DE2728625A1 - Corrosion inhibitor for use during acid pickling - contains aromatic hydroxy-iso:per:thiocyanic acid derivs. - Google Patents
Corrosion inhibitor for use during acid pickling - contains aromatic hydroxy-iso:per:thiocyanic acid derivs.Info
- Publication number
- DE2728625A1 DE2728625A1 DE19772728625 DE2728625A DE2728625A1 DE 2728625 A1 DE2728625 A1 DE 2728625A1 DE 19772728625 DE19772728625 DE 19772728625 DE 2728625 A DE2728625 A DE 2728625A DE 2728625 A1 DE2728625 A1 DE 2728625A1
- Authority
- DE
- Germany
- Prior art keywords
- pickling
- corrosion inhibitor
- iso
- per
- use during
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/065—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors sulfur-containing compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General 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)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
Beschreibung description
Die vorliegende Erfindung bezieht sich auf den Korrosionsschutz von Metallen, und zwar auf Korrosionsschutzmi.Lt£l für Fe- und NE-Metalle.The present invention relates to the corrosion protection of Metals, namely on anti-corrosion agent for ferrous and non-ferrous metals.
Es ist bekannt, daß nach der Wärmobehandlung oder nach einem längeren Aufenthalt der Fe- und NE-Metalle an der Luft sich auf ihnen eine Zunderschicht bildet, die vor der anschließenden mechanischen Bearbeitung entfernt werden muß.It is known that after heat treatment or after a long period If the ferrous and non-ferrous metals stay in the air, they form a layer of scale forms, which must be removed before the subsequent mechanical processing.
Das Entfernen des Zunders von der Metalloberfläche erfolgt bekanntlich durch das Beizen des Metalls in Lösungen von Säuren, vorzugsweise Schwefel-, Salz-, Phosphor-, Salpetersäure und anderen Säuren.It is known that the scale is removed from the metal surface by pickling the metal in solutions of acids, preferably sulfur, salt, Phosphoric, nitric and other acids.
Zu diesem Zweck werden die Erzeugnisse (Bleche, Draht, Rohre, Profilteil u.a.m.) aus Fe- oder NE-Metallen in die Beizlösung getaucht, die eine wässerige Lösung der Säure oder eines Gemisches von Säuren mit verschiedenen Zusätzen darstellt, und in diesen Lösungen so lange gehalten, wie dies für die vollständige Entfernung des Zunders notwendig ist.For this purpose, the products (sheet metal, wire, pipes, profile part etc.) made of ferrous or non-ferrous metals immersed in the pickling solution, which is an aqueous Represents a solution of the acid or a mixture of acids with various additives, and held in these solutions for as long as required for complete removal of the Zunders is necessary.
Da die Zunderdicke an der ganzen Oberfläche des Erzeugnisses nicht gleich ist, vollzieht sich die Entfernung des Zunders von der ganzen Oberfläche nicht gleichzeitig. An einigen Stellen der Erzeugnisoberfläche wird der Zunder entfernt, während andere Stellen noch init Zunder bedeckt sind. Dadurch kommt es an denjenigen Stellen, wo der Zunder entfernt wird, zur Auflösung des reinen tGetalls. Die Auflösung des Metalls kann auch bei in der Praxis unvermeidlich@m Zulangehalten der Erzeugnisse in Beizlösungen vor sich gehen. Die Auflösung des Metalls beim Beizen des Zunders ist ein unerwünschter Prozeß. J3r führt zu einer Steigerung des Aufwandes an Saure und zu Verlusten von Metall.Because the thickness of the scale on the entire surface of the product is not is the same, the scale is removed from the entire surface not at the same time. The scale is removed from some places on the surface of the product, while other places are still covered with tinder. This is how it comes to the one Places where the scale is removed to dissolve the pure tmetal. The resolution of the metal can also be unavoidable in practice if the products are too high going on in pickling solutions. The dissolution of the metal when pickling the scale is an undesirable process. J3r leads to an increase in the amount of acid used and loss of metal.
Zur Verhinderung unerwünschter Prozesse beim Beizen setzt man den Beizlösungen im allgemeinen eine geringe Menge (weniger als 1%) von Stoffen zu, die die auflösung des Metalls hemmen. Das sind die sogenannten Korrosionsschutzmittel.To prevent undesirable processes during pickling, the Pickling solutions generally add a small amount (less than 1%) of substances, which inhibit the dissolution of the metal. These are the so-called corrosion protection agents.
Als Korrosionsschutzmittel verwendet man beim Beizen verschiedene organische und anorganische Stoffe. Besonders wirksame Korrosionsschutzmittel sind organische Verbindungen, die funktionelle Gruppen aufweisen, die Atome von Stickstoff, Schwefel, Sauerstoff enthalten, sowie mehrfache Bindungen aufweisende Verbindungen.Various anti-corrosion agents are used in pickling organic and inorganic substances. Particularly effective anti-corrosion agents are organic compounds that have functional groups, the atoms of nitrogen, Contain sulfur, oxygen, as well as compounds having multiple bonds.
Es ist als Korrosionsschutzmittel das para-Doclecylbenzylpyridiniumchlorid bekannt (s. S.A. Balesin und andere "Schutz der Metalle" 1, Nr. 3, 337, 1965 in Russisch), das sich durch hohe Schutzeigenschaften auszeichnet. Die konplizierte Synthese dieses Korrosionsschutzmittels sowie die hohen Kosten der Ausgangsprodukte für die Synthese begrenzen dessen breite Verwendung beim Metallbeizen.As a corrosion protection agent, it is para-doclecylbenzylpyridinium chloride known (see S.A. Balesin and others "Protection of Metals" 1, No. 3, 337, 1965 in Russian), which is characterized by high protective properties. The implied Synthesis of this anti-corrosion agent as well as the high cost of Starting products for synthesis limit its wide use in metal pickling.
Empfohlen wird auch als Korrosionsschutzmittel beim Beizen von Fe-Metallen in Säuren ein Gemisch von Acetylalkohol der allgemeinen Formel RC=CCR2Oh (worin R ein Wasserstoffatom, einen Alkyl- oder Hydroxylalkylrest bedeutet) mit Pyridinderivaten (siehe US-PS 3 107 221). Die Nachteile dieses Korrosionsschutzmittels sind dessen hohe Kosten, komplizierte Herstellung, umständliches Arbeiten mit diesem, weil zu dessen Einführung in die Beizlösung gegen die Einwirkung der Säuren beständige oberflächenaktive Stoffe eingeführt werden müssen.It is also recommended as a corrosion protection agent when pickling ferrous metals in acids a mixture of acetyl alcohol of the general formula RC = CCR2Oh (where R denotes a hydrogen atom, an alkyl or hydroxylalkyl radical) with pyridine derivatives (see U.S. Patent 3,110,221). The disadvantages of this anti-corrosive agent are this high cost, complicated manufacturing, cumbersome work with this because too its introduction into the pickling solution, surface-active against the action of acids Substances have to be imported.
Aus der Zeitschrift Angewandte Chemie, 1952, 24, Seite 661-666 ist auch die Verwendung von Isoperthiocyansäure als Korrosionsschutzmittel bekannt. Bekannt sind schließlich auch α-Hydroxyderivate der Isoperthiocyansäure der oben angegebenen Formel, wobei R - CII2OH, C2H4OH und C3H6OH bedeutet.From the journal Angewandte Chemie, 1952, 24, pages 661-666 is also known the use of isoperthiocyanic acid as a corrosion inhibitor. Finally, α-hydroxy derivatives of isoperthiocyanic acid are also known Formula given above, where R - is CII2OH, C2H4OH and C3H6OH.
Die Korrosionsschutzmittel auf der Basis dieser bekannten Verbindungen können jedoch nicht an die Korrosionsschutzwirkung der erfindungsgemäß vorgeschlagenen heranreichen.The anti-corrosion agents based on these known compounds however, cannot affect the anti-corrosion effect of the proposed according to the invention reach out.
Gegenstand der Erfindung ist also ein Korrosionsschutzmittel auf der Basis von Isoperthiocyansäurederivaten für Bisen-und Nichteisenmetalle bei Beizen in Säuren, das dadurch gekennzeichnet ist, daß es aus OY α-Hydroxyderivaten der Isoperthiocyansäure der allgemeinen Formel besteht, worin R - α-Hydroxymethylphenyl α-Hydroxymethyl-p-dimethylaminophenyl α-Hydroxymethyl-o-jodphenyl oder α-Hydroxyphenylpropylen d.h. die OH-Gruppe sitzt immer am C-Atom benachbart zum N-Atom.The invention therefore relates to a corrosion protection agent based on isoperthiocyanic acid derivatives for ferrous and non-ferrous metals when pickling in acids, which is characterized in that it consists of OY α-hydroxy derivatives of isoperthiocyanic acid of the general formula consists in which R - α-hydroxymethylphenyl α-hydroxymethyl-p-dimethylaminophenyl α-hydroxymethyl-o-iodophenyl or α-hydroxyphenyl propylene ie the OH group is always on the C atom adjacent to the N atom.
Die erfindungsgemäßen Korrosionsschutzmittel werden in 0,1 bis 1X-igen Lösungen eingesetzt. Aus den folgenden Tabellen sind die Vorteile der erfindungsgemäß vorgeschlagenen Korrosionsschutzmittel klar ersichtlich.The anti-corrosion agents according to the invention are in 0.1 to 1X strengths Solutions used. The following tables show the advantages of the invention proposed anti-corrosion agent clearly visible.
Tabelle 1 Wirkung der Isoperthiocyansäurederivate beim Korrosionsschutz von Kohlenstoffstählen (Stahl 3) in Säuren mit einer Konzentration von 20% bei 200C (wobei k die Korrosionsgeschwindigkeit und Z den Korrosionsschutz darstellen). Table 1 Effect of isoperthiocyanic acid derivatives on corrosion protection of carbon steels (steel 3) in acids with a concentration of 20% at 200C (where k is the rate of corrosion and Z is the protection against corrosion).
H2S04 HCl Inhibitor k k g/m².h Z, % g/m².h Z, % ohne Inhibitor 35,72 - 46,18 -Isoperthiocyansäure 1,14 96,81 3,89 91,51 R = CH2OH 0,09 99,70 0,25 99,39 R CH2H4°H 0,15 99,49 0,27 99,38 R = -Hydroxymethylphenyl 0,11 99,59 0,26 99,39 R = a-Hydroxymethylp-dimethylaminophenyl 0,08 99,75 0,17 99,64 R = OC-Hydroxymethylo-Jodphenyl 0,01 99,90 0,09 99,80 R = α-Hydroxyphenyl- 0,01 99,90 0,08 99,93 propylen Tabelle 2 Einfluß einiger Isoperthiocyansäurederivate auf die Lösungsgeschwindigkeit von Kohlenstoffstählen (Stahl 10) in einer verdünnten Lösung von Schwefelsäure bei 400C. H2S04 HCl inhibitor k k g / m².h Z,% g / m².h Z,% without inhibitor 35.72 - 46.18 -Isoperthiocyanic acid 1.14 96.81 3.89 91.51 R = CH2OH 0.09 99.70 0.25 99.39 R CH2H4 ° H 0.15 99.49 0.27 99.38 R = -hydroxymethylphenyl 0.11 99.59 0.26 99.39 R = α-hydroxymethylp-dimethylaminophenyl 0.08 99.75 0.17 99.64 R = OC-hydroxymethylo-iodophenyl 0.01 99.90 0.09 99.80 R = α-hydroxyphenyl-0.01 99.90 0.08 99.93 propylene Tabel 2 Influence of some isoperthiocyanic acid derivatives on the rate of dissolution of Carbon steels (steel 10) in a dilute solution of sulfuric acid at 400C.
Korrosionsgeschwindigkeit Inhibitor (g/m2 x Std.) in 2n H2SO4 ohne Inhibitor 15,1738 Isoperthiocyansäure 7,3460 R = Hydrexymethyl 0,0117 R = α -Hydroxymethylphenyl 0,0205 R = X α-Hydroxyphenylpropylen 0,0072 Corrosion rate inhibitor (g / m2 x hours) in 2n H2SO4 without Inhibitor 15.1738 isoperthiocyanic acid 7.3460 R = hydrexymethyl 0.0117 R = α -Hydroxymethylphenyl 0.0205 R = X α-hydroxyphenylpropylene 0.0072
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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DE19772728625 DE2728625A1 (en) | 1977-06-24 | 1977-06-24 | Corrosion inhibitor for use during acid pickling - contains aromatic hydroxy-iso:per:thiocyanic acid derivs. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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DE19772728625 DE2728625A1 (en) | 1977-06-24 | 1977-06-24 | Corrosion inhibitor for use during acid pickling - contains aromatic hydroxy-iso:per:thiocyanic acid derivs. |
Publications (1)
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DE2728625A1 true DE2728625A1 (en) | 1979-01-11 |
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DE19772728625 Withdrawn DE2728625A1 (en) | 1977-06-24 | 1977-06-24 | Corrosion inhibitor for use during acid pickling - contains aromatic hydroxy-iso:per:thiocyanic acid derivs. |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2224339A1 (en) * | 1972-05-18 | 1973-11-29 | Uk Ni Uglechimitscheskij I | CORROSION PROTECTION AGENT FOR FEMALE AND NEMETALS DURING THEIR CORROSION WITH ACIDS AND PROCESSES TO PROTECT THEM AGAINST CORROSION |
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1977
- 1977-06-24 DE DE19772728625 patent/DE2728625A1/en not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2224339A1 (en) * | 1972-05-18 | 1973-11-29 | Uk Ni Uglechimitscheskij I | CORROSION PROTECTION AGENT FOR FEMALE AND NEMETALS DURING THEIR CORROSION WITH ACIDS AND PROCESSES TO PROTECT THEM AGAINST CORROSION |
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