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Detergentsfor Recyclingand Law-Emulsivity Putsa NewSpin on an OldProblem Canservatian,
ph'D'. and JanetteMoore Bakiamoh, Ph.D.,Stephen F.Severin, by Blaine

ater minimization and surfactant recYcle are two of the most imPortant issues facing efficient use of aqueous cleaning technologies. And that's why present philosoPhies based on strong emulsion-forming surfactants are being re-examined. Detergent formulations that form transient emulsions (lowemulsion detergents) can have very favorable cleaning potential. Several low-emulsivity surfactants remove oil from sand, glass, and aluminum as efficiently as strong emulsion forming detergents. The case for the use of low emulsion detergents to accomPlish water recycle, surfactant recoverY, and reclamation of high PuritY waste oil is presented in this article' The concePt that the formation 'of strong oil-water emulsions are required for cleaning solid matriceJ is deeply engrained in the environmental remediation, oil well recovery, and Parts cleaning markets. Technical reviews ot are environmental surfactant use 'l'989, ( L a k e , L . W . , available Prentice E n h n n c e dO i l R e c o a e r Y , Hall, Inc., Englewood Cliffs, N.]., Chapter 9, pP 354-476). And Kanegsberg, 8., and Kanegsberg, 8., 2002, Aqueous Accounting, CleanTech, Yol. 2, No' 6, June, pp. 20-25 Present a review of maintenance and cost issues involved in the adaPtation of

aqueous cleaning systems. Our laboratorY at the Michigan Biotechnology Institute (Lansing, MI), a not-for-Profit research center, began investigating environmental surfactants for soil remediation about two Years ago. With this fresh vision of the surfactant market, we were impressed that some cleaning solutions have excellent detergency, yet exhibit extremelY low emulsivity. Oily compounds aPPear to be reiected from the waterborne surfactant solution, in other words transient emulsions rapidly revert to relatively clear Phases' This solves two major drawbacks to soil cleaning, first, the minimization of contaminated water Production and second, the reuse of surfactant by recycling the recovered water phase. This article reviews some ot the properties of transient emulsion forming detergents and relates this information to the potential for parts cleaning'

The Right Surfactant

Surfactants work bY lowering the surface tension between Phases. Surfactants that are strong emulsifiers lower the surface tension between liquid phases, encouraging the formation of oil in water micelles (Windsor TYPe I), water in oil micelles (Windsor TYPe II),

or both (Lake 1989). Much of the technical literature on environmental and oil recovery surfactant use focuses on detergents that form these classes of strong emulsions. Many recommend the addition of co-solvents, such as isopropanol or butanol to form verY itr.r.g three-phase or "middlephase" emulsions (Windsor TYPe III). These surfactants are good detergents because theY cause_ water to hold large volumes of oil in thermodYnamicallY stable emulsions. UnfortunatelY, the emulsions are difficult to break, creating a large volume of wastewater that is difficult to treat. Since most municiPal wastewater treatment Plants are sensitive to more than about 10 PPm surfactant load, direct discharge of i n d u s t r i a l w a s t e w a t e r ,h e a v Y i n oil and surfactant, is discouraged. Disposal of emulsions can be verv costlv. The us-e of strong emulsionforming surfactants is well established in the Parts cleaning business.However, some equiPment manufacturers are beginning to promote transient emulsion technology for imProved water use, lower surfactant costs, extended bath life, and lower waste disposal costs. Figure 1 is an example of how continuous oil separation and solids mainte-

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nance is envisioned (AdaPted from Aqueous RecoverY Resources, Inc., Bedford Hills, NY). Other washer styles may also be adapted for non-emulsion aqueous claning. Three control loops are recommended. (1) norma1 cleanser maintenance, (2) solids filtration, and (3) high-efficiency oil/water skimmer to keep the surfactant in its most effective phase composition. In order for this technology to work, however, the proper surfactant must be selected.

in this study, Rhema Super Matrix, Witconol, Triton, SLS, and Dowfax. These are evaluated in terms of which surfactant gives the best results based on the following criteria: . Detergency or good oil removal from selected solid media Purity of recovered oil . Possibility of being recycled

Rhema Super Matrx (Rhema Products, Inc., Dearborne Heights, MI) is a L0 percent surfactant blend in watei. When mixed with oil, Rhema forms a relatively small and unstable emulsion that readily breaks up, leaving only a small amount of oil in the surfactant solution. Rhema is a blend of several surfactants in an alkaline builder and is manufac-

Applied Technology
Simpson by Charlie is a detergents 0r low-emulsifying nonleveraging manufacturers hundred For several For example, for time. here some has been but cgme, whose timehasnotonly trend (Racine, t0 n6nWis.) themgve Plating 0f Racine President to Scott Goodsell, accgrding Atthat show. at a trade it inoperation in 1999 after seeng started emulsifying detergents anddiscandbelt filtration, coalescing filtration, membrane wasexploring timeRacine thelifeof would extend to maintain, "We thatwaseasy had to finda system skmmers. gil-free," recalls plating wgrds, in other line cleaner keep the entire and thecleaners that cleaner that employs a splitting approach Racine selected a non-emulsifying Goodsell. technglggy recovery with skimming metals, along non-ferrous onferrous and beused can water. to reclaim oilfromitswash plans lines and ofitsplating units 0nthree recgvery has Racine, which skimming Today peryear for of oilthatis burned to fivedrums about three is recgvering twomore, to add lifebytwot0three thecleaner "skimming extended theoilhas fuel. According toGoodsell, per year'" 50percent at least expense oursoak cleaner thus cutting times, overhead maintenance low savings, cleaner to the obvious in addition ForGoodsell, pump The ontheunit. "There ormaintenance little upkeep isvery ideal. makes thesystem hose the it and isto drain part. required occasignally The only cleaning mgving istheonly Goodsell to clean. 0rmembranes cartridges There arenofilter sludge outofthebottom." line free ofoil theentire keeps thissystem costsr reducing cleaner thatbesides explains "This wedonot rnoney because saves also theline. down there isnooilto drag because t0 rewgrk due reduces to,lt also asweused asgften ur gther chemistries have to dump poor cleaning." plating "Parts arefirst applicatigns. plating prgcess barrel inboth rack and is used The plated." hotacld andthen then cleaner, theelectro then thesoak cleaner, runthrough of effluwithlover 99percent efficient extremely asbeing theprocess Goodsell describes This approach dooil. cleaner asthey asmuch remove Most systems can ent being oil. other - sudactanh oil." notinthewaste and etcetera, inthecleaner keeps allofthecomponents (EPl, Wis'). New Berlin, Products lnc. rom Electrochemical isE-Kleen The detergent used life, which saves thecleaner it extends because asa trend sees thisapproach Goodsell due todi pafts. reducing rejects keeping theline cleaner, money, ultimately Group division Home Products Manager atElectrolux Process Maria Rios Pre-Treatment a low-emulsifying using (Edison, Shehasbeen withGoodsell. NJ)agrees Frigidaire gil/water separation Prior to that it wasa thermal 2000. since September approach techprocess. (formerly Rios tothis introduced Calgon) Nalco supplier Electrolux's chemical separators. oil Ri0s coalescer-type nology. also explored permonth and isrecovering/recygroup once tothePOTW monitors thedischarge Rios' water ofoily gallgns cgsts with a savings ofdisposal day, ofolper 100 cling approximately in2001 of $11,000. permit Hydrocarbons Total Petroleum meets sewer thedischarge to sanitary Also today the havng to re-engineer withgut "We of parts twice theamount were to clean limit. able process," a caustic uses Products Group cunently Home Rios. Electrolux observes entre low Rios sites Like Goodsell Company. Chemical fromNalco withsuactant additive cleaner preventative operlS required to factthat no heat the as well aS maintenance asa benefit, heights; weir Rios faced wassetting issue The only to clean. atethesystem, andit iseasy runs beautithesystem areset, theheights oftheweirs that"once however, sherepofts fully."

Oil Holding Capacity

The following test demonstrates the principle that different detergents have different oil holding capacity. In this test, solutions of surfactant were prepared in 25 ml vials. Oil was added dropwise (SAE 30 non-detergent motor oil) and the vials were gently hand shaken. The shaking created transient emulsions. When the shaking stopped, the oil would be either relatively stable in emulsion form, or the emulsions would begin to break within a few seconds (transient emulsions). The point at which the surfactant solution became thermodYnamically unstable was an indication of the breakpoint between kinematically and thermodynamically stable emulsions, or an estimate of the oil carrying capacity of the surfactant. Figure 2 compares the oil carrying capacity ol Dawn dish soap, Palmolive dish soap, Alconox (common laboratory glassware detergent) and Rhema Super Matrix (commercially available industrial cleanser). Palmolive and Dawn are excellent detergents, with excellent oil solubility. Alconox and Rhema are excellent detergents with extremely low oil solubility. The mechanisms by which detergency (ability to remove dirt or oil from a solid surface) is achieved are different. Palmolive and Dawn are oil solubilizers, whereas, Alconox and Rhema are oil mobilizers.

Surfactant Evaluation
Five surfactants were evaluated

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tured as a 10 Dercent solids solution (as delivred). Our tests show that the product is 7.9 percent non-volatile solids in a 24 hour dehydration test at 105" C. Dorofax 2A-1" (Dow Chemical Company, Midland, MI) is a yellowish liquid that is completely soluble in water. It forms an unstable emulsion that readily breaks up to give a clear surfac-

tant solution with pockets of globular oil. The composition "asdelivered" is 47 percent ben- oxyb is,tetr aprop yl ene z ene,L,1 sulfonate sodium salt and 1 per-Our cent sodium sulfate in water. tests confirm that the oroduct is 44.4 percent non-volatil solids in a 24 hour dehydration test at 105' C. Witconol SN-90 (Crompton

LeverFollowingWeir

SoakTank

Corporation, Greenwich, CT) is a viscous whitish suspension that is readily soluble in water up to about 20 percent. Higher concentrations form water gels. It forms very stable emulsions in the presence of oil that are difficult to break. It solubilizes oil resulting in relatively large amounts of oil in the aqueous phase. Witconol is a non-ionic surfactant with a chemical composition of 100 percent C10-C14 ethoxylated alcohols. The product is 90 percent non-volatile solids in a 24 hour dehydration test at 105' C. Triton (Sigma Aldrich, Company, St. Louis, MO) is a colorless liquid, has good solubility in water up to about 20 percent in solution. Higher concentrations in water are achievable with difficulty. A higher concentration of surfactant in water form viscous gels and granular solids that are unsuitable for solution chemistry. In the presence of oil, Triton forms a stable oleic emulsion and dissolves oil into the water phase. R e l a t i v e l yl a r g e a m o u n t s o f o i l are observed in the aqueous phase. Triton is a non-ionic sur?actant with the chemical composition, p-tertiary-octyloxy, polyethyl alcohol. The product contains more than 99 r:ercent n o n - v o l a t i l es o l i d s i n a 2 4 h o u r d e h y d r a t i o nt e s t a t 1 0 5 " C . S o d i u n L a u r y l S u l f a t e( S L S ) o r sodium dodecyl sulfate (Fisher Scientific, Fair Lawn, NI) is a white powder thai is readily so1uble in water up to 25 percent but has extremely low solubility thereafter. It forms an unstable emulsion in water but solubilizes oil to a large extent into clear waterborne micelles. SLS is an anionic surfactant. Our tests show that the delivered product is 87.4 percent non-volatile solids as measured in a 24 hour dehydra-' tion test at 105' C.

Solids Filter Loop

Solids to Waste Thin-Film Oil

Figure 1: Dual circuit, oil, and solids management concept.

3.Oo/o o 2.5o/o u o
G

2.0o/o

A at Er ]A

1.5o/o

o
' o o r

1.0o/o

O.5o/o

=
O.Oo/o

Mass Fraction Detergent in Total Emulsion

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*

S u p e rM a t r i x ( n e a ts o l u t i o n , R h e m aP r o d u c t sI,n c . , F a r m i n g t o nH i l l s M , l) Alconox (10% in water,Alconox,Inc.,New York,NY) PalmoliveUltra (neat solution,Colgate PalmoliveCompany,New Yor[ NY) Dawn Lemon Scent

Rapid Oil Detection Method

To rapidly determine the recovery of oil from test surfaces, Sudan IV (Fisher Scientific,) was used to dye the test oil. Sudan IV preferentiallv dissolves in oil and

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Figure 2: Single phase emulsion carrying capacity of some common detergents.

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remains an insoluble Powder in water. The dye is intenselY red, as seen in the standard series of dyed SAE 30 motor oil dissolved in hexane (Figure 3). The red color may be quantified against a visual standard, or may be quantified with a spectroPhotometer. We used the Sudan dye concept to quantify an extraction test suitable for rapid analYsis of oil recovery from test samPles. Figure 3 shows that the red dYe gives a strong visual resPonse bY which dyed oil can be easilY traced. The test may be used to quantifv the oil in the water phut", r the oil phase maY be collected and the oil quantified by extracting the dye from the emulsion into hexane and acetone. All the detergents tested have slightly different phase distributions. Figure 4 shows a series of phase vials containing 10g oil

and 10g of 10 percent surfactant for each of the test surfactants. The surfactants are placed left to right (Dowfax, Rhema, Witconol, Triton, and SLS) based on the purity of the oil phase and the purity of the water phase. OnlY Dowfax and Rhema can be considered to be good phase sPlitting detergents (left). Note the strong emulsions formed bY Witconol and Triton and the large amount of oil present (red color) in the water phase of the SLS sample (right). Phase diagrams may be readilY constructed with these methods, as seen in Figures 5 and 6. Phase diagrams are presented in the total mass fraction format, with the surfactant reported "as delivered" by the manufacturer. As seen in these figures, the attributes of stable emulsionforming and transient-emulsion forming detergents are readilY

Figure 3: Example standard series for rapid visualization of oil solubility

Figure 4: Examples of phase splitting of various surfactants Dowflax, Rhema, Witconol" Triton' and SLS. January 2003 www.cleantechcentral.com

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distinguished. Figure 5 is a diagram for a standard detergent, sodium lauryl (dodecyl) sulfate (SLS). The region of the plot that lies above the curve, and below about 35 percent mass fraction SLS (near the limits of solubility) represents one phase behavior. The region below the curve represents two phase behavior. Three example test vials (A, B and C) are presented to give a visualization of the phase diagram construction. The diagram shows the associated operational tie-lines for the three sample examples.
0.0

The vials contain 5 g oil, 15 g surfactant solution at concentrations A = 5 percent, B = 10 percent, and C = 25 percent in water. Note that the water phase is red, an indication of the presence of oil in the water nhase. The tie-lines indicate that ihe oil phase contains a large mass fraction of water and the water phase contains a large mass fraction of oil. Both phases are therefore considered to be too difficult to treat for simple recovery and reuse. Figure 6 is the phase diagram for Rhema Super Matrix deter1.0

gent formulation. The phase diagram is distinctly different than for SLS. The location of the tielines indicates low-emulsion forming behavior. The two-phase region is extremely large. The one phase region incorporates the lower left corner and the right hand axis of the diagram. Note that the percent of water in the oil phase is initially low, and becomes a constant 20 percent of the oleic mass as the concentration of surfactant increases. The amount of oil in the water is consistently less than 5 percent total mass. Observe that the water layer in the example phase test vials is light pink compared to SLS (Figure 5). The tie-lines that represent the split of the component mass between the two phases, A, B, and C indicate that the water phase and the oil phase are very pure and relatively free of the other components.

Oil Removal: Single Volume Extraction

To determine the ability of the detergents to remove oil from surfaces, we performed a single extraction test of oil from white Ottawa play sand. Samples of sand (10 g) were dosed with 19 dyed oil, then contacted with 20 ml of detergent (2.5 percent solution in water). The slurry was hand shaken for 5 minutes then the liquid was removed and extracted with hexane and acetone to recover the dye. See the removal efficiency data for the various surfactants in Table L. SLS, Rhema, Triton, and Witconol all give removals exceeding 90 percent. There is no significant difference in these results. However, Dowfax is attracted to the sand particles and removes only aboui 64 percent of the oil from sand. The difference between Dowfax and the other detergents is significant. Rhema would be the superior product becauseof its high efficiency of oil removal coupled with its positive oil-splitting characteristics.

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

.1.0

Water
Figure 5: Phase diagram for SLS Detergent. Test vials are prepared with 5 g oil, 15 g surfactant solution. A=5o/", B=70"A, C=25"/".

Sufactant

one Phase o'8

Figure 6: Phase diagram for Rhema Super Matrix and SAE 30 motor oil. Test vials are prepared with 5 g oil, 15 g surfactant solution in water. A=5"/", B=10Y", C=25"A.

Oil Removal: PassiveCleaning

To test the wetting ability of the surfactants on various solids, a

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or in precision Parts washing' " passive" cleaning test was We simPIY cannot allow the voldfvised. ln this test, 1 g of oil umes of wastewater that are crewas placed on a clean surface ated by the use of emulsionglass' such as Plastic, metal, or forming surfactants. Whenever 2'5 of ml Pet' An aliqubt of 1o surfaciants can be recYcled, cent deiergent was then Poured money and materials can be on the surfce to cover the oil for saved. a contact Period of 30 seconds' Sand washing tests and surface drained then The suriaces were cleaning tests have shown that for 30 seconds to remove mobithere iJ verY little difference in lized oil and surfactant' The oil the efficiencY of some common remaining on the surface was surfactants to mobilize and hexane rinsed with acetone and remove oil from a varietY of surinto a collection beaker, and the faces. However, there is a great recovered dYe was quantified' deal of difference in the PuritY ot The removal of oil from glass' p ao s" es recovered based on the i s ' th u aluminum and PolYProPYlene of surfactant used' presented in Table 2' Note that Threfore, the choice of surfactant iemoval of oil from the various can be based on some other surfaces is dePendent uPon the parameter, such as Phase charactvpe of surfactant used' Triton ieristics. Having good detergency g l a s s f r o m .L-orr"t oil PoorlY d o e s n o t n e c e s s a r i l Ye q u a t e t o and. aluminum, whereas, Witconol creating strong emulsions, as removes oil PoorlY from demonstrated bY these data' polvproPYlene. It maY be conPerhaPs the 6est aPPlication .of iru'"a that the low-emulsion surfactants in the non-emulsion and (Rhema forming surfactants industrY can be p a r t s w a s h i n g Dowfai) can be just as effective Figure reviewing bY Lnderstood in oil removal as the surfactants left-hand corner lower the Note 6. f o r m i n g with strong emulsion and, lower right-hand corner of characteristics (Triton, Witconol' the diagram (low end tie-lines)' and SLS). In this Phate region, the detergent concentration is verY low (< The Applicaton 6 percent) and the Phase sPlit tieEnvironmental clean-up issues.are line yields two Phases that are changing how we view surtac,r".y ,trot-tglY oil >95-Percent and tantsl lt"does not matter if the waer >99 Percent. The detergent surfactant is used for soil remediremains stronglY in the water ation, or degreasing garage floors'

phase. This operational condition lan b" maintained in Parts washing systems bY having efficient un ctnstant rmoval of traces of oil Gieure 1). Low" emulsion-forming surfactants and detergent blends are available. Envirnmental market pull and simPle Process economics dictate that niw concePts for surfactant use incorPorate the broad Potential for water minimization, high PuritY oil recoverY' and surfac-tattt te,ts" Possible with these surfactant blends' S i m p l e P h as e d i a g r a m s a n d cleaning fests can helP determine the besl oPerating rangel for the process needs. ComPatible detergents and seParationequiPment re available to meet the new I ind"ustrial needs. References Fortin, 1., JvrY, W'A', and A n d e r s o n , M . A . e t a l , 1 9 9 7' Iournal of Contaminant Hydrolog) 24' (1997) 247-267' Kueper, B. H., Frind, E' O' ,1992' 2-Pase Flow in Heterogeneous Model Porous Media,2' Application. Water Resour' Res'' 27,1.059 -1070 Severin, B.F. and Nolan, S', 2002' "surfactant RecoverY in a Novel Three Phase Surfactant Washing System", Third International Conference, Proceedings of theBattelle Remediation ot and Recalcitrant thlorinated ComPounds Conference' MonteieY, CA MaY 20-23' Wilson, D.J., and Clarke, A'N'' 7994, Soil Surfactant Flushing/Washing, ChaPter 10, Science Pollution Environlental Control Series No. 6, Hazardous Site Soil Remediation Theor) and Tecnologies,PP' 493-550'

SLS Matrix Rhema Witconol Triton Dowfax

92o/o 930/o 990/o 98% 64Vo

Std. Dev. 13Yo

8o/o

1OYo 1lYa 9%

detergents; SAE 30 motor Table 1: Single extraction data for various oil from sand

Detergent SLS Rhema Witconol Triton Dowfax

87 /o 87o/o 81% 720 81%
5o/s 5o/o

Aluminum

PolyproPYlene

std790/o 83olo 8390,

6% 11W
4a/o

using a passive clean Table 2: Removal of oil from various surfaces and drain test January 2003 www.cleantechcentral'com

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82%' 61%

About the Authors B l a i n e F . S e a e r i n ,P h ' D ' , P ' E ' , Director of Enztironmental T e c h n o l o g i e sS , t e P h e nB a k i a m o h ' Ph.D., pist doctotatestudent chemistrv, and lanette Moore, Technician 3,"are with the Michigan Institute, Lansing, MI' Biotechnotogy

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