecaseforprimaryalcohols,butalsobytheethyleneoxidedistributionwhichinturncanbesupplierdepend (de Groot, 1991). The most common alcohol ethoxylates found asfeedstocks for sulfation have an average of 2 to 3 molecules of ethylene oxide(2EOor3EO).

During the sulfating of alcohol ethoxylates the by-products 1,4-dioxane maybe formed (Figure 4). Although the formation of 1,4-dioxane is governedpredominantly by sulfationand neutralization conditions and by the chemicalcomposition of the feedstock, otherfactors such as the quality of the rawmaterial also contribute.These factors must beconsideredduringthestoreandhandlingofthealcoholethoxylatefeedstock.


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Fig. 4. Reaction scheme of ethoxylated alcohol sulfation (adapted from deGroot,1991)

LES(C12-C14/15 2-3ethyleneoxide)canbeconsideredasthemostefficientanionicsurfactant in terms of: superior detergency power, good tolerance for waterhardness,andmildnessonhands and fibers.The application therefore is wide:from household to personal care andcosmetic product. Unfortunately, sulfatedalcoholethersulfatesshowa limitedstability tohydrolysisathightemperatures,and this restricts their use in heavy duty laundry powders, where hightemperatures occurinthespraydryingprocessofpowdermanufacture.

The high stability to calcium ions permits formulation of liquid detergents withlimited or no addition of water softeners even in case of use in hard water(Matthijsetal.,1999).Theoptimum compromise of ethylene oxide additionto keep adequate foam levels andsolubility/mildness ratio vary from 2 to 3moles per mole of fatty alcohol.The mostimportantworldwideapplicationof

AES 2-3 ethylene oxide (EO) are in dish washing liquid detergent, generallycombinedwithLABSandinshampoos/bubblebaths(Table2).

Liquidsdishwashdetergent

Shampoos/bubblebaths

LES(C12-C14/152-3EO) 510% 1030%

LABS(lowmolecularweight) 15-20%

CoconutEthanolAmides(CEA) 23% 23%

Hydrotopes(SodiumToluneneSulfonateSodiumXyleneSulfonate)

13%

Otheractives(i.e.amphoteric/nonionic) 510%

H2O,perfume,color,preservatives Balance Balance

Table2.ApplicationsworldwideofAES2-3EOcombinedwithLABSandinshampoos/bubblebaths(deGroot,1991)

2.4 Alfa-olefins sulfonates (AOS)

Alfa-olefins are a potential replacement for alkylbenzenes in detergentapplications. Olefin sulfonation is highly exothermic with H = -210 kJ/mol(Roberts, 2001).The neutralizedproduct of alfa-olefin sulfonation requires hydrolysis to remove the sultones,

which areskin sensitizers (Figure 5).Their exploitation, however, is largelylimited to the Far East, Centre onJapan, at present. Commercial supplies ofalfa-olefinsareproducedbythe


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Fig. 5. Reactions of alfa-olefin sulfonation (adapted from deGroot,1991)

oligomerisation of ethylene. The physical, detergency and biodegradationcharacteristics of alfa-olefins are affected by the carbon chain lengthdistribution and therefore each new supply may require testing to determinewhether the desired properties for the new chosenapplication can be achieved.

The Lion Corporation,Japan, is one of the principal producersand users of alfa-olefin sulfonates. In addition to fabric washing powders, they also market fabricwashing liquid, shampoos, tooth paste and foam bath products containing thisactive.IntheUSA,MinnetonkahasutilizedAOSinhandcleaners/liquidsoaps.AOSis a potential replacement for alkyl benzene sulfonates in dish wash detergentliquids formulations with performance peaking at C16 chain length (de Groot.,1991).

2.5 Fatty acid methyl esters sulfonates (FAMES)

FAMES are called to be the main feedstock for detergent formulating in thefuturedue totheirapplicabilityindetergentformulations(Ingegar&Martin,2001;

Johansson&Svensson,2001;Roberts&Garrett,2000;Satsuki,1998).Moreover,when it isderivedfrompalm oil presents special biodegradable properties that place them over thesurfactantsderivedfrompetrochemicals compounds.To date, the application ofFAMES is under development invariousdetergent products, and their presenceon the market is still highly restricted.Thetypical cut of FAMES (C16-C18) showsinteresting surface activity (about 90% compared to LABS), high detergent,dispersing and emulsifying power in hard water, high lime soapdispersion andmoderate foam levels. FAMES show high stability to pH and temperature

hydrolysis.Therefore,

they

can

be

easily

spray

dyer

and/or

incorporated

indetergentbars.Methyl ester sulfonates have a wide range of application

and important biological properties. As aggregated value the FAMES can beused in cosmetics, as auxiliary agents in the production of fibers, plastics, andrubber,andinleathermanufacture(Cohenetal.,2008;deGroot,1991;Robertsetal.,2008;Stein&Baumann,1975).

3. Sulfonation process used for the manufacturing of anionic surfactants

Sulfonation reactions can be carried out in different configurations, eitherliquid-liquidcontact,orgas-liquidcontact reactors,andadiversityofsulfonatingreagents can be applied for the sulfonation process, such as: Sulfuric acid, SO3

fromstabilized liquid SO3,SO3 fromsulfurburningandsubsequentconversionofthe SO2 formed, SO3 from boiling concentrated oleum and chlorosulfonic acid.However some reasons why SO3/air in gas-liquid contactor (sulfonator) isbecomingthepredominantprocessforthemanufactureofanionicsurfactantsare(Foster,1997):


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i. Adaptability: All types of organic feedstocks, like alkylbenzenes, primaryalcohols, alcohol ethers, alfa-olefins and fatty acid methyl esters, can besuccessfully transformed to high-quality sulfonate/sulfate active detergentsusingSO3/airassulfonatingreagent.Sulfonating reagents like sulfuric acid

and oleum are less desirable because onlyalkylbenzenefeedstockscanbeconvertedtohigh-qualityalkylbenzenesulfonicacids.

ii. Security: Concentrated sulfuric acid, liquid SO3, and oleum (20 or 65%) arehazardoustobe handled, transported, andstorage.Sulfur,either in liquid orsolid form, although less dangerous option as initial material for themanufactureofSO3,isstillrisky.

iii. Price: SO3 obtained directly from the sulfur combustion is the mosteconomicaloption

amongalltheothersoptionsmentionedaboveregardingtransport,handleandstorage.iv. Availability:LiquidSO3,65%and20%oleumandevensulfuric

acidarenotproducedeverywhere.Evenclosetosulfuricacidplants,itisnot

guaranteedtheavailabilityofallthegammaofoleumconcentrations.

SeveralstudieshavebeendoneaboutabsorptionalongwithexothermicreactioninaFallingFilm Reactor - FFR (Mann & Moyes, 1977; Villadsen & Nielsen,1986), particularly for dodecylbenzene and tridecylbenzene sulfonation.However, due to de complexity ofprocesses taking place inside the FFRhasnot been completely elucidated, being of special interest today. The SO3-sulfonation is carried out in tubular reactors where the organicmatter (liquid)wets the wall of the tubes while a gas stream containing the sulfonatingreagent flows in co-current with the organic matter to avoid over-sulfonation(MacArthuretal., 1999).The simplest FFR configuration can be described asa two concentric tubesarrangedinaverticalway(Figure6).

Fig. 6. Sketch of falling filmreactor

Organicmatterformsathinfilmcoveringtheinnerwalloftheinnertube.Thefilmdescendsfromthetopofthereactorinlaminarflowforminganannulusforwhoseinterioragasstream flows in turbulent regimen. In the first reaction section theconcentrated sulfonate reagent get in touch with fresh organic matter. Thereaction rate is high as well as the amount of heatreleased(150170kJ/mole).A coolantstream flows by the external wallof the inner tube inparallel with the

reactant streams. As long as the reaction advances the viscosity of the liquidphase increases (ca. 100 times the initial value).The depletion of reactantsreducesthereactionrateandtheincreaseofviscosityslowdownthemasstransferprocessinthefilm.Inthispointtheco-currentcoolant,thishasalreadyremovedahuge amount of heat from the first reactorzone,worksasaheatingcurrentthatcontrolstheviscosityofthefilm.


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Figure 7 shows a diagram of film SO3-sulfonation along with anadditional step(bleaching) than could be required depending of the feedstockand characteristic of the final product. Depending on the type of organicfeedstock andconsequent organic acid,further reaction steps may be required

before neutralization. Sulfonic acids of LABS areoneofthosematerialsthatnorequire an aging step to reach full conversion. Moreover, a hydrolysis orstabilization step is required to convert anhydrides form during thesulfonation process. Alcohol and alcohol ethoxylate sulfonic acids, as well asFAMES, must be neutralized immediately after a delayed aging to avoidundesired by-productsformedinsidereactions.

Fig. 7. Process diagram for film SO3-sulfonation

After aging and hydrolysis a stable product is obtained, then the neutralizationstagecanbecarried out with many alkaline chemicals like caustic, ammoniaand sodium carbonate. Neutralization with diluted caustic is recognized asinstantaneous and highly exothermic it may form gel at high temperatures or

undesired reactionsmay occur ifmicro-dispersionoforganic acid in the dilutedcaustic phase fails. Various loop-type reactors, consisting of acirculation pump,homogenizer (where the acid is introduced in the circulating alkalinepaste),andheatexchanger,areusedforthecomplexneutralization step(Foster,1997).

4. Phenomenological description of film sulfonation

Organicliquidflowthroughofthereactorwallinlaminarregimen,thehighflowofthegasphasebygravitationaleffects intensifies the formationof randomwavesall along the gasliquid interface. Depending on the flow rate of organic liquidandgasstream the thicknessof the film can increase or decrease up to twiceits average value in the zone where the waves are present (Daz, 2009).

This induced turbulence affects the local values of concentration andtemperature in the regions where appears, hence altering the masstransferand temperature profiles in the film. Mathematical models which describe thesulfonation of tridecylbenzene in FFRs have been developed by Akanksha etal. (2007),Daviset al., (1979), andJohnson & Crynes, (1974),while Dabir et al.(1996),Gutirrezetal.(1988) and Talens (1999) focused on dodecylbenzenesulfonation. Nevertheless, thesemodelshavebeensubjectofdebateduetotheassumptionthateitherthechemicalreactionis limitedtothegasliquidinterface,the mass transfer of the sulfonating reagent in the gas phase is the ratedetermining step, and/or the flow profiles in the film are neatly laminar,neglectingtheeffectsofthewavesformedatthegas-liquidinterface.

Recently Torres et al. (2009b) proposed a model for the methyl esterssulfonation that is appropriate for both laminar and turbulent films and itconsiders effects of wavy film


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flow by using eddy diffusivity parameter. The eddy diffusivity modelsproposed byLamourelle&Sandall (1972) for theouter regionandmodifiedbyvanDriest (1956) for theregion near the wall were used. Effects of interfacialdrag at the gasliquid interface andthe gasphase heat and mass transfer

resistance have also been considered in theproposed model.The modeltakes into account the variations of physical properties withtemperature andpredicts conversion profiles, gasliquid interface temperature in the axialdirection,andaverage liquidfilmthicknessalongthereactor length.Knowledgeof temperature distribution along with the reactor is important for theproduct qualitycontrol, since for highly exothermic reactions under certainconditions can producedegradation of the products.The equations describedin the followingsectionaccount forthe mass, momentum and heat transfer.In the development of these equations was considered the turbulentdiffusivity for mass transfer coupled with chemical reaction,according to thetheory ofYih & Seagrave (1978), and with heat transfer according withYih&

Liu(1983).Finally some additional assumptions were made for themathematicalmodel:

i. Noentrainments of liquiddroplets intogasorof gasbubbles into the liquidfilmoccur;ii. Fully developed film (entrance and exit effects to reactor areneglected);iii. The liquid film is symmetric with respect to thereactoraxis.

According with these assumptions the mathematical model is showed in the

followingsections.

4.1 Mass balance

Only three components are considered in the liquid phase: organic liquid, acidproduct and sulfonating reagent, therefore two microscopic balances aresufficient to determine theconcentration profiles (Figure8),whereyvaries fromy=0(at thewallsurface)toy= (atthe liquidsurface).

Fig.8.Massbalanceonfinitevolumeincludestheboundaryconditionsatthesolidwallandliquid/gasinterface

It isassumed that themassbalance for SO3(G) absorbing by the liquid (equation


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1) can alsobe applied to reagent in the liquid phase where reaction occurs,then equation 2 is thesteadystatemassbalanceontheabsorbingspeciesAinliquidphase.

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3 3 3


CSO

v 3 =C

SO

(D +D ) 3 r

y (1)

dz z y SO3 T y 2

C C vz A = (DA +DT) A

r0y (2)

z y y AsdiscussedbyKnaggs,(2004),eveniftheliquidfilmisturbulentanddoeswavyflowthenturbulentdiffusivitycannotbeneglected,thisandturbulentviscosityintheliquidphasecanbetakenofworksuggestedbyYih&Liu(1983).

DT 0,5+0,5

1+0,64(y

+2)

y (/ ) 1exp w

2 0,5

f (3)

+ 0,5

= T w A+

3y+

w =1 L (4) G +L

+

Turbulent Schmidt number is evaluated from the Cebecis modification of thevan Driestmodelandisfurthermodifiedas:

v 1exp(y+(/

)0,5 /A+)

Sc = T = w (5)TD 1exp(y+(/

)0,5 /B+)

T w

5

+ 0,5 i1B =Sc Ci(log10Sc)i=1

(6)

withA+=25,1;C1 =34,96;C2 =28,97;C3 =13,95;C4 =6,33andC5 =1,186.For nonvolatile liquids such as methyl stearate, the vapor pressure is zero atworking temperatures. At the interface, it is assumed that Henry and Raoultslaws are applicable to determine the SO3 solubility.The Henry constant m, isdeterminedfromtheSO3 vaporpressure:

G

( G i )NSO =kG CSO mCSO

(7)

kG =0,8Sc0,704

u

(McCready&Hanratty,1984) (8)


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wheretheturbulentvelocityisdefinedas:

u= G

G 0,

5(9)

4.2 Momentum balance

Axial liquid velocity vz, can be found from the momentum equation afterneglecting thepressure gradient and axial terms (Figure 9).The flow profileof the liquid falling is

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2


Fig.9.Schematicrepresentationofvelocityprofilesinlaminarandturbulentregimesforbothliquidandgasphase

predominantly laminar, while SO3 flow is clearly turbulent and consequentlythe SO3 isabsorbed at the gas/liquid interface. In equation 10 for co-currents

systemsJ is+1andforcountercurrentsystemsJis-1. g y2

v = L y y+J G (10)z L

2 L

Forhighgasflowwheretheshearforcepredominatesoverthegravitationalforce,thelinearvelocitydistributionis:

yvz = GL (11)

CalculationofG basedontherelationsproposedbyRiazi&Faghri(1986)showsthatwhenthegasflowisturbulent,theeffectsoftheinterfacialdragcannotbeneglected;G canalsobeverifiedbymeansofexperimentalpressuredropdata.Inthiswayasetofparameterscanbeintroducedandadjustedtominimizethedeviationfromadatasetforsulfonation:

=

Lg3 G2

(12)

3L

2L

G =CfGu (13)1

=4Log

5.02Log + 13 (Talens,1999) (14)

C2 3,7d ReG 3,7d ReG f

ln()=3,595,14viL (ifviL


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T

d


4.3 Heat balance

For exothermic reactions suchassulfonationa large amount ofheat may bereleased, theboundaryconditionsshowedatFigure10isapplyingfortheenergybalance(equation17).

Fig.10.Schematicrepresentationofmodelforasegmentheatbalance

cTvz z

=ykL

+(H)r

y(17)

1=1

+U

k dlm h1de

x

(18)

w w

ex in

Heat transport equations follow the Prandtl analogyand are equivalent to thoseused formasstransfer.

hG =0,8Sc0,704u

(19)

5. Main parameters of film SO3-sulfonation

An experimental set was developed to study the effect of follows factors: (i)mole ratio between SO3 and organic liquid, (ii) wall temperature and, (iii)volumetric percentageof SO3 in the phase gaseous.The variables representingthe quality of the sulfonated product are: active matter, unsulfonated matter,acidvalueandcolor(Ahmadetal.,2007;Inagaki,2001).Theexperimental matrixis presented inTable 3 and detailed informationabout the analysis ispresentedbelow(Torresetal.,2008b).

Conditions value

SO3/N2inlet(gaseoussulfonatemixture),% vol/vol 37

SO3/N2 temperatureinlet,C 5060

SO3/organicliquid,moleratio 1:11,2:1

Table3.Operatingconditionsusedforthemethylestersulfonation(Torresetal.,2009a)


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5.1 Active matter

Increase of active matter in product was proportional to the increase ofSO3/organicliquidmole ratio as well as the increase of SO3 percentage in the

gas stream. Slope changes observed with respect to the temperature areprobably due to side reactions occurring athighertemperatures;theformationsofundesiredmattersdecreaseactivematter(Figure11).

Fig. 11. Impact of the operation conditions on the degree ofsulfonation

5.2 Unsulfonated matter

Theimpactoftheexperimentalfactorsisinitiallyinversecomparedwiththeeffectobtained with the active matter; however the SO3/organic liquid mole ratiosbeyond 1,1 produce an increase in the quantified unsulfonated matter. Thischange can be explained by oversulfonationof reactantand formationofsideproducts.This assumption is consistent with the effects of temperature on thepercentageofnon-sulfonatedmatter(Figure12).

Fig. 12. Effects of the experimental factors on theunsulfonatedmatter

Over-sulfonated products do not have the same characteristics of thewashing activesubstance and therefore are not identified as active matter butyetasfreeoil(unsulfonated).


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Figure 12 proves that the unsulfonated matter percentage decreases thesame as thesulfonatingreagentinthegasmixtureincreases.

5.3 Acid value

Figure 13 shows the effect of the conditions process on acid value. Increase inthe sulfurtrioxide has a positive effect in agreement with expectations;also the increase of temperature in process enlarges the acidity in theproduct. Change in the slope can beexplained by kinetics effects favored bytemperature rising. Both the increase in the moleratioandsulfurtrioxide inthesulfonating mixture can be explained by the effectiveness of the reactionbecause an excess of SO3 promotes the consumption of the same reactants forthegenerationofover-sulfonatedmatter.

Fig.13.Acidvaluesobtainbychangesofmoleratio,temperatureandSO3inlet

5.4 Coloration

Figure14 presents the trends for thecoloration in the sulfonated product whichintensifies the values of concentration of SO3 some that the mole ratio andSO3 content in the gas stream. All variables show a direct influence to theincreaseincolorwhichisassociatedwith

Fig.14.Impactoncolorationinthesulfonatedproductduetovariationsofprocess


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higher sulfonation degrees. Although the coloration is identified mostly as anestheticfactorforthecommercializationofsulfonates,highercolorationscanalsobea qualitative indicatorof over-sulfonation. Anionic surfactants in aqueoussolution have colors ranging fromyellowtoreddishorange(Inagaki,2001).

6. Film SO3-sulfonation applied

6.1 Sulfonation of methyl ester with SO3

Use of methyl esters (ME) in the industry detergent, although underinvestigation anddevelopmentsincemore than25years,hasnotyetexpandedtohighlevels,mainlybecausethefollowingreason:

i. Controversialforecastsaboutavailabilityofpetrochemicalfeedstockswithrelatedcostcomparisonviavs.naturalsources;

ii. Viabilityofsufficientqualityofsulfonationgrademethyl

esters;iii. The process to produce high quality -sulfonated methyl ester (SME) isgenerallymore

complexthanthatforalkylbenzenesulfonates;iv. Application know-how is not yet completely availed and low FAMES

solubilityinvolvessomerestrictionsinapplication,notablyconcerningtheuseinliquiddetergentproductsandlowtemperaturewashingcycles.

Complex chemistry is not yet fully elucidated, but may be summarized as isshown inFigure 15 (Morales & Martnez,

2009).

Fig.15.Mechanismofmethylestersulfonation insulfonator(Torresetal.,2009b)

The methyl ester molecule is initially di-sulfonated in a relatively fast reactionaccompaniedwith a high amount of heat released (Roberts, 2003).There isa third reaction stageconsiderablyslowerthanthepreviousones,whereanSO3group is liberated (on aging). For some researchers, this SO3 group justreleased would be especially active and therefore capable of directlysulfonating another methyl ester molecule in an alfa position.The


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diffusivities of reagents are estimated from the Wilke-Chang equations anddiffusivities in the mixture are estimated through the Vignes equation (Vignes,1966). Generally, in methylester sulfonation the amount of intermediate III inthe final product varies from 10-20% (Foster, 2004), but this amount can be

reducedbyalongandheateddigestion(agingstage).An experimental apparatus showed in Figure 16 was utilized by Torres(2009) forresearching the parameters of film SO3-sulfonation of methylester derived from hydrogenated stearin palm, this apparatus wasdesigned by Chemical Engineering Laboratory fromUniversidad NacionaldeColombia(Bogot,Colombia).

Fig.16.Experimentalapparatus formethylestersulfonationusinga falling filmreactorandSO3 stripped from 65% oleum with dried airprocess

High degree of sulfonation is obtained in the aging step controllingsimultaneously thetemperature and residence time. At higher temperatures itis feasible to obtain higher conversion levels, whereas at low temperatures(below 80C) the time required to reach high conversions is considerably long.

Thesereactionsarehighlyexothermicinorderof150170kJ/mole (including25kJ/mole of the absorption heat of gaseous SO3). A kinetic model has beendevelopment by Roberts (2007) based on the proposal that two majorintermediates areinvolvedinaging(Figure17).


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Fig.17.Reactionsintheagingstep(adaptedfromRoberts,2001)

=B

k=Ae T (20)

kf,(s- ks,(s-LogA 12,1 11,5

B 12,06 12,13

Table4.Valuesforequation20onagingstage(Roberts,2008)

TheoverallconversionasfunctionoftimeandmoleratioMofSO3/MEisgivenby:

%conversion =100M 1 k t kt0.25e f 0.167e s

(21)

M100

M100 is mole ratio for a conversion at 100%, after a delayed aging M100 = 1,2.Theseequations,for aging in a batch reactor system or in a plug flow systems,can be used as guidelineswhen setting initial conditions before fine-tuningplant operation to meet a required specification (Roberts, 1998). Methylesters are less active than aromatic compounds tosulfonating due to the lesselectronic density of the aliphatic chains.The methyl estersulfonation include a neutralization step to obtain monosodium salts of -sulfo methylesters as desire products (Kapur et al. 1978). If neutralization is immediate

disodiumsaltisformed (see Figure 18a). However, if neutralization of the acid is delayed, thesulfo estermonodisodiumsaltisobtainedasfinalproduct(seeFigure18b).

Fig.18.Neutralization chemistryofSME(Torresetal.,


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2009b)

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Generally, feedstock for the manufacture of FAMES containing unsaturated fattyacids and these has been attributed to the formation of polysulfone in thedouble bonds (Yamada &Matsutani, 1996). Unsaturated in methyl ester makeit an olefin with a carboxyl methylgroup at the end of the chain. Olefins are

more rapidly sulfonated by SO3 also unsaturated bound producesoversulfonation and oxidation of the olefin which competes with thesaturated ester obtain product more colored, however the color can beimproved bybleaching. Unsaturated make it an olefin with a carboxyl methylgroup at the end of thechain. Olefins are more rapidly sulfonated alsounsaturated bound producesoversulfonationandoxidationoftheolefinwhichcompetes with the saturated ester obtain product more colored, however thecolorcanbeimprovedbybleaching(Figure19).

Fig.19.Reactionschemeforthecolorationinagingstep(adaptedfromRobertset

al., 2008) Mechanism proposed by Roberts (2007) suggests a reversible

formationof-dioxidecycleandCH3SO3Hthis-anhydridereactsopeningitscycle,sinteringitself,andlosingacarbonmonoxide to become an alkene sulfonic acid. This is formed mainly inreactions ofsulfonation of alfa-olefins, these are very intensive in color when aged in theacid form(Clippinger,

1964).

6.2 Validation of model

The input variables more important for the conversion are: the length anddiameterreactor, flow of liquid reactant, mole ratio between SO3 and organic


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liquid, in this casemethyl stearate derived ofhydrogenated stearin frompalmoil(Narvezetal.,2005;Torres

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et al., 2005), and amount sulfur trioxide in the gas phase (SO3/N2), finally thetemperature of the process. This mathematical model permits to calculatethe profiles of interfacial liquid temperature, liquid film density, liquidviscosity for any column height and longitudinal profiles ofconversion.The

proposedmodelmaybesuitable foruse indesignand operation of industrialfilm reactors. To ensure convergence of the system ofequations thentransformation of the equations proposed by Agrawal & Peckover (1980)waschosen following the same development by Talens (1999). The set ofequations resulting from the mass, momentum and heat transfer is solvednumerically. Figure 20 shows schematic view from the top of a reactor: theliquid is evenly distributed around the wall, and the gas mixture is injectedthrough the center of the column.The interfacial temperature is affected bythe SO3 amount in the gas mix. It is clear an increase of interfacetemperature result of the SO3 excess in the gas flow.The temperature ofthereagents is a key control variable to avoid undesirable side impact thatdamage theproductmainlybystrongcoloration.

Fig. 20. An example of interfacial temperature profiles fall in the reactorlongitudinal

Other example of the results provided by the model for longitudinal conversionprofile from top of the reactor (expressed as percentage of active matter) isshown in Figure 21(a).Theinputvaluesof themodelare: SO3/N2 percentageat5%,SO3/methylstearatemoleratioat1; TG, TL, and Tw at 343 K, 333 K and 313 K, respectively.This figure showsschematicallythe

fastconversionregionatthetopofthereactor(associatedwithgasphasecontrol)andslowconversion region at the bottom (linked with liquid phase control). Thewashing activesubstance was determinate using a two titration technique withHyamine1622asthe titrantreagent and methylene blue as indicator (Tsubochietal.,1979;Milwdsky&Gabriel,1982;


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Battaglinietal.,1986;Schambil&Schwuger,1990).Theprogressofthereactionisdecisiveforsulfonationdegreeexpressedasamountactivematter.

PhysicalsandchemicalspropertiesusedinmodelarelistedinTable5.

Parameter Correlation

Kineticinsulfonator,kmol/m3s (Torresetal.,2008a)

r=kCSO CME (22)3

= 14.350

Diffusivity,m2/s(Wilke&Chang,1955)

D = 3,121011 TL (24)SME-ME2/3L

D = 6,2881011 TL (25)ME-SME2/3L

D = 2,0311010T

L

(26)Gasthermalconductivity,J/msK(Davisetal.,1979)

kG =Heatcapacityofliquid,J/kmolK(Brostrm,1975;

cL =507,300+101,010x (27)Heatcapacityofgasmix,J/kmolK(Sameatnitrogen)

cG =Liquidmixturedensity,kg/m3 (Talens&Gutirrez,1995;Brostrm,1975)

L =980+192x0,66TL (28)Liquidthermalconductivity,J/msK(Davisetal., kL =Surfacetension,N/m(deGroot,1991) =Viscosityofmethylestersmix,kg/ms(Torres&Snchez,2008)

1949,

6

6 273+TLViscosityofmethylesterssulfonicacid,kg/ms

5700

=1,36108 eTL+5,88 (30)SMEViscosityofgasmix,kg/ms(Sameat G =

Viscosityofliquidmix,kg/ms(Brostrm,1975;Talens&Gutirrez,1995)

a)0


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The model was constructed to predict the sharp increase in the conversion thattakesplacein the first stage inside of the falling film reactor. It confirms thatthe mass transfer is initially controlled by the resistance in the gas phase.After due to several factors the resistance occurs in the liquid phase. Figure

21(a) presents the conversion profile in the film reactor from the model,experimental results showed conversions lower than thosepredictedbythereactormodel inupperreactorregion.This isduethatthemodelassumesafullydeveloped flow and entrance effects of the streams to the reactor areneglected. However, the model is able to predict adequately conversionsdownstream for longer lengths. In the bottom of reactor is a smalljump in theconversion predicted by the model, perhaps due to kinetic effects that reachimportancebytheconsumptionofreactants.

Fig.21.(a)LongitudinalconversionprofileforSMEand(b)densityandviscositymodelestimatedbythemodel

Themost importantoutletdataobtainedbysolvingthemathematicalmodelareconversion,densityandviscosityoftheproduct.Thedensityandviscosityof theeffluent, downstream in the reactor film, estimated by the mathematicalmodel is similar to that obtainedexperimentally, as shown in the Figure21(b).The increase of temperature produces adecreaseinviscosityenhancingthesolubilityofSO3 intheliquid,andcausingadecreaseinfilmthickness.Thesevariationsaretheresultofabruptchangeincompositionandreleaseofheatintheinitialpartofthereactor,whichproduceanincreasingofthetemperatureinthis


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area. Same phenomena occur with the film thickness.Thejump in conversiontakes place inthe top reactor, the temperature rises considerably and reducesthe viscosity of the liquid, even canceling the effect of viscosity then in thebottom reactor increases composition and the interfacial velocity.

Subsequently, the reduced generation heat and descent of thetemperatureisincreasetheviscosityagain.

7. Conclusions

Transfer rates in the gas phase are affected by changes in the tubular reactor.Increasesuncontrolled inthegas flowcoulddragsome liquid intothegasphase.

Therefore thegasvelocity has to be set at the point where no liquid drops canbe pulled to the gas phase.Temperature is a critical parameter in the qualitycontrol of the sulfonated products.Althoughinletstreamstemperatureshouldbeadjustedaboveroomtoenhancethereactionandavoidthesolidificationoftheorganic matter, an adequate control is required due to the high release of heat

attributed to the sulfonation reaction.The SO3/organic liquid mole ratio requiresrigorous control. Excess of SO3 enhance side reactions and extended reactiontimeswillalsoenhancesidereactions.

The comparison obtained for thissame process with petrochemicals compoundsindicatesthat the model could be applied to any film sulfonation but adjustingthe parametersandspecificconditions,suchasthephysicochemicalpropertiesofthecompoundsused,sincethesulfonation process described in this work is oneof the more complicated cases. Although some of the physical and chemicalproperties of mixture are obtained of a similar form,theseshouldbetestedandapproach toachieveconvergenceofthemodel;theseyielded thebestresults inthemathematicalmodeloffallingfilmreactor.

The model predicts two distinct transfer areas.The first is characterized byan abruptincrease in conversion and temperature, in which the controllingstepdepends initially of the gas phase and in accordance with the extent of thesulfonation reaction, the viscosity fluid increases, the film thickness is alsohigher and the film velocity decreases, then the liquid phase becomes thecontrolling stage with a mild increase of the temperature andconversion.Themathematical modelproposedforafilmSO3-sulfonationfitsadequatelythetrendof experimental results, so it is now possible to make a prediction on theconversionina falling film reactor,because theprofilesof temperature,density,viscosityandconversionareconsistentwithexperimentalresultsthatsatisfytheconditionstominimizethestrictestmathematical calculationsmistakesduetotheusageofnumericalsolutions.

8. Notation

A pre-exponentialfactor,s-1

A+ a van DriestconstantB+ a van DriestparameterC concentration, kmol/m3; van Driestconstantsc heat capacity, J/

(kmolK)Cf friction factor,dimensionlessD diffusivity,m2/sd reactor diameter,


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mf dampingfactor,

f =e1.66(1/w)g accelerationduetogravity,m/s2

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H reactionenthalpy,J/kmolh heattransfercoefficient,J/(m2sK)k reaction rate constant, m3/kmols; thermal conductivity,J/msK; masstransfer

coefficient,kmol/m2s

L reactorlength,mM moleratioSO3/MEm Henryconstant,(kmolofSO3/m3 ofgas)/(kmolofSO3/m3ofliquid)N massfluxofgaseousreactant,kmol/m2sP pressure,atmQ heatofreaction,J/molr reactionrateRe Reynoldsnumber,dimensionless:ReG =u(d2)/;ReL=4/.Sc Schmidtnumber,dimensionless

T temperature,KU globalheattransfercoefficient,J/(m2sK)u turbulencecharacteristicvelocityofgas,m/s

x conversionexpressedasmolarfractionofthesulfonicacid,dimensionlessv axialvelocityofliquidfilm,m/s

y transversalcoordinate(fromwalltowardtheliquidfreesurface)y+ non-dimensional distancetothewall:y(wg/)/z axialcoordinate

Greekletters

volumetricflowrateoftheliquidperunitwettedperimeter,m2/s

filmthickness,m+ dimensionlessfilmthickness,+ =u/ roughnessenhancementfactor,dimensionless liquidviscosity,kg/ms kinematicviscosity,m2/s liquiddensity,kg/m3

interfacialshearstress,N/m2

Surfacetension,N/m

Subscripts

A absorbingspecieex

exteriorG gasphasei interfacein interiorL liquidphaselm logarithmicmeanT turbulentw wall

9. Acknowledgment

Gratefully acknowledge at Dr. Federico I.Talens Alesson from University ofNottingham(UK), Dr. David W. Roberts from LiverpoolJohn Moores University (UK) and Dr.Icilio


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Adami from Ballestra S.p.A. (Italy) by communications received. Same wishto thankCOLCIENCIAS (Departamento Administrativo de Ciencia,Tecnologa eInnovacin) for providing financial support.The experimental work presentedhere was finished at 2009 in the Chemical Engineering Laboratory from

Universidad Nacional de Colombia (Colombia), under the direction fromProfessor FranciscoJ. Snchez C. Dr. Paulo C. Narvez R., Dr.OscarY.SurezP.andMSc.LuisA.DazA.assistedwiththeexperiments.

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Advances in Chemical Engineering

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Jess AlfonsoTorres Ortega (2012). Sulfonation/SulfationProcessingTechnology forAnionicSurfactant

Manufacture,Advances inChemicalEngineering,DrZeeshan Nawaz (Ed.), ISBN: 978-953-51-0392-9,

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sulfation-processing-technology-for-anionic-surfactant-manufacture

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