EP0652305B1 - Verfahren zur korossionsinhibierung fur geschlossenen Kühlkreislaufer. - Google Patents

Verfahren zur korossionsinhibierung fur geschlossenen Kühlkreislaufer. Download PDF

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Publication number
EP0652305B1
EP0652305B1 EP94117381A EP94117381A EP0652305B1 EP 0652305 B1 EP0652305 B1 EP 0652305B1 EP 94117381 A EP94117381 A EP 94117381A EP 94117381 A EP94117381 A EP 94117381A EP 0652305 B1 EP0652305 B1 EP 0652305B1
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EP
European Patent Office
Prior art keywords
ppm
fluid
corrosion
sorbitol
water
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Expired - Lifetime
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EP94117381A
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English (en)
French (fr)
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EP0652305A1 (de
Inventor
Kaveh Sotoudeh
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ChampionX LLC
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Nalco Chemical Co
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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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds

Definitions

  • the invention relates to methods for the prevention of scale and corrosion on metal surfaces in contact with water based fluids, in particular aqueous fluids, having a conductivity of 100 micromhos or less in closed cooling or heating systems.
  • Closed recirculating water systems are used for a variety of heating and cooling systems. These systems range from those used in automobile and truck cooling systems, heating and cooling of buildings, the cooling of molten steel in continuous casting units, the cooling of industrial process equipment, and many other applications. In all of these systems, the prevention of scaling and the minimization of corrosion of metal parts in contact with the heating or cooling liquid are of paramount importance. While the liquids used in the heating or cooling systems are primarily aqueous, these fluids may contain in certain instances high levels of anti-freeze compounds such as ethylene glycol. In other instances, the cooling systems may be required to be relatively pure aqueous fluids such as in high heat flux or low conductivity systems which are employed in the steel industry.
  • nitrites are suspected carcinogens
  • molybdates and chromates are heavy metals
  • amines are reactive
  • phosphates provide a nutrient source for algae when discharged.
  • US-A-5 330 683 discloses the use of certain sorbitol, and gluconate mixtures which may optionally contain borates as effective corrosion and scale inhibitors for brine based refrigeration systems. Surprisingly, when the additives of the above patent were tested as corrosion and scale inhibitors for non-brine systems, they performed well, at lower dosages than those required in the above patent.
  • DE-A-39 04 733 discloses corrosion inhibitors for protecting metals being in contact with water, in particular in boiler water systems.
  • the corrosion inhibitors disclosed therein consist of tannic acid, a sugar and an aldonic acid in a proportion (parts by weight) of 100:(100-500):(250-500).
  • the corrosion inhibitors described in the above document are used in concentrations of 500 to 2000 ppm in the boiler water.
  • GB-A-2 027 002 refers to a process of inhibiting corrosion of ferrous metal in an aqueous medium by adding to the aqueous medium sorbitol in combination with benzotriazole or tolyltriazole and a water-soluble phosphate.
  • the object of this invention is in particular to provide to the art a scale and corrosion control method that performs in normal closed cooling or heating systems, but which also offers protection to mild steel in contact with closed cooling or heating system liquids in critical systems including high heat flux and low conductivity systems.
  • Subject-matter of the present invention is according to a first aspect a method for the prevention of corrosion on metal surfaces in contact with a water based fluid having a conductivity of 100 micromhos or less in a closed cooling or heating system which method comprise maintaining in the fluid from 5 ppm to 4000 ppm, preferably von 40 ppm to 2000 ppm, of sorbitol, from 5 ppm to 4000 ppm, preferably from 40 ppm to 2000 ppm, of an alkali metal gluconate, and up to 700 ppm, preferably from 5 ppm to 200 ppm, of borax as sodium tetraborate pentahydrate.
  • the fluid contains at least one additional ingredient selected from the group consisting of inert fluorescent tracers, anti-foam compounds, biocide control agents, and yellow metal corrosion inhibitors.
  • a particular useful yellow metal corrosion inhibitor is selected from the group consisting of tolyltriazole, mercaptobenzotriazole, and benzotriazole.
  • the water based fluid in the method of the present invention preferably is water, most preferably deionized water.
  • the fluid used in the method of the present invention preferably is maintained at a pH of from 6.5 to 11.5, in particularly of from 7.5 to 9.5.
  • an inert fluorescent tracer is added to the fluid in proportion to the amount of sorbitol present.
  • a corrosion inhibitory package is added to the fluid, the package comprising in weight%: 26.5 % of 50 weight% of gluconic acid 19.0 % of 70 weight% of sorbitol 8.4 % of 50 % of NaOH 1 % of 50 weight% of sodium tolyltriazole 3,13 % of sodium tetraborate pentahydrate balance water.
  • the present invention relates to a method for the prevention of scale and corrosion on metal surfaces in contact with aqueous fluids having a conductivity of 100 micromhos or less in closed cooling or heating systems which method comprises adding to the aqueous fluid present in such cooling or heating system a concentrate composition comprising (in weight%):
  • the closed cooling systems to which the corrosion and scale inhibitors used in this invention are applicable are those normally encountered in the heating and cooling systems of large buildings, machinery, and metals processing. These systems differ from open recirculating systems in that they are not exposed to the ambient air, and cooling is not achieved through evaporation as in the case of open recirculating systems.
  • Typical closed cooling systems operate by picking up heat at a heat rich point, and releasing the heat at a heat deficient point, generally a heat exchanger. While the term cooling system is used herein, the invention is equally applicable to closed hot water heating systems such as those found in large buildings, and the term cooling system is meant to encompass heating systems as well.
  • this invention finds particular utility in low conductivity water systems which without treatment are highly corrosive to mild steel as naturally occurring waters but do not accomodate conventional inhibitors because their conductivity contributions are too significant.
  • Systems of this type include but are not limited to: hot water boiler coolant systems, chilled water systems, air compressors, heating and ventilating equipment systems (comfort systems), thermal storage, and ice systems and other systems where the presence of foreign materials in the event of leakage could cause severe contamination or scaling problems.
  • the coolant fluid in the closed system is generally pumped from point to point, although gravity may be used to move the fluid from an upper point to a lower point without the use of supplementary mechanical pumps.
  • Coolant fluids are generally aqueous, and depending upon their ultimate use, may be simple well water containing high levels of dissolved hardness ions (calcium and magnesium), treated municipal drinking water, or ion-exchanged, low conductivity water.
  • the fluids may on occasion be winterized in those locations requiring such treatment through the use of ethylene glycol or methanol anti-freeze additives. It is desirable in certain instances to use aqueous coolant fluids having low levels of alkali or alkaline earth metals contained therein. In these cases, it may be desirable to use a distilled or deionized water as the basis for the aqueous coolant fluid.
  • Typical coolants to which this invention finds applicability are water based, have a conductivity of 100 micromhos or less and contain from 0.1 - 1000 ppm of hardness expressed as CaCO 3 .
  • the coolants to which this invention finds applicability are water based and contain from 1.0 - 750 ppm of hardness expressed as CaCO 3 .
  • the coolants to which this invention finds applicability are water containing as little as 0.5 - 500 ppm of hardness expressed as CaCO 3 .
  • the metals used in closed cooling systems are categorized as mild steel or galvanized steel, although special steel alloys may be used in certain high heat flux or low conductivity applications. Occasionally, so called yellow metals, copper, and brass may be present in the system and the selection of corrosion and scale inhibitors must be weighed with these metals in mind.
  • most coolant systems which are the intended beneficiaries of the corrosion and scale protection agents of this invention are made of mixtures of various steel alloys including mild steel. When used with yellow metals, it is optional to add from 1-100 ppm of known copper corrosion inhibitors such as tolyltrizaole, benzotriazole and mercaptobenzothiazole.
  • the pH values of the aqueous coolant fluids contained in the closed cooling systems of this invention are maintained in the range of 6.5 to 11.5 and preferably from 7.5 to 9.5.
  • the corrosion and scale inhibitor used in the method of this invention is a blend of sorbitol, an alkali metal gluconate, and optionally borax. If yellow metals are present in the system, typical copper corrosion inhibitors such as tolyltriazole may also be added.
  • the corrosion and scale inhibitors used in this invention are added in enough quantity to provide from 5 ppm to 4000 ppm of gluconate, from 5 ppm to 4000 ppm of sorbitol and from 0 to 700 ppm of sodium tetraborate pentahydrate in the coolant contained in the system.
  • from 40 ppm to 2000 ppm of gluconate is present and most preferably from 80 ppm to 200 ppm of gluconate is added.
  • from 40 ppm to 2000 ppm of sorbitol is present in the coolant liquid.
  • Most preferably, from 80 ppm to 200 ppm of sorbitol is added to the coolant liquid.
  • borax as sodium tetraborate pentahydrate
  • from 10 ppm to 60 ppm of sodium tetraborate pentahydrate is added to the coolant liquid.
  • While the dosages to the coolant fluids given above are typical, they may vary depending upon the hardness present in the coolant. Dosages of active ingredients are typically lowered in the case of low conductivity systems containing little hardness, and increased for coolants containing hardness causing constituents.
  • a typical formulation for use in this invention may broadly comprise in percentages by weight: Water 95-10 Sodium Gluconate 2-25 Sorbitol 2-25 Sodium Tetraborate 0-9
  • a formulation for use in this invention will comprise: Water 90-15 Sodium Gluconate 3-20 Sorbitol 3-20 Sodium Tetraborate 0.5-7
  • a formulation for use in this invention will comprise: Water 85-25 Sodium Gluconate 5-15 Sorbitol 5-15 Sodium Tetraborate 1-5
  • a preferred corrosion inhibitory package used for the practice of this invention comprises in percentages by weight:
  • the gluconate used in this invention is an alkali metal gluconate salt.
  • sodium gluconate is employed although other alkali metal salts of gluconate may be utilized.
  • Sodium gluconate is available commercially from the American International Chemical Inc as sodium gluconate.
  • gluconic acid may also be used in the preparation of the corrosion inhibitors of this invention, although, if the acid form is utilized, it is preferred to neutralize it with an alkali metal hydroxide either prior to addition to the formula, or after the other ingredients have been mixed so as to avoid the possibility of having a low pH in the coolant system that is being treated.
  • the sorbitol utilized as an ingredient in this invention is generally of a technical grade, although food grades may also be employed.
  • a preferred sorbitol for use in this invention is available from ICI Americas Inc. under the tradename SORBO.
  • the borate material utilized in this invention is generally categorized as borax, Na 2 B 4 O 7 . While the sodium salt is preferred, other alkali metal tetraborate salts can be used.
  • an inert fluorescent indicator described and claimed in US-A-5,006,311 and US-A-5,132,096 rather than the transition metal tracers described in US-A-4,966,711 and US-A-5,200,106 above.
  • an inert fluorescent tracer dye is added to the system in known concentration to the sorbitol ,gluconate or borax, and is used to monitor the dosage of active treatment chemicals in the coolant system through the use of fluorescence spectroscopy.
  • gluconate/sorbitol/blends of this invention have been shown to not foster the growth of bacteria, mold, slime or algae in coolant systems, process leaks into the system may necessitate the inclusion of a microbiocide into the system. While prior art systems employing nitrite based corrosion inhibitors could not utilize the so called oxidizing biocides, oxidizing biocides may be used in the processes of the instant invention.
  • Typical oxidizing biocides which are compatible with the gluconate/sorbitol/blends of this invention include chlorine, calcium hypochlorite, stabilized chlorine, sodium hypochlorite, and mixtures of sodium bromide with chlorine or hypochlorite.
  • Non-oxidizing biocides may also be employed in conjunction with the formulations of this invention.
  • Typical non-oxidizing biocides that may find utility in the corrosion and scale control formulations of this invention include: 2,2-dibromo-3-nitrilopropionamide, polyoxyethylene (dimethyliminio)ethylene (dimethyliminio)ethylene; 5-chloro-2-methyl-4-isothiazolin-3-one; 2-methyl-4-isothiazolin-3-one; glutaraldehyde, kathon** , tetrabuthylazine* , and methylenebisthiocyanate.
  • the examples of biocides given herein are meant to be representative and are no in way inclusive of the current commercially available oxidizing and non-oxidizing biocides which may find utility in the coolant system treatments of this invention.
  • the corrosion inhibitors of this invention were evaluated against several commonly available commercial closed system cooling inhibitor formulations. The experiments were conducted in the following manner:
  • a liter of water containing the ingredients to be tested is placed into a one liter container.
  • the container is then placed in a constant temperature bath.
  • the corrosive water is agitated to 0,30 m/s (1 foot/second) using a magnetic stirrer.
  • the constant temperature bath is heated to maintain 43°C (110°F) inside the container.
  • the corrosion coupons are suspended in the container using an ordinary Teflon tape. the tape needs to be rolled into a string before it can be inserted into the small hole at one end of the corrosion coupon.
  • the coupon is suspended in the corrosion cell by pinching the ends of the rolled Teflon tape against the outside wall of the corrosion cell with a rubber band. Excessive evaporation of the corrosive water is eliminated by covering the top of the corrosion cell with a plastic wrap, Saran brand wrap being preferred.
  • the test duration is 14 days, and the temperature of the corrosive water as well as the stirring action of the magnetic stirrer are checked daily.
  • the coupon is removed from the cell and cleaned of its corrosion products by an abrasive Nylon pad. After rinsing with deionized water, the coupon is dried and weighed.
  • the corrosion inhibitors of this invention were evaluated in a pilot high heat flux recirculating cooling unit.
  • This unit consisted of a 946 l (250 gallon) tank equipped with a heat exchanger to allow regulation of the temperature in the tank, a bottom outlet leading to an adjustable recirculating pump. After the pump, water passed through a 240 volt copper clad electrical heater having a high output and back to the top opening of the tank. Sufficient electrical energy could be added to the heater. Temperature and flow could be monitored at several points. Corraters were installed to measure corrosion rates, and corrosion coupons could be added to the system.
  • the final dosage of Compound A was approximately 300 ppm and total chlorine was 3.04 ppm. It was apparent that as the product dosage was increased, mild steel corrosion decreased over time. Over the next 120 hrs., the corrosion rate on mild steel decreased from 0,12 to 0,05 mm/year (4.80 to 1.80 mpy) and still appeared to be decreasing over time as the test was ended. Copper corrosion remained at approximately 0,0025 mm/year (0.10 mpy). The corrosion rate on the mild steel coupon was determined to be 0,07 mm/year (3.12 mpy), which was approximately the average corrosion rate for mild steel during the period.
  • the heat transfer surface (mild steel) had a yellowish color with some raised, brownish spots and the unheated surface had more of the raised deposits, which left pits on the heater material.
  • the deposit on the heated and unheated areas were analyzed and the analytical results showed that the material was approximately 99% iron as Fe 2 0 3 and less than 1% carbonate as CO 2 . There was less than 1% dichloromethane extractables.
  • the initial dosage of Compound A was 183 ppm with stabilized chlorine added to provide chlorine present at 5 ppm. During the first 35 hrs. the product dosage did not provide enough protection against corrosion when maintaining this dosage of chlorine. Mild steel corrosion increased from 0,015 to 0,030 mm/year (0.6 to 1.20 mpy) during that period. As a result, dosage of Compound A was increased to 300 ppm over the next 60 hours. As Compound A was added, corrosion rate on mild steel increased for a short period of time and then continued to again increase. Copper corrosion remained at .10 mpy for the duration of the test, while mild corrosion was increasing over time. The copper surface of the heater was smooth and no deposition or discoloration was observed. The corrosion rate that was obtained on the mild steel coupon was about 1,08 mm/year (20 mpy).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (11)

  1. Verfahren zur Verhinderung der Korrosion auf Metalloberflächen, die mit einer Flüssigkeit auf Wasserbasis in Kontakt stehen, die eine elektrische Leitfähigkeit von 100 Mikromhos oder weniger aufweist, in einem geschlossenen Kühl- oder Heizsystem, wobei das Verfahren umfaßt das Aufrechterhalten in der Flüssigkeit von
    5 ppm bis 4000 ppm Sorbit,
    5 ppm bis 4000 ppm eines Alkalimetallgluconats und
    bis zu 700 ppm Borax als Natriumtetraborat-pentahydrat.
  2. Verfahren nach Anspruch 1, das umfaßt das Aufrechterhalten in der Flüssigkeit von
    40 ppm bis 2000 ppm Sorbit,
    40 ppm bis 2000 ppm eines Alkalimetallgluconats und
    5 ppm bis 200 ppm Borax.
  3. Verfahren nach Anspruch 1 oder 2, worin die Flüssigkeit mindestens einen zusätzlichen Bestandteil enthält, der ausgewählt wird aus der Gruppe, die besteht aus inerten fluoreszierenden Tracern, Antischaum-Verbindungen, biociden Kontrollmitteln und Gelbmetall-Korrosionsinhibitoren.
  4. Verfahren nach Anspruch 3, worin der Gelbmetall-Korrosionsinhibitor ausgewählt wird aus der Gruppe, die besteht aus Tolyltriazol, Mercaptobenzotriazol und Benzotriazol.
  5. Verfahren nach einem der Ansprüche 1 bis 4, worin die Flüssigkeit Wasser ist.
  6. Verfahren nach Anspruch 5, worin die Flüssigkeit entionisiertes Wasser ist.
  7. Verfahren nach einem der Ansprüche 1 bis 6, worin die Flüssigkeit bei einem pH-Wert von 6,5 bis 11,5 gehalten wird.
  8. Verfahren nach Anspruch 7, worin die Flüssigkeit bei einem pH-Wert von 7,5 bis 9,5 gehalten wird.
  9. Verfahren nach einem der Ansprüche 3 bis 8, worin ein inerter fluoreszierender Tracer der Flüssigkeit zugesetzt wird proportional zur Menge des vorhandenen Sorbits.
  10. Verfahren nach einem der Ansprüche 3 bis 9, worin der Flüssigkeit ein Korrosionsinhibitor-Paket zugegeben wird, das (in Gew.-%) umfaßt:
       26,5 % von 50 Gew.-% Gluconsäure
       19,0 % von 70 Gew.-% Sorbit
       8,4 % von 50 % NaOH
       1 % von 50 Gew.-% Natriumtolyltriazol
       3,13 % Natriumtetraborat-pentahydrat
       Rest Wasser.
  11. Verfahren zur Verhinderung von Scale-Bildung und Korrosion auf Metalloberflächen im Kontakt mit wäßrigen Flüssigkeiten, die eine elektrische Leiffähigkeit von 100 Mikromhos oder weniger aufweisen, in geschlossenen Kühl- oder Heizsystemen, wobei das Verfahren umfaßt die Zugabe zu der wäßrigen Flüssigkeit, die in einem solchen Kühl- oder Heizsystem vorliegt, einer Konzentrat-Zusammensetzung, die (in Gew.-%)umfaßt:
    a) 2-25 % Sorbit
    b) 2-25 % eines Alkalimetallgluconats
    c) 0-9 % Borax und
    d) Rest Wasser
    in einer Menge, die ausreicht, um innerhalb der Flüssigkeit aufrechtzuerhalten
    5 ppm bis 4000 ppm Sorbit,
    5 ppm bis 4000 ppm eines Alkalimetallgluconats und
    bis zu 700 ppm Borax als Natriumtetraborat-pentahydrat.
EP94117381A 1993-11-04 1994-11-03 Verfahren zur korossionsinhibierung fur geschlossenen Kühlkreislaufer. Expired - Lifetime EP0652305B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14555693A 1993-11-04 1993-11-04
US145556 1993-11-04

Publications (2)

Publication Number Publication Date
EP0652305A1 EP0652305A1 (de) 1995-05-10
EP0652305B1 true EP0652305B1 (de) 1999-04-07

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EP (1) EP0652305B1 (de)
JP (1) JP3383441B2 (de)
BR (1) BR9404329A (de)
CA (1) CA2134908A1 (de)
DE (1) DE69417685T2 (de)

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USD752712S1 (en) 2013-03-16 2016-03-29 Kohler Co. Shower faceplate for shower device
US9315624B2 (en) 2007-11-15 2016-04-19 The University Of Montana Hydroxypolyamide gel forming agents
US9347024B2 (en) 2011-04-21 2016-05-24 Rivertop Renewables, Inc. Calcium sequestering composition
US9346736B2 (en) 2013-03-13 2016-05-24 Rivertop Renewables, Inc. Oxidation process

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JP2005508248A (ja) * 2001-11-06 2005-03-31 バディ ドン グレイ， 冷却液処理処方物
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AU2003248060A1 (en) 2003-07-11 2005-01-28 Shishiai-Kabushikigaisha Cooling fluid composition for fuel battery
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JP2007255788A (ja) * 2006-03-23 2007-10-04 Aquas Corp 蓄熱冷温水系の管理方法
JP4936772B2 (ja) * 2006-04-10 2012-05-23 三菱電機株式会社 水処理方法
US20090250653A1 (en) 2006-08-07 2009-10-08 Kiely Donald E Hydroxycarboxylic Acids and Salts
US7692041B2 (en) 2006-08-07 2010-04-06 The University Of Montana Method of oxidation using nitric acid
US8025840B2 (en) 2008-10-31 2011-09-27 General Electric Company Compositions and methods for inhibiting corrosion in aqueous media
US8021607B2 (en) 2008-10-31 2011-09-20 General Electric Company Methods for inhibiting corrosion in aqueous media
CN102408880A (zh) * 2010-09-23 2012-04-11 中国石油化工集团公司 一种乙二醇水溶液冷却剂
CN106048616A (zh) * 2010-11-11 2016-10-26 里弗领袖可再生能源公司 腐蚀抑制组合物
JP6047781B2 (ja) * 2012-08-28 2016-12-21 中部キレスト株式会社 防錆剤組成物および水性防錆潤滑剤、並びにこれを用いた金属材の加工法
EP2925826A1 (de) 2012-11-28 2015-10-07 Rivertop Renewables Korrosionshemmende und gefrierpunktsenkende zusammensetzungen
US9670124B2 (en) 2013-03-13 2017-06-06 Rivertop Renewables, Inc. Nitric acid oxidation process
BR112015022284A2 (pt) 2013-03-13 2017-07-18 Rivertop Renewables Inc processos de oxidação de ácido nítrico melhorados
US9677031B2 (en) 2014-06-20 2017-06-13 Ecolab Usa Inc. Catalyzed non-staining high alkaline CIP cleaner

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EP0652305A1 (de) 1995-05-10
BR9404329A (pt) 1995-07-04
DE69417685T2 (de) 1999-09-16
JP3383441B2 (ja) 2003-03-04
DE69417685D1 (de) 1999-05-12
JPH07258871A (ja) 1995-10-09
CA2134908A1 (en) 1995-05-05

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