Poster PresentationsPoster presentations are located on the 5th floor of theMontreux Convention & Exhibition Centre and will be ondisplay for the duration of the conference. Authors havebeen requested to be present at their posters onThursday, 12 October 10.20–10.50 and 16.00–16.20

1. Biodegradation of Nonylphenol Ethoxylate,Accumulation and Ecotoxicity of Stable Metabolitesand Byproducts. M. Renkin1, A. Verhoeven2, and D.Develter1, 1Ecover Belgium NV, Malle, Belgium; and2Hogeschool Antwerpen, Departement IndustriëleWetenschappen & Technologie, Belgium.

The biodegradation of nonylphenol ethoxylate wasdetermined by the OECD 303A activated sludge simulationtest method. Nonylphenol ethoxylate was degraded for 93+/- 2 % leaving at a 95% confidence level, room for thepresence of stable metabolites or by-products. Stablemetabolites were accumulated for a given period using amodification of the OECD 303A test method. Ecotoxicity ofstable metabolites was evaluated in the crustacea Daphniamagna and in the micro algae Pseudokirchneriella subcapi-tata. In Daphnia magna a 48h-EC50 of 4,5 mg DOC/l wasestimated. At a concentration of 8 mg DOC/l no toxicity wasobserved in Pseudokirchneriella subcapitata.

2. The Changing Marketplace in the Middle East—Opportunities and Challenges. Farrokh B. Malihi,Fargol Research Group, Iran.

The Middle East, also called Southwestern Asia, is aregion comprising the lands extended from the easternMediterranean Sea to the Persian Gulf. Thus defined itencompasses several countries with many cultural and eth-nic groups including: Egypt, Turkey, Cyprus, Iran, Iraq,Jordan, Lebanon, Israel, Syria, Palestinian Territories, Kuwait,and countries of the Arabian peninsula (Saudi Arabia,Yemen, Oman, United Arab Emirates, Qatar, Bahrain). With arelatively young and educated population of over 330 mil-lion, a total GDP/PPP of over $ 2,100 billion, and a wealth ofnatural resources, the area offers enormous potential forgrowth of the detergent industry.

Oil and gas remain the core element of economic per-formance in several countries of this region. Recent increasein oil prices, has resulted in increased purchase power par-ticularly for consumer goods. There is however a broad dis-tribution of income resulting in significant differences in theconsumption profile and consumer habits in this market. Asubstantial segment of population is well able to affordproducts further up the hierarchy of household and person-al care products.

The laundry category is by far the largest detergent cat-egory in this market. Per capita consumption is in the rangeof 3-6 Kg depending on the market. The region is mostly ahand wash detergent market, with high foam all purposepowder detergents accounting for over 60% of consumptionin most countries. Significant growth of the automatic pow-

der detergents is evident in several markets, as ownership ofthe washing machines has increased in recent years. Cleaningefficiency and stain removal are key claims and are used bymajor brands. Many products claim additional benefits suchas multi-purpose, pleasant fragrance, and softness.

The use of all purpose, high foam, powder detergents forhousehold cleaning (floors and dishes) is wide-spread con-sumer practice in many markets. This has restricted the devel-opment and growth of household cleaning products (APC,Spray Cleaners) as available in developed markets. Comparedto the European market, penetration of liquid laundry deter-gents, and rinse cycle fabric softeners is low, and limited tothe high income regions. Manual dishwashing is the primaryconsumer practice, with low active products dominating themarket. Liquid bleach, fragranced or without scent, is widelyused for laundry, and for cleaning and disinfecting of house-hold surfaces.

This presentation will discuss changes in consumer atti-tudes and habits, and address major trends in product andtechnology in fabric care and home care markets.

3. Palm Oil Methyl Esters: Feedstock forEnvironmentally Friendly Surfactants. SalmiahAhmad, Parthiban Siwayanan, Zulina Abd Murad, HalizaAbdul Aziz, Norin Zamiah Kassim Shaari, RazmahGhazali, and Zahariah Ismail, Advanced OleochemicalTechnology Division (AOTD), Malaysian Palm Oil Board.Malaysia.

The use of fatty alcohol for the production of environ-mentally friendly surfactants is widely practiced in the indus-try. Fatty alcohols are used to produce fatty alcohol sul-phates, fatty alcohol ethoxylates and fatty alcohol ether sul-phates and these surfactants are extensively used in cleaningas well as personal care products. For these surfactants thedesired fatty chain length is in the range of C12-14 and thesefatty chain lengths can be obtained from lauric oils. One ofthe lauric oils available in the world is palm kernel oil (PKO).

Malaysia produces about 0.1 tonne of PKO for every 1tonne of palm oil (PO) and palm oil is usually cheaper. It hasbeen MPOB’s interest to promote more uses of PO productsin the non-edible sector in particular for the manufacture ofsurfactants. MPOB has been conducting research toincrease the use of PO for the production of surfactants andone surfactant in particular, that has been thoroughlyresearched on, is Methyl Ester Sulphonates (MES) alsoknown as Alpha-sulphonated methyl ester (Alpha-SME).Another strategy of MPOB is to avoid fatty alcohol since thisis an expensive intermediate.

A 20kg/hr pilot plant was purchased from Chemithonand used to produce MES based on PO-based methyl ester(ME). C16-18 (palm stearin) and pure C12, C14 and C16methyl ester were used as feedstock. To convert ME to MES,liquid SO2 was first converted to SO3 gas. This is thenallowed to react with the ME in a falling film reactor. Afterdigestion, bleaching, neutralization and drying, MES of highactive (>80%) and low disalt (<6%) were obtained.

The MES were used to formulate cleaning products(powder detergent, liquid detergent, hand wash, liquid dish

Posters6th World Conference on Detergents

wash etc.). The performances of these products were similarif not better than the products available in Malaysian market,most of which are based on alkyl benzene sulphonates(LAS). However, MES has better hardness tolerance andcomparable biodegradability and ecotoxicity characteristicscompared to LAS.

With the escalating price of petroleum and thereforepetroleum-based products, palm oil based methyl estersoffer good alternative as feedstock for the production ofenvironmentally friendly and cheaper surfactants. Besidesthe large oleochemical complex (capacity approximately 2million tonnes) the development of biodiesel in Malaysiaensures their availabilities at competitive prices.

4. Delivery of Hydrophobic Biocides and Dis-infectants in Water-Based Formulations. Kolazi S.Narayanan, Domingo Jon, Jay Patel, and Sotiri A.Papoulias, International Specialty Products, USA.

Many key cleaning product actives, including certain bio-cides and disinfectants, are hydrophobic in nature and there-fore more difficult to formulate in aqueous solutions. Thereare different approaches employed to deliver these importantactives in water-based formulations that are preferred formost consumer and industrial applications. In many cases,aqueous suspensions are prepared using polymeric disper-sants and emulsification of the hydrophobic components isaccomplished using a combination of solvents, surfactantsand emulsifiers. However the use of many solvents is oftenundesirable due to the hazardous nature, high volatility andflammability of these chemicals. Furthermore, biologicalactivity and performance of the final products depend on theability to produce fine particle suspensions delivering theactive ingredients in an effective manner.

This paper examines novel delivery approaches to pro-duce concentrates, which upon dilution in water can pro-duce stable fine dispersions and micro-emulsions ofhydrophobic biocides and disinfectants. In addition, theintroduction of film forming polymers in the concentratesextends the performance of these active components inmany cleaning products. The concentrates of these compo-nents can be added to commercial aqueous cleaning com-positions to provide the required performance in terms ofantimicrobial and antibacterial protection.

Examples of the designed delivery systems will be pro-vided along with the stability and/or biological activity ofselected biocides and disinfectants used in typical water-based cleaning products. Extensions of this deliveryapproach are also considered to enhance the yield of fra-grances and the dispersion of oils formulated in severalcleaning applications.

5. Environmental Concentration and Risk Assess-ment of Surfactants in Japan. Naohiro Nishiyama1,Akiko Yamamoto2, and Kazuaki Miura3, Environmentaland Human Safety Task Force, Japanese Soap andDetergent Association (JSDA); 1Kao Corporation, Japan;2Procter & Gamble Far East, Inc., Japan; 3LionCorporation, Japan.

In order to evaluate environmental concentration ofLinear alkylbenzene sulfonate (LAS), Alcohol ethoxylates(AE), Alkyldimethylamine oxide (AO) and Dihydrogenatedtallow -dimethylammonium chloride (DHTDMAC), whichare Class 1 designated chemical substances of JapanesePRTR Law, we have been monitoring the surfactant concen-trations of river water in 4 rivers of two metropolitan areasin Japan. The mean concentrations of LAS, AE, AO andDHTDMAC of the 7 monitoring sites during the period from2000 to 2004 were 0.010 mg/L, 0.0011 mg/L, 0.00004 mg/L,and 0.0008 mg/L, respectively. The environmental concen-trations of those surfactants have been constantly very lowduring recent 5 years. Before the JSDA monitoring program,there were no reported AO monitoring studies in the worldfor actual environment such as river and lake. We analyzedC10-16 AO concentrations of river water samples using LC-MS method, and were able to obtain exposure level infor-mation in actual environment. In the most samples only C12AO was detected. Using the monitoring data, environmentalrisk assessment of the 4 surfactants in the aquatic environ-ment in Japan was also conducted. PEC/PNEC ratios of the4 surfactants were estimated to be below 1 to give the con-clusion that the environmental risk of the surfactants waslow in Japan.

6. The EU REACH Regulatory System: Pre-Registration Evaluation of OECD SIDS-ApprovedChemicals—LAB and LAS as Case Studies. David J.Kent and John E. Heinze, CLER, the Council for LAB/LASEnvironmental Research, c/o John Adams Associates,USA; and ECOSOL, the European producers of LinearAlkylbenzene, a sector group of Cefic, Belgium.

The new REACH regulatory system for registration, eval-uation and authorization of chemicals will be implemented inthe European Union beginning next year. This far-rangingprogram requires the preparation and submission of registra-tion dossiers for most chemicals that are manufactured orimported in Europe. Following the initial registration submis-sion, some chemicals may also have to undergo further eval-uation to determine potential hazard and risk; and a smallerset of chemicals may also have to undergo an authorizationprocedure in which uses of the chemicals might be severelyrestricted or banned. While all chemicals meeting the volumethresholds will have to be registered, some chemicals havealready been extensively reviewed and assessed under theexisting Organization for Economic Cooperation andDevelopment (OECD) Screening Information Data Set (SIDS)assessment program. This poster presents case studies usinglinear alkylbenzene (LAB) and linear alkylbenzene sulfonate(LAS) to address the process for pre-registration evaluation ofchemicals that already have previously approved OECD SIDSassessments. The evaluation will consider use of “equivalentdata” from published literature, weight of evidence, structure-activity relationships, read-across within chemical categories,and use and exposure information. The case studies will alsoexamine whether LAB and/or LAS meet the criteria for theevaluation and authorization phases of REACH given theextensive data available, including OECD SIDS assessments.

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7. Microemulsion Formation of Palm Oil Relating toDetergency. Parichat Korphol1, Sumaeth Chavadej1, JohnF. Scamehorn3, Chantra Tongcumpou2, 1The Petroleumand Petrochemical College, Chulalongkorn University,Thailand; 2National Research Center for Environmentaland Hazardous Waste Management, ChulalongkornUniversity, Thailand; 3School of Biological, Chemical andMaterials Engineering, University of Oklahoma, USA.

The ultimate objective of this work is to formmicroemulsions with palm oil for detergency application.Secondary alcohol ethoxylate, a nonionic surfactant andbranced alcohol propoxylate sulfate sodium salt, ahydrophobic anionic surfactant are selected to formmicroemulsion with palm oil at different temperatures anddifferent volumetric ratios of oil to surfactant solution. Bothsingle and mixed surfactant systems which exhibit very lowor ultralow interfacial tension will be selected as formula-tions for detergency experiments. Effects of surfactantconcentration, temperature, salinity and oil loading ondetergency performance will be carried out. Furthermore,spreading coefficient of each formulation, effect of coales-cence time, surfactant adsorption isotherm and the dynam-ic interfacial tension will be measured in order to obtain abetter understanding the mechanism of oily soil detergency.

8. Synergism Effect Between Sodium Dodecyl-benzene Sulfonate and Block Copolymer In AqueousSolution. E.M.S. Azzam, Applied Surfactants Laboratory,Petrochemicals Department, Egyptian Petroleum ResearchInstitute, Egypt.

The synergism behavior of sodium dodecylbenzene sul-fonate (SDBS) with Poly(ethylene oxide)-poly(propyleneoxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymerwas studied using surface tension measurements. The surfaceand thermodynamic parameters of adsorption and micelliza-tion for single and mixed solutions were investigated. Theresults show that the surface and micellization properties ofSDBS were improve as a result of mixing with the blockcopolymer. The mole fraction in micelle and interactionparameters of mixed solutions were calculated. The foam sta-bility of single and mixed solutions was determined. Themixed solutions show a good foam stability than the singlesolutions of SDBS and block copolymer.

9. New Patented Technology Provides SuperiorOxygen Bleach Performance. George Nunes1, BobScarella2, and Georg Borchers3, 1Clariant, Brazil; 2OCI,USA; 3Clariant, Germany.

Sodium Percarbonate has already been used for a longtime as an effective bleaching agent. Its mechanism of actionbasically involves the generation of hydrogen peroxide in anaqueous medium and its optimum performance is seen athigher temperature washing conditions.

Often, detergent formulations include a bleach activatoralong with the sodium percarbonate for the purpose of anin-situ formation of peracetic acid, an even more effectivebleaching agent than the oxygen bleach itself.

As a new alternative of activated bleach, a cogranule of

the bleach agent and an activator, and a process for its man-ufacture have been developed to insure a higher probability ofbleach-activator reactions in the wash. The benefits of such acogranule are a consequence of its dissolution mechanismand the synergistic interaction between its main components.

This alternative bleaching system gives more effectiveperformance at lower temperature washing conditions andso becomes very attractive to world regions such as theUnited States, Asia and Latin America, where heating is notpart of the typical washing cycle.

Such cogranules are especially suitable to be used aspart of heavy duty powder detergents or bleach boosterformulations.

10. Recent Improvements in Linear AlkylbenzeneTechnology. Dennis J. Bellville, Larry C. Erickson, andSrikantiah Raghuram, UOP LLC, USA.

Linear alkylbenzene sulfonate, commonly referred to asLAS, is the workhorse surfactant used in home laundry deter-gents. Continuous process innovation for the production ofits precursor linear alkylbenzene (LAB) has been developedand commercialized to maintain the market viability of LAS.Depending upon whether or not the production of LAB canbe integrated within the infrastructure of an oil refinery, thereare two basic types of LAB plants. For those plants whererefinery kerosene is available on site the LAB plant processscheme starts with the production of normal paraffins as theprincipal feedstock. Process innovation involving the produc-tion of normal paraffins has been targeted to increase capac-ity while reducing capital cost. The normal paraffins are thenconverted to normal olefins which are finally then alkylatedwith benzene to produce the desired LAB. For plants not inte-grated with a refinery, but which can otherwise purchase nor-mal paraffins the LAB plant process scheme starts with theconversion of the normal paraffins to normal olefins followedagain by the alkylation of those normal olefins with benzeneto produce the final LAB. The use of a new generation of cat-alysts for the conversion of the normal paraffins to normalolefins has allowed LAB producers the opportunity to opti-mize capacity and operating costs. In addition to these twobasic types of LAB plants a third even less integrated type ofplant is possible whereby purchased normal olefins, eitherinternal or alpha type, are directly alkylated with benzene toproduce the LAB. Value engineering associated with the alky-lation step has similarly resulted in the opportunity for pro-ducers to reduce operating cost by reducing utilities con-sumption. This poster will address the most recent technolo-gy improvements made to the various process steps alongthese possible LAB plant process schemes for improved prof-itability for either the present or future LAB producer.

11. Recent Shifts in the Linear Alkylbenzene SupplyCenter of Gravity. Dennis J. Bellville, Larry C. Erickson,and Srikantiah Raghuram, UOP LLC, USA.

Concurrent with the increased demand for detergentproducts in Asia and the Middle East, the supply center ofgravity of linear alkylbenzene (LAB), the most dominant ofthe many precursors used in finished detergents, also

Posters9–12 October 2006 ◆ Montreux, Switzerland

appears to have shifted. In 1994 for example, supply of LABexceeded local demand by a mere 40 kilo metric tones perannum (kMTA) in India whereas demand exceeded supplyby 75 kMTA in the Middle East (M.E.). In 2011, indigenousIndian supply is expected to exceed demand by 120 kMTAand local M.E. supply is expected to exceed demand byalmost 170 kMTA. The very direction of trade will havereversed and traditional LAB importers will have becomeexporters in just over a decade and a half!” Simultaneouslyhowever, high kerosene and benzene prices continue to putpressure on the sustained growth of the use of LAB. Recentenhancements to the technology have attempted to addressthese issues of increased price pressures by developingtechnology to allow the use of lower value feeds while pro-ducing higher value products such as heavy n-paraffins thatcan be sulfonated to secondary alkane sulfonates. Whilesome of these improvements have already been translatedto commercial reality, others are being discussed with bothexisting and new customers. This poster will discuss each ofthese developments in detail and provide concrete examplesof the economic impact that each one of them has on pro-duction costs and gross profit.

12. New Trend for the Development of VisbreakinHeavy Gas Oil by Cationic Surfactants (PhaseTransfercatalysts). A.K. El Morsi, and A.M.A. Omar,Egyptian Petroleum Research Institute, Egypt.

Thermal cracking (visbreaking) of the gas oil with boil-ing point above 350oC was carried out in presence of 0.5 wt% of phase transfer catalyst. The catalysts used were P-methyl toloyltriethyl ammonium chloride and P- methyltoloyl triethanol ammonium chloride. These catalysts wereprepared and analysed in this study. Cracking reactions wereconducted in an autoclave and the operating variables; reac-tion temperature, contact time and structure of hydrophilicgroup of phase transfer catalysts, were studied. The reactionpressure through the whole reaction was 20kg/cm2. Theadsorption behaviour of synthesized phase transfer cata-lysts on barite was measured using a modified version of theFranmkin adsorption isotherm. The DG, DH, DS. parametersof the adsorption reaction were calculated. The yield of theisoparaffin was 39%. The effectiveness of the adsorption of(PTC) and its efficiency as a promoter for the free radicalchain reaction were investigated. The resulting adsorptionparameters confirm the suggested reaction mechanism.

13. Preparation of Soap from the Mixture ofCoconut and Olive Oils and its Application inWashing Process of Reactive Printed Cotton Fabric.Hossein Najafi1 and Mazeyar Parvinzadeh2, 1TextileEngineering Group, Shahre Rey Branch of Islamic AzadUniversity, Iran; 2Color Control and Color ReproductionDepartment, Iran Color Research Center, Iran.

In this research, a new soap was prepared from the mix-ture of coconut and olive oils, sodium hydroxide, sodiumoleate and sodium chloride. The solubility, washing and ionicproperties of soap was evaluated at different pH conditions.Washing properties of mentioned soap was compared with

an industrial soap and it was examined on reactive printedcotton fabric according to Standard AATCC 61 and ISO CO1-CO6. The coconut and olive mixture soap shows relativelyexcellent washing properties comparing to an industrial soapand it is suitable for washing process of textiles.

14. Effect of Wetting Agents in Bleaching of KenafCellulosic Fibers. Mazeyar Parvinzadeh1, HosseinNajafi2, and Amir Kiumarsi1, 1Color Control and ColorReproduction Department, Iran Color Research Center,Iran; 2Textile Engineering Group, Shahre Rey Branch ofIslamic Azad University, Iran.

Kenaf contains a relatively high content of lignin, hemi-celluloses and other materials in addition to cellulose.Therefore, it is expected that the bleaching and dyeingbehavior will be different as compared to cotton. Bleachingleads to loss in the tensile strength of the fibers, caused bypartial removal of the non-cellulosic components that con-stitute are responsible for intercellular binding materials. Thekenaf fibers bundles can be bleached, dyed and used forvarious textile applications. Wetting and penetrating agentscan help to remove impurities from fibers.

In this research, the effect of wetting agents in bleachingprocess of kenaf fibers was examined. For this purpose,kenaf yarns were bleached with hydrogen peroxide using1%, 2%, 4% and 8% of the wetting agent as auxiliary inbleaching solution at boil. The effect of different percentagesof wetting agent and duration of process were discussed onwhiteness and yellowness of samples were measured usinga reflectance spectrophotometer. According to the results,the whiteness of samples was increases with an increase inthe percentage of wetting agent percentages in solution.Also, some decrease in yellowness value of samples wasobserved due to wetting agent usage in solution.

15. Evaluation of Soil Removal by Quartz CrystalMicrobalance Technique. Keiko Gotoh1 and YumikoTagawa2, 1Kyoto University of Education, Japan; 2KobeUniversity of Fashion and Design, Japan.

The removal of oily and particulate contaminants fromgold and polymer substrates was evaluated by the quartzcrystal microbalance (QCM) technique and discussed on thebasis of surface energetics. Polyethylene, nylon 6, and cellu-lose acetate films were prepared on gold electrodes of theQCM by a spin-coating method. As model oily and particulatecontaminants, arachidic acid and polyethylene particle wereused, respectively. Arachidic acid was deposited onto thesubstrates by the Langmuir–Blodgett (LB) technique andpolyethylene particle from the aqueous dispersion. After thesoil deposition, the substrates were cleaned in water/ethanolmixtures by applying mechanical action. The removal efficien-cy was determined from the frequency changes of the QCMdue to soil deposition and cleaning. The efficiency was great-ly dependent on the substrates in both cases of oily and par-ticulate contaminants. In all systems, the soil removalincreased with increasing ethanol concentration. In the pres-ence of sodium hydroxide, the removal efficiency of arachidicacid further increased because of the saponification. The

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Lifshitz-van der Waals and acid-base components of the sur-face free energy of the soil and substrate were estimated fromthe contact angles of three probe liquids. The soil removalbehavior in the present system was explained in terms of thefree energy change resulting from liquid penetration betweenthe soil and substrate in the zone of contact, which was cal-culated from the surface free energy components.

16. Study Of Diffusion Factor and Kinetics of a RapeFatty Acid Methyl Ester Ethoxylation. TomaszKozlecki1, Adam Sokolowski1, Arkadiusz Chrusciel2,Wieslaw Hreczuch2, and Marek Marcinski3, 1Departmentof Chemistry, Wroclaw University of Technology, Poland;2MEXEO, Poland; 3ICSO Chemical Production, Poland.

The influence of diffusion on the ethoxylation of a rapefatty acid methyl ester was investigated in a batch reactor.Ensuring constant environment, the hydrodynamic parame-ter of the system was changed and the effect on kinetics wasobserved. The analysis has demonstrated the importance ofconvective mass transfer in the process. The values of calcu-lated Sherwood numbers showed that in the investigatedenvironment convection contributes four times more thanpure diffusion. This result allows us to focus the optimisa-tion process on increasing the dynamics of convection andthe mass transfer surface, for example, by modifying theabsorber construction.

17. Study on the Stability of Amino-Cyanogen. Yun Liu,Ya-li Shen, Yu-mei Sun, and Jin Zhao, School of Chemicaland Environmental Engineering, Beijing Technology andBusiness University, China.

A series of amino-cyanogen bleaching activators wassynthesized, and their activity and stability were determinedusing cloth soiled with alizarin and tea flavin, and with cot-ton cloth with aged soil. It was demonstrated that the saidcompounds were more effective at low temperature com-paring with TAED. Upon perhydrolysis, they might generatea peroxy imidic acid as the highly reactive bleaching species,without the loss of weight associated with leaving groupsuch as TAED and AOBS. However some of them had a seri-ous drawback since they were highly hygroscopic in nature.Eventually they hydrolyzed to the corresponding inactiveamide. Stability tests indicated that at long time, high tem-perature, and high humidity the new compounds becamedark as well as viscous. Among the Amino-cyanogens, suchas M-SJA, Trimethylamine-SJA, Triethylamine-SJA, Pyridine-SJA, Betain-SJA, acetic-SJA, the last had the worst stability,lost the main activity, while M-SJA was the best. UV-Visagave a strong red shift to the structure, λmax 586nm (A 0.188)for the dark acetic-SJA, while λmax 353nm (A 0.134) to thenew prepared one, even though IR did not show significantchange to the structure. Protecting experiments adding kindsof inner additive or encapsulation were carried out. It wasfound that dryness and high pH were effective in protectingacetic-SJA; fatty acids with 12-16 carbon atoms and waxwith low melting point as coating shell gave positive results.

18. RETAIN—Increasing the Deposition Efficiency of aBenefit Agent Onto Fabric From a LaundryDetergent Formulation. Alan McClellan, AshokeSengupta, and Melanie Hughes, AMCOL DetergentSpecialties, Colin Stewart Minchem Ltd., United Kingdom.

The laundry process is one of the most difficult process-es in which to deposit desired benefit agents onto the fabricin the wash, especially within automated washing machines.The very nature and purpose of the “detergent” is to removedirt which is a contradiction to the process of depositingsomething onto the fabric. This and the quantities of waterintroduced and then drained in the washing and rinse cyclesleads to a hostile environment for a particle required todeposit itself onto the fabric and to stay there for the duration.

This “Retain” technology utilises a high molecular weightpolymer to enhance deposition of a softness-inducing activeonto the fabric by way of forming an active-polymer emulsionin a surfactant formulation. The increased deposition efficien-cy of the active agent is attributed to the specific form in whichthe active agent is included in the detersive composition, pro-duced upon mixing or diluting certain cationic oil-in-wateremulsions of the active agent with detersive surfactants.

The resulting cationic emulsion of the active agent ishighly stable against coalescence and this stability is retainedeven when the emulsion is diluted with water. The individualcationic emulsifier particles are pre-adsorbed and remainadsorbed on the emulsion droplets which contain the activeand this leads to enhanced substrate-deposition of the active.

19. Environmental Performance of LAS Producedfrom GTL Normal Paraffin and Different AlkylationRoutes. Bas Maase1, Henk Dirkzwager2, CharlesEadsforth3, John Handley4, Chris Mead4, and John Hill4,1Shell International Gas Ltd., UK; 2Shell Global SolutionsInternational BV, The Netherlands; 3Shell InternationalLtd., UK; 4SafePharm Laboratories Ltd., UK.

Normal paraffin from Gas to Liquids (GTL) plants is ofimportance to the LAB industry, since it provides LAB produc-ers with a more cost-effective feedstock than normal paraffinextracted from kerosene. At the CESIO 2004 conference, workwas presented that demonstrated that GTL Normal Paraffinprocesses well in both HF and Detal alkylation routes. It alsoshowed that LAS made using GTL Normal Paraffin has adetergency performance equal to commercially available LAS.This poster now focuses on the environmental performanceof LAS produced from GTL Normal Paraffin.

LAS samples, typical of LAS produced from kerosenederived normal paraffin and from GTL Normal Paraffin, weresynthesised. These differed in terms of composition, mainlylinearity and phenyl isomer composition, as a result of (a)the GTL Normal Paraffin feedstock and (b) the type of alky-lation process. Samples with a relatively low 2-phenyl isomercontent were prepared via an HF alkylation route using twodifferent sources of normal paraffin (GTL and keroseneextraction). Other samples that differed in linearity were pre-pared with a relatively high 2-phenyl isomer content via aDetal alkylation route.

An environmental test programme, including biodegrad-

Posters6th World Conference on Detergents

ability and aquatic ecotoxicity testing of all samples, was car-ried out. It confirmed that there was no significant differencein either biodegradability or aquatic toxicity results for any ofthe samples. All samples achieved >60% biodegradabilityafter 28 days (OECD 301B), with fish (LC50), invertebrate (EC50)and algal (IC50) ecotoxicity data in the range 1–10 mg/l, 1–10mg/l and 10–100 mg/l, respectively. All data are the same asprevious results on LAS samples summarised in IUCLID andHERA databases, confirming the environmental acceptabilityof LAS derived from GTL Normal Paraffin.

20. GTL Normal Paraffin: the Future LAB Feedstockof Choice. Bas Maase1 and Henk Dirkzwager2, 1ShellInternational Gas Ltd., UK; 2Shell Global SolutionsInternational BV, The Netherlands.

The Gas to Liquids (GTL) industry is coming of age, withlarge-scale plants being built and proposed in Qatar,Nigeria, Algeria and other countries where there are suitablegas reserves. In parallel, the use of different inputs to providesynthesis gas for the Fischer-Tropsch process are beingexplored, like coal and biomass, where the product slate isidentical to that of a GTL plant.

In addition to clean transport fuel, GTL plants can alsoproduce a range of other products, such as naphtha, lubri-cant base oils and normal paraffin. The production of nor-mal paraffin from GTL is of importance to the detergentsindustry, especially the LAB industry, since it provides LABproducers with a more cost-effective feedstock than normalparaffin extracted from kerosene. GTL Normal Paraffin alsoprovides additional benefits to LAB producers such asincreased flexibility in plant location and decreased depend-ency on local kerosene availability. All this means that in thenear future GTL Normal Paraffin could largely replacekerosene derived normal paraffin to meet the growth indemand for normal paraffin.

This poster will describe these developments and theaccompanying benefits for LAB producers in more detail. Itwill also investigate the future option of producing “heavy”(C14-C17) GTL Normal Paraffin for the production of paraffinsulphonates.

21. Influence of Surfactant Hydrophobe Structureon Performance in Hand Dishwashing and HardSurface Cleaning. Julian Barnes1*, JanElsa Carty2, VickiJud2, Kim Millspaugh2, Kirk Raney2, Warren Schmidt2,Greg Shpakoff2, Bryan White2, and Paul Tortorici2, 1ShellGlobal Solutions International BV, The Netherlands;2Shell Global Solutions US Inc., USA.

The foaming performance of a variety of alcohol sul-fates and alcohol ethoxysulfates has been evaluated.Foaming was determined with and without a model soil,foaming with this artificial soil correlating well with handdishwashing performance. Detergent alcohols ranging from99 % linear to 99 % branched were evaluated. Foaming ofalcohol sulfates reduced with hydrophobe branching andwas dependent on the type of branching and the total num-ber of branches. Alcohol ethoxysulfates displayed a similarpattern. A totally linear (C12, C14) hydrophobe and Shell’s

modified-OXO (C12, C13) hydrophobe gave similar and thehighest level of foaming performance that was significantlygreater than conventional OXO derivatives of the samemolecular weight. The stability of hand dishwashing formu-lations is influenced by hydrophobe structure, the modified-OXO (C12, C15) hydrophobe demonstrating improved for-mulation stability compared to the linear (C12, C14)hydrophobe.

Several non-ionic surfactants were screened in a modelhard surface cleaning formulation using a simple scrubbingtest with a linoleum panel and an oily/pigment soil. Othertests measured oily soil removal from a metal surface usinga specially designed cabinet. Short chain hydrophobes (suchas C11 or C9-11) gave superior dynamic surface tensionreduction and higher cleaning performance compared tothose of longer chain analogues (such as C12-15). Mixingtwo C9-11 ethoxylates with low and high ethylene oxidecontents (such as 2.5 and 8 moles of ethylene oxide) gaveenhanced (synergistic) cleaning performance.

22. Antifoam Granules with Excellent Low TemperatureDefoaming Performance. C. Roos1, A. Di Pietro1, S.Mabire1, A. Baranyai2, Z. Szilágyi2, and D. Kramer2, 1GEBayer Silicones, Germany; 2inprotec AG, Germany.

The high active content in detergent formulations andlow water usage in modern automatic cleaning processesyields strong foam formation with the subsequent danger ofreduction of cleaning efficiency, poor rinsing and foam leak-age, even machine damage. Accurate foam control is a needto make modern detergent formulations efficient in mechan-ical cleaning devices like washing machines and automaticdish washers, keeping the cleaning performance at the high-est requested levels within different washing conditions andhabits.

Silicone antifoams have proven to provide a potentantifoam effect at lowest concentrations of dosage in manydetergents. Development and manufacturing of the rightantifoam compound already takes into account the overallperformance needed within the final detergent formulation,bringing the antifoam effect into optimum efficiency. Thus,silicone-antifoam based emulsions are included into liquiddetergents whereas solid granulates embedding the dropletsof the silicone antifoam compound are added to washingpowders in a post-addition processing step.

Herewith we introduce a new silicone-based antifoamcompound generated by GE Bayer Silicones that possessesexcellent foam knockdown and defoaming persistenceproperties and an outstanding antifoam performance at lowwashing temperatures (T = 30°C /40°C). Its granular versioncreated by inprotec AG through Matrix-Encapsulation of theliquid active by means of Fluidized Bed Spray GranulationTechnology combines the foam suppressing effect of thenew silicone compound with the effect of foam controlthrough ‘slow-release’ of the active silicone droplets fromthe solid carrier. Antifoam performance data based on testsat different temperatures and washing conditions are pre-sented and effects are discussed.

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23. Transalkylation—A Heterogeneous CatalyticProcess to Convert Heavy Alkylates (HAS) Back inLinear Alkylbenzene (LAB), Using Solid AcidCatalysts. Donato A.G Aranda and Expedito PereiraSantos, Chemical Engineering Department; School ofChemistry; Federal University of Rio de Janeiro-UFRJ,Brazil.

We present a new heterogeneous catalytic process toconvert heavy alkylates (HAs) (C10-13 polyalkyl benzene),usual by-product in the production of C10-13 linear alkylben-zene (LAB), to monoalkylated aromatic compound, that is,producing back the desired detergent intermediate, oversolid acid catalysts. The HAs are often used in some indus-trial applications, however sometimes this by-product isburned as such or mixed with fuel oil, what is a non-envi-ronmentally correct use.

Operating conditions like temperature, pressure, spacevelocity and reactant concentrations are varied in favor oflarger selectivities. The best catalyst produces up to 90%conversion and up to 80% selectivity to on-spec C10-13 linearalkylbenzene.

The process can be conducted in batch or continuousreactors, always using the catalysts in fixed bed systems.Either a dedicated new transalakylation unit or an appendixunit for current LAB plants can be adopted in this process.Any improvement in the conversion of normal paraffin toLAB is desired.

This new process, being able to convert a residue in themain intermediate for the detergent industry, can be a verypositive factor in the economics of the overall operation ofLAB plants.

This process can also be evaluated for the reactions thatproduce cumene and ethyl benzene, and their polyalkylatedby-products.

24. Cloud Point Extraction of Phenolic Compoundsfrom Solutions Containing Oxyethylated Tri-glycerides. Katarzyna Materna, Institute of ChemicalTechnology and Engineering, Poznan University ofTechnology, Poland.

Surfactants have several applications in industry, agri-culture and household. They are also used in analyticalchemistry to separate and pre-concentrate various sub-stances. One of such methods is cloud point extraction(CPE), where phase separation is induced by change of tem-perature. The separated phases differ in their hydrophilicityand hydrogen bond basicity and acidity. As a result, organicsolutes can be transferred to the surfactant rich phase of arelatively small volume in comparison with the volume of theinitial feed. Thus, the method permits both, a separation andenrichment of the solute.

It was the aim of this work to study the separation ofselected phenolic compounds by the cloud point techniqueusing oxyethylated triglycerides as a new type of nonionic sur-factants obtained by a recently developed catalytic process.

It was found that the cloud point phenomenon can besuccessfully used to recover the toxic phenolic pollutantsfrom aqueous solutions and that oxyethylated triglycerides

were convenient nonionic surfactants for such separations.The recovery of phenols depended mainly on the hydropho-bicity and proton donor acidity of the investigated solutes.The results obtained could be explained by the linear solva-tion energy relationship (LSER) proposed by Abraham formicellar systems. The efficiency of separation also increasedwith an increase of pollutant hydrophobicity. The hydrogenbond basicity and dipolarity of the pollutants decreased therecovery. The derived models enable optimum selection ofpollutants, which can be effectively removed from aqueousstreams by the cloud point extraction method.

25. Characterization of Alkylglycopyranosides andAlkylglycofuranosides by HPLC-MS and Ion-TrapMS2. Miriam Beneito-Cambra, Virginia Bernabé-Zafón,José Manuel Herrero-Martínez and Guillermo Ramis-Ramos, Departament de Química Analítica, Facultat deQuímica, Universitat de València, Spain.

Alkylpolyglycosides (APGs) in technical mixtures andtoiletries were characterised by RP-HPLC-MS. Both alky-lamide and CN columns, with ACN/ water mixtures, wereused. The α- and β-epimers and ring isomers (pyranosidesand furanosides) of the alkyl monoglycosides were resolvedwith the alkylamide column. The isomers of alkyl diglyco-sides and triglycosides were also partially resolved. With theCN column, the ring isomers were also well resolved, andthe equilibration times were much shorter. The alkylamideand CN columns were applied to characterise APGs in toi-letries using isocratic and gradient elution, respectively.Further, the MS and MS2 spectra of glucose and alkyl mono-glycosides were studied. The positive-ion spectra showedsingle peaks of the [M+Na]+ ions. These peaks gave a com-plex pattern, common to all the compounds, in MS2.Schemes of the fragmentation pathways, including adductsof the sodium ion with fragments of the glucose moiety, anddimer and trimer clusters are presented. Using HPLC-MS2,the differences between the MS2 spectra of the alkyl gly-copyranosides and alkyl glycofuranosides were established.The glycofuranosides showed a lower propensity to formdimer and trimer clusters than the pyranosides. This wasuseful in identifying ring isomers in the chromatograms

26. The Use of a Derivative Containing Polyamide asa Detergent. Azza M. Mazroua1, M.Y. Abed1, and D.A. Ismail2, 1Petroleum Research Institute, PolymerLaboratory, Petrochemical Department, Egypt; 2PetroleumResearch Institute, Surfactant Petrochemical Department,Egypt.

Four novel polymeric surfactant were prepared by con-densation of a polyamide of low molecular weight with along chain fatty acid which was linked at one of its ends withL-alanine or L-aspartic acid. Surface properties of their solu-tions, including surface tension, critical micelle concentra-tion, effectiveness, maximum surface excess, and minimumsurface area, were investigated for different concentrationsat 25°C. Standard free energies of micellization and adsorp-tion were calculated for the prepared surfactants in aqueoussolution.

Posters9–12 October 2006 ◆ Montreux, Switzerland