WO1996017033A1 - Nitrite-, phosphate- and amine-free coolant and heat-transfer agent - Google Patents
Nitrite-, phosphate- and amine-free coolant and heat-transfer agent Download PDFInfo
- 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
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- 239000002826 coolant Substances 0.000 title claims description 21
- 239000011551 heat transfer agent Substances 0.000 title abstract description 10
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 title description 2
- 238000005260 corrosion Methods 0.000 claims abstract description 30
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 12
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 9
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical class OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- BOVWCHJGJQJKQA-UHFFFAOYSA-N 2-nitrohexanoic acid Chemical compound CCCCC(C(O)=O)[N+]([O-])=O BOVWCHJGJQJKQA-UHFFFAOYSA-N 0.000 claims 1
- PTYVBEKOPJHZLJ-UHFFFAOYSA-N 2-nitropropanoic acid Chemical compound OC(=O)C(C)[N+]([O-])=O PTYVBEKOPJHZLJ-UHFFFAOYSA-N 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 22
- 239000003112 inhibitor Substances 0.000 abstract description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000002528 anti-freeze Effects 0.000 abstract description 2
- 108010053481 Antifreeze Proteins Proteins 0.000 abstract 1
- 239000007798 antifreeze agent Substances 0.000 abstract 1
- 150000005338 nitrobenzoic acids Chemical class 0.000 abstract 1
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 12
- 239000002609 medium Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 150000002826 nitrites Chemical class 0.000 description 9
- 235000021317 phosphate Nutrition 0.000 description 9
- 239000002905 metal composite material Substances 0.000 description 6
- 235000010288 sodium nitrite Nutrition 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 150000001559 benzoic acids Chemical class 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- -1 alkali metal salts Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 3
- 235000010234 sodium benzoate Nutrition 0.000 description 3
- 239000004299 sodium benzoate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 2
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000004005 nitrosamines Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- SLAMLWHELXOEJZ-UHFFFAOYSA-M 2-nitrobenzoate Chemical compound [O-]C(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910001060 Gray iron Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
The invention concerns an aqueous or glycol-containing anti-freeze and heat-transfer agent with the usual corrosion and cavitation inhibitors, nitrite being replaced by a combination of nitrobenzoic acids with a pKa value > 3 plus polyacrylic acid with an ethylacrylic acid content of 5 to 30 % and a molecular weight of 10,000 to 100,000.
Description
Nitrit-, phosphat- und aminfreies Kühl- und Wärmeübertragungsmittel Nitrite, phosphate and amine free coolant and heat transfer medium
Die Erfindung beinhaltet ein Kühl- und Wärmeübertragungsmittel auf wäßriger und 5 glykolhaltiger Basis für Klimaanlagen , Wärmetauscher und Kühlsysteme von Verbrennungsmotoren, das frei von giftigen und umweltschädigenden Stoffen, wie Phosphaten, Nitraten, Nitriten und Aminen ist.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.
Gleichzeitig wird ein optimaler Schutz von Metallen und Metallverbunden in den entsprechenden Wärmeübertragungssystemen gewährleistet.At the same time, optimal protection of metals and metal composites is guaranteed in the corresponding heat transfer systems.
1010
Wässrige und glykolhaltige Kühl- und Wärmeübertragungsmittel, die keine weiteren Zusätze enthalten, führen bei allen elektrochemischen Metallen zur Korrosion. Ihr Ausmaß ist von der Konzentration des gelösten Sauerstoffs, dem Gehalt an Mineralsalzen, insbesondere Chloriden und Sulfaten, dem Gehalt an Kohlensäure,Aqueous and glycol-containing coolants and heat transfer agents that contain no other additives lead to corrosion in all electrochemical metals. Their extent depends on the concentration of dissolved oxygen, the content of mineral salts, especially chlorides and sulfates, the content of carbonic acid,
I s der Konzentration der in Lösung gegangenen Metallionen , dem pH-Wert und der Temperatur abhängigIt depends on the concentration of the metal ions in solution, the pH and the temperature
Darüber hinaus kommt es beim direkten Kontakt von Metallen mit unterschiedlichen Standardelektrodenpotentialen in Metallverbunden zur Lokalelementbildung, in deren Folge das unedlere Metall stärker und das edlere geringfügiger korrodiert, alsIn addition, the direct contact of metals with different standard electrode potentials in metal composites leads to the formation of local elements, as a result of which the less noble metal corrodes more strongly and the nobler one less so than
20 wenn es allem mit dem Elektrolyt in Verbindung stunde.20 when it is all in contact with the electrolyte.
Damit die üblichen wasser- und/oder glykolhaltigen Kühl- bzw. Wärmeübertragungsmittel an den eingesetzten Metallen möglichst eine geringe Korrosion bedingen, werden sie seit langem mit bestimmten korrosionshemmenden l's Zusatzstoffen versehen. Übliche Zusätze sind zum Beispiel Chromate, Nitrite,So that the usual water and / or glycol-containing coolants or heat transfer agents cause as little corrosion as possible on the metals used, they have long been provided with certain corrosion-inhibiting oil additives. Common additives are, for example, chromates, nitrites,
Nitrate, Borate, Phosphate, Phosphonate, Silicate, organische Nitroverbindungen, Benzotriazole und -thiazole, Amme, Alkanolamine, Carbonsäuren, insbesondere Benzoesäuren und deren Alkalisalze. Art und Konzentration dieser kavitations- und korrosionshemmenden Zusätze sowie ) deren Kombination im jeweiligen Inhibitorpaket hängen hauptsächlich von den verwendeten Werkstoffen , ihrer Oberflächenbeschaffenheit , der Temperatur, den Stromungsbedingungen und der Anwesenheit weiterer Wasseπnhaltsstoffe ab Je nach Hauptbestandteil der Inhibitorsysteme unterscheidet man Zusätze auf Natπumbenzoat/Natπumnitht - Basis undNitrates, borates, phosphates, phosphonates, silicates, organic nitro compounds, benzotriazoles and thiazoles, ames, alkanolamines, carboxylic acids, especially benzoic acids and their alkali salts. 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
.s Alkali- bzw Alkanolammoniumphosphat - Basis.s Alkali or alkanolammonium phosphate base
ERSATZBLATT
Für eine Vielzahl von Stoffen und Stoffkombinationen wurde für bestimmte Prozeßbedingungen eine Wirksamkeit als Korrosionsinhibitor nachgewiesen.REPLACEMENT LEAF For a number of substances and combinations of substances, effectiveness as a corrosion inhibitor has been demonstrated for certain process conditions.
Es ist allgemein bekannt, daß Natriumnitrit Stahl, Gußeisen und Aluminium in 5 wässrigen Medien schützt, bei Messing, Blei und Lotwerkstoffen jedoch die Korrosion verstärkt. Seine Schutzwirkung ist an die Anwesenheit von gelöstem Sauerstoff gebunden und verlangt pH-Werte > 6,5, da es sich sonst schnell zersetzt. Es gelangt daher gewöhnlich in Kombination mit einem den pH-Wert im schwach alkalischen Bereich stabilisierenden Salz wie Natriumbenzoat und/oder Borax zumIt is well known that 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
10 Einsatz. Typische Rezepturen auf Benzoat/Nitritbasis werden beansprucht durch DE-PS 1 201 121,10 use. Typical formulations based on benzoate / nitrite are claimed by DE-PS 1 201 121,
DE-PS 1 492 522, DE-OS 1 771 985, DE-OS 2 046 791 , DE-AS 2 149 138, DE-OS 2 207 375, DE-AS 2 235093 , DE-OS 2406056 , DE-OS 2 841 908 , DE-PS 2 938868, Brit. PS 910 138, und Brit. PS 1 221 996.DE-PS 1 492 522, DE-OS 1 771 985, DE-OS 2 046 791, DE-AS 2 149 138, DE-OS 2 207 375, DE-AS 2 235093, DE-OS 2406056, DE-OS 2 841 908, DE-PS 2 938868, Brit. PS 910 138, and Brit. PS 1 221 996.
15 Von prinzipiellem Nachteil ist, daß Nitrite Gifte sind. Bereits aus diesem Grund gibt es intensive Bestrebungen, Nitrite als Bestandteile von Kühl - und Wärmeüber¬ tragungsmitteln zu ersetzen. Nitrite besitzen gegenüber Chromaten eine geringere Neigung zur Oxidation der organischen Bestandteile von Kühl- und Wärmeübertragungsmitteln. Es ist jedoch von erheblichem Nachteil, daß Nitrite dasA fundamental disadvantage is that 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
20 zum Gefrierschutz dienende Glykol bzw. organische Komponenten des20 antifreeze glycol or organic components of the
Inhibitorsystems aufoxydieren und damit die Langzeitstabilität des Kühl- und Wärmeübertragungsmittels beeinträchtigen.Oxidize inhibitor systems and thus impair the long-term stability of the coolant and heat transfer medium.
Desweiteren ist von Nachteil, daß bei der Reduktion des Nitrits toxische nitrose Gase entstehen , die mit im Kühl- und Wärmeübertragungsmittel enthaltenenA further disadvantage is that the reduction of the nitrite produces toxic nitrous gases which are contained in the coolant and heat transfer medium
25 Aminen bzw. Alkanolaminen kanzerogene Nitrosamine bilden. Aus diesem Grund gibt es seit einiger Zeit intensive Bemühungen, Nitrite als Bestandteile des Inhibitorsystems für wässrige und/oder glykolhaltige Kühl- bzw. Wärmeübertragungsmittel zu ersetzen. Die zu diesem Zweck in der DF-PS 1 49 522 vorgeschlagenen Nitrophenole bzw. deren Alkalisalze erzielen nur einen25 amines or alkanolamines form carcinogenic nitrosamines. For this reason, intensive efforts have been made for some time to replace nitrites as components of the inhibitor system for aqueous and / or glycol-containing coolants or heat transfer agents. The nitrophenols or their alkali metal salts proposed for this purpose in DF-PS 1 49 522 achieve only one
_ o unbefriedigenden Korrosionsschutz, weshalb in der DE-OS 2 938 868 vorgeschlagen wird, noch einen geringen Anteil Nitrit zusätzlich zu dosieren.Unsatisfactory corrosion protection, which is why it is proposed in DE-OS 2 938 868 to additionally meter in a small proportion of nitrite.
55
ERSATZBLATT
Es ist weiterhin bekannt, daß Natriumnitrit durch im Kern mit stark elektronenanziehenden Gruppen (z.B. NO2 OH, Halogenen) substituierten Benzoesäuren mit einem pK-, - Wert < 3 ersetzt werden kann. Die DE-OS 3 000687 benennt als bevorzugten Vertreter insbesondere die o- und p- Nitrobenzoesäure. Von Nachteil ist jedoch, daß damit die mit Natriurπnitiit hergestellten Schutzwerte der Kühl- und Wärmeübertragungsmittel nicht erreicht werden.REPLACEMENT LEAF It is also known that sodium nitrite can be replaced by benzoic acids with a pK, - value <3 substituted in the nucleus with strongly electron-withdrawing groups (for example NO 2 OH, halogens). DE-OS 3 000687 names in particular the o- and p-nitrobenzoic acid as preferred representatives. It is disadvantageous, however, that the protective values of the coolants and heat transfer agents produced with sodium initiator are not achieved.
Die DE-AS 2 235 093 schlägt ebenfalls die Verwendung von Salzen substituierter Benzoesäuren vor. Dabei werden auch die Alkalisalze der o-, m- und p- Nitro- benzoesäure genannt, jedoch stets in Kombination mit einem unvermindert hohen Anteil an Natriumnitrit. Die substituierten Benzoesäuren bzw. ihre Salze werden dabei als Benzoatersatz und nicht als Nitritersatz verwendet. Der beanspruchte effektivere Korrosionsschutz für Verbünde von Leichtmetallegierungen mit unlegierten Massenstählen ist deshalb eindeutig der Optimierung des Nitritsystems zuzuordnen.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.
In der DD-PS 218635 wird neben Nitrit enthaltenden Beispielen auch in einem Exempel der Zusatz von Nitrobenzoat im Sinne eines bisher üblichen Inhibitorzusatzes ohne gleichzeitige Anwesenheit von Natriumnitrit benannt, jedoch wird die mit dieser Mischung erzielte Korrosionsschutzwirkung auf die synergistische Wirkung des Umsetzungsproduktes von Carboxymethylcellulose mit Mercaptobenz- thiazol und 2- Ethylhexansäure mit herkömmlichen Inhibitorkomponenten zurückge¬ führt. Von prinzipiellem Nachteil ist die Tatsache, daß dieses Zusatzinhibitorpaket einer gesonderten Herstellungstechnologie bedarf.In 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.
Es ist weiterhin bekannt, daß Alkalinitrite durch Antrachinonderivate ersetzt werden können (DD-PS 225723). Der Nachteil dieser Stoffklasse besteht darin, daß ihre Herstellung sehr aufwendig und ihr Kostenanteil am Inhibitorpaket sehr hoch ist.It is also known that alkali nitrites can be replaced by antrachinone derivatives (DD-PS 225723). The disadvantage of this class of substances is that their production is very complex and their cost share in the inhibitor package is very high.
Alkali- bzw. Ammoniumphosphate weisen als Hauptbestandteile der zweiten Gruppe von Basisinhibitorsystemen ebenfalls einen deutlichen Korrosionsschutz für Metalle und Metallverbunde aus.As main components of the second group of basic inhibitor systems, alkali or ammonium phosphates also have a clear corrosion protection for metals and metal composites.
Typische Rezepturen auf Phosphatbasis werden beansprucht durch DE-OS 2 918 967 , USP 4 085063, DE-OS 2 806 342. Der Nachteil der Inhibitorpakete auf Phosphatbasis besteht darin, daß f> bei Dauerbeanspruchung infolge des Abscheidens von Zink - und/oderTypical 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
Calciumphosphat zu Inkrustationen kommt, die die Funktionstüchtigkeit des Kühl¬ bzw. Wärmeübertragungssystems mindern bzw. in Frage stellen.Calcium phosphate comes to incrustations, which reduce the functionality of the cooling or heat transfer system or question it.
ERSATZBLATT
In neuer Zeit werden durch die zunehmende Verwendung von Aluminiumlegierungen im Kühlerbau , durch den Einsatz von Intensivkühlern mit geringem Innenrohrdurchmesser und durch das Arbeiten mit geschlossenen Kühlsystemen im Automobilbau erhöhte Anforderungen an Kühl- bzw. Wärmeübertragungsmittel gestellt, die Inkrustationen nicht zulassen. Aus diesem Grund gibt es seit geraumer Zeit Bemühungen, Phosphate als Bestandteile des Inhibitorsystems für wässrige und/oder glykolhaltige Kühl- bzw. Wärmeübertragungsmittel zu vermeiden.REPLACEMENT LEAF In recent times, the increasing use of aluminum alloys in cooler construction, the use of intensive coolers with a small inner tube diameter and the work with closed cooling systems in automobile construction have placed increased demands on coolants and heat transfer media that do not allow incrustations. For this reason, efforts have been made for some time to avoid phosphates as components of the inhibitor system for aqueous and / or glycol-containing coolants or heat transfer agents.
Aus der Charakteristik der bekannten technischen Lösungen wird deutlich, daß sowohl nitrit- als auch phosphathaltige Inhibitorsysteme erhebliche Nachteile für den Korrosions- und Kavitationsschutz von Metallen und Metall verbunden in Kühl- und Wärmeübertragungssystemen sowie für die Umwelt besitzen.It is clear from the characteristics of the known technical solutions that both nitrite and phosphate-containing inhibitor systems have considerable disadvantages for the protection against corrosion and cavitation of metals and metal associated in cooling and heat transfer systems and for the environment.
Der Einsatz von Acrylsäurepolymerisaten zur Verhinderung der Korrosion ist ebenfalls bekannt ,so verwendet die US-PS 4 876 945 als Inhibitor dasThe use of acrylic acid polymers to prevent corrosion is also known, so US Pat. No. 4,876,945 uses this as an inhibitor
Reaktionsprodukt von Monoethylenglykol mit Acrylsäure im Zusammenwirken mit Acrylaten.Reaction product of monoethylene glycol with acrylic acid in interaction with acrylates.
In der US-PS 4 876 945 wird die Kupferkorrosion durch Einsatz von Acrylsäure/In US Pat. No. 4,876,945 copper corrosion is caused by the use of acrylic acid /
Methacrylsäurecopolymerisaten im Zusammenwirken mit Sulfonsäuren undMethacrylic acid copolymers in interaction with sulfonic acids and
Acrylamiden zurückgedrängt.Acrylic amides pushed back.
In US-PS 4 869 845 wird zur Verhinderung der Korrosion Acrylsäureallylhydroxy- propylsulfonat in Zusammenwirken mit Zinksalzen verwendet.In US Pat. No. 4,869,845, acrylic acid allyl hydroxypropyl sulfonate is used in cooperation with zinc salts to prevent corrosion.
Durch den Einsatz von Polyacrylamid sollen nach US-PS 4 961 878 in KühlsystemenThe use of polyacrylamide, according to US Pat. No. 4,961,878, is said to be used in cooling systems
Eisen und Aluminium geschützt werden.Iron and aluminum are protected.
Ein Einsatz von Polyacrylaten mit oben genannten Basisinhibitorkombinationen ist nicht bekanntThe use of polyacrylates with the above-mentioned basic inhibitor combinations is not known
Es besteht die Aufgabe, ein Kühl- bzw. Wärmeübertragungsmittel auf Glykolbasis mit einem Korrosionsschutzsystem bereitzustellen, das eine Langzeitwirkung für den Korrosions- und Kavitationsschutz von Metallen und Metallverbunden in Kühl- und Wärmeübertragungssystemen gewährleistet .Phosphatzusatz vermeidet und aus Umweltschutzgründen am in- und nitritfrei ist.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.
ERSATZBLATT
Erfindungsgemäß wird die Aufgabe durch ein nitrit-, phosphat- und aminfreies Kühl- 5 und Wärmeübertragungsmittel auf Glykolbasis mit Korrosionsschutz- undREPLACEMENT LEAF According to the invention the object is achieved by a nitrite-, phosphate- and amine-free coolant and heat transfer agent based on glycol with corrosion protection and
Kavitationsschutzwirkung auf Metalle und Metallverbunde gelöst , indem übliche korrσsions- und kavitationshemmende Zusätze mit Nitrocarbonsäuren mit einem pKa-Wert >3 und Polyacrylsäuren mit einem Anteil von 5 - 30 % Ethylacrylsäure bezogen auf Gesamtacrylat kombiniert werden, wobei das Verhältnis von lϋ Nitrocarbonsäure zu Polyacrylsäure 1 : 0,001 bis 1 : 1 bei einer Gesamtkonzentration an Nitrocarbonsäure plus Polyacrylsäure im Wärmeübertragungsmittel 0,1 - 5 % vorzugsweise 0,5 - 3,5 % beträgt. Die verwendete Polyacrylsäure hat ein Molekulargewicht im Bereich von 10000 bis 100000. Das fertige Wärmeübertragungsmittel wird auf einen pH-Wert von 7,5 bisCavitation protection effect on metals and metal composites solved by combining the usual corrosion and cavitation-inhibiting additives with nitrocarboxylic acids with a pKa value> 3 and polyacrylic acids with a proportion of 5 - 30% ethyl acrylic acid based on total acrylate, whereby the ratio of lϋ nitrocarboxylic acid to polyacrylic acid 1: 0.001 to 1: 1 for a total concentration of nitrocarboxylic acid plus polyacrylic acid in the heat transfer medium is 0.1-5%, preferably 0.5-3.5%. 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
15 9,2 eingestellt15 9.2 set
Überraschend wurde gefunden, daß der Zusatz der genannten Kombination zu einem Korrosionsschutzsystem mit einem Gehalt an üblichen korrosions- und kavitationshemmenden Zusätzen wie Beπzoat und Borat den Wegfall von Nitriten erlaubt, wobei sich der Korrosions- und Kavitationsschutz für Metalle und 0 Metallverbunde verbessert.Surprisingly, it was found that the addition of the combination mentioned to a corrosion protection system with a content of conventional corrosion and cavitation-inhibiting additives such as benzoate and borate allows nitrites to be eliminated, the corrosion and cavitation protection for metals and metal composites being improved.
Gleichzeitig wird ein erhöhter Langzeitschutz erzielt. Dadurch ist eine längere Nutzung der Kühl- bzw. Wärmeübertragungsmittel möglich. Weiterhin ist von Vorteil, daß durch den Wegfall von Phosphaten als Schutzstoffe die Gefahr der Bildung von Inkrustationen und Schlämmen, und damit die GefahrAt the same time, increased long-term protection is achieved. This allows longer use of the coolant or heat transfer medium. Another advantage is that by eliminating phosphates as protective substances, the risk of incrustation and sludge formation, and thus the danger
25 von Verstopfungen und des vorzeitigen Ausfalls der Kühl- bzw. Wärmeübertragungssysteme vermieden wird.25 of blockages and premature failure of the cooling or heat transfer systems is avoided.
Schließlich ist durch Wegfall des Nitrits als Korrosionsschutzkomponente eine deutliche Minderung der Umweltbelastung durch austretendes Kühl- bzw. Wärmeübertragungsmittel gegeben und eine Gesundheitsgefährdung des MenschenFinally, by eliminating the nitrite as a corrosion protection component, there is a significant reduction in the environmental impact caused by escaping coolant or heat transfer medium and a health hazard to humans
.10 durch Nitrosamine ausgeschlossen..10 excluded by nitrosamines.
.15.15
4040
ERSATZBLATT
AusführungsbeispieleREPLACEMENT LEAF Embodiments
Beispiel 1 zeigt die Anwendung der erfindungsgemäßen Zusatzstoffe als Korrosionsschutzmittel gegenüber unlegiertem Massenstahl St 38 im Dauertauchversuch bei 40°C in synthetisch hartem Wasser nach ASTM D 1384 bei ständiger Sättigung des Prüfmediums mit Luft nach DIN 50905 T 3 + 4. l()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 ()
Tabelle 1Table 1
Aus der tabellarischen Gegenüberstellung wird deutlich, daß die Alkalisalze der erfindungsgemäßen Nitrocarbonsäuren dem bekannten KorrosionsinhibitorIt is clear from the comparison in table form that the alkali metal salts of the nitrocarboxylic acids according to the invention are the known corrosion inhibitor
1 Natriumnitrit in hartem Wasser hoher Aggressivität auch dann überlegen sind, wenn dieser in Kombination mit dem Inhibitor Natriumbenzoat vorgegeben wird1 sodium nitrite in hard water of high aggressiveness are superior even if this is specified in combination with the inhibitor sodium benzoate
ERSATZBLATT
Beispiel 2REPLACEMENT LEAF Example 2
Das Beispiel zeigt die Anwendung eines erfindungsgemäßen Zusatzstoffes in einer multifunktionellen Inhibitormischung in Gegenüberstellung mit typischen nitrithaltigen Mischungen, wie sie in gebräuchlichen Kühlerschutzmitteln auf Ethylenglykol - Basis verwendet werden. Die in Tabelle 2 angegebenen Mischungen von Kühlerschutzmitteln werden entsprechend ASTM D 1384 geprüft.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.
Tabelle 2Table 2
Korrosionsabtrag nach ASTM D 1384 in mm/ιτι2 * 14 cCorrosion removal according to ASTM D 1384 in mm / ιτι2 * 14 c
Kupfer 0,35 1.2 1,2 1,0 1 ,4 0,95 1.5 3,0Copper 0.35 1.2 1.2 1.0 1, 4 0.95 1.5 3.0
Weichlot 1 ,3 1 ,4 2,75 3,6 3,3 3,95 4,4 6,2Soft solder 1, 3 1, 4 2.75 3.6 3.3 3.95 4.4 6.2
Messing 0,80 1.4 0,9 1 ,05 1 ,4 1 ,45 1 ,7 3.5Brass 0.80 1.4 0.9 1, 05 1, 4 1, 45 1, 7 3.5
Stahl 0,23 0,43 0,45 0,26 1 ,32 0.6 1 ,9 5,8Steel 0.23 0.43 0.45 0.26 1, 32 0.6 1, 9 5.8
Grauguß 0,11 0.22 0.8 0,7 1 ,29 0,39 1.4 2,0Gray cast iron 0.11 0.22 0.8 0.7 1, 29 0.39 1.4 2.0
Aluminium 0,50 0,63 0,7 1.6 1 ,8 +0,07 2,1 4.7Aluminum 0.50 0.63 0.7 1.6 1, 8 +0.07 2.1 4.7
TZBLATT
Die in Tabelle 2 dargelegten Inhibitorrezepturen 1 - 4 entsprechen der erfindungs¬ gemäßen Kombination mit m - Nitrobenzoesäure und Polyacrylsäure. Die Rezeptur 5 enthält nur m - Nitrobenzoesäure aber kein Polyacrylsäure. Dadurch erhöht sich der Korrosionsabtrag.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.
5 Bei Rezeptur 6 werden neben m - Nitrobenzoesäure und Polyacrylsäure noch Natriumnitrit und Natriumnitrat eingesetzt, ohne daß sich die Korrosionsabträge im Vergleich mit den Rezepturen 1 - 4 verbessern.5 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.
Die Rezepturen 7 und 8 sind üblich zur Herstellung nitrithaltiger Kühlerschutzmittel. Aus den gezeigten Beispielen ergibt sich eine Überlegenheit der 0 erfindungsgemäßen Rezeptur.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.
1 51 5
00
55
1010
1515
00
■15■ 15
ERSATZBLATT
REPLACEMENT LEAF
Claims
1. Nitrit- , phosphat und aminfreies Kühl- und Wärmeübertragungsmit.ei auf wäßriger /glykolischer Basis mit Korrosionsschutz- und Kavitations¬ schutzwirkung mit bekannten korrosionshemmenden Zusätzen, dadurch gekennzeichnet, daß Nitrocarbonsäuren mit einem pKa-Wert > 3 und Polyacrylsäuren mit einem Anteil von 5 - 30 Gew.% Ethylacryisäure im Verhältnis Nitrocarbonsäure zu Polyacrylsäure von 1 : 0,001 bis 1 : 1 bei einer Gesamtkonzentration von 0,1 bis 5 Gew.% enthalten sind und der pH- Wert des fertigen Wärmeübertragungsmittels auf 7,5 bis 9,2 eingestellt ist.1. Nitrite, phosphate and amine-free cooling and heat transfer medium on an aqueous / glycolic basis with anti-corrosion and anti-cavitation effects with known anti-corrosion additives, characterized in that nitrocarboxylic acids with a pKa value> 3 and polyacrylic acids with a proportion of 5 30% by weight of ethyl acrylic acid in a ratio of nitrocarboxylic acid to polyacrylic acid of 1: 0.001 to 1: 1 at a total concentration of 0.1 to 5% by weight are included and the pH of the finished heat transfer medium is adjusted to 7.5 to 9.2 is.
2. Kühl- und Wärmeübertragungsmittel nach Anspruch 1, dadurch gekenn¬ zeichnet, daß m - Nitrobenzoesäure enthalten ist.2. Cooling and heat transfer medium according to claim 1, characterized gekenn¬ characterized in that m - nitrobenzoic acid is included.
3. Kühl- und Wärmeübertragungsmittel nach Anspruch 1, dadurch gekenn¬ zeichnet, daß Nitropropionsäure enthalten ist.3. Cooling and heat transfer medium according to claim 1, characterized gekenn¬ characterized in that nitropropionic acid is included.
4 Kühl- und Wärmeübertragungsmittel nach Anspruch 1, dadurch gekenn¬ zeichnet, daß Nitrocapronsäure enthalten ist.4 coolant and heat transfer medium according to claim 1, characterized gekenn¬ characterized in that nitrocaproic acid is included.
5. Kühl- und Wärmeübertragungsmittel nach Anspruch 1 bis 4,dadurch gekenn¬ zeichnet, daß die Polyacrylsäure ein Molekulargewicht im Bereich von 10 000 bis 100 000 hat5. Cooling and heat transfer medium according to claim 1 to 4, characterized gekenn¬ characterized in that the polyacrylic acid has a molecular weight in the range of 10,000 to 100,000
6 Kühl- und Wärmeübertragungsmittel nach Anspruch 1 - 5,dadurch gekennzeichnet, daß die Gesamtkonzentrationkonzentration an Nitrocarbonsäure plusPol acrylsäure im Wärmeübertragungsmittel 0,5 bis 3.5 Gew.% beträgt.6 coolant and heat transfer medium according to claims 1-5, characterized in that the total concentration of nitrocarboxylic acid plus pol acrylic acid in the heat transfer medium is 0.5 to 3.5% by weight.
ERSATZBLATT REPLACEMENT LEAF
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DE19944442114 DE4442114A1 (en) | 1994-11-25 | 1994-11-25 | Nitrite, phosphate and amine free coolant and heat transfer medium |
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DE2815016C2 (en) * | 1978-04-07 | 1986-04-10 | Henkel KGaA, 4000 Düsseldorf | Corrosion inhibitor for domestic water systems |
US4277366A (en) * | 1979-09-26 | 1981-07-07 | Union Carbide Corporation | Poly(alkylene oxide) composition |
DE3000687A1 (en) * | 1980-01-10 | 1981-07-16 | Basf Ag, 6700 Ludwigshafen | RADIATOR PROTECTION FOR WATER-BASED COOLING LIQUIDS |
DE3148230C2 (en) * | 1981-12-05 | 1983-12-01 | Hoechst Ag, 6230 Frankfurt | "Nitrite-free cooling liquids based on glycols" |
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 (en) * | 1988-06-07 | 1989-12-14 | Hoechst Ag | CORROSION-INHIBITED AND PHYSIOLOGICALLY ADVANTAGEOUS FUNCTIONAL LIQUIDS BASED ON GLYCOLS |
DE3832592A1 (en) * | 1988-09-24 | 1990-03-29 | Basf Ag | NITRITE AND PHOSPHATE-FREE COOLANT MIXTURES ON GLYCOL BASE |
-
1994
- 1994-11-25 DE DE19944442114 patent/DE4442114A1/en not_active Withdrawn
-
1995
- 1995-11-03 WO PCT/DE1995/001516 patent/WO1996017033A1/en active Application Filing
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CA1027348A (en) * | 1974-02-22 | 1978-03-07 | Betz Laboratories | Closed cooling system corrosion inhibition |
JPS52103338A (en) * | 1976-02-26 | 1977-08-30 | Kouriyuu Kougiyou Kk | Anticorrosive composition for metals |
JPS6086286A (en) * | 1983-05-31 | 1985-05-15 | Nippon Nohyaku Co Ltd | Water treating chemical agent |
EP0352120A2 (en) * | 1988-07-20 | 1990-01-24 | The British Petroleum Company p.l.c. | Antifreeze agent for liquid coolants |
EP0524546A2 (en) * | 1991-07-23 | 1993-01-27 | Ashland, Inc. | Antifreeze/coolant additive |
EP0557761A1 (en) * | 1992-02-18 | 1993-09-01 | BASF Aktiengesellschaft | Hard water stable coding composition containing phosphate |
Non-Patent Citations (2)
Title |
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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 |
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DE4442114A1 (en) | 1996-05-30 |
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