WO2008122388A1 - Agent nettoyant biodégradable - Google Patents

Agent nettoyant biodégradable Download PDF

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Publication number
WO2008122388A1
WO2008122388A1 PCT/EP2008/002601 EP2008002601W WO2008122388A1 WO 2008122388 A1 WO2008122388 A1 WO 2008122388A1 EP 2008002601 W EP2008002601 W EP 2008002601W WO 2008122388 A1 WO2008122388 A1 WO 2008122388A1
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WIPO (PCT)
Prior art keywords
composition
water
acid
use according
systems
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PCT/EP2008/002601
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English (en)
Inventor
Susanne Bellmann
Johann Schulte
Frank De Cordt
Original Assignee
Ashland Licensing And Intellectual Property Llc
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Priority claimed from EP07012419A external-priority patent/EP2008976A1/fr
Application filed by Ashland Licensing And Intellectual Property Llc filed Critical Ashland Licensing And Intellectual Property Llc
Publication of WO2008122388A1 publication Critical patent/WO2008122388A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/105—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances combined with inorganic substances
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2096—Heterocyclic compounds
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/08—Corrosion inhibition
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/04—Surfactants, used as part of a formulation or alone

Definitions

  • the invention relates to a biodegradable cleaning agent and its use, particularly for removing and/or preventing deposits from surfaces of water-bearing systems, e.g., in papermaking industry.
  • inorganic or organic composition form a fundamental problem as regards the operation of industrial plants in which fluids, particularly aqueous media move through pipe systems or are stored (intermediately) in containers.
  • inorganic deposit of scales can interfere with the operation of refrigerating plants or, in the worst case, cause a total shutdown thereof.
  • biofilms are formed when micro-organisms settle at the interface.
  • the biofilm contains, other than the micro-organisms, primarily water and extracellular polymeric substances exuded by the micro-organisms which, in conjunction with the water, form hydro-gels and contain other nutrients or substances.
  • particles are included in the resulting slimy matrix that are found in the aqueous medium adjacent the interface.
  • the deposits can grow to a substantial layer thickness. For example, in industrial plants, this can lead to operational errors owing to reduced pipe cross-sections or choking of filters. Moreover, fragments can be released from the biofilm that can affect the operation of the plant. Finally, the material released by the biofilm organisms can additionally accelerate the corrosion of their substrates.
  • biofilms and other deposits are formed in papermaking plants, particularly in the components that are used for the accommodation and transfer of an aqueous fiber suspension.
  • the biofilm also called “fouling" which forms in such a papermaking plant is also characterized by the fact that it contains a high proportion of fibers, fine substances, and inorganic pigments that are bound by the organic matrix.
  • Such biofilms typically are accompanied by protective exopolysaccharides ("slime", EPS) and occur at the interface of these equipment surfaces and process water streams.
  • inorganic contaminants such as calcium carbonate (“scale”) and organic contaminants often deposit on such surfaces. These organic contaminants are typically known as “pitch” (e.g., resins from wood) and “stickies” (e.g., glues, adhesives, tape, and wax particles).
  • the layer thickness of the deposit is too great, it might break away from the substrate. The portions thus released might cause faulty operation, particularly tearing of the paper webs during paper manufacture, which leads to high consequential costs.
  • deposit control agents are added, which, however, pose a health hazard and also suffer from comparatively poor biodegradability.
  • aqueous compositions comprising a combination of (i) ascorbic acid, (ii) a monocarboxylic acid, (iii) a multicarboxylic acid and (iv) a defoaming agent may be advantageously used to treat surfaces of water-bearing systems, in particular to clean pulp, paper, paper board, or cardboard-making machines or their parts from deposits, such as adhering synthetic polymers, natural resins, biofilms, oils and grease, or to prevent adhesion of these deposits on the surfaces of these machines or machine parts.
  • deposits such as adhering synthetic polymers, natural resins, biofilms, oils and grease
  • Fig. 1 shows drying screens that had been used in a paper plant and were treated with the composition according to the invention (percentages indicate the concentrations of the composition that was used).
  • compositions comprising a combination of monocarboxylic acids and multicarboxylic acids are known from the prior art.
  • DE 199 23 303 A1 discloses a rinse aid for eliminating detergent residues and making textiles compatible with the skin after laundry.
  • the rinse aid is to be employed instead of a fabric softener as the final cleaning agent.
  • the rinse aid contains citric acid and lactic acid for adjusting a skin-neutral pH value during the last rinsing step as well as ascorbic acid and 4-amino benzoic acid, respectively, as skin vitamin.
  • the rinse aid does neither contain a defoaming agent, nor is it intended for removing and/or preventing deposits from surfaces of water bearing systems.
  • compositions comprising a combination of monocarboxylic acids and multicarboxylic acids show a synergistic effect with ascorbic acid and have the property of cleaning machines and plant elements from special impurities and of preventing adherence of these special contaminants on the surfaces of machines units or parts of plants.
  • the combinations exhibit an excellent biodegradability and extremely low toxicity.
  • a first aspect of the invention relates to the use of a composition
  • a composition comprising (i) ascorbic acid, (ii) a monocarboxylic acid, (iii) a multicarboxylic acid and (iv) a defoaming agent for removing and/or preventing deposits from surfaces of waterbearing systems, preferably of machines or parts of machines, preferably for processing cellulosic material.
  • the ascorbic acid, the monocarboxylic acid and the multicarboxylic acid may be present either as the free acid (ascorbic acid as the free alcohol) or as a salt, such as a salt of an alkali metal or of an alkaline earth metal.
  • the term "surface of a water-bearing system” preferably refers to the surface of any item, article, unit, system, component and the like, e.g., any device, apparatus, equipment, gadget, machine, engine, or part thereof that comes into contact with water or an aqueous medium during operation.
  • the surface of said item, article, unit, system, component may be organic or inorganic.
  • the surface comprises an inorganic material, such as metal, metal oxide, a silicious material (e.g. concrete), glass or enamel.
  • the surface comprises an organic material, such as a polymer, e.g. a duroplast, thermoplast or elastomer.
  • the term "water bearing system” does not refer to any items, articles, and the like, that are typically processed by means of the water bearing system, i.e. that are subject to a process the water bearing system is devoted for.
  • the water bearing system of a conventional washing machine includes all parts and components of the washing machine it is typically equipped with and that typically come into contact with water upon operation.
  • the clothes to be washed by means of said washing machine are preferably not encompassed by the term “water bearing system” in the meaning according to the invention.
  • the term “deposit” preferably refers to any material that has deposited, i.e. formed, e.g. precipitated, settled, sedimented, adhered, etc., on the surface of the water-bearing system.
  • the deposit may be dense or spongy, hard or soft, smooth or rough, and the like.
  • the deposit may be of any material, e.g. organic or inorganic, amorphous or crystalline, low-molecular or polymeric, ionic or nonionic, and the like.
  • the term "deposit” shall refer to any material adhering to the surface of the water bearing system which material was not present before the water bearing system has been used the first time.
  • the composition according to the invention has a 5 day Biological Oxygen Demand (BOD 5) of at least 45%, more preferably at least 50%, still more preferably at least 55%, most preferably at least 60% and in particular at least 65%.
  • the Biological Oxygen Demand is a test used to measure the concentration of biodegradable organic matter present in a sample of water. It can be used to infer the general quality of the water and its degree of pollution by biodegradable organic matter. It is used in water quality management and assessment, ecology and environmental science. BOD measures the rate of uptake of oxygen by microorganisms in the sample of water at a fixed temperature (20 0 C) and over a given period of time (usually 5 days) in the dark. To ensure that all other conditions are equal, a very small amount of micro-organism seed is added to each sample being tested. This seed is typically generated by diluting activated sludge with de-ionised water. The test generally takes place over an elapsed period of 5 days.
  • the BOD test is usually carried out by diluting the sample with de-ionised water saturated with oxygen, inoculating it with a fixed aliquot of seed, measuring the dissolved oxygen and sealing the sample (to prevent further oxygen dissolving in). The sample is kept at 2O 0 C in the dark (to prevent photosynthesis and thereby the addition of oxygen) for five days and the dissolved oxygen is measured again. The difference between the final value and initial value is the BOD.
  • the apparent BOD for the control is subtracted from the control result to provide the corrected value.
  • the BOD 5 may be expressed as percentage of the oxygen concentration after storage for 5 days in relation to the initial oxygen concentration.
  • BOD is similar in function to chemical oxygen demand (COD), in that both measure the amount of organic compounds in water.
  • COD is less specific since it measures everything that can be chemically oxidised rather than just levels of biology active organic matter.
  • BOD is used as a gauge of the effectiveness of wastewater treatment plants.
  • Various commercial devices are available for its determination. For further details it can be referred e.g. to Clair N. Sawyer, Perry L. McCarty, Gene F. Parkin (2003). Chemistry for Environmental Engineering and Science, 5th edition, New York: McGraw-Hill; Lenore S. Clescerl, Arnold E. Greenberg, Andrew D. Eaton. Standard Methods for Examination of Water & Wastewater, 20th edition, Washington, DC: American Public Health Association; Stevens Institute of Technology.
  • the composition according to the invention passes the test for "substantial biodegradability", i.e. may be regardes as “readily biodegardable”, according to the BOD 5 measurement (i.e. the BOD5 is > 50%).
  • the composition according to the invention has a 5 day Chemical Oxygen Demand (COD 5) of at least 45%, more preferably at least 50%, still more preferably at least 55%, most preferably at least 60% and in particular at least 65%.
  • COD 5 Chemical Oxygen Demand
  • the Chemical Oxygen Demand (COD) test is commonly used to indirectly measure the amount of organic compounds in water. Most applications of COD determine the amount of organic pollutants found in surface water (e.g. lakes and rivers), making COD a useful measure of water quality. It is expressed in milligrams per liter (mg/L), which indicates the mass of oxygen consumed per liter of solution.
  • mg/L milligrams per liter
  • the composition according to the invention is "primarily biodegradably", more preferably “ultimately biodegradable” according to EC Regulation No. 648/2004 on detergents (of 31 March 2004).
  • compositions according to the invention exhibit a level of biodegradability is said specified tests of at least 65%, more preferably at least 70%, still more preferably at least 75%, most preferably at least 80% and in particular at least 85%.
  • EC Regulation No. 648/2004 on detergents it can be referred e.g. to the Official Journal of the European Union, 8.4.2004, L 104/1-35.
  • the composition according to the invention is "easily biodegradable" according to OECD-test 301 F (DIN EN ISO 9408).
  • composition according to the invention contains a monocarboxylic acid and a multicarboxylic acid.
  • multicarboxylic acid shall mean any compound bearing at least two carboxyl (or carboxylate) moieties.
  • the monocarboxylic acid and/or the multicarboxylic acid are hydroxy- carboxylic acids, i.e. comprise one or more hydroxy groups, preferably one hydroxy group.
  • the monocarboxylic acid is aliphatic and/or comprises 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms and most preferably 3 carbon atoms.
  • 2- hydroxy-propionic acid and 3-hydroxyproprionic acid are particularly preferred, especially (+)-2-hydroxypropionic acid (L-(+)-lactic acid).
  • the multicarboxylic acid is a bicarboxylic acid or a tricarboxylic acid.
  • the multicarboxylic acid is aliphatic and/or comprises 4 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, most preferably 6 carbon atoms.
  • Citric acid is particularly preferred, especially its monohydrate. It has been surprisingly found that the cleaning capacity of citric acid monohydrate is superior over the cleaning capacity of citric acid anhydrate.
  • the relative weight ratio of the multicarboxylic acid to the monocarboxylic acid is within the range of from 50:1 to 10:1 , more preferably 45:1 to 12.5:1 , most preferably 40:1 to 15:1.
  • the weight ratio of the multicarboxylic acid to the monocarboxylic acid is within the range of from 60:1 to 20:1 , more preferably 55:1 to 25:1 , still more preferably 50:1 to 30:1 , most preferably 45:1 to 35:1 and in particular 42.5:1 to 37.5:1.
  • the weight ratio of the multicarboxylic acid to the monocarboxylic acid is within the range of from 30:1 to 1 :1 , more preferably 25:1 to 5:1 , most preferably 20:1 to 10:1 and in particular 17.5:1 to 12.5:1.
  • the relative weight ration of the monocarboxylic acid to ascorbic acid is within the range of from 10:1 to 1 :10, more preferably 5:1 to 1 :5, still more preferably most preferably 4:1 to 1 :1 and in particular 2.5:1 to 1.5:1.
  • the content of ascorbic acid is within the range of from 0.01 to 5.0 wt.-%, more preferably 0.05 to 4.0 wt.-% and most preferably 0.1 to 1.0 wt.-%, based on the total weight of the composition.
  • the content of the monocarboxylic acid is within the range of from 0.01 to 10 wt.-%, more preferably 0.1 to 5.0 wt.-% and most preferably 0.5 to 2.5 wt.-%, based on the total weight of the composition.
  • the content of the multicarboxylic acid is within the range of from 1.0 to 90 wt.-%, more preferably 5.0 to 60 wt.-% and most preferably 7.5 to 42.5 wt.-%, based on the total weight of the composition.
  • the content of the multicarboxylic acid is within the range of from 20 to 60 wt.-%, more preferably 25 to 55 wt.-%, still more preferably 30 to 50 wt.-%, most preferably 35 to 45 wt.-%, and in particular 37.5 to 42.5 wt.-%, based on the total weight of the composition.
  • the content of the multicarboxylic acid is within the range of from 1 to 30 wt.-%, more preferably 5 to 25 wt.-%, still more preferably 7.5 to 22.5 wt.-%, most preferably 10 to 20 wt.-%, and in particular 12.5 to 17.5 wt.-%, based on the total weight of the composition.
  • the composition comprises ascorbic acid, lactic acid as monocarboxylic acid and citric acid as multicarboxylic acid.
  • the composition comprises 0.01 to 5.0 wt.-%, more preferably 0.05 to 4.0 wt.-% and most preferably 0.1 to 1.0 wt.-% ascorbic acid, 0.01 to 10 wt.-%, more preferably 0.1 to 5.0 wt.-% and most preferably 0.5 to 2.5 wt.-% lactic acid and 1.0 to 90 wt.-%, more preferably 5.0 to 60 wt.-% and most preferably 7.5 to 42.5 wt.-% citric acid, based on the total weight of the composition.
  • the composition according to the invention may be solid, e.g., a powder, or liquid, e.g., a solution, suspension, emulsion or a gel.
  • the composition according to the invention is aqueous.
  • the water content of the composition is preferably within the range of from 20 to 90 wt.-%, more preferably 30 to 80 wt.-%, based on the total weight of the composition.
  • the pH value of the aqueous composition is below 4.5, more preferably at most 4.0, still more preferably at most 3.5, yet more preferably at most 3.0, most preferably at most 2.5 and most preferably at most 2.0.
  • the pH value is within the range of 1.6 ⁇ 4, more preferably 1.6 ⁇ 3, still more preferably 1.6 ⁇ 2, and most preferably 1.6 ⁇ 1.
  • the pH value is at most 1.0, more preferably at most 0.9, still more preferably at most 0.8, and most preferably at most 0.7. If the content of ascorbic acid, the monocarboxylic acid and the multicarboxylic acid as such is not sufficient in order to provide the desired pH value, further acids may be added, preferably inorganic mineral acids, such as hydrochloric acid, sulphuric acid and phosphoric acid, the latter being particularly preferred.
  • composition according to the invention further comprises a defoaming agent (foam control agent, antifoam agent).
  • Defoaming agents are known to the person skilled in the art. In this regard it can be referred to, e.g., Peter R. Garrett, Defoaming (Surfactant Science Series), CRC; 1 edition, 1992.
  • the defoaming efficiency can be measured in accordance with EP 1 561 727.
  • a defoaming agent is a chemical additive that inhibits the formation of foam.
  • defoamers are needed in pulp and paper mills to 1 ) reduce unwanted foam and thereby enhance water drainage from the pulp mat, 2) minimize loss of process chemicals, and 3) increase equipment capacity.
  • a defoaming agent can be identified by comparing the form formation properties of a composition containing the agent with an otherwise identical comparative composition not containing the agent. If the foam formation property in the presence of the agent is reduced, said agent is to be regarded as a "defoaming agent".
  • the presence of the defoaming agent reduces to form formation property of the composition by at least 25%, more preferably at least 50%, still more preferably at least 75%, yet more preferably at least 85%, most preferably at least 90% and in particular at least 95%.
  • the defoaming agent is selected from the group consisting of hydrocarbon-based mineral oils, organo-silicon-compounds, organosiloxanes, metal soaps, and mixtures of the foregoing (e.g., Drewplus ® 2100 EFG).
  • the defoaming agent is biodegadable and/or has a LD 5O value (rat, oral) of at least 100 mg/kg, more preferably at least 1000 mg/kg, still more preferably at least 4000 mg/kg.
  • the defoaming agent has a HLB value of 1 to 6, more preferably 1 to 5, most preferably 1 to 4 and in particular 1 to 3.
  • the defoaming agent is an aqueous blend comprising a polysiloxane derivative and/or a fatty acid derivative.
  • a defoamer comprised of silica having hydrophobic surfaces dispersed in a water insoluble hydrophobic organic liquid, wherein the silica has a surface area of no greater than 0.1 m 2 /g and the hydrophobic silica comprises in excess of 25 wt. percent of the composition (cf. US 4,377,493).
  • a synergistic, aqueous, free flowing defoaming composition comprising as the primary component an aqueous hydrophobic dispersion of an alcohol of 14-28 carbon atoms, a fatty acid of 14-28 carbon atoms, a soap of a fatty acid of 14-28 carbon atoms and a nonionic or anionic surfactant, and as a secondary component a dispersion of a hydrophobic solid in a water insoluble organic liquid (cf. US 4,477,370).
  • a composition comprising as the primary component a 5-30% aqueous hydrophobic dispersion of a solid alcohol of 14-28 carbon atoms, a solid fatty acid of 14-28 carbon atoms, a soap of a solid fatty acid of 14-28 carbon atoms and a nonionic or anionic surfactant, the ratio by weight of acid and soap to alcohol being 0.2-0.4:1.0 and 0.1-0.5:1.0, respectively, and the ratio by weight of surfactant to combined alcohol, acid and soap being 0.1-0.4:1.0; and as the secondary component a dispersion of finely divided hydrophobic silica or ethylene-bis-stearamide in a water insoluble organic liquid, said primary and secondary components being present in a ratio by weight of the composition of 50-99.5% and 50-0.5%, respectively (cf. US 4,626,3).
  • a foam control agent having no volatile organic compounds comprising: (a) soybean oil, (b) a hydrophobic wax having an average particle size of from about 5 to 75 microns, and a surface energy of from about 20 to about 30 dynes/cm 2 , and (c) a polydimethylsiloxane, a substituted polydimethyl-siloxane, or mixtures thereof, wherein the weight ratio of soybean oil to hydrophobic wax to polydimethylsiloxane is about 85:5:0.5 to 90:10:2, said weight ratio being based upon the total weight of the foam control agent (cf. 5,510,409).
  • a foam control agent which comprises a reaction product prepared by reacting: (a) a hydrocarbon carrier; (b) a precipitated amorphous silicate; (c) an effective stabilizing amount of a refractory clay; and (d) a reactive silicone, in the presence of a catalytically effective amount of a basic catalyst (cf. US 6,090,857).
  • a defoamer composition comprising: (a) hydrophobic silica; (b) a linear polysiloxane having end-blocked polyoxypropylene groups having the following structural formula:
  • x is from about 12 to about 25 and n, which may be the same or different for each polyoxypropylene group, is from about 8 to 15;
  • a nonionic surfactant cf. US 6,426,379).
  • a foam control agent for coatings comprising comprising: (a) from 1 to 20 weight percent of a siloxane polyalkyleneoxide copolymer having the following structural formula
  • the defoaming agent Preferably, the defoaming agent
  • the content of the defoaming agent is within the range of from 0.01 to 5.0 wt.-%, more preferably 0.05 to 1.0 wt.-% and most preferably 0.1 to 0.5 wt.-%, based on the total weight of the composition.
  • the composition according to the invention further comprises an alkoxylated, preferably ethoxylated alcohol or an ester of an alkoxylated, preferably ethoxylated alcohol.
  • the ester of the ethoxylated alcohol is a compound according to general formula (I),
  • Ri is Ci-C ⁇ -alkyl, preferably CrC 3 -alkyl
  • R 2 is d-C ⁇ -alkyl, preferably C 2 -C 6 -alkyl; and n is an integer of 1 to 10, preferably 1 , 2, 3, 4 or 5.
  • the ethoxylated alcohol is a compound according to general formula (II),
  • R 3 is CrCi 8 -alkyl, preferably C 5 -Ci 6 -alkyl, more preferably Cg-Cn-alkyl; and m is an integer of 1 to 20, preferably 2, 3, 4, 5, 6, 7 or 8 (e.g., Sol Cleaner ® 300).
  • the ethoxylated alcohol is biodegadable and/or has a LD 50 value (rat, oral) of at least 100 mg/kg, more preferably at least 200 mg/kg still more preferably at least 1000 mg/kg.
  • LD 50 value rat, oral
  • the ethoxylated alcohol Preferably, the ethoxylated alcohol
  • the content of the ethoxylated alcohol is within the range of from 0.1 to 30 wt.-%, more preferably 0.5 to 20 wt.-% and most preferably 0.5 to 12.5 wt.-%, based on the total weight of the composition.
  • the composition according to the invention further comprises a corrosion inhibitor.
  • Corrosion inhibitors are known to the person skilled in the art. In this regard it can be referred to, e.g., Vedula S. Sastri, Corrosion Inhibitors: Principles and Applications, Wiley, 1998 and Michael and Irene Ash, Handbook of Corrosion Inhibitors (Synapse Chemical Library), Synapse Information Resources, Inc. 2000.
  • the corrosion inhibitor is selected from the group consisting of alkali metal borates, alkali metal molybdates, hydrocarbyl triazoles, silicates, morpholine, ethylenediamine, pyridine, pyrrolidine and acetylene derivatives.
  • the corrosion inhibitor is biodegadable and/or has a LD 5O value (rat, oral) of at least 1.0 mg/kg, more preferably at least 5.0 mg/kg.
  • the corrosion inhibitor Preferably, the corrosion inhibitor
  • the corrosion inhibitor comprises a compound having a C- C-triple bond (alkyne derivative).
  • the compound is an alkoxylated prop-2- yn-1-ol, more preferably a propoxylated prop-2-yn-1-ol (e.g., Korantin ® PP).
  • the content of the corrosion inhibitor is within the range of from 0.01 to 5.0 wt.-%, more preferably 0.05 to 1.0 wt.-% and most preferably 0.1 to 0.5 wt.-%, based on the total weight of the composition.
  • the composition according to the invention further comprises one or more surfactants.
  • the surfactant may be non-ionic, anionic or cationic.
  • the surfactant is an amine-oxide (N-oxide).
  • the surfactant is a compound according to general formula (III)
  • R 4 is CrCi 8 -alkyl, preferably Ci-C 6 -alkyl
  • R 5 and Re are independently H or CrCi ⁇ -alkyl, preferably H or d-C ⁇ -alkyl; and p is an integer of 1 to 10, preferably 2, 3, 4 or 5, more preferably 3 (e.g., Tomah ®
  • surfactants are salts, preferably sodium salts, of alkylamino- carboxylates, such as N-(2-carboxyethyl)-N-(2-ethylhexyl)- ⁇ -alanine monosodium salt (e.g., Amphotensid ® EH).
  • the surfactant is biodegradable and/or has a daphnia toxicity of at least 300 mg/l, more preferably at least 450 mg/l (OECD 202, EC 50 after 48 hours), and/or has a LD 50 value (rainbow trout) of at least 80 mg/kg, more preferably at least 100 mg/kg.
  • the surfactant has a HLB value of 5 to 20, more preferably 6 to 19, still more preferably 7 to 18, most preferably 8 to 17 and in particular 9 to 16.
  • the surfactant Preferably, the surfactant
  • the content of the surfactant is within the range of from 0.01 to 20 wt.-%, more preferably 0.05 to 15 wt.-% and most preferably 0.1 to 5.0 wt.-%, based on the total weight of the composition.
  • the composition comprises substantially no proteins, particularly substantially no whey proteins.
  • the composition described above is used for removing and/or preventing deposits from surfaces of water-bearing systems, preferably of machines or parts of machines, preferably for processing cellulosic material.
  • the machines or parts of machines are for the manufacture of pulp, paper, paper board, or cardboard.
  • the water-bearing system is a component of a papermaking plant that is used to accommodate and transfer aqueous fiber suspensions for paper manufacture.
  • the water-bearing system is a circuit system.
  • the composition according to the invention it may be employed continuously or by an interval dosage.
  • the surface is of a component selected from the group consisting of screens, drying screens, felts, filters, membranes, tanks, vessels, towers, pipes, tubes, valves, seals, gaskets, showers, channels, headboxes, frames, scaffolds, pumps, refiners, pulpers, flotation units, rollers, cylinders and wires.
  • compositions to be used according to the present invention are most surprisingly suitable as cleaners or agents having an impregnating action against impurities, such as adhesives, resins, waxes, fats, and/or a bitumen-repellent action at any site of pulp, paper, and cardboard-making machines.
  • impurities such as adhesives, resins, waxes, fats, and/or a bitumen-repellent action at any site of pulp, paper, and cardboard-making machines.
  • compositions may be used according to the invention on the surface of the units, in particular under treatment of the units in the wet section of the machines and/or of the units in the drying section.
  • compositions may be used according to the invention while the machine is running (online) or while the machine is stopped (offline). When the machine is stopped, it is preferred that the residence time of the composition on the surfaces is several seconds to several minutes.
  • the composition may be used in the return movement of the wire, and the wire is optionally inflated with air prior to its contact with the paper web.
  • compositions may be used according to the present invention as such or after dilution with water and/or solvents, preferably water.
  • water having temperatures in the range of 5°C-80°C, preferably 20°C-50°C, is used for this purpose.
  • the composition is used in aqueous dilution in a concentration of 0.001-50 wt.-%, more preferably 0.1-20 wt.-%.
  • the dilute composition may be applied in desired manner, preferably via a spray pipe provided with flat-jet nozzles having an overlapping spray region.
  • the emulsion may be added to the wash water. Owing to the action of the agents to be used according to the present invention tacky impurities lose their adhesiveness and are released from the surface of the units, either automatically or when sprayed with water, and are removed.
  • the water-bearing system is selected from the group consisting of waste water effluents; membrane purification systems; reverse osmosis filtration units; ultrafiltration units; sand filters; steam generating systems; boilers; heat exchangers; evaporative condensers; cooling towers; cooling water systems; closed cooling systems; air washers; devices for heating, ventilating and air conditioning (HVAC); pasteurizers; sterilizers; engines; biodiesel plants; oil separators; medical devices; and devices for processing food.
  • HVAC heating, ventilating and air conditioning
  • the water bearing system as such may be selected from the group specified above, or the water-bearing system may be a component of an apparatus, device, unit or system specified above.
  • the composition according to the invention is used for removing and/or preventing deposits from surfaces of membranes.
  • the membranes are for reversed osmosis, e.g. in kitchens, hospitals, refineries, power plants, food production, semiconductor manufacturing facilities, pharmaceutical manufacturing facilities, manned spacecraft, sailboats, etc.
  • the membranes may also be used in electrodialysis.
  • the membranes are for membrane bioreactors.
  • Reversed osmosis is increasingly the technology of choice for many waste water treatment applications. Reversed osmosis is used to create drinking water from well and seawater. It is used to make high purity water for specialized industrial processes such as pharmaceutical and semiconductor manufacturing. Over the past years, reversed osmosis has also increased its market share in the pretreatment of boiler feedwater.
  • Preferred applications include the treatment of circulating cooling water in power stations in order to reduce water consumption and discharge of contaminated waste water, the treatment of pulp and paper effluents for water recovery and chemical reclamation, the treatment of drainage water from coal mines to achieve zero discharge water and produce drinking water and chemical byproducts, the treatment of uranium conversion effluent to facilitate recovery of uranium and yield satisfactorily safe wastewater, the desalination of agricultural drainage to reduce downstream salinity or river, and the desalination of effluent from biologically treated municipal wastewater prior to recharging into the ground.
  • Suitable membranes are manufactured from, e.g., cellulose acetate, polyamide, and the like. Hollow fine fiber (HFF) membranes and spiral wound (SP) membranes are preferred.
  • the systems may also be coated onto a polysulphone support sheet (thin film composite).
  • Fouling increases with increasing flux rate (the flow of water through the membrane) and with decreasing feed flow (velocity). If left uncorrected, the accumulation of these foulants can cause a severe loss of performance in the system: pressure requirements increase to maintain flow, pressure drops increase, and salt rejection can suffer. If the system is not cleaned and continues to build up foulants, the elements may "telescope", or shear internally; causing the integrity of the membrane surface to be compromised and rendering the membrane irreversibly damaged. Fouling tends to occur in membranes at the feed end of the system, where the flux rate is the highest.
  • Bio fouling can also occur due to the growth of algae or other biological contaminants in the membrane element. Although this type of fouling is caused by contamination rather than flow problems, the resulting blockade of the membrane is the same.
  • the first effect of biofouling on membrane operation is a substantial increase in the electrical costs to operate the unit. If biofouling remains out of control, it can contribute to other combinations of fouling and eventually is responsible for premature membrane replacement.
  • Scaling of the membrane surface occurs due to the precipitation of sparingly soluble salts. As water passes through the membrane, dissolved minerals from the feedwater become concentrated in the reject stream. If the concentration of the minerals in the reject stream exceeds their solubility products, crystals will precipitate onto the membrane. Scaling occurs first in the last elements of a reversed osmosis system because the feedwater is more concentrated near the end of the process. Typical types of scale that may occur on the reversed osmosis system membranes include calcium and magnesium carbonates, calcium and magnesium sulfates, metal oxides, silica as well as strontium and barium sulfates.
  • composition according to the invention may be advantageously used to remove and/or prevent deposits from surfaces of membranes in water-bearing systems, preferably of membranes for reversed osmosis or for membrane bioreactors.
  • the tendency of fouling and scaling can be controlled, whereas hazardous cleansing agents, such as sulfuric acid, may be avoided. Operation efficiency is maintained at high recovery rates.
  • Cleaning of the membrane can be made in place whereby the piping is provided to allow for recirculation of the composition according to the invention, preferably after dilution.
  • valves are manipulated to allow for recirculation of the composition through the membrane until the membrane is cleaned to the point where it can be returned into a reverse osmosis system.
  • a membrane cartridge is removed and placed in a cleaner mode where the composition is recirculated through the membrane in the cartridge until the membrane is sufficiently clean for reuse.
  • the composition is prepared which is capable of removing scale and other foulants from the membrane.
  • the composition according to the invention is preferably used for reducing the number of cleaning cycles of membranes.
  • composition according to the invention may also be used.
  • Membrane bioreactor systems may combine ultra filtration technology with biological treatment for municipal, commercial and industrial wastewater treatment and water reuse applications.
  • the membrane bioreactor (MBR) process is an emerging advanced wastewater treatment technology that has been successfully applied at an ever increasing number of locations around the world.
  • Membrane bioreactor systems preferably incorporate reinforced hollow fiber membranes specifically designed to meet the requirements of wastewater treatment. For details it may be referred to e.g. S. Judd, The MBR Book: Principles and Applications of Membrane Bioreactors for Water and Wastewater Treatment, Elsevier Science, 2006.
  • the composition according to the invention is used for removing and/or preventing deposits from surfaces of sand filters in water-bearing systems.
  • Sand filters may be used for water purification. There are three main types: rapid (gravity) sand filters, upflow sand filters and slow sand filters. All three methods are used extensively in the water industry throughout the world. The first two usually require the use of flocculant chemicals to work effectively whilst slow sand filters can produce very high quality water free from pathogens, taste and odour without the need for chemical aids. Passing flocculated water through a rapid gravity sand filter strains out the floe and the particles trapped within it reducing numbers of bacteria and removing most of the solids. The medium of the filter is sand of varying grades. Where taste and odour may be a problem (organoleptic impacts), the sand filter may include a layer of activated carbon to remove such taste and odour.
  • Sand filters are occasionally used in the treatment of sewage as a final polishing stage. In these filters the sand traps residual suspended material and bacteria and provides a physical matrix for bacterial decomposition of nitrogenous material, including ammonia and nitrates, into nitrogen gas.
  • Sand filters become clogged with floe after a period in use and they are then backwashed or pressure washed to remove the floe. This backwash water is run into settling tanks so that the floe can settle out and it is then disposed of as waste material. The supernatant water is then run back into the treatment process or disposed off as a waste-water stream.
  • the sludge may be used as a soil conditioner. Inadequate filter maintenance has been the cause of occasional drinking water contamination. For further details it can be referred to e.g. D. Purchas, Handbook of Filter Media, Elsevier Science; 1st Ed edition, 1996 and I. M. Marshall Hutten, Handbook of Nonwoven Filter Media, Elsevier Science, 2007.
  • composition according to the invention may be advantageously used for removing and/or preventing deposits from the surface of sand in sand filters, preferably during backwashing.
  • composition according to the invention is used for removing and/or preventing deposits from surfaces of heat exchangers.
  • a heat exchanger is a device built for efficient heat transfer from one fluid to another, whether the fluids are separated by a solid wall so that they never mix, or the fluids are directly contacted.
  • Heat exchangers are widely used in petroleum refineries, chemical plants, petrochemical plants, natural gas processing, refrigeration, power plants, air conditioning and space heating.
  • Typical heat exchangers are shell and tube heat exchangers, plate heat exchangers, regenerative heat exchangers, adiabatic wheel heat exchangers, fluid heat exchangers, dynamic scraped surface heat exchangers, phase-change heat exchangers and HVAC air coils.
  • phase-change heat exchangers are preferred.
  • phase-change heat exchangers can be used either to heat a liquid to evaporate (or boil) it or used as condensers to cool a vapor to condense it back to a liquid.
  • reboilers used to heat incoming feed for distillation towers are often phase- change heat exchangers.
  • Distillation set-ups typically use condensers to condense distillate vapors back into liquid.
  • Power plants which have steam-driven turbines commonly use phase-change heat exchangers to boil water into steam.
  • Phase- change heat exchangers or similar units for producing steam from water are often called boilers.
  • phase-change heat exchangers which pass heat from the primary (reactor plant) system to the secondary (steam plant) system, producing steam from water in the process, are called “steam generators". All power plants, fossil-fueled and nuclear, using large quantities of steam have large condensers to recycle the water back to liquid form for re-use.
  • regenerative phase-change heat exchangers can be used to transfer heat from one stream that needs to be cooled to another stream that needs to be heated, such as distillate cooling and reboiler feed pre-heating.
  • phase-change heat exchanger can also refer to heat exchangers that contain a material within their structure that has a change of phase. This is usually a solid to liquid phase due to the small volume difference between these states. This change of phase effectively acts as a buffer because it occurs at a constant temperature but still allows the heat exchanger to accept additional heat.
  • This has been investigated is for use in high power aircraft electronics.
  • the phase-change heat exchanger is a condenser selected from the group consisting of evaporative cooling systems, evaporative condensers, water- cooled condensers, dry coolers, evaporative coolers, cooling towers, and evaporative industrial fluid coolers.
  • evaporative cooling systems evaporative condensers
  • water- cooled condensers dry coolers
  • evaporative coolers cooling towers
  • evaporative industrial fluid coolers e.g. S. Kakac et al., Heat Exchangers: Selection, Rating and Thermal Design, CRC; 2 edition, 2002; R.K. Shah, Fundamentals of Heat Exchanger Design, Wiley; 1 edition, 2002; J. E. Brumbaugh, Audel HVAC Fundamentals, Air Conditioning, Heat Pumps and Distribution Systems, Audel; 4 Sub edition, 2004; and S. Kakac, Boilers, Evaporators, and Condensers, Wiley- Interscience; 1 edition, 1991.
  • a cooling tower is a device whose main purpose is to cool a fluid, usually water, by direct contact between that fluid and a stream of gas, usually air.
  • an evaporative condenser is a device whose main purpose is to cool a fluid by passing that fluid through a heat exchanger which is itself cooled by contact with another fluid, usually water, passing through a stream of air.
  • composition according to the invention may be advantageously used for removing and/or preventing deposits from the surface of heat exchangers, preferably phase-change heat exchangers, more preferably condensers, most preferably evaporative condensers.
  • composition according to the invention is used for removing and/or preventing deposits from surfaces of steam generating systems or boilers. It has been surprisingly found that the composition according to the invention may be advantageously used for removing and/or preventing deposits from the surface of steam generating systems or boilers.
  • Still another aspect of the invention relates to the use of the composition according to the invention, as described above, for removing and/or preventing deposits from surfaces of rail wagons or vehicle parts.
  • the composition according to the invention may be applied by spraying or rolling.
  • the contact time depends upon the degree of contamination and/or oxidation. Moderate contamination/oxidation usually requires contact times of about 5 to about 30 minutes, heavy contamination/oxidation about 30 to about 90 minutes.
  • the rail wagon is preferably hosed down with water at increased pressure, preferably with hot water (e.g. 60 0 C), and the vehicle parts are preferably rinsed with clean water, respectively.
  • composition according to the invention relates to the composition as described above, i.e. to the composition as such.
  • the composition according to the invention comprises
  • a monocarboxylic acid preferably a hydroxymonocarboxylic acid, more preferably lactic acid, most preferably L-(+) lactic acid
  • a multicarboxylic acid preferably a hydroxymulticarboxylic acid, more preferably citric acid, most preferably citric acid monohydrate
  • a defoaming agent optionally, a corrosion inhibitor
  • a surfactant preferably a non-ionic, cationic or anionic surfactant
  • a still further aspect of the invention relates to a method for removing and/or preventing deposits from surfaces of water-bearing systems, preferably of machines or parts of machines, preferably for processing cellulosic material, comprising the step of treating a surface, preferably a surface of a machine or a part of a machine, with the composition according to the invention.
  • treating shall include contacting, adding, spraying, pouring, bathing, dipping, coating, and the like. Treating may also include mechanical action, such as rubbing, brushing, wire brushing, shot blasting, and the like.
  • the duration of the treatment depends on the individual circumstances. Depending on the kind of deposit, exposure times may vary from a few seconds to several minutes or even hours. Suitable conditions may be revealed by routine experimentation.
  • compositions were prepared:
  • Drying screens that had been used in a paper plant were cut into pieces of 5x10 cm and dried in an oven for 30 min at 75°C. Thereafter, the drying sieves were dipped into aqueous solutions of the composition of example 3 in different concentrations: 1 %, 3%, 5% and 10%. By means of a magnetic stirrer, the probes were stirred for 30 min at 60 0 C. Finally, the sieves were washed for 30 seconds with distilled water at a pressure of 1 bar and then dried in an oven at 75°C.
  • Compositions 1 to 3 exhibit excellent biodegradability.

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Abstract

La présente invention concerne l'utilisation d'une composition comprenant (i) de l'acide ascorbique, (ii) un acide monocarboxylique, (iii) un acide multicarboxylique et (iv) un agent antimousse pour éliminer les dépôts et/ou empêcher les dépôts sur des surfaces de systèmes de type milieu aqueux, de préférence des machines ou des parties de machines, utilisées de préférence pour traiter de la matière cellulosique.
PCT/EP2008/002601 2007-04-05 2008-04-02 Agent nettoyant biodégradable WO2008122388A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP07007254 2007-04-05
EP07007254.1 2007-04-05
EP07012419A EP2008976A1 (fr) 2007-06-25 2007-06-25 Agent de nettoyage biodégradable
EP07012419.3 2007-06-25

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017189703A1 (fr) 2016-04-27 2017-11-02 Dow Corning Corporation Composition détergente comprenant un trisiloxane à fonction carbinol

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4199469A (en) * 1978-06-21 1980-04-22 Feldmann Chemie Composition and method for cleaning drinking water tanks
US4895658A (en) * 1987-06-15 1990-01-23 The B. F. Goodrich Company Membrane cleaning compositions containing acrylic polymer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4199469A (en) * 1978-06-21 1980-04-22 Feldmann Chemie Composition and method for cleaning drinking water tanks
US4895658A (en) * 1987-06-15 1990-01-23 The B. F. Goodrich Company Membrane cleaning compositions containing acrylic polymer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017189703A1 (fr) 2016-04-27 2017-11-02 Dow Corning Corporation Composition détergente comprenant un trisiloxane à fonction carbinol
US10829718B2 (en) 2016-04-27 2020-11-10 Dow Silicones Corporation Detergent composition comprising a carbinol functional trisiloxane

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