US3072502A - Process for removing copper-containing iron oxide scale from metal surfaces - Google Patents

Process for removing copper-containing iron oxide scale from metal surfaces Download PDF

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Publication number
US3072502A
US3072502A US89116A US8911661A US3072502A US 3072502 A US3072502 A US 3072502A US 89116 A US89116 A US 89116A US 8911661 A US8911661 A US 8911661A US 3072502 A US3072502 A US 3072502A
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United States
Prior art keywords
solution
copper
citric acid
scale
cleaning
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Expired - Lifetime
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US89116A
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English (en)
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Alfano Salvatore
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Pfizer Inc
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Pfizer Inc
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Priority to US89116A priority Critical patent/US3072502A/en
Priority to GB20707/61A priority patent/GB904515A/en
Priority to BE613507A priority patent/BE613507A/fr
Priority to DEP28782A priority patent/DE1264351B/de
Priority to FR887882A priority patent/FR1314838A/fr
Application granted granted Critical
Publication of US3072502A publication Critical patent/US3072502A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • 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

Definitions

  • Operational scale deposited in steam-generating equipment usually consists of oxides of iron, often magnetite (Fe O .FeO) together with some red iron oxide (Fe O
  • Fe O magnetite
  • Fe O red iron oxide
  • the unit is fabricated in part from alloys of copper, e.g. for the condensers, the scale will be found to contain copper as well, in the form of the elemental metal and sometimes as cuprous and cupric oxides.
  • Such scale is generally tightly adherent and low in porosity. Its gradual build-up reduces heat transfer and water circulation to the point where, usually every one to four years, it must be removed. Since the shutdown of a high capacity boiler can easily represent losses of thousands of dollars per day, it is obvious that the most rapid and effective cleaning is desirable.
  • a further object is a process which is safe to both per- Patented Jan. 8, 1963 sonnel and equipment, and which may be used even with very high pressure units containing austenitic alloys.
  • Another object is a process which is rapidly efiective even where tightly adherent magnetite scale predominates. Still another object is a cleaning process which efiiciently utilizes relatively lowconcentrations of inexpensive, readily available cleaning ingredients.
  • the first step of the new process consists of contacting the scaled surfaces with an aqueous solution of citric acid adjusted to a pH between about 2.5 and about 5 with a nitrogen base. While other acids, such as gluconic, tartaric, oxalic, lactic, glucoheptonic, glycollic, saccharic or malic acids, or mixtures thereof, may be effective in varying degree in the first step of my new process, citric acid possesses the virtues of high effectiveness, low corrosion rate, non-toxicity, ready availability and low cost. Mineral acids are not suitable.
  • the nitrogen base which I employ for the pH adjustment may be ammonia, an ethanolamine, or an aliphatic hydrocarbon amine.
  • an ethanolamine I mean ethanolamine, diethanolamine or triethanolamine. Any aliphatic hydrocarbon amine, primary, secondary or tertiary, may be employed, provided that it is water-soluble.
  • Such amines include trimethylamine, 'diethylamine, the various primary butyland amylamines, ethylamine, propylamine, dimethylamine, triethylam% and the like. Ordinarily, ammonia will be preferred for its low cost and high effectiveness.
  • citric acid for high capacity and rapid cleaning I employ the citric acid in a concentration of at least about 1% W./v. Any concentration above 1% up to saturation may be used,but ordinarily concentrations above 10% w./v. offer no added advantage and are unnecessary. Concentrations between about 1.5 and about 3% w./v. are generally preferred.
  • the expression w./v. means grams per 100 milliters; of page xiii, Merck Index, 6th edition, 1952.
  • the solution is light or freshly deposited, room temperature treatment is adequate.
  • temperatures from about 140 F. up to the boiling point of the solution are most efiective. If desired, temperatures above the atmospheric boiling point may be employed by operating under pressure. However, this expedient is generally unnecessary. It is noteworthy that the process is so safe that no corrosion inhibitor is normally required, even at the higher temperatures.
  • the progress of the cleaning is conveniently followed by withdrawing liquid samples periodically and assaying for iron according to any of the standard procedures. When the iron content of the solution becomes substantially constant the first phase of the operation may be regarded as substantially complete. Generally this will be found to occur after about one to three hours at temperatures of about 140-160 F.
  • Alkaline step.--In this step I utilize the same cleaning solution, merely raising the pH with one of the nitrogen bases already described, without even draining the boiler.
  • Triethanolamine is a particularly convenient base to Work with, since its low vapor pressure avoids fumes at the higher pHs.
  • ammonia is eminently suitable, and economy may often dictate its use.
  • the base is conveniently introduced in water solution, which may be pumped into the boiler. This will displace a small portion of the cleaning solution to waste, but the loss is inconsequential.
  • the pH should be adjusted to between about 8 and about 10, preferably about pH 9. If mineral acid had been used in the first step, adherent iron oxides would reprecipitate upon thus raising the pH to the effective range.
  • oxidizing agent is often beneficial in increasing the reaction rate.
  • a Wide range of oxidants are suitable. Air or oxygen are eminently suitable and are readily introduced by injection into the solution through a sparger or bubbler during alkaline cleaning.
  • gaseous oxidants which may be employed in the same manner is nitrogen tetraoxide.
  • liquid or solid oxidants such as potassium permanganate or nitrophenylsulfonic acid sodium salt
  • Particularly convenient and effective are watersoluble inorganic salts, especially persulfates, perchlorates, bromates or nitrites.
  • Suitable salts include, for example, the sodium, potassium and ammonium salts. Very little of such oxidant is required for the desired beneficial effect, ordinarily about one part by Weight for each part by Weight of copper to be removed.
  • the temperature for this step is not critical. Room temperature (or even lower) is quite suitable, but temperatures up to boiling may be used if desired.
  • the solution at pH 8-10 is best circulated as before, until standard analysis of liquid samples indicates that the copper content is substantially constant. With air or other added oxidant one to two hours will usually suffice.
  • the cleaning solution may be drained to waste and the unit rinsed with water.
  • the treated surfaces are left silvery grey in color, scale-and copper-free, and ready for return to service.
  • the entire operation usually requires only about 5-8 hours, even for a large unit.
  • Example I A conventional controlled circulation boiler having a capacity of 1.5 million lbs. steam per hour at about 2000 psi. is shut down to remove operational deposits from the inner surfaces of the steel boiler, steam drum, risers and downcomer. The deposits are estimated to contain about 1000 lbs. of Fe O and about 50-100 lbs. of copper picked up from the condenser.
  • the boiler water temperature is allowed to cool to 200 While a solution of 3000 lbs. citric acid in about 3000 gallons of Water is prepared in a separate tank and adjusted to about pH 2.7 with aqueous ammonia. This solution is then pumped into the bottom of the boiler, displacing an equal amount of water which is permitted to overflow to waste from the steam drum.
  • the diluted cleaning solution in the boiler has a volume of about 22,000 gallons and a pH of approximately 3.7.
  • the boiler pumps are operated to slowly circulate the solution through the system (about 1 ft./sec. in the tubes) while periodic samples are withdrawn for iron analysis. After about two hours the iron content of the cleaning solution has become substantially constant at a value corresponding to about 900 pounds of dissolved iron, and the solution temperature has dropped to about F.
  • the solution is slowly circulated by means of the boiler pumps and aeration is continued without applying heat. After an hour the copper content Of the cleaning solution has leveled off at a value corresponding to approximately 80 pounds of dissolved copper.
  • Example II A mild steel boiler tube sample, coated with a scale which proves upon analysis to contain magnetite, Fe O copper, and oxides of copper, is immersed in a 1% w./v. aqueous citric acid solution previously adjusted to pH 2.5 with triethanolamine, and the solution is heated at about 140 F. with gentle agitation for about 3 hours. At this time the iron content of the solution is substantially constant at a level corresponding to the original molar concentration of citric acid. The surface is free of scale and coated with copper.
  • Example III A number of scaled tube samples similar to that of Example II are immersed in 1.5% citric acid solutions which have been adjusted to pH 5 with a series of amines:
  • Trimethylamine Diethylamine Diethanolamine Isobutylamine n-Amylamine Each solution with its immersed plate is boiled until the scale is removed and the plates covered with a light copper film. The molar iron content of the solutions corresponds closely to the citrate introduced. Each pH is now adjusted to about 8 with the amine previously employed. Air is then bubbled into the solutions with gentle stirring'until the copper has dissolved and clean metal surface exposed.
  • Example V A number of scaled boiler tube samples similar to those of Examples II and IV are immersed in 3% w./v. citric acid solutions adjusted to pH 4 with ammonia.
  • the various solutions are heated at F. with gentle agitation until the copper plating has dissolved.
  • a process for the removal of copper-containing ir n oxide scale from metal surfaces which comprises contacting said surfaces with an aqueous solution containing at least about 1% w./v. citric acid together with sufficient base to provide a pH between about 2.5 and about 5, said base being selected from the group consisting of ammonia, an unsubstituted ethanolamine and a water-soluble aliphatic hydrocarbon amine, continuing said contact until the iron content of said solution becomes substantially constant, subsequently adjusting the pH of said solution with one of said bases to a value between about 8 and about 10, and maintaining the pH within said alkaline range while continuing said contact until the copper content of said solution becomes substantially constant.
  • said salt is selected from the group consisting of persulfates, perchlorates, bromates and nitrites.
  • a process for the removal of copper-containing iron oxide scale from metal surfaces which comprises contacting said surfaces with an aqueous monoamrnonium citrate solution at a concentration equivalent to between about 1.5 and about 3% w./v. citric acid and a temperature between about 140" F. and the boiling point of said solution until the iron content of said solution becomes substantially constant, sub equently adjusting said solution with ammonia to a pH between about 8 and about 10 at a free citrate concentration equivalent to at least about 0.5% w./v. citric acid, and maintaining said alkaline solution in contact with said surfaces while injecting air until the copper content of said solution becomes substantially constant.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
US89116A 1961-02-14 1961-02-14 Process for removing copper-containing iron oxide scale from metal surfaces Expired - Lifetime US3072502A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US89116A US3072502A (en) 1961-02-14 1961-02-14 Process for removing copper-containing iron oxide scale from metal surfaces
GB20707/61A GB904515A (en) 1961-02-14 1961-06-08 Treatment of metal surfaces
BE613507A BE613507A (fr) 1961-02-14 1962-02-05 Procédé pour le traitement de surfaces métalliques
DEP28782A DE1264351B (de) 1961-02-14 1962-02-10 Verfahren zur Entfernung von kupferhaltigem Eisenoxydkesselstein
FR887882A FR1314838A (fr) 1961-02-14 1962-02-13 Perfectionnements apportés aux procédés pour le décapage de surfaces métalliques

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US89116A US3072502A (en) 1961-02-14 1961-02-14 Process for removing copper-containing iron oxide scale from metal surfaces

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US (1) US3072502A (fr)
BE (1) BE613507A (fr)
DE (1) DE1264351B (fr)
FR (1) FR1314838A (fr)
GB (1) GB904515A (fr)

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3447965A (en) * 1966-10-31 1969-06-03 Dow Chemical Co Removal of copper containing scale from ferrous surfaces
US3522093A (en) * 1967-02-27 1970-07-28 Chem Cleaning & Equipment Serv Processes of cleaning and passivating reactor equipment
US3639278A (en) * 1967-12-27 1972-02-01 Grace W R & Co Composition and method for inhibiting and removing scale using glycolic acid and lignosulfonic acid
US3664870A (en) * 1969-10-29 1972-05-23 Nalco Chemical Co Removal and separation of metallic oxide scale
US3993575A (en) * 1975-05-27 1976-11-23 Fine Organics Inc. Hard surface acid cleaner and brightener
US3996148A (en) * 1974-07-25 1976-12-07 Pierre Fusey Basic detergent for liquid lyes
US4209418A (en) * 1978-07-18 1980-06-24 Union Carbide Corporation Gelatin benzimidazole blends as inhibitors for carboxylic acids
US4250048A (en) * 1979-07-03 1981-02-10 Custom Research And Development Metal oxide remover containing a strong mineral acid, chelating agent and a basic ammonia derivative
US4264418A (en) * 1978-09-19 1981-04-28 Kilene Corp. Method for detersifying and oxide coating removal
USRE30714E (en) * 1965-10-18 1981-08-18 The Dow Chemical Company Removal of copper containing incrustations from ferrous surfaces
USRE30796E (en) * 1962-07-23 1981-11-17 The Dow Chemical Co. Scale removal, ferrous metal passivation and compositions therefor
US4452643A (en) * 1983-01-12 1984-06-05 Halliburton Company Method of removing copper and copper oxide from a ferrous metal surface
US4590100A (en) * 1983-10-28 1986-05-20 The United States Of America As Represented By The Secretary Of The Navy Passivation of steel with aqueous amine solutions preparatory to application of non-aqueous protective coatings
US4678597A (en) * 1986-03-17 1987-07-07 Am International, Inc. Chemical cleaning solution and method
US4692252A (en) * 1986-03-24 1987-09-08 Vertech Treatment Systems, Inc. Method of removing scale from wet oxidation treatment apparatus
US4810405A (en) * 1987-10-21 1989-03-07 Dearborn Chemical Company, Limited Rust removal and composition thereof
US4828743A (en) * 1987-11-20 1989-05-09 Boyle-Midway Household Products, Inc. Composition for rust removal and method of use thereof
US4861386A (en) * 1986-12-12 1989-08-29 Dowell Schlumberger Incorporated Enhanced cleaning procedure for copper alloy equipment
US5009714A (en) * 1989-08-25 1991-04-23 Halliburton Company Process for removing copper and copper oxide deposits from surfaces
US5015298A (en) * 1989-08-22 1991-05-14 Halliburton Company Composition and method for removing iron containing deposits from equipment constructed of dissimilar metals
US5021096A (en) * 1988-11-10 1991-06-04 Khodabandeh Abadi Method for removal of scale
US5296042A (en) * 1992-11-06 1994-03-22 C. L. R. Resources, Inc. Composition and process for treating sheet steel
US5482174A (en) * 1993-08-02 1996-01-09 Fujitsu Limited Method for removing copper oxide on the surface of a copper film and a method for patterning a copper film
WO1996009994A1 (fr) * 1994-09-26 1996-04-04 E.R. Squibb & Sons, Inc. Traitement alcalin d'acier inoxydable
US5529637A (en) * 1994-02-17 1996-06-25 Hydrochem Industrial Services, Inc. Formic-carboxylic acid mixtures for removing iron oxide sclae from steel surfaces
US5542981A (en) * 1994-06-22 1996-08-06 Lee, Sr.; Clel E. Process for removing mineral deposits from lagoon recycle lines
US5766684A (en) * 1994-09-26 1998-06-16 Calgon Vestal, Inc. Stainless steel acid treatment
DE19857342A1 (de) * 1998-12-11 2000-02-17 Siemens Ag Verfahren zum Reinigen eines Behälters
US6042742A (en) * 1994-10-07 2000-03-28 Whittemore; Michael Composition and method for inhibiting chloride-induced corrosion of and limescale formation on ferrous metals and alloys
US6395693B1 (en) 1999-09-27 2002-05-28 Cabot Microelectronics Corporation Cleaning solution for semiconductor surfaces following chemical-mechanical polishing
US6827090B2 (en) * 1999-12-10 2004-12-07 R. Späne KG Process for removing deposits from water-carrying systems and devices for water supply
US20070267046A1 (en) * 2004-11-11 2007-11-22 Areva Np Gmbh Cleaning Process For Removing Magnetite-Containing Deposits From A Pressure Vessel Of A Power Station
WO2008107072A1 (fr) * 2007-03-07 2008-09-12 Areva Np Gmbh Procédé d'élimination de dépôts contenant de la magnétite et du cuivre de contenants d'installations industrielles et de centrales électriques
US20120145187A1 (en) * 2009-07-06 2012-06-14 Naigai Chemical Products Co., Ltd. Method for treatment of iron-based metal surface exposed to superheated steam
WO2014018787A1 (fr) * 2012-07-26 2014-01-30 Dominion Engineering, Inc. Procédés de réutilisation d'une solution de nettoyage
US11028680B2 (en) 2019-04-29 2021-06-08 Saudi Arabian Oil Company Forming mineral in fractures in a geological formation
US11186806B2 (en) * 2016-09-01 2021-11-30 Saudi Arabian Oil Company Treatment of sulfide scales
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US11885790B2 (en) 2021-12-13 2024-01-30 Saudi Arabian Oil Company Source productivity assay integrating pyrolysis data and X-ray diffraction data

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DE3533886A1 (de) * 1985-04-16 1987-03-26 Kraftwerk Union Ag Reinigungsverfahren

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US865700A (en) * 1907-01-30 1907-09-10 Maurice Hernsheim Pickling process.
US2567835A (en) * 1949-08-29 1951-09-11 Dow Chemical Co Removing copper-containing incrustations from steam generators
US2676900A (en) * 1947-07-08 1954-04-27 Hooker Electrochemical Co Processes for removal of oxides from the surface of metals
US2817606A (en) * 1955-03-01 1957-12-24 Klenzade Products Inc Cleaning process
CA602414A (en) * 1960-07-26 National Aluminate Corporation Scale removal
US2995477A (en) * 1955-05-26 1961-08-08 Celanese Corp Boiler cleaning process
US3000767A (en) * 1959-04-30 1961-09-19 Solvent Service Inc Method of cleaning internal ferrous metal surfaces of steam generating equipment
US3003899A (en) * 1957-05-17 1961-10-10 Dow Chemical Co Removal of scale deposits
US3013909A (en) * 1960-03-31 1961-12-19 Guyon P Pancer Method of chemical decontamination of stainless steel nuclear facilities

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DE708369C (de) * 1939-01-06 1941-07-19 Mansfeld A G Fuer Bergbau U Hu Verfahren zum Abloesen von aus Kupfer oder Kupferlegierungen bestehenden Auflagen von damit plattiertem Eisen oder Stahl
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FR1105891A (fr) * 1953-05-13 1955-12-08 Universal Oil Prod Co Inhibiteurs de corrosion et leurs applications
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Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA602414A (en) * 1960-07-26 National Aluminate Corporation Scale removal
US865700A (en) * 1907-01-30 1907-09-10 Maurice Hernsheim Pickling process.
US2676900A (en) * 1947-07-08 1954-04-27 Hooker Electrochemical Co Processes for removal of oxides from the surface of metals
US2567835A (en) * 1949-08-29 1951-09-11 Dow Chemical Co Removing copper-containing incrustations from steam generators
US2817606A (en) * 1955-03-01 1957-12-24 Klenzade Products Inc Cleaning process
US2995477A (en) * 1955-05-26 1961-08-08 Celanese Corp Boiler cleaning process
US3003899A (en) * 1957-05-17 1961-10-10 Dow Chemical Co Removal of scale deposits
US3000767A (en) * 1959-04-30 1961-09-19 Solvent Service Inc Method of cleaning internal ferrous metal surfaces of steam generating equipment
US3013909A (en) * 1960-03-31 1961-12-19 Guyon P Pancer Method of chemical decontamination of stainless steel nuclear facilities

Cited By (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE30796E (en) * 1962-07-23 1981-11-17 The Dow Chemical Co. Scale removal, ferrous metal passivation and compositions therefor
USRE30714E (en) * 1965-10-18 1981-08-18 The Dow Chemical Company Removal of copper containing incrustations from ferrous surfaces
US3447965A (en) * 1966-10-31 1969-06-03 Dow Chemical Co Removal of copper containing scale from ferrous surfaces
US3522093A (en) * 1967-02-27 1970-07-28 Chem Cleaning & Equipment Serv Processes of cleaning and passivating reactor equipment
US3639278A (en) * 1967-12-27 1972-02-01 Grace W R & Co Composition and method for inhibiting and removing scale using glycolic acid and lignosulfonic acid
US3664870A (en) * 1969-10-29 1972-05-23 Nalco Chemical Co Removal and separation of metallic oxide scale
US3996148A (en) * 1974-07-25 1976-12-07 Pierre Fusey Basic detergent for liquid lyes
US3993575A (en) * 1975-05-27 1976-11-23 Fine Organics Inc. Hard surface acid cleaner and brightener
US4209418A (en) * 1978-07-18 1980-06-24 Union Carbide Corporation Gelatin benzimidazole blends as inhibitors for carboxylic acids
US4264418A (en) * 1978-09-19 1981-04-28 Kilene Corp. Method for detersifying and oxide coating removal
US4250048A (en) * 1979-07-03 1981-02-10 Custom Research And Development Metal oxide remover containing a strong mineral acid, chelating agent and a basic ammonia derivative
US4452643A (en) * 1983-01-12 1984-06-05 Halliburton Company Method of removing copper and copper oxide from a ferrous metal surface
US4590100A (en) * 1983-10-28 1986-05-20 The United States Of America As Represented By The Secretary Of The Navy Passivation of steel with aqueous amine solutions preparatory to application of non-aqueous protective coatings
US4678597A (en) * 1986-03-17 1987-07-07 Am International, Inc. Chemical cleaning solution and method
US4692252A (en) * 1986-03-24 1987-09-08 Vertech Treatment Systems, Inc. Method of removing scale from wet oxidation treatment apparatus
EP0239701A3 (en) * 1986-03-24 1988-08-10 Vertech Treatment Systems, Inc. Method of removing scale from wet oxidation treatment apparatus
US4861386A (en) * 1986-12-12 1989-08-29 Dowell Schlumberger Incorporated Enhanced cleaning procedure for copper alloy equipment
US4810405A (en) * 1987-10-21 1989-03-07 Dearborn Chemical Company, Limited Rust removal and composition thereof
US4828743A (en) * 1987-11-20 1989-05-09 Boyle-Midway Household Products, Inc. Composition for rust removal and method of use thereof
US5021096A (en) * 1988-11-10 1991-06-04 Khodabandeh Abadi Method for removal of scale
US5015298A (en) * 1989-08-22 1991-05-14 Halliburton Company Composition and method for removing iron containing deposits from equipment constructed of dissimilar metals
US5009714A (en) * 1989-08-25 1991-04-23 Halliburton Company Process for removing copper and copper oxide deposits from surfaces
US5296042A (en) * 1992-11-06 1994-03-22 C. L. R. Resources, Inc. Composition and process for treating sheet steel
US5482174A (en) * 1993-08-02 1996-01-09 Fujitsu Limited Method for removing copper oxide on the surface of a copper film and a method for patterning a copper film
US5529637A (en) * 1994-02-17 1996-06-25 Hydrochem Industrial Services, Inc. Formic-carboxylic acid mixtures for removing iron oxide sclae from steel surfaces
US5679170A (en) * 1994-02-17 1997-10-21 Hydrochem Industrial Services, Inc. Methods for removing iron oxide scale from interior surfaces of steel vessels using formic acid-citric acid mixtures
US5542981A (en) * 1994-06-22 1996-08-06 Lee, Sr.; Clel E. Process for removing mineral deposits from lagoon recycle lines
WO1996009994A1 (fr) * 1994-09-26 1996-04-04 E.R. Squibb & Sons, Inc. Traitement alcalin d'acier inoxydable
US5766684A (en) * 1994-09-26 1998-06-16 Calgon Vestal, Inc. Stainless steel acid treatment
US5858118A (en) * 1994-09-26 1999-01-12 Calgon Vestal, Inc. Stainless steel alkali treatment
US6042742A (en) * 1994-10-07 2000-03-28 Whittemore; Michael Composition and method for inhibiting chloride-induced corrosion of and limescale formation on ferrous metals and alloys
DE19857342A1 (de) * 1998-12-11 2000-02-17 Siemens Ag Verfahren zum Reinigen eines Behälters
US6395693B1 (en) 1999-09-27 2002-05-28 Cabot Microelectronics Corporation Cleaning solution for semiconductor surfaces following chemical-mechanical polishing
US6541434B2 (en) 1999-09-27 2003-04-01 Cabot Microelectronics Corporation Cleaning solution for semiconductor surfaces following chemical-mechanical polishing
US6827090B2 (en) * 1999-12-10 2004-12-07 R. Späne KG Process for removing deposits from water-carrying systems and devices for water supply
US20070267046A1 (en) * 2004-11-11 2007-11-22 Areva Np Gmbh Cleaning Process For Removing Magnetite-Containing Deposits From A Pressure Vessel Of A Power Station
EP1819845B1 (fr) * 2004-11-11 2011-09-21 Areva NP GmbH Procede de nettoyage permettant d'eliminer les depots contenant de la magnetite d'une cuve sous pression d'une centrale electrique
US20100012154A1 (en) * 2007-03-07 2010-01-21 Areva Np Gmbh Method for removing deposits containing magnetite and copper from containers in industrial and power plants
US7931753B2 (en) 2007-03-07 2011-04-26 Areva Np Gmbh Method for removing deposits containing magnetite and copper from containers in industrial and power plants
WO2008107072A1 (fr) * 2007-03-07 2008-09-12 Areva Np Gmbh Procédé d'élimination de dépôts contenant de la magnétite et du cuivre de contenants d'installations industrielles et de centrales électriques
RU2453636C2 (ru) * 2007-03-07 2012-06-20 Арева Нп Гмбх Способ удаления отложений, содержащих магнетит и медь, из контейнеров промышленных и электроэнергетических установок
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BE613507A (fr) 1962-08-06
FR1314838A (fr) 1963-01-11
DE1264351B (de) 1968-03-21
GB904515A (en) 1962-08-29

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