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WO2015077737A1 - Concentré de nettoyage destiné à éliminer le tartre d'une surface d'un système - Google Patents

Concentré de nettoyage destiné à éliminer le tartre d'une surface d'un système Download PDF

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Publication number
WO2015077737A1
WO2015077737A1 PCT/US2014/067202 US2014067202W WO2015077737A1 WO 2015077737 A1 WO2015077737 A1 WO 2015077737A1 US 2014067202 W US2014067202 W US 2014067202W WO 2015077737 A1 WO2015077737 A1 WO 2015077737A1
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WIPO (PCT)
Prior art keywords
cleaning
surfactant
cleaning concentrate
set forth
alternatively
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PCT/US2014/067202
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English (en)
Inventor
Nancy Almasarweh
Ashish Taneja
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids
    • 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
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates

Definitions

  • the present disclosure generally relates to a cleaning concentrate for removing scale from a surface of a system.
  • proteins, fats, lactose, calcium and magnesium phosphates, and various vitamins and minerals form scale.
  • proteins, fats, lactose, calcium and magnesium phosphates, and various vitamins and minerals react to form milk stone, a particular type of scale, especially when the milk is heated in milk manufacturing and packaging processes.
  • Acid cleaning is a conventional process for removing scale from surfaces in systems in an effort to maintain the efficiency of system and avoid operational problems. Because these systems include parts (e.g. piping, filters, and heat exchangers) having surfaces formed from various materials (e.g. metals, polymers, and ceramics), the cleaning composition must be strong enough to remove the scale quickly without mechanical scrubbing, and also compatible with the surfaces in the system to prevent the surfaces from being damaged by the acid during the acid cleaning process. To this end, acid cleaning processes typically require the use of cleaning compositions at higher temperatures (e.g. greater than 60°C) to efficiently remove scale.
  • higher temperatures e.g. greater than 60°C
  • the present disclosure provides a cleaning concentrate for removing scale from a surface of a system.
  • the cleaning concentrate for removing scale from a surface of a system comprises an acidic component comprising an alkanesulfonic acid, a first surfactant comprising a C 6 through C 2 o alcohol alkoxylate having an HLB value of greater than 8, and a second surfactant, different than said first surfactant, having an HLB value of less than 11.
  • the first and second surfactants are present in the cleaning concentrate in a weight ratio of from 10: 1 to 0.5:1.
  • the acidic component and a sum of the first and second surfactants are present in the cleaning concentrate in a weight ratio of from 30:1 to 1:1.
  • the acid component, the first surfactant, and the second surfactant are collectively present in the cleaning concentrate in an amount of at least 25 parts by weight based on 100 parts by weight of the cleaning concentrate.
  • the present disclosure also provides a method of removing scale from a surface of a system.
  • the method includes the steps of providing the cleaning concentrate, diluting the cleaning concentrate with water to form the cleaning composition, and contacting the surface of the system with the cleaning composition.
  • the cleaning concentrate has excellent scale removal properties and is ecologically friendly.
  • the cleaning concentrate is also easier to handle and use relative to other conventional cleaning compositions.
  • the method provides for excellent removal of the scale from the system, particularly at lower temperatures, with minimal foaming.
  • the present disclosure provides a cleaning concentrate for removing scale from a surface of a system.
  • the cleaning concentrate can be used as is or diluted to form a cleaning composition.
  • the cleaning concentrate is at least useful for removing (e.g. dissolving) scale on the surface of the system, and can also be useful for inhibiting the re-deposition of scale on the surface of the system, if such a problem arises.
  • the scale may also be referred to in the art as foul/fouling.
  • the cleaning concentrate is especially useful to replace conventional acid washing solutions, e.g. nitric acid washing solutions, as described further below. Further, use of the cleaning concentrate as an additive in aqueous systems for dissolving and/or inhibiting deposition of scale on the surface of the system is also contemplated herein.
  • the surface of the system is typically formed of a metal or an alloy thereof, such as iron, steel, aluminum, chromium, copper, etc., or a combination thereof. More specific examples of alloys include, but are not limited to, mild steel, stainless steel, and galvanized steel.
  • the cleaning concentrate is especially useful for such surfaces.
  • the surface can be formed from other materials as well, such as a composite, a plastic, a ceramic, etc.
  • the surface may comprise a polymeric material, such as polyvinyl chloride (PVC).
  • PVC polyvinyl chloride
  • the surface may also comprise a combination of different materials, such as an alloy and a plastic.
  • the surface may be an inner or an outer surface of the system.
  • inner surfaces include those found in pipelines, filters, heat exchanges, boilers, in chemical plants, food and beverage plants, or the like.
  • outer surfaces include those found on evaporators, conveyors, in manufacturing plants, in households, or the like.
  • the system is one in which the build up of scale is problematic.
  • the system can be of various types, such as being a heat transfer system, a filtration system, an evaporation system, a food and beverage system, etc.
  • the cleaning concentrate has been found to be useful for food and beverage systems, in particular for milk systems and the removal of scale comprising milk stone.
  • any system where scale concerns arise can be benefitted with use of the cleaning concentrate.
  • Further examples of surfaces/systems include, but are not limited to, turbines, ship hulls, solar panels, reverse osmosis membranes, heating elements, reactors, petroleum reservoirs, water wells, geo thermal wells, and oil wells.
  • the system can be in an industrial, commercial, or residential setting.
  • the scale can be made up of various components, depending on the type of surface/system.
  • a heat transfer system may include scale typically encountered with use of hard water
  • an evaporation system may include scale stemming from concentrating the product, e.g. phosphoric acid.
  • scale include crystals or amorphous forms of solid salts, oxides, and hydroxides from water solutions (e.g. calcium carbonate and calcium sulfate), corrosion/rust, beer stone, milk stone, vegetable stone, phosphates, lime, silicates, etc.
  • the cleaning concentrate is most useful for scales which are considered in the art to be basic. The cleaning concentrate has been found to be especially useful for scale formed from milk, such as milk stone.
  • the cleaning concentrate includes an acidic component comprising an alkanesulfonic acid.
  • the acidic component further comprises water.
  • the acidic component can comprise one or more alkanesulfonic acids.
  • the acidic component may be the alkanesulfonic acid itself or may include one or more additional components, such as water, other acids, etc. If the acidic component includes water, the alkanesulfonic acid can be provided in various concentrations. The acidic component is useful for dissolution of the scale.
  • the alkanesulfonic acid can be a short chain alkanesulfonic acid, such as one containing from 1 to 4 carbon atoms (e.g. one having propyl, ethyl, or methyl moieties).
  • the alkanesulfonic acid is methanesulfonic acid (MSA).
  • MSA is a strong organic acid that is believed to be completely non-oxidizing and thermally stable that forms highly soluble salts. Further, MSA is a biodegradable strong acid, which is not necessarily the case with other acids used to clean scale. The salt solubility of MSA makes the cleaning concentrate especially useful for replacing conventional acid cleaners.
  • MSA has a low vapor pressure, has no odor, and is biodegradable.
  • the cleaning concentrate and cleaning compositions formed therefrom are easy to handle and use and environmentally friendly, especially in comparison to cleaning compositions comprising strong acids known in the art such as sulfuric acid, nitric acid, and hydrochloric acid.
  • the acidic component can comprise the alkanesulfonic acid (e.g. MSA) and one or more additional acids.
  • the acidic component comprises the alkanesulfonic acid (e.g. MSA) and one or more additional acids selected from hydrochloric acid, nitric, sulfuric acid, phosphoric acid, formic acid, and combinations thereof.
  • the acidic component comprises MSA, phosphoric acid, and water.
  • the acidic component comprises MSA, formic acid, and water.
  • the cleaning concentrate is substantially free to completely free of phosphoric acid. In another embodiment, the cleaning concentrate is substantially free to completely free of nitric acid. In yet another embodiment, cleaning concentrate is substantially free to completely free of sulfuric acid. These embodiments are effective in quickly removing scale, provide improved ease of handling, and are environmentally friendly. However, in some embodiments, the acidic component can also comprise MSA and one of, or any combination of, these acids.
  • substantially free refers to a sufficiently low amount of these acids.
  • the amount of these acids is less than 5, alternatively less than 4, alternatively less than 3, alternatively less than 2, alternatively less than 1, alternatively less than 0.5, and alternatively less than 0.3, parts by weight based on 100 parts by weight of the cleaning concentrate.
  • the cleaning concentrate is completely free of these acids.
  • the acidic component consists essentially of MSA and water. In another embodiment, the acidic component consists essentially of MSA, phosphoric acid, and water. In yet another embodiment, the acidic component consists essentially of MSA, formic acid, and water.
  • the acidic component is aqueous.
  • the acidic component consists essentially of MSA and water.
  • the alkanesulfonic acid e.g. MSA
  • the alkanesulfonic acid is typically present in an amount of from 35 to 95, alternatively from 50 to 85, alternatively from 65 to 85, alternatively about 70, alternatively greater than 99 parts by weight, each based on 100 parts by weight of the acidic component.
  • more than one alkanesulfonic acid may be included in the acidic component, in which case the total amount of all the alkanesulfonic acid included is typically within the above ranges.
  • Non-limiting examples of suitable alkanesulfonic acids are commercially available from BASF Corporation of Florham Park, NJ, under the trade name LUTROPUR ® , such as LUTROPUR ® M, LUTROPUR ® MSA, and LUTROPUR ® MSA 100.
  • the MSA is one which is formed by an air oxidation process, rather than from a chlorooxidation process. As such, the MSA has less metal content, such as less than 1 mg/kg, and little to no chloro compounds, which are generally corrosive.
  • suitable alkanesulfonic acids are described in U.S. Pat. No.
  • the cleaning concentrate typically includes the acidic component in an amount of greater than 10 parts by weight, alternatively from 10 to 80, alternatively from 12 to 60, alternatively from 15 to 55, parts by weight based on 100 parts by weight of the cleaning concentrate.
  • the amount of acidic component may vary outside of the ranges above, but is typically both whole and fractional values within these ranges. Further, it is to be appreciated that more than one alkanesulfonic acid and one or more additional acids may be included in the acidic component, in which case the total amount of all the acids included is typically within the above ranges. Of course, when the acidic component is concentrated or, alternatively, diluted, the ranges above may vary.
  • the cleaning concentrate also includes a first surfactant comprising a C 6 through C 2 o alcohol alkoxylate having a hydrophilic-lipophilic balance value ("HLB value") value of greater than 10.
  • the first surfactant is useful for aiding in removal and dissolution of the scale. When used with the acidic component, it is believed that the first surfactant has a synergistic effect on the removal and dissolution of the scale, especially at lower temperatures, as is described in greater detail below.
  • the first surfactant typically comprises the reaction product of a base molecule and an alkylene oxide, in a chemical reaction also known as alkoxylation.
  • Alkoxylation enables control of HLB value, number average molecular weight ("M n "), and various other properties of the resulting surfactant. That is, the type and amount of alkylene oxide used for alkoxylating the base molecule may be varied to achieve certain properties, such as calculated HLB value and M n .
  • the alkylene oxide is typically selected from the group of ethylene oxide (“EO”), propylene oxide (“PO”), butylene oxide (“BO”), and combinations thereof.
  • EO ethylene oxide
  • PO propylene oxide
  • BO butylene oxide
  • the type and amount of alkylene oxide used for alkoxylating the base molecule is varied to form the first surfactant as set forth herein, having HLB values, M n , and other properties in the ranges disclosed.
  • HLB numbers are calculated using various formulas which involve the weight fraction of the hydrophilic part or any values proportional to this fraction, e.g. the saponification number.
  • V is the saponification number or coefficient of the compound (the quantity of the potassium hydroxide, in mg, required for the neutraliza ion of free acids and the saponification of ethers, per 1 g of fat)
  • S is the acid number (the quantity of potassium hydroxide, in mg, required for the neutralization of free acids, per 1 g of fat).
  • E the weight fraction of EO (in percent)
  • P the weight fraction of alcohol groups (glycerine, sorbite, etc).
  • HLB values through the subject disclosure are generally calculated with the following equation:
  • HLB value (Molecular weight of EO / Total Molecular Weight)*20.
  • calculated HLB value is essentially a proxy for the ratio of hydrophilic EO groups to more hydrophobic PO and/or BO groups in the reactive surfactant.
  • the first surfactant has an HLB value of greater than 8, alternatively equal to or greater than 10, alternatively equal to or greater than 10.3, alternatively greater than 10.5, alternatively greater than 11.0, alternatively greater than 11.5, alternatively greater than 12.0, alternatively greater than 12.5, alternatively greater than 13.0, alternatively greater than 14.0, alternatively greater than 15.0.
  • the first surfactant has an HLB value of from 8 to 15. In other embodiments, the first surfactant has an HLB value of between 10 and 12.
  • the first surfactant described herein when used in combination with the second surfactant described below, with an HLB value within the ranges set forth herein, provides excellent results with respect to the removal of scale from surfaces in a system, especially at lower temperatures (as is explained in detail further below.)
  • the first surfactant typically comprises a C 6 through C 2 o, alternatively a C 6 through Ci 8 , alternatively a C 6 through C 15i alternatively a C 10 through C 15 , alternatively a C 12 through C 15 alcohol alkoxylate having a M n of from 200 to 2,000, alternatively from 250 to 1 ,800, alternatively from 300 to 900, g/mol.
  • the first surfactant typically has a pH (5% aqueous) of from 4 to 8, alternatively from 5.5 to 7.5, alternatively from 6.0 to 7.5.
  • the pH is typically determined with a pH meter.
  • the beaker is placed on a magnetic stirrer and pH electrodes of the pH meter are inserted into the beaker.
  • the pH on the pH meter is read and adjusted to 7.0 +/- 0.1 by adding 0.01N KOH or 0.01N HC1.
  • the pH of the solution is allowed to reach a steady state (it typically takes about 1 minute) and the pH on the pH meter is recorded.
  • the first surfactant has the following formula:
  • R is selected from the group of linear carbon chains, branched carbon chains, aromatic rings, and combinations thereof
  • AO is an alkyleneoxy group selected from the group of EO groups, PO groups, BO groups, and combinations thereof, and n is from to 1 to 50.
  • the first surfactant is a C 12 -C 15 alcohol ethoxylate.
  • the first surfactant is a linear C 12 - Ci5 alcohol ethoxylate having a molecular weight of about 462, a specific gravity of 0.975 g/c m3 , and a pH (1% aqueous solution ) from 5.5 to 7.5.
  • the first surfactant is a C 10 through C 15 alcohol alkoxylate, i.e., R is a C 10 through C 15 carbon chain.
  • the C 12 through Ci5 alcohol alkoxylate is a C 12 through C 15 alcohol ethoxylate.
  • the alcohol alkoxylate is a tridecyl alcohol alkoxylate.
  • the alcohol alkoxylate is a tridecyl alcohol ethoxylate.
  • the alcohol alkoxylate typically has the following formula:
  • n is from 4 to 10.
  • n is 6.
  • the tridecyl alcohol ethoxylate has a M n of about 505, a specific gravity of about 0.98 g/cm 3 , a pH (5% aqueous solution) of from 6.0 to 7.5, and is dispersible in water at 25°C.
  • n is 10.
  • n is 10.
  • the tridecyl alcohol ethoxylate has a number average molecular weight (M n ) of about 640, a specific gravity of about 1.03 g/cm 3 , a pH (5% aqueous solution) of from 6.0 to 7.5, and is greater than 10% dispersible in water at 25°C.
  • the first surfactant comprises an alcohol alkoxylate formed from a C 15 oxoalcohol.
  • the first surfactant has an HLB value of about 11.6, an M n of about 840, a specific gravity of about 1.01 g/cm 3 , a pH (5% aqueous solution) of about 7, and a cloud point of about 42°C when tested in accordance with EN 1890 Method A.
  • the first surfactant comprises an alcohol alkoxylate formed from a C 6 through C 10 alcohol.
  • the first surfactant has an HLB value of about 10.3, an M n of about 655, a specific gravity of about 1.01 g/cm 3 , a pH (5% aqueous solution) of about 7, and a cloud point of about 62°C when tested in accordance with EN 1890 Method A.
  • the cleaning concentrate typically includes the first surfactant in an amount of less than 20 parts by weight, alternatively from 0.5 to 15, alternatively from 1 to 13, alternatively from 2 to 12, parts by weight based on 100 parts by weight of the cleaning concentrate.
  • the amount of first surfactant may vary outside of the ranges above, but is typically both whole and fractional values within these ranges.
  • the cleaning concentrate also includes a second surfactant having an HLB value of less than 10.
  • the first surfactant is useful for aiding in dissolution of the scale. When used in combination with the first surfactant, it is believed that the first surfactant has a synergistic effect on the dissolution of the scale, and also reduces the foaming of the cleaning concentrate during use.
  • the second surfactant typically comprises the reaction product of a base molecule and an alkylene oxide, in a chemical reaction also known as alkoxylation.
  • alkoxylation enables control of HLB value, M n , and various other properties of the second surfactant.
  • the type and amount of alkylene oxide used for alkoxylating the base molecule is varied to form the second surfactant set forth herein, having HLB values, M n , and other properties within the ranges disclosed.
  • the second surfactant has an HLB value of less than 11 , alternatively less than 10, alternatively less than 9, alternatively equal to or less than 8, alternatively less than 7, alternatively less than 6, alternatively less than 5, alternatively less than 4, alternatively less than . In some embodiments, the second surfactant has an HLB value of from 0 to 9.5. In other embodiments, the second surfactant has an HLB value of about 0.
  • the second surfactant described herein with an HLB value within the ranges set forth herein, when used in combination with the first surfactant, provides excellent results with respect to the removal of scale from surfaces in the system, especially at lower temperatures (as is explained in detail further below) and also reduces the amount of foaming which occurs with use of the cleaning concentrate.
  • the second surfactant typically comprises a C 6 through C 2 o, alternatively a C 6 through Cis , alternatively a Cs through C15, alternatively a C1 0 through C15, alternatively a C9 through C1 3 , alternatively a C12 through C15 alcohol alkoxylate having a M n of from 200 to 2,500, alternatively from 350 to 2,000, alternatively from 450 to 1,800, g/mol.
  • the first surfactant typically has a pH (5% aqueous) of from 4 to 10, alternatively from 5.5 to 7.5, alternatively from 6.0 to 7.5, alternatively from 9 to 10.
  • the second surfactant comprises a C 6 through C1 3 alcohol propoxylate.
  • the second surfactant comprises an alcohol propoxylate formed from 2-propanolheptanol having an HLB value of about 6.4, an M n of about 1672, a specific gravity of about 1 g/cm 3 , a pH (5% aqueous solution) of from 6 to 7, and a cloud point of from 16 to 21 °C when tested in accordance with EN 1890 Method A.
  • the second surfactant comprises an alcohol propoxylate formed from a C9-C11 oxoalcohol, and has an HLB value of about 0, an M n of about 750, a specific gravity of about 0.96 g/cm 3 .
  • the second surfactant is liner alcohol alkoxylate having an HLB value of about 9, an M n of about 780, a specific gravity of about 1.01 g/cm 3 , a pH (5% aqueous solution) of about 7, and a cloud point of about 38°C when tested in accordance with EN 1890 Method A.
  • the cleaning concentrate typically includes the second surfactant in an amount of less than 15, alternatively from 0.1 to 10, alternatively from 0.25 to 8, parts by weight based on 100 parts by weight of the cleaning concentrate.
  • the amount of second surfactant may vary outside of the ranges above, but is typically both whole and fractional values within these ranges.
  • the first surfactant and the second surfactant are present in the cleaning concentrate in a weight ratio of from 20: 1 to 0.1 : 1 , alternatively from 15: 1 to 0.5:1, alternatively from 10: 1 to 0.5: 1, alternatively from 8: 1 to 1 : 1. This ratio is based on the total weight of the surfactants excluding water.
  • the cleaning concentrate comprises the surfactant in the weight ratios set forth, and a dilution of the cleaning concentrate (a cleaning composition) also comprises the first and second surfactants in the weight ratios set forth.
  • the acidic component and a sum of the first and second surfactants are present in the cleaning concentrate in a weight ratio of from 30: 1 to 1 : 1, alternatively from 20: 1 to 1 : 1. This ratio is based on the total weight acid(s) in the acidic component and the total weight of the surfactants excluding water.
  • the cleaning concentrate comprises the components in the weight ratios set forth, and a dilution of the cleaning concentrate (a cleaning composition) also comprises the components in t in the weight ratios set forth.
  • the weight ratios may also be referred to in the art as weight ratios of percent actives.
  • the acidic component, the first surfactant, and the second surfactant are typically collectively present in the cleaning concentrate in an amount of at least 25, alternatively at least 30, alternatively at least 35, alternatively at least 40, alternatively at least 45, alternatively at least 50, alternatively at least 55, parts by weight based on 100 parts by weight of the cleaning concentrate.
  • the collective amount of the acidic component, the first surfactant, and the second surfactant may vary outside of the ranges above, but is typically both whole and fractional values within these ranges.
  • the cleaning concentrate typically includes water. That is, in certain embodiments, the cleaning concentrate further includes water such that the alkanesulfonic acid and the alcohol alkoxylate are diluted, i.e., such that the cleaning concentrate is aqueous.
  • the water can be of various types. In certain embodiments, the water is de-mineralized and/or de-ionized.
  • the water is present in the cleaning concentrate in various amounts, as is set forth below, depending on the embodiment.
  • the water can be added to the cleaning concentrate as a separate component. However, it is to be appreciated that some of the water can also be imparted by one or more of the components of the cleaning concentrate, such as by the acidic component, when aqueous.
  • the cleaning concentrate typically includes water in an amount of less than 80 parts by weight, alternatively from 1 to 69, alternatively from 1 to 60, alternatively from 1 to 55, alternatively from 1 to 40, alternatively from 1 to 30, parts by weight based on 100 parts by weight of the cleaning concentrate.
  • the amount of water may vary outside of the ranges above, but is typically both whole and fractional values within these ranges.
  • the cleaning concentrate can also include additives/conventional components such as, colorants, thickeners, corrosion inhibitors, and wetting agents and surfactants, which are different than the first and second surfactants described above.
  • the wetting agent may be the surfactant or may include one or more additional components, such as water. If the wetting agent includes water, the surfactant can be provided in various concentrations.
  • the surfactant of the wetting agent is selected from the group of nonionic surfactants, amphoteric surfactants, or combinations thereof.
  • the wetting agent includes a nonionic surfactant.
  • the wetting agent includes an amphoteric surfactant.
  • the wetting agent includes an anionic surfactant.
  • the wetting agent includes a cationic surfactant.
  • the wetting agent includes a combination of two or more of the aforementioned surfactants.
  • the cleaning concentrate consists essentially of MSA, the first surfactant, the second surfactant, and water. In another embodiment, the cleaning concentrate consists essentially of MSA, phosphoric acid, the first surfactant, the second surfactant, and water. In yet another embodiment, the cleaning concentrate consists essentially of MSA, formic acid, the first surfactant, the second surfactant, and water. In further embodiments, the cleaning concentrate is substantially free to completely free of other additives/conventional components, such as surfactants, defoamers, and corrosion inhibitors. The cleaning concentrate generally has excellent dissolution and/or inhibition properties without requiring supplemental components.
  • the cleaning concentrate typically has a pH of from 0 to 6, alternatively from 0 to 4, alternatively from 0 to 4, alternatively from 0 to 3, alternatively from 0.1 to 2.5.
  • the pH of the cleaning concentrate is imparted by the type and amount of components employed to form the cleaning concentrate. When the cleaning concentrate is diluted with water to form the cleaning composition, the pH will generally increase.
  • the present disclosure also provides a method of removing scale from the surface of the system.
  • the method includes the steps of: providing the cleaning concentrate forth, described, and exemplified above; diluting the cleaning concentrate with water to form a cleaning composition; and contacting the surface of the system with the cleaning composition.
  • the method includes the step of providing the cleaning concentrate.
  • the cleaning concentrate can be provided in 1 part, e.g. all of the components are provided as a mixture in a single container.
  • the cleaning concentrate can be provided in 2 or more parts, e.g. the acidic component can be provided in first container, and the first and second surfactants in a second container, or the acidic component, the first surfactant, and the second surfactant can be provided in three different containers.
  • the method also includes the step of diluting the cleaning concentrate with water to form a cleaning composition.
  • the various weight ratios between the acidic component, the first surfactant, and the second surfactant remain the same within the cleaning concentrate and the cleaning composition which is formed therefrom.
  • the cleaning composition which includes the components in the ratios set forth above, is also provided in the present disclosure.
  • the step of diluting typically includes adding hard water to the cleaning concentrate.
  • the DI water can be added.
  • the cleaning composition typically includes water in an amount of greater than 90, alternatively greater than 95, alternatively greater than 98, alternatively greater than 99, alternatively greater than 99.5, parts by weight based on 100 parts by weight of the cleaning composition.
  • the amount of water may vary outside of the ranges above, but is typically both whole and fractional values within these ranges.
  • the cleaning composition typically includes the acidic component in an amount of from 0.05 to 0.5, alternatively from 0.08 to 0.4, alternatively from 0.1 to 0.35, parts by weight based on 100 parts by weight of the cleaning composition.
  • the amount of the acidic component may vary outside of the ranges above, but is typically both whole and fractional values within these ranges.
  • the cleaning composition typically includes the first surfactant in an amount of from 0.001 to 0.50, alternatively from 0.005 to 0.40, parts by weight based on 100 parts by weight of the cleaning composition.
  • the amount of the first surfactant may vary outside of the ranges above, but is typically both whole and fractional values within these ranges.
  • the cleaning composition typically includes the second surfactant in an amount of from 0.001 to 0.50, alternatively from 0.005 to 0.40, parts by weight based on 100 parts by weight of the cleaning composition.
  • the amount of the second surfactant may vary outside of the ranges above, but is typically both whole and fractional values within these ranges.
  • the method includes the step of contacting the surface of the system with the cleaning concentrate (as is, or diluted in a cleaning composition).
  • the cleaning concentrate can be brought into contact with the surface by various methods, such as by applying the cleaning concentrate to the surface, e.g. by dipping the surface in the cleaning concentrate, spraying the cleaning concentrate on the surface, rolling the cleaning concentrate on the surface, etc.
  • Various application apparatuses understood in the art can be employed, such as a spraying apparatus, a dip tank, etc. It is efficient to apply the cleaning concentrate to the surface such that it is directed primarily toward the scale rather than on surface that lacks scale.
  • the cleaning concentrate can also be flowed or circulated onto and/or past the surface, such as in a pipeline. That is, in various embodiments the step of bringing the surface of the system into contact with the cleaning composition is further defined as circulating the cleaning composition in the system.
  • the surface does not need to be pretreated, such as being mechanically cleaned by scrapping, scrubbing, etc., prior to bringing the cleaning concentrate into contact with the surface.
  • pretreatment steps may be employed to expedite removal of the scale from the surface of the system.
  • the surface is an internal surface, such as those found in pipelines
  • the scale can be removed by filling the system with the cleaning composition (i.e., soaking), and optionally, circulating the cleaning concentrate in the system, e.g. by pumping.
  • the surface can also be prewashed, such as with water, in order to remove other residues prior to bringing the cleaning concentrate into contact with the scale/surface.
  • the method may further include the step of applying heat to the cleaning composition and/or the system.
  • the step may be useful for expediting dissolution of the scale from the surface of the system.
  • the cleaning composition may also be brought into contact with the scale at room temperature.
  • increasing temperature of the cleaning composition either directly or indirectly, will accelerate the rate at which the scale is dissolved by the cleaning composition once contacted.
  • Heating can be accomplished by various means understood in the art.
  • the cleaning composition can be heated in the system by heating means already present in the system.
  • a separate heat exchanger can be used to heat the cleaning composition.
  • the cleaning concentrate and the cleaning composition formed therefrom are not only formed with environmentally friendly components such as the acidic component and the alcohol alkoxylate, but are formulated for use at lower temperatures, which reduces the energy required to clean the system.
  • the step of bringing the surface of the system into contact with the cleaning composition is conducted at a temperature of less than 60, alternatively less than 59, alternatively less than 55, alternatively from 10 to 65, alternatively from 20 to 59, alternatively from 20 to 57, alternatively from 20 to 55, °C. That is, the cleaning concentrate/composition has a temperature as set forth above during the step of bringing the surface of the system into contact with the cleaning composition.
  • the method includes the step of circulating the cleaning concentrate (or the cleaning composition) in the system.
  • the cleaning concentrate (or the cleaning composition) is typically circulated at a temperature of less than 60, alternatively less than 59, alternatively less than 55, alternatively from 10 to 65, alternatively from 20 to 59, alternatively from 20 to 57, alternatively from 20 to 55, °C.
  • the step of circulation the cleaning concentrate of the cleaning concentration is conducted in less than 60, alternatively less than 25, alternatively less than 25, alternatively less than 20, alternatively less than 15, alternatively less than 10, minutes.
  • the cleaning composition should be allowed to contact the scale for a least a period of time.
  • the cleaning composition can be kept in contact for a period of time of from less than 60, alternatively less than 30, alternatively less than 25, alternatively less than 20, alternatively less than 15, alternatively less than 10, minutes.
  • the cleaning concentrate and the cleaning composition formed therefrom clean (i.e., dissolve, remove, and prevent scale) quickly. That is, the cleaning concentrate and the cleaning composition formed therefrom are formulated to work quickly to minimize system downtime.
  • the scale is removed from surface of the system.
  • the longer the cleaning composition is in contact with the surface the greater the amount of scale removed from the surface.
  • Removal can be increased via agitation of the cleaning composition when in contact with the surface, such that the cleaning composition also physically removes the scale (e.g. by shear) in addition to chemically removing the scale. Agitation can be accomplished via the circulation as described above or by other means understood in the art.
  • Cleaning Concentrates 1-15 which are set forth in Table 1, are formed in accordance with the cleaning concentrates of the subject disclosure. Cleaning Concentrates 1-15 are diluted with hard water at a ratio of 1:190 to form Cleaning Compositions 1-15 which are tested for cleaning efficiency in accordance with the method of removing scale from a surface of a system of the subject disclosure.
  • the cleaning concentrate can be defined as a "higher active content" cleaning concentrate.
  • a higher active content cleaning concentrate can be defined as including greater than 30, alternatively from 30 to 60, alternatively from 30 to 70, alternatively from 30 to 50, alternatively from 35 to 45, % by weight of the acidic component.
  • a higher active content cleaning concentrate can be defined as including greater than 40, alternatively greater than 45, alternatively greater than 50, alternatively from 45 to 75, alternatively from 45 to 65, alternatively from 45 to 55, % by weight total actives (total actives includes the active amounts of the acidic component, and the first and second surfactants).
  • the higher active content cleaning concentrate comprises the acidic component comprising a solution of aqueous MSA, a first surfactant having an HLB value of from 10 to 12, alternatively from 11 to 14, and a second surfactant having an HLB value from 0 to 7, alternatively from 6 to 7.
  • the cleaning concentrates of these embodiments are diluted with water at a weight ratio of from 1:150 to 1:250, alternatively from 1: 175 to 1:225 (cleaning concentrate: water)
  • the cleaning compositions generate less foam than cleaning compositions which do not include both of the first and second surfactants described above.
  • a non-limiting example of a higher active content cleaning concentrate is Cleaning Concentrate 1 set forth in the Examples below.
  • the cleaning concentrate can be defined as a "lower active content” cleaning concentrate.
  • a lower active content cleaning concentrate can be defined as including less than 40, alternatively from 20 to 40, alternatively from 25 to 45, % by weight of the acidic component.
  • a lower active content cleaning concentrate can be defined as including greater than 45, alternatively from 45 to 75, alternatively from 45 to 65, alternatively from 45 to 55, % by weight total actives (total actives includes the active amounts of the acidic component, and the first and second surfactants).
  • the lower active content cleaning concentrate comprises the acidic component comprising a solution of aqueous MSA and phosphoric acid in a ratio by weight of from 2: 1 to 1 :2 and, a first surfactant having an HLB value of from 10 to 12, alternatively from 11 to 14, and a second surfactant having an HLB value from 0 to 7, alternatively from 6 to 7.
  • cleaning concentrates of these embodiments When the cleaning concentrates of these embodiments are diluted with water at a weight ratio of from 1 : 150 to 1 :250, alternatively from 1 : 175 to 1 :225 (cleaning concentrate: water), they exhibit cleaning efficiencies of greater than 90, alternatively greater than 91, alternatively greater than 92, alternatively greater than 93, % at 45 °C when tested in accordance with the cleaning efficiency procedure described in the examples below. Further, in these embodiments, the cleaning compositions generate less foam than cleaning compositions which do not include both of the first and second surfactants described above.
  • a non-limiting example of a lower active content cleaning concentrate is Cleaning Concentrate 15 set forth in the Examples below.
  • the cleaning efficiency of Cleaning Compositions 1-15 is set forth in Table 1.
  • clean stainless steel panels are weighed to determine Wi.
  • the stainless steel panels are aged in milk, and milk stone forms on the surface thereof.
  • the stainless steel panels having the milk stone thereon are dried and weighed to determine W 2 .
  • the stainless steel panels having the milk stone thereon are immersed in the respective compositions for 8 minutes at 350 ppm hardness at 45°C. Once immersion is complete, the panels are rinsed, dried, and weighed, to determine W 3 .
  • the percent cleaning value is ((Wi-W2)/(W 2 -W 3 ))*100.
  • Each data point in Table 1 represents an average of 3-6 test results.
  • Acidic Component A is a 40% by weight active solution of aqueous MSA.
  • Acidic Component B is a 9.3% by weight active MSA and 9.3% by weight active phosphoric acid aqueous solution.
  • Acidic Component C is a 20% by weight active MSA and 19% by weight active formic acid aqueous solution.
  • First Surfactant 1A comprises an alcohol alkoxylate formed from a C 15 oxoalcohol having an HLB value of about 11.6.
  • First Surfactant IB comprises an alcohol alkoxylate formed from a C 6 through do alcohol having an HLB value of about 10.3.
  • First Surfactant 1C comprises an alcohol alkoxylate formed from a C 6 through do alcohol having an HLB value of about 8.0.
  • Second Surfactant 2 A comprises a C 6 through C 13 alcohol propoxylate and has an HLB value of about 6.4.
  • Second Surfactant 2B comprises a polypropoxylate, and has an HLB value of about 0.
  • Second Surfactant 2C comprises a liner alcohol alkoxylate having an HLB value of about 9.0.
  • Second Surfactant 2D comprises a linear alcohol alkoxylate having an HLB value of about 10.7.
  • cleaning efficiency of Cleaning Composition 1 is very effective, even at 23 °C.
  • cleaning composition 1 with MSA and the alcohol alkoxylate outperforms comparative composition 3, which includes the same active concentration of phosphoric acid (as opposed to MSA).
  • MSA is a biodegradable, and phosphoric acid is not.
  • Comparative Compositions 1 and 2 demonstrate excellent cleaning efficiency at temperatures between 23 and 60°C, with particularly effective performance at 45 °C.
  • Cleaning Concentrates 12, 13, 14, and 15 are tested for foam generation at 45°C. Specifically, 50 mL of solutions of Cleaning Concentrate are formed from a dilution of 5.28g of Cleaning Concentrate with 1 L with water having 350 PPM hardness (to form Cleaning Compositions 12 and 13). The 50 mL solutions are preheated to 45 °C and then poured into a glass column (40 mm Inner diameter.) Air is passed into the column through a glass filter plate at 0.4 L/min for 15 seconds, and foam is generated. After 15 seconds of air flow, the height of the foam is measured in millimeters (mm).
  • any ranges and subranges relied upon in describing various embodiments of the present disclosure independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein.
  • One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present disclosure, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on.
  • a range "of from 0.1 to 0.9" may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims.
  • a range such as "at least,” “greater than,” “less than,” “no more than,” and the like, it is to be understood that such language includes subranges and/or an upper or lower limit.
  • a range of "at least 10" inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims.
  • an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims.
  • a range "of from 1 to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1, which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

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Abstract

L'invention concerne un concentré de nettoyage destiné à éliminer le tartre d'une surface d'un système comprenant un composant acide comprenant un acide alcanesulfonique, un premier tensio-actif comprenant un alcoxylate d'alcool en C6 à C20 ayant une valeur HLB de plus de 8, et un second tensio-actif, différent dudit premier tensio-actif, ayant une valeur HLB de moins de 11. Les premier et second tensio-actifs sont présents dans le concentré de nettoyage dans un rapport en poids de 10:1 à 0,5:1. Le composant acide et une somme des premier et second tensio-actifs sont présents dans le concentré de nettoyage dans un rapport en poids de 30:1 à 1:1. Un procédé d'élimination du tartre d'une surface d'un système avec une composition de nettoyage comprend les étapes de fourniture du concentré de nettoyage, dilution du concentré de nettoyage avec de l'eau pour former la composition de nettoyage, et mise en contact de la surface du système avec la composition de nettoyage.
PCT/US2014/067202 2013-11-25 2014-11-25 Concentré de nettoyage destiné à éliminer le tartre d'une surface d'un système Ceased WO2015077737A1 (fr)

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WO2017007416A1 (fr) * 2015-07-07 2017-01-12 Delaval Holding Ab Détergent acide
CN110709321A (zh) * 2017-06-02 2020-01-17 天体电子学先进电子系统公司 驾驶舱和机组人员休息区空气质量传感器
WO2021029805A1 (fr) * 2019-08-15 2021-02-18 Delaval Holding Ab Composition détergente pour dissoudre un dépôt minéral
CN113543883A (zh) * 2019-01-31 2021-10-22 米罗库鲁斯公司 非结垢组合物以及用于操控和处理包封的微滴的方法
US11413617B2 (en) 2017-07-24 2022-08-16 Miroculus Inc. Digital microfluidics systems and methods with integrated plasma collection device
US11421191B1 (en) 2018-11-15 2022-08-23 Ecolab Usa Inc. Acidic cleaner
US11471888B2 (en) 2015-06-05 2022-10-18 Miroculus Inc. Evaporation management in digital microfluidic devices
US11623219B2 (en) 2017-04-04 2023-04-11 Miroculus Inc. Digital microfluidics apparatuses and methods for manipulating and processing encapsulated droplets
US11738345B2 (en) 2019-04-08 2023-08-29 Miroculus Inc. Multi-cartridge digital microfluidics apparatuses and methods of use
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US12037538B2 (en) 2019-03-28 2024-07-16 Ecolab Usa Inc. Synergistic blends of fluoro-inorganics and inorganic acids for removing deposits and stimulating geothermal wells

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US11890617B2 (en) 2015-06-05 2024-02-06 Miroculus Inc. Evaporation management in digital microfluidic devices
US12263483B2 (en) 2015-06-05 2025-04-01 Integra Biosciences Ag Evaporation management in digital microfluidic devices
US12239988B2 (en) 2015-06-05 2025-03-04 Miroculus Inc. Air-matrix digital microfluidics apparatuses and methods for limiting evaporation and surface fouling
US11471888B2 (en) 2015-06-05 2022-10-18 Miroculus Inc. Evaporation management in digital microfluidic devices
US11944974B2 (en) 2015-06-05 2024-04-02 Miroculus Inc. Air-matrix digital microfluidics apparatuses and methods for limiting evaporation and surface fouling
CN107849498A (zh) * 2015-07-07 2018-03-27 利拉伐控股有限公司 酸性洗涤剂
WO2017007416A1 (fr) * 2015-07-07 2017-01-12 Delaval Holding Ab Détergent acide
US12172164B2 (en) 2016-12-28 2024-12-24 Miroculus Inc. Microfluidic devices and methods
US11833516B2 (en) 2016-12-28 2023-12-05 Miroculus Inc. Digital microfluidic devices and methods
US11623219B2 (en) 2017-04-04 2023-04-11 Miroculus Inc. Digital microfluidics apparatuses and methods for manipulating and processing encapsulated droplets
CN110709321A (zh) * 2017-06-02 2020-01-17 天体电子学先进电子系统公司 驾驶舱和机组人员休息区空气质量传感器
US11413617B2 (en) 2017-07-24 2022-08-16 Miroculus Inc. Digital microfluidics systems and methods with integrated plasma collection device
US11857969B2 (en) 2017-07-24 2024-01-02 Miroculus Inc. Digital microfluidics systems and methods with integrated plasma collection device
US11992842B2 (en) 2018-05-23 2024-05-28 Miroculus Inc. Control of evaporation in digital microfluidics
US12134114B2 (en) 2018-11-15 2024-11-05 Ecolab Usa Inc. Acidic cleaner
US11421191B1 (en) 2018-11-15 2022-08-23 Ecolab Usa Inc. Acidic cleaner
US12233390B2 (en) 2019-01-31 2025-02-25 Miroculus Inc. Nonfouling compositions and methods for manipulating and processing encapsulated droplets
CN113543883A (zh) * 2019-01-31 2021-10-22 米罗库鲁斯公司 非结垢组合物以及用于操控和处理包封的微滴的方法
US12037538B2 (en) 2019-03-28 2024-07-16 Ecolab Usa Inc. Synergistic blends of fluoro-inorganics and inorganic acids for removing deposits and stimulating geothermal wells
US11738345B2 (en) 2019-04-08 2023-08-29 Miroculus Inc. Multi-cartridge digital microfluidics apparatuses and methods of use
WO2021029805A1 (fr) * 2019-08-15 2021-02-18 Delaval Holding Ab Composition détergente pour dissoudre un dépôt minéral
US11857961B2 (en) 2022-01-12 2024-01-02 Miroculus Inc. Sequencing by synthesis using mechanical compression

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