EP0690944B1 - Verfahren zum reinigen von bohrleitungen von trinkwasserversorgungsanlagen - Google Patents

Verfahren zum reinigen von bohrleitungen von trinkwasserversorgungsanlagen Download PDF

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Publication number
EP0690944B1
EP0690944B1 EP94912283A EP94912283A EP0690944B1 EP 0690944 B1 EP0690944 B1 EP 0690944B1 EP 94912283 A EP94912283 A EP 94912283A EP 94912283 A EP94912283 A EP 94912283A EP 0690944 B1 EP0690944 B1 EP 0690944B1
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EP
European Patent Office
Prior art keywords
scale
acid
pipe
cleaning solution
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP94912283A
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English (en)
French (fr)
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EP0690944A1 (de
Inventor
Allen C. Hieatt
Jerome H. Ludwig
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HERC Products Inc
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HERC Products Inc
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Filing date
Publication date
Priority claimed from US08/036,188 external-priority patent/US5360488A/en
Application filed by HERC Products Inc filed Critical HERC Products Inc
Publication of EP0690944A1 publication Critical patent/EP0690944A1/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto 
    • B08B9/02—Cleaning pipes or tubes or systems of pipes or tubes
    • B08B9/027—Cleaning the internal surfaces; Removal of blockages
    • B08B9/032—Cleaning the internal surfaces; Removal of blockages by the mechanical action of a moving fluid, e.g. by flushing
    • 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
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—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
    • 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
    • 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
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3218—Alkanolamines or alkanolimines
    • 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
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03B—INSTALLATIONS OR METHODS FOR OBTAINING, COLLECTING, OR DISTRIBUTING WATER
    • E03B7/00—Water main or service pipe systems
    • E03B7/006—Arrangements or methods for cleaning or refurbishing water conduits
    • 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

  • scale and sedimentation will increase the possibility of corrosion in the water distribution pipe along with promoting the growth of organisms.
  • the organisms also can be a health hazard, promoting corrosion and biomass which binds scale and sediment together and to the surfaces of the system. Corrosion will eventually lead to the leakage of the system and the necessity to replace the leaking section.
  • a proper cleaning and maintenance program for water distribution systems will prevent decreased water flow capacity, corrosion and the necessity to replace the system or portions thereof.
  • a simple and effective method for cleaning and maintaining these systems is needed.
  • ES-A-533818 discloses a method for eliminating lime incrustations from domestic water supply installations which represents the prior art as referred to in the preamble to Claim 1.
  • US-A-4025359 discloses an inhibited acid composition for cleaning water systems which has a reduced tendency to attack galvanized pipe or steel pipe.
  • WO-A-92/20629 discloses soap compositions of carboxylic acids and amines useful in removal and prevention of scale containing calcium or magnesium carbonate, oxide or hydroxide.
  • FR-A-2602571 discloses a method and apparatus for cleaning a conduit of a potable water distribution network in which pulses of fluid under pressure, such as water, are passed through the conduit.
  • a method of cleaning a potable water distribution pipe system of scale comprises providing a reservoir for containing an aqueous cleaning solution for the removal of the scale, circulating the cleaning solution from the reservoir through a section of pipe in the system and returning the solution to the reservoir for the removal of the scale, characterised in that the aqueous cleaning solution is suitable for removal of scale associated with sulfate-reducing and iron bacteria consisting primarily of iron oxide, biomass and sediment from inside surfaces of the water distribution system, in that the section of pipe is an underground section of a distribution pipe system and in that the method includes sealing off the underground section for circulation for cleaning solution therethrough.
  • This invention is directed to a method of cleaning and maintaining water distribution systems.
  • Water systems having interior scale and sediment deposits are cleaned by introducing and circulating an effective amount of an aqueous treatment solution for a sufficient period of time which results in the solution, loosening and suspension of the undesired scale and sediment. Thereafter, the spent treating solution containing the dissolved or suspended scale and sediment is flushed from the water distribution system to provide a clean system with improved water flow and operation. Additionally, further flushing with high pressure water will also remove additional scale that had been loosened by the treating solution.
  • the cleaning solution may be acidic, neutral or basic.
  • mineral acids or organic acids, and mixtures thereof are employed as acidic treatment solutions.
  • the acidic treatment solution may contain further additives such as inhibitors, chelating agents, penetrating and/or dispersing agents to assist in the removal of scale and sediment and to minimize any adverse effects on the pipes, valves, or other system surfaces due to the acids employed.
  • This invention provides a simple, low cost and effective method of removing water scale and sediment from water distribution systems in order to maintain proper water flow, operation and to prevent corrosion of the system which would require the high cost and inconvenience of replacement.
  • acidic treatment solutions found to be useful in practicing the method of this invention are aqueous solutions of mineral acids such as hydrochloric, nitric, phosphoric, polyphosphoric, hydrofluoric, boric, sulfuric, sulfurous, and the like.
  • Aqueous solutions of mono-, di- and polybasic organic acids have also been found to be useful and include formic, acetic, propionic, citric, glycolic, lactic, tartaric, polyacrylic, succinic, p-toluenesulfonic, and the like.
  • the useful treatment solutions may also be aqueous mixtures of the above mineral and organic acids.
  • Alkaline, acid, or neutral cleaning solutions may also be employed, as indicated above, depending upon the type of scale that needs to be removed.
  • Sequestering or chelating agents such as EDTA (ethylenediamine tetraacetic acid), NTA (nitrilotriacetic acid), and derivatives, i.e., basic alkali salts, and the like have also been found to be useful in the treatment solution in certain cases.
  • the acidic treatment solution may also contain acid inhibitors which substantially reduce the acidic action on metal surfaces of the water distribution system, particularly valves, fire hydrants, etc., and these various inhibitors for acids have been well documented in the patent art. Typical, but not necessarily all inclusive, examples of acid inhibitors are disclosed in the following U.S.
  • Patents 2,758,970; 2,807,585; 2,941,949; 3,077,454; 3,607,781; 3,668,137; 3,885,913; 4,089,795; 4,199,469; 4,310,435; 4,541,945; 4,554,090; 4,587,030; 4,614,600; 4,637,899; 4,670,186; 4,780,150 and 4,851,149 which are incorporated herein by reference.
  • the treatment solution may also contain dispersing, penetrating or emulsifying agents to assist in the removal of the scale and sediment.
  • These surface active agents may be anionic, cationic, nonionic or amphoteric as defined in the art.
  • Compounds such as alkyl ether sulfates, alkyl or aryl sulfates, alkanolamines, ethoxylated alkanolamides, amine oxides, ammonium and alkali soaps, betaines, hydrotropes such as sodium aryl sulfonates; ethoxylated and propoxylated fatty alcohols and sugars, ethoxylated and propoxylated alkylphenols, sulfonates, phosphate esters, quarternaries, sulfosuccinates, and mixtures thereof, have been found to be useful in admixture with the acid treating solution.
  • Fig. 1 is a schematic of a laboratory test system illustrating the method of this invention.
  • Fig. 2 is a diagram of a field system for cleaning a potable water distribution system.
  • a laboratory test system is shown to evaluate the removal of scale and sediment by acidic treating solutions from a test pipe sample taken from a water distribution system.
  • This system includes a 56.8 L (15 gallon) acidic treating solution reservoir 5, submersible acidic treating solution circulation pump 6 rated at 4543 L/h (1200 gallons per hour) 2.54 cm (1") inlet transfer line 7, drain valve 8, heavy rubber diaphragm seals 9 for the ends of the test pipe specimen 10, 2.54 cm (1") outlet transfer line 11 and the treating solution 12.
  • the test pipe specimen 10 is mounted at about a 30 degree angle so that the test solution will contact essentially the entire inner pipe surface to be treated.
  • the scale on the inside of the pipe consisted of nodules of up to 2.5 to 3.8 cm (1 to 11 ⁇ 2 inches) in height covering 100% of the inside pipe surface which had substantially reduced the opening inside the pipe for water to flow.
  • FIG. 2 a field equipment and system diagram is shown which may be employed in the cleaning of a potable water pipe distribution system.
  • Two 1.89 kl (500 gallon) treating solution reservoir tanks 20 and 21 along with a 6.3 L/s (100 gallon per minute) circulation pump 22 and sight glass 23 are mounted on a flat bed truck (not shown).
  • a 6.4 cm (21 ⁇ 2) inlet pipe 24 is secured to a 198 m (650 foot) section of 15.2 cm (6") water distribution pipe 25 after the main shut off valve 26.
  • the fire hydrant 27 and fire hose 28 were employed for the acidic treating solution return to tanks 20 and 21.
  • the section of pipe 25 to be treated was isolated by closing off the two water main shut-off valves 26 and 29 along with all service line valves, typically 30 and 31. With valves 32 and 33 closed, 3785 L (1000 gallons) of acidic treating solution was prepared in tanks 20 and 21. With the coupling 34 open, the treating solution was allowed to enter the system by opening valves 33 and 35 and turning on the circulation pump 22. The pH of the water coming from the open coupling was then monitored until a decrease was noted which indicated the acid treating solution had displaced the water in the section to be treated. The circulation pump 22 was turned off and the coupling 34 connected. Valves 36 and 37 were then closed and valve 32 opened for circulation. The circulation pump 22 was then started again for the treatment period. Valve 37 was closed to allow for scale solids to accumulate in tank 20 while the treating solution could overflow at 38 to tank 21 which reduces the chances of plugging during treatment.
  • the treating solution was then circulated in the system of Fig. 2 for a period of 5 hours. Observation of the treating solution through the sight glass 23 showed an increasingly darker discoloration with time.
  • the circulation pump 22 was turned off, and valves 33 and 35 were closed.
  • the main shut-off valve 26 was slowly opened and fresh water allowed to enter the system until the treating solution was displaced as noted when the tanks 20 and 21 were full. Valve 32 was then closed.
  • the fire hose 28 was then disconnected from the fire hydrant 27 and the main shut-off valve 26 opened full to allow high pressure flushing of the treated water main 25. As the flush water emerged from the fire hydrant 27 it was dark in color with considerable scale and sediment solids. Flushing continued until the flush water was clean of solids for a period of time prior to putting the treated section of the water distribution system back into service.
  • the flow rate through the fire hydrant 27 prior to treatment had been determined by a Pitot Gauge to be 588 gallons per minute. After treatment, the flow rate was determined to be 790 gallons per minute. This was an increase of 34.5%.
  • cleaning solutions may be employed as follows: Preblend Ingredients % by wt 31% Hydrochloric acid in water 87.14 +/- 2% 70% Glycolic acid in water 5.27 +/- 0.3% 40% Sodium xylene sulfonate in water 2.06 +/- 0.2% Triethanolamine and diethanolamine mixture (85%/15%) 2.96 +/- 0.2% Water 2.57 +/- 0.2%
  • the above preblended cleaning solution is used in an amount of about 12.5% by weight with water in the field for cleaning an underground potable water distribution pipe system.
  • the solution may be employed in amounts of from about 5 to about 50% by weight with water in the field, depending upon such variables as the amount of scale, pipe volume to be cleaned, circulation time and other factors.
  • the amounts of anhydrous chemicals in a broader range of ingredients are about 1% to 27% HCl, 0.1% to 4% glycolic acid, 0.04% to 1% sodium xylene sulfonate and about 0.1% to 2.5 % of the triethanolamine/diethanolomine mixture (hereinafter referred to as "TEA").
  • hydrochloric acid may be added to a concentrate of the glycolic acid, sodium xylene sulfonate and TEA.
  • an underground section of the pipe to be cleaned is sealed off from the rest of the system.
  • the cleaning solution is then introduced from a tank into the pipe section and, if water is in that section of pipe, it is removed upon the introduction of the cleaning solution.
  • circulation of the cleaning solution through the underground pipe is initiated for a sufficient period of time for solubilization, loosening and/or suspension of the scale and sediments.
  • a soap having a 1:1 stoichiometric equivalent of the acid (HCl and glycolic acid) and TEA base is formed with an excess of the acid.
  • This composition has been found to work effectively in the field for the removal of scale associated with sulfate-reducing and iron bacteria consisting primarily of iron oxide, biomass and sediment.
  • These 1:1 soaps have also been described in the above referred to co-pending Application WO92/20629 and the disclosure thereof is incorporated herein in its entirety by reference.
  • These soaps may be more generally categorized as soaps of mineral and/or organic acids and a base such as an amine and ammonia.
  • soaps include 1:1 soaps of TEA and glycolic acid (also known as hydroxyacetic acid); TEA and acetic acid; TEA and citric acid; TEA and benzoic acid; hydrochloric acid and ammonia; sulfuric acid and ammonia; nitric acid and ammonia; TEA and hydrochloric acid; TEA and sulfuric acid; TEA and nitric acid; ammonia and glycolic acid; ammonia and benzoic acid; and ammonia and p-toluenesulfonic acid.
  • TEA and glycolic acid also known as hydroxyacetic acid
  • TEA and acetic acid also known as hydroxyacetic acid
  • TEA and citric acid TEA and benzoic acid
  • hydrochloric acid and ammonia sulfuric acid and ammonia; nitric acid and ammonia
  • TEA and hydrochloric acid TEA and sulfuric acid
  • TEA and nitric acid ammonia

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Hydrology & Water Resources (AREA)
  • Public Health (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Cleaning In General (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Processing Of Solid Wastes (AREA)

Claims (14)

  1. Verfahren zum Reinigen eines Trinkwasser-Rohrverteilungssystems von Ablagerungen, welches die folgenden Schritte enthält:
    Bereitstellen eines Reservoirs (20, 21), das eine wässrige Reinigungslösung zum Entfernen der Ablagerungen aufnimmt,
    Umwäzlen der Reinigungslösung aus dem Reservoir (20, 21) durch einen Rohrabschnitt (25) in dem System, und
    Zurückführen der Lösung zu dem Reservoir (20, 21), um die Ablagerungen zu entfernen,
    dadurch gekennzeichnet, daß die wässrige Reinigungslösung für das Entfernen von Ablagerungen geeignet ist, in denen sulfatreduzierende Bakterien sowie Eisenbakterien vorkommen und die hauptsächlich aus Eisenoxid, Biomasse und Sedimenten von den Innenoberflächen des Wasserverteilsystems bestehen, daß der Rohrabschnitt (25) ein unter der Erde befindlicher Abschnitt eines Rohrverteilungssystems ist, und daß das Verfahren das Abdichten des unter der Erde befindlichen Abschnittes (25) zum Umwälzen der Reinigungsflüssigkeit darin enthält.
  2. Verfahren nach Anspruch 1,
    bei dem der Rohrabschnitt (25) zwischen zwei Feuerhydranten (27) abgedichtet wird und bei dem die Reinigungsflüssigkeit umgewälzt wird, indem einer der Feuerhydranten (27) mit dem Reservoir (20, 21) verbunden wird, um Reinigungsflüssigkeit durch den Rohrabschnitt hindurchzupumpen.
  3. Verfahren nach Anspruch 1 oder 2,
    das den Schritt des Spülens des Systems mit klarem Wasser nach dem Entfernen der verbrauchten Reinigungsflüssigkeit enthält.
  4. Verfahren nach einem der vorstehenden Ansprüche,
    das den Schritt des Spülens des Systems mit Hochdruckwasser zum Entfernen der Reste von verbrauchter Reinigungslösung, Ablagerungen und Sedimenten enthält.
  5. Verfahren nach einem der vorstehenden Ansprüche,
    bei dem die wässrige Behandlungslösung sauer ist.
  6. Verfahren nach Anspruch 5,
    bei dem die saure Lösung weiterhin Additive enthält, die aus der Gruppe ausgewählt sind, welche aus Säurehemmern, Chelatbildnern, oberflächenaktiven Mitteln, Penetriermitteln und Dispergiermitteln sowie Gemischen davon besteht, um das Entfernen der Ablagerungen und Sedimente zu unterstützen.
  7. Verfahren nach Anspruch 5 oder 6,
    bei dem die Säure aus der Gruppe ausgewählt wird, die aus anorganischen und organischen Säuren sowie Gemischen davon besteht.
  8. Verfahren nach Anspruch 7,
    bei dem die anorganische Säure aus der folgenden Gruppe ausgewählt wird: Chlorwasserstoffsäure, Salpetersäure, Phosphorsäure, Polyphosphorsäure, Fluorwasserstoffsäure, Borsäure, Schwefelsäure und schweflige Säuren sowie Gemische davon.
  9. Verfahren nach Anspruch 7 oder 8,
    bei dem die organische Säure aus der folgenden Gruppe ausgewählt wird: Ameisensäure, Essigsäure, Propionsäure, Zitronensäure, Glykolsäure, Milchsäure, Weinsäure, Polyacrylsäure, Bernsteinsäure, p-Toluolsulfonsäure sowie Gemische davon.
  10. Verfahren nach einem der vorstehenden Ansprüche,
    bei dem die Reinigungslösung ein Gemisch aus Chlorwasserstoffsäure, Glykolsäure, einem Alkanolamin und einem oberflächenaktiven Mittel ist.
  11. Verfahren nach einem der vorstehenden Ansprüche,
    bei dem die Reinigungslösung eine Seife, die eine Säure und eine Base im stöchiometrischen Äquivalenzverhältnis 1:1 enthält, wobei die Säure aus der Gruppe ausgewählt wird, die aus anorganischen Säuren und organischen Säuren besteht, und wobei die Base aus einer Gruppe ausgewählt wird, die aus einem Amin und Ammoniak besteht, wo eine wirksame Menge an freier Säure in der Lösung vorhanden ist, um mit den Ablagerungen zu reagieren.
  12. Verfahren nach einem der vorstehenden Ansprüche,
    bei dem das Reservoir auf einem Lastkraftwagen angeordnet ist, um die Reinigungslösung nachzufüllen, aufzubewahren und abzugeben.
  13. Verfahren nach einem der vorstehenden Ansprüche,
    bei dem das Rohrverteilsystem ein Haushalts- oder Industriewasserverteilsystem ist.
  14. Verfahren nach einem der vorstehenden Ansprüche,
    bei dem die wässrigen Behandlungslösung die Anforderungen der US National Sanitation Foundation Standard 60 für Trinkwasserbehandlungschemikalien zum Einsatz in Trinkwasserverteilsystemen erfüllt.
EP94912283A 1993-03-23 1994-03-22 Verfahren zum reinigen von bohrleitungen von trinkwasserversorgungsanlagen Expired - Lifetime EP0690944B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US36188 1993-03-23
US08/036,188 US5360488A (en) 1993-03-23 1993-03-23 Method of cleaning and maintaining water distribution pipe systems
US20995394A 1994-03-17 1994-03-17
US209953 1994-03-17
PCT/US1994/003065 WO1994021865A1 (en) 1993-03-23 1994-03-22 Method of cleaning and maintaining potable water distribution pipe systems

Publications (2)

Publication Number Publication Date
EP0690944A1 EP0690944A1 (de) 1996-01-10
EP0690944B1 true EP0690944B1 (de) 1998-09-02

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EP94912283A Expired - Lifetime EP0690944B1 (de) 1993-03-23 1994-03-22 Verfahren zum reinigen von bohrleitungen von trinkwasserversorgungsanlagen

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Country Link
EP (1) EP0690944B1 (de)
JP (1) JP3597193B2 (de)
AT (1) ATE170583T1 (de)
AU (1) AU673426B2 (de)
BR (1) BR9406139A (de)
CA (1) CA2157916C (de)
DE (1) DE69413017T2 (de)
WO (1) WO1994021865A1 (de)

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DE202019003089U1 (de) * 2019-07-24 2020-10-27 Josef Schallameier Entkalkung von unter Druck stehenden Rohrleitungen beliebiger Länge

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DE4015201A1 (de) * 1990-05-11 1991-11-14 Heimo Wessollek Reiniger fuer trinkwasseranlagen
DE4015202A1 (de) * 1990-05-11 1991-11-14 Heimo Wessollek Reiniger fuer trinkwasseranlagen
US5322635A (en) * 1991-05-16 1994-06-21 H.E.R.C. Incorporated Soap compositions of carboxylic acids and amines useful in removal and prevention of scale
DE4125315C2 (de) * 1991-07-31 1995-09-28 Oertzen Arndt H Gmbh & Co Vorrichtung zum Reinigen von Rohrleitungen

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CA2157916A1 (en) 1994-09-29
WO1994021865A1 (en) 1994-09-29
ATE170583T1 (de) 1998-09-15
JPH08509908A (ja) 1996-10-22
DE69413017T2 (de) 1999-01-28
AU6490394A (en) 1994-10-11
BR9406139A (pt) 1996-01-30
CA2157916C (en) 2000-01-25
EP0690944A1 (de) 1996-01-10
DE69413017D1 (de) 1998-10-08
JP3597193B2 (ja) 2004-12-02
AU673426B2 (en) 1996-11-07

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