WO2009028757A1 - Composition aqueuse d'agent de nettoyage écologique pour le nettoyage de conduites intérieures d'alimentation en eau - Google Patents

Composition aqueuse d'agent de nettoyage écologique pour le nettoyage de conduites intérieures d'alimentation en eau Download PDF

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Publication number
WO2009028757A1
WO2009028757A1 PCT/KR2007/005009 KR2007005009W WO2009028757A1 WO 2009028757 A1 WO2009028757 A1 WO 2009028757A1 KR 2007005009 W KR2007005009 W KR 2007005009W WO 2009028757 A1 WO2009028757 A1 WO 2009028757A1
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WO
WIPO (PCT)
Prior art keywords
weight
acid
cleaning
composition
water supply
Prior art date
Application number
PCT/KR2007/005009
Other languages
English (en)
Inventor
Jae Heum Bae
Woo Dal Sik
Hyoun Dek Shin
Original Assignee
Chem-C Tech Co., Ltd.
Korean Interfacial Science And Engineering Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chem-C Tech Co., Ltd., Korean Interfacial Science And Engineering Institute filed Critical Chem-C Tech Co., Ltd.
Publication of WO2009028757A1 publication Critical patent/WO2009028757A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0042—Reducing agents
    • 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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines

Definitions

  • the present invention relates to an environmentally- friendly cleaning agent composition for cleaning indoor water supply pipes. More specifically, the present invention relates to a cleaning agent composition for cleaning indoor water supply pipes capable of considerably efficiently dissolving iron oxide and zinc oxide which are firmly adhered to internal walls of indoor water supply pipes.
  • Galvanized steel pipes generally buried as indoor water supply pipes in large buildings and apartments are exposed through galvanized zinc that has peeled away and are thus readily corroded. As a result, a rusty water flows out and corrosion products are formed in the pipes, thereby the diameter of the pipes is reduced. For this reason, public distrust about city water has been growing. Replacement of old indoor water supply pipes by new ones is hardly used in the field of construction due to an inconvenience associated with dismantlement of required parts of buildings and high costs .
  • the present invention is directed to an environmentally-friendly cleaning composition where harmfulness to human body and stability are taken into consideration.
  • Korean Patent No. 725948 discloses a cleaning solution capable of preventing corrosion of various pipes and removing scale from the pipes.
  • the solution is prepared by reacting 10 to 30 parts by weight of a carboxylic acid-phosphorous acid conjugate, 10 to 30 parts by weight of hydroxypolycarboxylic acid, and 10 to 30 parts by weight of at least one alkaline neutralizing agent selected from NaOH, KOH, K 2 CO 3 , KHCO 3 , Na 2 CO 3 , and NaHCO 3 at 80 to 110"C for 1 to 2 hours with stirring.
  • the 1 wt% aqueous solution shows an acidity of pH ⁇ to 8.
  • the solution is considered to have a limitation in that it cannot sufficiently removes iron oxide, one of the major corrosion products present in indoor water supply pipes .
  • CMP agent available from DUPONT, Corp. comprises glycolic acid (0.0383g), citric acid (0.0368g), oxalic acid (0.0394g), sulfamic acid (0.0378g), sulfuric acid (0.0357g), HCl (0.0262g), nitrilotriacetic acid (0.0389g).
  • the CMP agent is known to be effective for dissolving iron oxide (Fe 2 Os) .
  • the CMP agent cannot satisfactorily remove zinc oxide, and particularly, disadvantageously contains toxic acids which are harmful to human body.
  • US Patent No. 4,430,128 (issued on Feb. 7, • 1984) discloses an aqueous acid composition and preparation thereof.
  • the composition comprises 3 wt% of trisodium-HEDTA and sulfuric acid (H 2 SO 4 , 98%) to adjust to pH 1.6, and 0.3 wt% of an amine-based corrosion inhibitor.
  • the scale (90%) was removed from pipes with 400 mL of the cleaning composition at 100 0 F (37.7 0 C) at a flow rate of 200 mL/min for one hour and eight hours.
  • the cleaning composition comprising an aqueous ammonium solution to adjust to pH 9.2 and sodium nitrite 1 wt% is capable of completely cleaning scale within 15 minutes. However, this composition also contains toxic acids and is not considered as environmentally-friendly.
  • the present inventors have assayed constituent ingredients of scale present in old galvanized steel pipes generally used as indoor water supply pipes with the use of an X-ray fluorescence (XRF) spectrometer.
  • XRF X-ray fluorescence
  • Table 1 As apparent from the data in Table 1, of ingredients constituting scale, iron oxide (Fe 2 Cb) showed the highest content (i.e., 65.2%) and zinc oxide (ZnO) showed the second highest content (i.e., 25.8%).
  • the present invention provides a cleaning agent that is capable of primarily removing Fe 2 O 3 , the most major ingredient of scale, and secondly removing ZnO. More specifically, the present invention provides a cleaning composition with improved iron oxide solubility that contains secondary contamination-free organic acid as a main ingredient, a reducing agent to maximize cleaning effects, and a sterilizer to sterilize organism membranes which are adhered to internal walls of old indoor water supply pipes.
  • an aqueous cleaning agent composition for indoor water supply pipes comprising: 5 to 10% by weight of citric acid; 1 to 10% by weight of oxalic acid; 1 to 10% by weight of malic acid; 0.1 to 1% by weight of phosphoric acid; 5 to 15% by weight of hydrochloric acid; 1 to 2% by weight of hydrogen peroxide; 0.01 to 0.1% by weight of LEA; 0.01 to 0.1% by weight of ascorbic acid; and the remaining weight percentage of water, based on a total of 100% by weight of the composition.
  • FIG. 1 is a graph showing Fe 2 ⁇ 3 dissolution efficiencies of organic acids contained in the composition of the present invention.
  • FIG. 2 is a graph showing Fe 2 O 3 dissolution efficiencies of hydrogen peroxide contained in the composition of the present invention.
  • Citric acid (CeHgO 7 )
  • the cleaning agent composition shows unsatisfactory cleaning performance for iron oxide
  • the cleaning agent composition shows cleaning performance comparable to the case where the content thereof is 10 wt%
  • the content of citric acid in the present invention is in a range of 5 to 10 wt%.
  • Oxalic acid (C 2 H 2 O 4 ) , another constituent component of the composition, is a hygroscopic solid having a molecular weight of 90.0 and a specific weight of 1.90 (at 25°C) . Oxalic acid is decomposed at 180 to 190 0 C to produce formic acid, carbon monoxide and carbon dioxide. When oxalic acid is allowed to stand, it is converted into its dihydrate.
  • Example 1 when the content of oxalic acid is in a range of 1 to 10 wt%, the cleaning agent composition shows substantially similar solubility efficiency, and that when the content of oxalic acid is 15 wt%, the cleaning agent composition shows no satisfactory cleaning performance for iron oxide. Accordingly, the content of oxalic acid in the present invention is in a range of 1 to 10 wt%.
  • Malic acid (CiH 6 Os) , another constituent component of the composition, is called also an "apple acid” and has one asymmetric carbon atom and may thus exist as D-, L- and/or DL- type of three optical isomers. It can be seen from Example 1 that when the content of malic acid is in a range of 1 to 10 wt%, the cleaning agent composition shows a gradual increase in cleaning efficiency for iron oxide, and that when the content of malic acid is 15 wt%, the cleaning agent composition unexpectedly shows poor cleaning efficiency, as compared to the case where the content is 10 wt%. Accordingly, the content of citric acid used in the present invention is in a range of 1 to 10 wt% .
  • Phosphoric acid another constituent component of the composition, is a general term of HaP 2 Os"nf ⁇ O, a series of acid which are derived from hydration of phosphorus pentoxide (P 2 O 5 ) .
  • the content of phosphoric acid used in the present invention is in a range of 0.1 to 1 wt%.
  • Hydrochloric acid (HCl) another constituent component of the composition, increases the concentration of hydrogen ions in a solution and allows the solution to be converted into a strongly acidic solution.
  • the content of phosphoric acid in the present invention is in a range of 5 to 15 wt% where the cleaning composition shows superior dissolution efficiency for iron oxide, as shown in Example 3.
  • Hydrogen peroxide another constituent component of the composition, has strong oxidizing properties and excellent microorganism-sterilizing properties and is well soluble in water, ethanol and ether.
  • An aqueous hydrogen peroxide solution is weakly acidic by partial dissociation of hydrogen ions therein.
  • the content of hydrogen peroxide used in the present invention is in a range of 1 to 2 wt% where the cleaning composition shows superior dissolution efficiency for iron oxide, as compared to the case where no hydrogen peroxide is used, as shown in Example 2.
  • LAE non-ionic surfactant
  • LAE another constituent component of the composition
  • lauryl alcohol ethoxylate is an acronym of lauryl alcohol ethoxylate.
  • the properties of LAE may be varied depending on molar numbers of ethylene oxide (EO) added to lauryl alcohol.
  • EO ethylene oxide
  • LAE generally used in environmentally-friendly aqueous cleaning agents is expected to be capable of efficiently removing organic contaminants as well as scale (e.g., iron oxide) present in indoor water supply pipes.
  • scale e.g., iron oxide
  • LAE efficiently prevents re-attachment of removed scale.
  • the content of LAE in the present invention is in a range of 0.01 to 0.1 wt% .
  • Ascorbic acid (CeH 8 Oe) used as a reducing agent in the composition is also called “vitamin C” and is one of the vitamins that have an antiscorbutic factor.
  • Vitamin C Ascorbic acid used as a reducing agent in the composition is also called “vitamin C” and is one of the vitamins that have an antiscorbutic factor.
  • the content of ascorbic acid in the present invention is in a range of 0.01 to 0.1 wt%.
  • An aqueous cleaning composition for cleaning indoor water supply pipes of the present invention is prepared by dissolving the constituent ingredients in water with homogeneously mixing the ingredients one another in a mechanical stirrer at ambient temperature.
  • Example 1 An aqueous cleaning composition for cleaning indoor water supply pipes of the present invention was prepared by adjusting the contents of all major ingredients (i.e., citric acid, oxalic acid and malic acid) to 1, 5, 10 and 15 wt%, based on the total weight of the composition; adding the minor ingredients (phosphoric acid 1 wt%, hydrochloric acid 5 wt%, hydrogen peroxide 0.1 wt%, LEA 0.01 wt%, ascorbic acid 0.01 wt% thereto, based on the total weight of the composition; and homogeneously mixing the ingredients with a predetermined amount of water at ambient temperature such that the total weight of the composition is adjusted to 100 wt%.
  • major ingredients i.e., citric acid, oxalic acid and malic acid
  • minor ingredients phosphoric acid 1 wt%, hydrochloric acid 5 wt%, hydrogen peroxide 0.1 wt%, LEA 0.01 wt%, ascorbic acid 0.01 wt
  • the test was carried out by mixing the diluted organic acid composition with Fe 2 ⁇ 3 1.0 g, stirring the mixture in a mechanical stirrer at 500 rpm for 120 minutes at ambient temperature, filtering the resulting mixture under reduced pressure though a l p filter paper, and weighting the filter paper before and after the test.
  • the results are shown in Table 2.
  • the composition of the present invention exhibits superior dissolution efficiency. Accordingly, the major ingredients were employed in contents as defined above in the composition of the present invention.
  • An aqueous cleaning composition for cleaning indoor water supply pipes of the present invention was prepared at ambient temperature under various contents of hydrogen peroxide (i.e., 0, 1, 2, 4 wt%, based on the total weight of the composition) , by homogeneously mixing citric acid 5 wt%, oxalic acid 5 wt%, malic acid 5wt%, phosphoric acid 1 wt%, hydrochloric acid 5 wt%, LEA 0.01 wt% and ascorbic acid 0.01 wt% with a predetermined amount of water such that the total weight of the composition is adjusted to 100 wt%.
  • the dissolution efficiency of the composition thus prepared for Fe 2 O 3 was tested in the same manner as Example 1.
  • An aqueous cleaning composition for cleaning indoor water supply pipes of the present invention was prepared in the same manner in Example 1, except that the content of hydrochloric acid is varied (i.e., 5, 7, 10, 15 wt%, based on the total weight of the composition) and the remaining ingredients are used in contents as shown in Table 3.
  • the test results are shown in Table 3. It can be confirmed from Table. 3 that as the content of hydrochloric acid increases, the composition of the present invention exhibits a gradual increase in dissolution efficiency after the reaction for 20 minutes .
  • An aqueous cleaning composition for cleaning indoor water supply pipes of the present invention was prepared by mixing citric acid 5 wt%, oxalic acid 5 wt%, malic acid 5 wt%, phosphoric acid 1 wt%, hydrochloric acid 15 wt%, H 2 O 2 0.1wt%, LEA 0.1 wt%, ascorbic acid 0.1 wt% with a predetermined amount of water at ambient temperature such that the total weight of the composition is adjusted to 100 wt%.
  • a cleaning agent composition for chemically cleaning indoor water supply pipes according to the present invention is capable of efficiently dissolving iron oxide and zinc oxide.
  • the cleaning agent composition causes no environmental pollution and does no harm to human health and is utilized in preventing rust-containing city water from flowing out.
  • the environmentally-friendly chemical cleaning agent is suitable for use in cleaning methods, in accordance with mandatory cleaning of indoor water supply pipes under the provision of the revised Water Supply and Waterworks Installation Act, thus contributing to realizing of a more stable and efficient city water supply.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention porte sur une composition d'agent de nettoyage écologique pour le nettoyage de conduites intérieures d'alimentation en eau. La composition d'agent de nettoyage comprend 5 à 10 % en poids d'acide citrique, 1 à 10 % en poids d'acide oxalique, 1 à 10 % en poids d'acide malique, 0,1 à 1 % en poids d'acide phosphorique, 5 à 15 % en poids d'acide chlorhydrique, 1 à 2 % en poids de peroxyde d'hydrogène, 0,01 à 0,1 % en poids de lauryl d'alcool éthoxylate(LEA), 0,01 à 0,1 % en poids d'acide ascorbique, le pourcentage en poids restant étant formé par de l'eau, sur la base d'un total de 100 % en poids de la composition. La composition d'agent de nettoyage est capable de dissoudre de façon extrêmement efficace l'oxyde de fer et l'oxyde de zinc qui adhèrent solidement aux parois internes des conduites intérieures d'alimentation en eau.
PCT/KR2007/005009 2007-08-30 2007-10-12 Composition aqueuse d'agent de nettoyage écologique pour le nettoyage de conduites intérieures d'alimentation en eau WO2009028757A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020070087925A KR100808373B1 (ko) 2007-08-30 2007-08-30 옥내급수관 세척용 세정제 조성물
KR10-2007-0087925 2007-08-30

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WO2009028757A1 true WO2009028757A1 (fr) 2009-03-05

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011077144A1 (fr) * 2009-12-22 2011-06-30 Md Technical Solutions Limited Composition détachante contre les taches de transpiration au niveau des aisselles
CN105039037A (zh) * 2015-07-02 2015-11-11 苏州永创达电子有限公司 一种常温工业清洗剂
US20170203340A1 (en) * 2014-07-28 2017-07-20 General Electric Company Rapid cleaning method for ultrapure water piping system
WO2020230626A1 (fr) * 2019-05-10 2020-11-19 花王株式会社 Procédé de retrait de biofilm
GB2584653A (en) * 2019-06-07 2020-12-16 Bae Systems Plc Improvements in and relating to ice pigging
CN113795339A (zh) * 2019-05-10 2021-12-14 花王株式会社 去除生物膜的方法
CN113811186A (zh) * 2019-05-10 2021-12-17 花王株式会社 水性系统用生物膜除去用组合物

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101021035B1 (ko) 2010-12-03 2011-03-09 주식회사그린바이오 무독성 및 친환경성 저수조 세정액을 이용한 저수조 세정방법
KR101582215B1 (ko) * 2014-10-28 2016-01-05 (주)어울림이비즈 락트산을 포함한 친환경 세척제 조성물
RU2596250C1 (ru) * 2015-05-19 2016-09-10 Федор Иванович Лобанов Состав для очистки и защиты поверхности трубопроводов подачи питьевой воды

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JPS55109498A (en) * 1979-02-15 1980-08-22 Ichiro Kudo Silicic acid scale removing agent
JPH01212786A (ja) * 1988-02-22 1989-08-25 Neos Co Ltd 配管の洗浄方法
JPH03190999A (ja) * 1989-12-20 1991-08-20 Mitsubishi Materials Corp 洗浄剤組成物
JPH07252498A (ja) * 1994-03-17 1995-10-03 Puronetsuto:Kk 洗浄剤

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JPS59185786A (ja) 1983-04-07 1984-10-22 Mitsubishi Heavy Ind Ltd 酸化鉄スケ−ルの洗浄方法
JPS605888A (ja) 1983-06-23 1985-01-12 Mitsubishi Heavy Ind Ltd 酸化鉄スケ−ルの化学的洗浄法
US5294364A (en) 1988-02-10 1994-03-15 Colgate Palmolive Safe acidic hard surface cleaner
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Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55109498A (en) * 1979-02-15 1980-08-22 Ichiro Kudo Silicic acid scale removing agent
JPH01212786A (ja) * 1988-02-22 1989-08-25 Neos Co Ltd 配管の洗浄方法
JPH03190999A (ja) * 1989-12-20 1991-08-20 Mitsubishi Materials Corp 洗浄剤組成物
JPH07252498A (ja) * 1994-03-17 1995-10-03 Puronetsuto:Kk 洗浄剤

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011077144A1 (fr) * 2009-12-22 2011-06-30 Md Technical Solutions Limited Composition détachante contre les taches de transpiration au niveau des aisselles
US20170203340A1 (en) * 2014-07-28 2017-07-20 General Electric Company Rapid cleaning method for ultrapure water piping system
CN105039037A (zh) * 2015-07-02 2015-11-11 苏州永创达电子有限公司 一种常温工业清洗剂
WO2020230626A1 (fr) * 2019-05-10 2020-11-19 花王株式会社 Procédé de retrait de biofilm
CN113795339A (zh) * 2019-05-10 2021-12-14 花王株式会社 去除生物膜的方法
CN113811514A (zh) * 2019-05-10 2021-12-17 花王株式会社 生物膜的除去方法
CN113811186A (zh) * 2019-05-10 2021-12-17 花王株式会社 水性系统用生物膜除去用组合物
EP3967416A4 (fr) * 2019-05-10 2023-06-28 Kao Corporation Procédé de retrait de biofilm
CN113811514B (zh) * 2019-05-10 2023-09-19 花王株式会社 生物膜的除去方法
CN113795339B (zh) * 2019-05-10 2023-09-26 花王株式会社 去除生物膜的方法
GB2584653A (en) * 2019-06-07 2020-12-16 Bae Systems Plc Improvements in and relating to ice pigging
GB2584653B (en) * 2019-06-07 2023-04-19 Bae Systems Plc Improvements in and relating to ice pigging

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