EP2925844B1 - Cleaning composition and use thereof - Google Patents

Cleaning composition and use thereof Download PDF

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Publication number
EP2925844B1
EP2925844B1 EP13814444.9A EP13814444A EP2925844B1 EP 2925844 B1 EP2925844 B1 EP 2925844B1 EP 13814444 A EP13814444 A EP 13814444A EP 2925844 B1 EP2925844 B1 EP 2925844B1
Authority
EP
European Patent Office
Prior art keywords
cleaning composition
och
hard surface
surface cleaning
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP13814444.9A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2925844A2 (en
Inventor
Alan Keasey
Jawahar WAKHLOO
Guy Johnson
Caroline Kelly
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
OTI Greentech Group AG
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OTI Greentech Group AG
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Publication date
Priority claimed from GB201307589A external-priority patent/GB201307589D0/en
Application filed by OTI Greentech Group AG filed Critical OTI Greentech Group AG
Publication of EP2925844A2 publication Critical patent/EP2925844A2/en
Application granted granted Critical
Publication of EP2925844B1 publication Critical patent/EP2925844B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/385—Cationic compounds containing P
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C11D2111/16—
    • C11D2111/20—

Definitions

  • the present invention relates to a method for cleaning profiled hard surfaces, especially those coated with zinc silicate, and to compositions suitable for cleaning such surfaces.
  • Zinc silicate primers are extensively used throughout industry to coat ferrous metal structures and combat corrosion thereof by acting as a sacrificial anode.
  • Examples of such primers typically include compositions formulated with a builder or binder such as a polysiloxane or epoxy resin.
  • a builder or binder such as a polysiloxane or epoxy resin.
  • primed surfaces are less smooth than the corresponding bare metal. This profiling makes them somewhat difficult to clean which in turn can lead to problems in certain circumstances. For example, when a ship's hold, which has previously contained say a heavy hydrocarbon, is to be used subsequently to transport another cargo, e.g. an alcohol such as methanol, the cleaning cycle can be lengthy and require the entry of humans into a closed, hazardous environment to ensure that cleaning is complete.
  • a ship's hold which has previously contained say a heavy hydrocarbon
  • another cargo e.g. an alcohol such as methanol
  • US 6716804 discloses a three-component cleaning composition comprising an amphoteric surfactant and two different non-ionic surfactants which are ethoxylates of differing water solubilities.
  • US 2012/0277140 generally discloses a surfactant system for surface cleaning comprising one or more anionic surfactants and one or more non-ionic surfactants.
  • a wide range of candidate surfactants is speculated upon including unspecified EO/PO block copolymers but exemplified are systems in which a combination of two ethoxylate non-ionic surfactants, one of which is water soluble and the other water-insoluble, is also employed.
  • an inorganic salt is also included.
  • WO96/21712 teaches an industrial or marine cleaner comprising an organic solvent; a blend of two non-ionic ethoxylated surfactants; a phosphate ester hydrotrope; a primary amino acid and water. None of the examples teach the use of a non-ionic surfactant component containing both propoxy and ethoxy units.
  • GB2259518 discloses a microemulsion cleaning composition
  • a microemulsion cleaning composition comprising an anionic surfactant; a non-ionic surfactant system consisting of two ethoxylates; an aromatic hydrocarbon and water.
  • US5707948 discloses a cleaning composition comprising two ethoxylated non-ionic surfactants with differing numbers of ethoxy units; an optional alkoxylated solvent with a short chain alkyl group; a suds suppressor comprising a fatty acid and a secondary alcohol; potassium carbonate and water.
  • a liquid industrial hard surface cleaning composition characterised in that it is water dilutable and comprises a mixture of three surfactant types consisting of (a) from 5 to 50% by weight of an anionic surfactant, (b) from 5 to 50% by weight of a first non-ionic surfactant comprised of both ethoxy and propoxy groups and having the general formula R'-(AO) n -OH wherein R' is C 9 to C 20 alkyl, each AO unit is either -OCH 2 CH 2 - or -OCH 2 CH(CH 3 )-; the molar ratio [-OCH 2 CH(CH 3 )-]/[-OCH 2 CH 2 -] is in the range up to 8 and n is greater than 6 and (c) from 5 to 50% by weight of a second non-ionic surfactant having the general formula, R'-(OCH 2 CH 2 ) n -OH wherein R' is C 9 to C 20 alkyl,
  • the various surfactants described above may be sourced in water-diluted as opposed to pure form.
  • commercially available anionic surfactants typically comprise a 25-40% solution of the active component in water. Since the various weight ranges defined herein are with respect to 100% actives, any dilution effect will need to be taken into account when making up any cleaning composition derived therefrom.
  • the density of the individual components are approximately equal to 1 g/cc so that the formulations can alternatively be made up using the same ranges on a volume basis to give substantially the same result.
  • the cleaning composition comprises a concentrate suitable for spot cleaning duties.
  • it comprises a corresponding diluted form derived from the concentrate by addition of water in one or more steps.
  • diluted forms will comprises less than less than 5%, more preferably less than 1%, most preferably less than 0.75% by volume of the concentrate itself.
  • the diluted form of the cleaning composition will be one which is prepared directly by mixing water with the three constituent surfactants whose relative proportions are in accordance with the various ranges defined above.
  • the pH of the cleaning composition is suitably in the range from 6 to 9 most preferably from 7 to 8.
  • the first non-ionic surfactant has a cloud point in the range 50-90, preferably 60-70°C as determined by ASTM D-2024 09 at a 1% by weight level of the surfactant in deionised water and/or the second non-ionic surfactant has a cloud point in the range 30-70, preferably 40-60°C as determined with 5g surfactant in 25g of a 25% butyl diglycol (BDG) aqueous solution.
  • BDG butyl diglycol
  • the anionic surfactant in the un-ionised, acid form
  • the first non-ionic surfactant has a log 10 P value in the range 0.1 to 3
  • the second non-ionic surfactant has a log 10 P value in the range 0.1 to 3.
  • log 10 P means the logarithm of the partition coefficient P for the given component measured with respect to a standard two-phase n-octanol/water system. Further information about this methodology may be found, for example, ion Ecotoxicology and Environmental Safety, 11(3) 1986, pp.251-260 .
  • anionic surfactant in one embodiment it is one or a mixture of compounds selected from C 12 to C 18 alkyl sulphonic or sulphuric acids or a corresponding salt thereof, preferably a Group IA or Group IIA metal or an amine or alkanolamine salt, or from linear alkyl benzene sulfonic acids or a salt thereof, preferably a Group IA or Group IIA metal salt or an amine or alkanolamine salt.
  • it is selected from C 12 to C 18 alkyl polyether sulphuric acids or a corresponding salt thereof, preferably a Group IA or Group IIA metal or an amine or alkanolamine salt.
  • preferable anionic surfactants include sodium lauryl sulphonate or sulphate, magnesium lauryl sulphonate or sulphate, tetraethylammonium lauryl sulphonate or sulphate, mixed C 14 to C 16 alkyl sulphate or sulphonate salts of sodium, potassium or magnesium and mixed C 12 to C 14 alkyl sulphate or sulphonate salts of sodium, potassium or magnesium.
  • Preferable linear alkyl benzene sulphonic acids or salts thereof include C 6 to C 12 alkyl benzene sulphonic acids or salts thereof.
  • polyether sulphates which are characterised by a polyether unit between the aliphatic or aromatic component and the sulphate group
  • this is suitably a polyether comprised of up to 20 -OCH 2 CH 2 - units.
  • the alkyl groups in any of the above may be branched or unbranched.
  • the anionic surfactant is an amine or alkanolamine salt
  • the corresponding cation is suitably selected from the genus of species having the general formula R 3 NH + wherein each R group is independently H or a C 1 to C 6 substituted or un-substituted hydrocarbyl group with the proviso that at least one is a substituted hydrocarbyl group.
  • the term 'substituted hydrocarbyl group' means a hydrocarbyl, preferably an alkyl group of general formula C x H 2x+1 , which has been substituted with one or more polar groups such as -OH, -SH, -NH 2 , -NHR or the like.
  • such substituted alkyl groups are hydroxyalkyl groups comprising at least one hydroxyl group; in a sub-embodiment at least one of these hydroxyl groups is attached to the end of the alkyl group remote from that connected to the nitrogen.
  • at least two of the R groups are hydroxyalkyl groups and in yet another all three R groups are hydroxyalkyl groups.
  • each R group is suitably independently H or a C 2 to C 6 un-substituted or substituted alkyl group; more preferably H or a C 2 to C 4 un-substituted or substituted alkyl group.
  • One especially preferred sub-genus of the R 3 NH + cations described above is comprised of species which can be regarded as protonated mono-, di- or tri- alkanolamines in which each alkanol group has from two to four carbon atoms.
  • species which can be regarded as protonated mono-ethanolamine, di-ethanolamine, tri-ethanolamine, mono-propanolamine, di-n-propanolamine, tri-n-propanolamine, di-iso-propanolamine or tri-iso-propanolamine.
  • the cation is protonated tri-ethanolamine or protonated tri-n-propanolamine.
  • the first non-ionic surfactant which is employed in the cleaning composition and which is relatively hydrophilic, is suitably one or mixture of compounds having the general formula, R'-(AO) n -OH wherein R' is C 9 to C 20 alkyl, preferably C 9 to C 16 alkyl; each AO unit is either -OCH 2 CH 2 -or -OCH 2 CH(CH 3 )- and n is greater than 6.
  • the molar ratio [-OCH 2 CH(CH 3 )-]/[-OCH 2 CH 2 -] is in the range up to 8, preferably from 0.1 to 4 and/or n is from 7 to 15.
  • the different AO units may be arranged randomly or in blocks.
  • the end block of the AO chain is made of - OCH 2 CH(CH 3 )- units; in others it is made of -OCH 2 CH 2 - units.
  • the first non-ionic surfactants are typically prepared by alkoxylating the corresponding fatty alcohol R'OH which itself can be derived from naturally-occurring sources or from precursor lower molecular weight alcohols using for example the Guerbet synthesis. Such surfactants are sometimes referred to as 'linker surfactants' and are characterised by exhibiting a critical micelle concentration (CMC) which is relatively low.
  • CMC critical micelle concentration
  • the alkyl groups mentioned above can be branched or unbranched.
  • the second non-ionic surfactant which is employed in the cleaning composition and which is relatively hydrophobic, is suitably one or mixture of compounds having the general formula, R'-(OCH 2 CH 2 ) n -OH wherein R' is C 9 to C 20 alkyl, preferably C 9 to C 16 alkyl, and n is less than 6, preferably from 2 to 5.
  • Such surfactants are also typically prepared by ethoxylating the corresponding fatty alcohol R'OH which itself can be derived from naturally-occurring sources or from precursor lower molecular weight alcohols using by the Guerbet synthesis.
  • the alkyl groups mentioned above can be branched or unbranched.
  • the R' groups employed in the first and second non-ionic surfactants can be the same or different.
  • first and second non-ionic surfactants comprise from 10 to 45% by weight of the cleaning composition.
  • the use of the cleaning composition of the present invention is generally applicable to the cleaning of all fouled hard surfaces which have become profiled (i.e. roughened) by virtue of use, corrosion or being coated with a corrosion-resistant layer (e.g. a primer). Its use is beneficial where the hard surface includes a profiled, sacrificial coating of zinc silicate or an equivalent and is especially so for cleaning the dirty surfaces of coated stainless or mild steel storage tanks. It can be used to particular advantage to clean the cargo tanks or holds of ships where the space is confined and discharge of the waste cleaning composition is environmentally problematic. Any method of using the cleaning composition can be employed to effect cleaning although typically it will be brought into contact with the dirty surface using an industrial sprayer assembly which is adapted to collect and recirculate the liquid.
  • the surfaces can at the same time be brushed or scrubbed. Thereafter, once a suitable period of cleaning time has elapsed, the cleaned surfaces can be rinsed with clean water and/or a sample of the next cargo to be used.
  • the cleaning composition is sprayed onto the dirty surfaces at a temperature of less than 100°C, typically from 60 to 80°C.
  • the cleaning composition of the present invention which is designed for industrial as opposed to personal care or household use, is especially suitable for removing contaminants comprising high molecular weight hydrocarbons such as diesel, gas-oil, kerosene_and vegetable oils from hard surfaces of the type mentioned above.
  • Typical vegetable oils which can be removed with the cleaning compositions of the present invention include palm oil, soya bean oil, rapeseed oil, sunflower oil, peanut oil, olive oil, cottonseed oil, palm kernel oil and coconut oil along with refined fractions thereof.
  • Test panels made of stainless steel or mild steel coated with an industry standard zinc silicate coating were immersed in ultra-low sulphur diesel for a period of three days to simulate the contamination occurring in a cargo tank. After removal and being allowed to drain, the panels were tested in a rig designed to remove as much of the residual diesel adhering to the panel as possible under a standard set of cleaning conditions.
  • the cleaning composition was applied to the test panel by means of a sprayer adapted for continuous liquid recycle thereby enabling the contaminated panel surfaces to be continuously contacted with the cleaning composition for a period of 2 hours. During this time, the temperature of the cleaning composition was maintained at 70°C.
  • the panels washed with clean water and the residual diesel on the panels determined by immersing the panels in a standard volume of methanol at room temperature for 5 minutes and then measuring the amount of diesel extracted using UV/visible spectroscopy.
  • the amount of diesel in the methanol was quantified as an average residual hydrocarbon reading (ARHR) indicative of the effectiveness of the cleaning composition.
  • ARHR average residual hydrocarbon reading
  • a baseline was established using water at 70°C.
  • the ARHR reading was 550.
  • the cleaning composition was a 0.5% by weight aqueous solution of Accell ® Clean (ex-Advanced BioCatalytics Corporation) a material which has been rated for use in cleaning marine tanks and which comprises a mixture of a surfactant and proteins having a pH in the range 5.5 to 6.5.
  • the ARHR reading obtained was 50.
  • the cleaning composition (pH 7-8) was a 0.5% by weight aqueous solution of a cleaning composition concentrate according to the present invention comprising (by volume):
  • Example 3 was repeated except that the weight component of the three surfactants was respectively 35%, 30% and 35% and no anti-foam was employed. The ARHR reading obtained was 35.
  • Example 4 was repeated except that 35% Serdet DSK-30 ® (sodium salt of a C12-C14 alcohol sulphate (30% solution); ex Elementis Specialities) was employed instead of the Hansanol AS240A.
  • the ARHR reading was 28.
  • the cleaning composition (pH 7-8) was a 0.8% by weight aqueous solution of a cleaning composition concentrate comprising (by volume):
  • the cleaning composition concentrate comprised 25% Serdet DLK-9/30 ® , 45% Lutensol XP90 ® and 30% Ethylan 1005 ® and was used at a 1% dilution level in water.
  • the ARHR reading was 40.
  • a binary cleaning composition concentrate comprising 30% Hostapur SAS30 ® (sodium secondary C 14-17 alkyl sulphonate; ex Hostapur) and 70% Lutensol XP90 ® was employed at 1% dilution.
  • the ARHR reading was 48.
  • the cleaning composition concentrate comprised 25% by weight Biosoft D-40, 45% by weight Berol 185 and 30% by weight Ethylan 1005 together with 0.1% by weight of NFA antifoam.
  • the product so obtained was used at a 0.5% dilution level in water.
  • the ARHR reading was 48 (average of two results).
  • Example 9 was repeated except that the Berol 185 was replaced with Lutensol XP90.
  • the product so obtained was used at a 0.5% dilution level in water.
  • the ARHR reading was 60 (average of two results).
  • Example 9 was repeated except that the Ethylan 1005 was replaced with a 50:50 by weight mixture of Ethylan 1005 and Dowanol EPH ® (aromatic ethylene glycol ether C- 6 H 5 OCH 2 CH 2 OH; ex Dow Chemicals). Thereafter a further 10% by weight water was added to the mixture. The product so obtained was used at a 0.5% dilution level in water. The ARHR reading was 58 (average of two results).
EP13814444.9A 2012-11-30 2013-11-27 Cleaning composition and use thereof Active EP2925844B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB201221630 2012-11-30
GB201307589A GB201307589D0 (en) 2013-04-26 2013-04-26 Industrial cleaning composition
PCT/EP2013/074867 WO2014083062A2 (en) 2012-11-30 2013-11-27 Cleaning method and composition

Publications (2)

Publication Number Publication Date
EP2925844A2 EP2925844A2 (en) 2015-10-07
EP2925844B1 true EP2925844B1 (en) 2022-06-29

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ID=49885193

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EP13814444.9A Active EP2925844B1 (en) 2012-11-30 2013-11-27 Cleaning composition and use thereof

Country Status (7)

Country Link
EP (1) EP2925844B1 (ru)
KR (1) KR20150102023A (ru)
CN (1) CN104870624A (ru)
BR (1) BR112015012632A2 (ru)
CA (1) CA2892430C (ru)
EA (1) EA031115B1 (ru)
WO (1) WO2014083062A2 (ru)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102270164B1 (ko) * 2020-10-22 2021-06-28 한국화학연구원 세정제 조성물

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997011150A1 (de) * 1995-09-21 1997-03-27 Henkel-Ecolab Gmbh & Co. Ohg Pastenförmiges wasch- und reinigungsmittel
US20120277140A1 (en) * 2005-12-20 2012-11-01 Novozymes Biologicals, Inc. Surfactant Systems For Surface Cleaning

Family Cites Families (15)

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FR1472561A (fr) * 1965-03-30 1967-03-10 Henkel & Cie Gmbh Agent liquide pour le traitement des taches sur textiles
DE2100114C3 (de) * 1971-01-02 1980-04-10 Henkel Kgaa, 4000 Duesseldorf Plastisch verformte seifenhakige Waschmittel
DE2448532A1 (de) * 1973-10-15 1975-04-24 Procter & Gamble Zusammensetzungen zur oelentfernung
DE2361448A1 (de) * 1973-12-10 1975-06-12 Henkel & Cie Gmbh Neutrale bis schwach alkalische waschflotten lieferndes waschmittel
GB1526942A (en) * 1975-01-03 1978-10-04 Procter & Gamble Liquid detergent compositions
DE2559225A1 (de) * 1975-01-03 1976-07-15 Procter & Gamble Europ Fluessiges wasch- und reinigungsmittel sowie seine anwendung
DE2543998A1 (de) * 1975-10-02 1977-04-07 Henkel & Cie Gmbh Lagerbestaendiges, klares fluessigwaschmittel mit einem gehalt an optischen aufhellern
GB1562801A (en) * 1976-01-02 1980-03-19 Procter & Gamble Liquid detergent composition
FR2645876B1 (fr) * 1989-04-13 1994-05-13 Hoechst Ste Fse Concentre detergent, son procede de preparation et son application a la fabrication de lessives en poudre par le procede dit de melange a sec
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US5707948A (en) * 1993-03-19 1998-01-13 The Procter & Gamble Company Stable and clear concentrated cleaning compositions comprising at least one short chain surfactant
EP0616027A1 (en) * 1993-03-19 1994-09-21 The Procter & Gamble Company Concentrated cleaning compositions
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US20090023626A1 (en) * 2007-07-16 2009-01-22 Anne Carner Blangiforti Natural fibers wash and rinse and method of using same
CN101514307B (zh) * 2008-12-31 2011-07-20 北京绿伞化学股份有限公司 一种透明高浓度衣物洗涤剂及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997011150A1 (de) * 1995-09-21 1997-03-27 Henkel-Ecolab Gmbh & Co. Ohg Pastenförmiges wasch- und reinigungsmittel
US20120277140A1 (en) * 2005-12-20 2012-11-01 Novozymes Biologicals, Inc. Surfactant Systems For Surface Cleaning

Also Published As

Publication number Publication date
CN104870624A (zh) 2015-08-26
EA031115B1 (ru) 2018-11-30
EP2925844A2 (en) 2015-10-07
WO2014083062A3 (en) 2014-07-24
CA2892430A1 (en) 2014-06-05
CA2892430C (en) 2019-10-29
KR20150102023A (ko) 2015-09-04
BR112015012632A2 (pt) 2017-07-11
EA201590990A1 (ru) 2015-08-31
WO2014083062A2 (en) 2014-06-05

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