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WO1996017033A1 - Agent de transfert de froid et de chaleur exempt de nitrite, de phosphate et d'amine - Google Patents

Agent de transfert de froid et de chaleur exempt de nitrite, de phosphate et d'amine Download PDF

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Publication number
WO1996017033A1
WO1996017033A1 PCT/DE1995/001516 DE9501516W WO9617033A1 WO 1996017033 A1 WO1996017033 A1 WO 1996017033A1 DE 9501516 W DE9501516 W DE 9501516W WO 9617033 A1 WO9617033 A1 WO 9617033A1
Authority
WO
WIPO (PCT)
Prior art keywords
heat transfer
transfer medium
acid
nitrite
corrosion
Prior art date
Application number
PCT/DE1995/001516
Other languages
German (de)
English (en)
Inventor
Andreas Wagner
Sigrid Kehrer
Dieter Schnurpfeil
Georg Reinhard
Klaus Schiller
Original Assignee
Buna Sow Leuna Olefinverbund Gmbh
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 Buna Sow Leuna Olefinverbund Gmbh filed Critical Buna Sow Leuna Olefinverbund Gmbh
Publication of WO1996017033A1 publication Critical patent/WO1996017033A1/fr

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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
    • 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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/144—Aminocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/20—Antifreeze additives therefor, e.g. for radiator 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
    • C23F11/14—Nitrogen-containing compounds

Definitions

  • Nitrite, phosphate and amine free coolant and heat transfer medium Nitrite, phosphate and amine free coolant and heat transfer medium
  • the invention includes a coolant and heat transfer medium based on water and 5 glycol for air conditioning, heat exchangers and cooling systems of internal combustion engines, which is free of toxic and environmentally harmful substances such as phosphates, nitrates, nitrites and amines.
  • the type and concentration of these cavitation and corrosion inhibiting additives as well as their combination in the respective inhibitor package mainly depend on the materials used, their surface properties, the temperature, the flow conditions and the presence of other water constituents. Depending on the main constituent of the inhibitor systems, a distinction is made between additives on sodium benzoate / sodium nitrate - Base and
  • sodium nitrite protects steel, cast iron and aluminum in 5 aqueous media, but increases corrosion in brass, lead and solder materials. Its protective effect is linked to the presence of dissolved oxygen and requires pH values> 6.5, otherwise it will decompose quickly. It is therefore usually used in combination with a salt which stabilizes the pH in the weakly alkaline range, such as sodium benzoate and / or borax
  • nitrites are poisons. For this reason alone, there are intensive efforts to replace nitrites as components of coolants and heat transfer agents. Nitrites are less prone to oxidize the organic components of coolants and heat transfer agents than chromates. However, it is a considerable disadvantage that nitrites
  • DE-AS 2 235 093 also proposes the use of salts of substituted benzoic acids.
  • the alkali salts of o-, m- and p-nitrobenzoic acid are also mentioned, but always in combination with an undiminished high proportion of sodium nitrite.
  • the substituted benzoic acids or their salts are used as a benzoate substitute and not as a nitrite substitute.
  • the claimed more effective corrosion protection for composites of light metal alloys with unalloyed bulk steels can therefore be clearly assigned to the optimization of the nitrite system.
  • DD-PS 218635 in addition to examples containing nitrite, the addition of nitrobenzoate in the sense of a previously customary inhibitor addition without simultaneous presence of sodium nitrite is also mentioned in an example, however the corrosion protection effect achieved with this mixture is on the synergistic effect of the reaction product of carboxymethyl cellulose with mercaptobenz - thiazole and 2-ethylhexanoic acid with conventional inhibitor components.
  • a fundamental disadvantage is the fact that this additional inhibitor package requires a separate manufacturing technology.
  • alkali nitrites can be replaced by antrachinone derivatives (DD-PS 225723).
  • DD-PS 225723 antrachinone derivatives
  • alkali or ammonium phosphates also have a clear corrosion protection for metals and metal composites.
  • Typical phosphate-based formulations are claimed by DE-OS 2 918 967, USP 4 085063, DE-OS 2 806 342.
  • the disadvantage of the phosphate-based inhibitor packages is that f> in the case of continuous use due to the deposition of zinc and / or
  • Calcium phosphate comes to incrustations, which reduce the functionality of the cooling or heat transfer system or question it.
  • Methacrylic acid copolymers in interaction with sulfonic acids in interaction with sulfonic acids
  • the task is to provide a glycol-based coolant or heat transfer medium with a corrosion protection system that ensures long-term action for the corrosion and cavitation protection of metals and metal composites in cooling and heat transfer systems.
  • the object is achieved by a nitrite-, phosphate- and amine-free coolant and heat transfer agent based on glycol with corrosion protection and
  • the polyacrylic acid used has a molecular weight in the range from 10,000 to 100,000.
  • the finished heat transfer medium is brought to a pH of 7.5 to
  • Example 1 shows the use of the additives according to the invention as anti-corrosion agents against unalloyed bulk steel St 38 in a continuous immersion test at 40 ° C. in synthetic hard water according to ASTM D 1384 with constant saturation of the test medium with air according to DIN 50905 T 3 + 4. l ()
  • the example shows the use of an additive according to the invention in a multifunctional inhibitor mixture in comparison with typical nitrite-containing mixtures, such as are used in conventional coolants based on ethylene glycol.
  • the mixtures of radiator protection agents specified in Table 2 are tested in accordance with ASTM D 1384.
  • TZBLATT The inhibitor formulations 1-4 set out in Table 2 correspond to the combination according to the invention with m-nitrobenzoic acid and polyacrylic acid. Recipe 5 contains only m - nitrobenzoic acid but no polyacrylic acid. This increases the corrosion removal.
  • recipe 6 In addition to m - nitrobenzoic acid and polyacrylic acid, recipe 6 also uses sodium nitrite and sodium nitrate, without the corrosion removal improving compared to recipes 1-4.
  • Formulations 7 and 8 are customary for the production of nitride-containing coolant. The examples shown show that the formulation according to the invention is superior.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

L'invention concerne un agent aqueux de transfert de froid et de chaleur qui contient du glycol et des inhibiteurs de corrosion et de cavitation classiques, dans lequel le nitrite est remplacé par une combinaison d'acides nitrobenzoïques ayant un indice pKa > 3 et d'acide polyacrylique avec 5 à 30 % d'acide éthylacrylique et un poids moléculaire compris entre 10.000 et 100.000.
PCT/DE1995/001516 1994-11-25 1995-11-03 Agent de transfert de froid et de chaleur exempt de nitrite, de phosphate et d'amine WO1996017033A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4442114.1 1994-11-25
DE19944442114 DE4442114A1 (de) 1994-11-25 1994-11-25 Nitrit-, phosphat- und aminfreies Kühl- und Wärmeübertragungsmittel

Publications (1)

Publication Number Publication Date
WO1996017033A1 true WO1996017033A1 (fr) 1996-06-06

Family

ID=6534217

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1995/001516 WO1996017033A1 (fr) 1994-11-25 1995-11-03 Agent de transfert de froid et de chaleur exempt de nitrite, de phosphate et d'amine

Country Status (2)

Country Link
DE (1) DE4442114A1 (fr)
WO (1) WO1996017033A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52103338A (en) * 1976-02-26 1977-08-30 Kouriyuu Kougiyou Kk Anticorrosive composition for metals
CA1027348A (fr) * 1974-02-22 1978-03-07 Betz Laboratories Repression de la corrosion dans un systeme de refroidissement en circuit ferme
JPS6086286A (ja) * 1983-05-31 1985-05-15 Nippon Nohyaku Co Ltd 水処理薬剤
EP0352120A2 (fr) * 1988-07-20 1990-01-24 The British Petroleum Company p.l.c. Agent antigel pour liquides de refroidissement
EP0524546A2 (fr) * 1991-07-23 1993-01-27 Ashland, Inc. Additif pour anti-gel/réfrigérant
EP0557761A1 (fr) * 1992-02-18 1993-09-01 BASF Aktiengesellschaft Composition réfrigerante stabile à l'eau dure contenant du phosphate

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU28635A1 (fr) * 1946-10-25
ZA713188B (en) * 1970-07-13 1972-08-30 Union Carbide Corp Corrosion inhibitors for alkanolamine gas treating systems
GB1461136A (en) * 1974-10-14 1977-01-13 Ici Ltd Corrosion inhibitors
DE2815016C2 (de) * 1978-04-07 1986-04-10 Henkel KGaA, 4000 Düsseldorf Korrosionsinhibitor für Brauchwassersysteme
US4277366A (en) * 1979-09-26 1981-07-07 Union Carbide Corporation Poly(alkylene oxide) composition
DE3000687A1 (de) * 1980-01-10 1981-07-16 Basf Ag, 6700 Ludwigshafen Kuehlerschutzmittel fuer wasserhaltige kuehlfluessigkeiten
DE3148230C2 (de) * 1981-12-05 1983-12-01 Hoechst Ag, 6230 Frankfurt "Nitritfreie Kühlflüssigkeiten auf der Basis von Glykolen"
AU617739B2 (en) * 1987-12-23 1991-12-05 Pharmacia & Upjohn Company Chimeric glycoproteins containing immunogenic segments of the glycoproteins of human respiratory syncytial virus
DE3819353A1 (de) * 1988-06-07 1989-12-14 Hoechst Ag Korrosionsinhibierte und physiologisch vorteilhafte funktionelle fluessigkeiten auf der basis von glykolen
DE3832592A1 (de) * 1988-09-24 1990-03-29 Basf Ag Nitrit- und phosphatfreie kuehlstoffmischungen auf glykolbasis

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1027348A (fr) * 1974-02-22 1978-03-07 Betz Laboratories Repression de la corrosion dans un systeme de refroidissement en circuit ferme
JPS52103338A (en) * 1976-02-26 1977-08-30 Kouriyuu Kougiyou Kk Anticorrosive composition for metals
JPS6086286A (ja) * 1983-05-31 1985-05-15 Nippon Nohyaku Co Ltd 水処理薬剤
EP0352120A2 (fr) * 1988-07-20 1990-01-24 The British Petroleum Company p.l.c. Agent antigel pour liquides de refroidissement
EP0524546A2 (fr) * 1991-07-23 1993-01-27 Ashland, Inc. Additif pour anti-gel/réfrigérant
EP0557761A1 (fr) * 1992-02-18 1993-09-01 BASF Aktiengesellschaft Composition réfrigerante stabile à l'eau dure contenant du phosphate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 7741, Derwent World Patents Index; AN 77-73214Y *
DATABASE WPI Week 8526, Derwent World Patents Index; AN 85-155528 *

Also Published As

Publication number Publication date
DE4442114A1 (de) 1996-05-30

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