EP0101126B1 - Process for treating waste pickling pastes - Google Patents
Process for treating waste pickling pastes Download PDFInfo
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- EP0101126B1 EP0101126B1 EP83201149A EP83201149A EP0101126B1 EP 0101126 B1 EP0101126 B1 EP 0101126B1 EP 83201149 A EP83201149 A EP 83201149A EP 83201149 A EP83201149 A EP 83201149A EP 0101126 B1 EP0101126 B1 EP 0101126B1
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- Prior art keywords
- paste
- pickling
- calcium carbonate
- process according
- fluoride
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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
- C23G1/025—Cleaning or pickling metallic material with solutions or molten salts with acid solutions acidic pickling pastes
Definitions
- the invention relates to a method for converting processed, fluoride-containing pickling pastes located on metal surfaces into environmentally compatible products.
- metal surfaces e.g. B. of steel and / or aluminum and their alloy
- unsightly and corrosion-promoting oxide layers such as z. B. in the heat treatment of metals (welding) or caused by the effect of the environment.
- acid solutions such. B. based on hydrochloric acid, sulfuric acid, phosphoric acid or hydrofluoric acid.
- Acid-containing pastes can also be applied to the areas to be cleaned, especially for large parts or local oxide formation. This dissolves part of the oxides and the base metal attached to them, so that the oxides lose their adhesion to the metal surface. After an appropriate time, they are rinsed off with water or removed by brushing.
- Such pickling or rust removal paste based on phosphoric acid contains z. B. as a thickener saponifiable oil or a convertible fatty acid into a soap (DE-AS 10 82 475).
- Another known cleaning and etching agent consists of hydrofluoric acid, a magnesium compound, at least one acid from the group consisting of nitric acid, phosphoric acid and sulfuric acid in the form of free acid or in the form of their salts and a certain sulfonic acid (DE-AS 19 50 560).
- pickling and rust removal pastes have been proposed which, in addition to fluoride ions, contain a mixture of compounds of calcium and of trivalent iron and / or aluminum and have an acidity corresponding to at least 10% by weight of free acid (calculated as 100% HF) (DE -OS 31 505 508).
- Such pickling pastes are primarily intended for the treatment of alloyed steels.
- the object of the invention is to provide a method for transferring processed fluoride-containing pickling pastes located on metal surfaces, which avoids the disadvantages of the known methods and yet can be carried out simply and without cost.
- the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that an aqueous, calcium carbonate with a particle size of max. 5 km and paste containing alkali hydrogen carbonate with a pH value of max. 9.5 applies.
- the amount of calcium ions offered must be so high that the fluoride ions of the processed pickling paste can be converted into insoluble calcium fluoride by the calcium.
- the simultaneous presence of alkali hydrogen carbonate has a neutralizing effect, the pH in aqueous solution - even when overdosed - not exceeding 8.4 (measured as a 1% sodium bicarbonate solution).
- alkaline compounds e.g. B. of sodium carbonate
- the pH to max. 9.5 can be increased.
- the particle size of the calcium carbonate plays a role in that particles larger than 5 Am react only imperfectly.
- the inner calcium carbonate is removed from a further reaction with fluoride ions or acid.
- the completeness of the implementation, but also the speed of the reaction is increased.
- the spreadability of the paste improves.
- a preferred embodiment of the invention therefore provides to apply a paste whose calcium carbonate component has a particle size below 2 ⁇ m, preferably below 1 ⁇ m.
- a further, particularly advantageous embodiment of the invention is based on the
- processed pickling paste to apply a paste containing calcium carbonate in an amount of 20 to 50% by weight, preferably 30 to 40% by weight, and alkali hydrogen carbonate in an amount of 20 to 50% by weight, preferably 30 to 40% by weight % (calculated as NaHCO 3 ).
- the surfactant in an amount of 0.1 to 10 g / kg paste, preferably 0.3 to 3 g / kg paste.
- Particularly suitable surfactants are nonionic or anionic surfactants, in particular ethoxylated alkylphenols.
- the paste is usually applied by brush application. However, spray application is also possible, especially if the viscosity is set to a low level.
- the amount to be applied should be at least as large as the amount of pickling paste applied. A surplus is absolutely no problem because of the environmental compatibility.
- the conversion of the processed pickling paste into environmentally friendly products is associated with a carbon dioxide gas evolution, the completion of which simultaneously indicates the end of the reaction. It is therefore not necessary to observe the course of the reaction, for example by measuring the pH.
- the duration of the reaction is generally from 1 to 5 minutes.
- the reaction products on the metal surface are most conveniently removed with water. Depending on the nature of the treated metal surface, this can be done by brushing or spraying. Insofar as this is possible, the washing liquid can be freed from insoluble constituents by filtering or decanting and the aqueous phase can be drained into the sewage system.
- the chemicals required for formulating the paste are inexpensive, that the paste has a long shelf life and that handling it requires no special precautionary measures.
- a significant further advantage is that the metering presents no difficulties, in particular even a considerable overdosing does not require any special measures.
- the reaction products obtained can also be deposited without special measures or their aqueous phase can be discharged into a sewage system which may be present.
- a pickling paste was applied in a quantity of 100 g / m weld seam to various pipe sections made of chromium-nickel steel with a weld seam.
- the pickling paste consisted of
- the exposure time was set to 15 minutes.
- a paste of likewise 40% by weight solids content (pH 8.5) was made from precipitated calcium carbonate with a particle size of about 1 IJ.m and in a quantity of 100 g / m weld seam on the processed pickling paste upset.
- reaction products were rinsed off and a washing liquid with a pH of 5.4 and a fluoride content of 70 mg / l was obtained. It too could not be drained without a pH correction.
- a paste was produced which duration. It was again applied in a quantity of 100 g / m of weld seam to the pickling paste being worked off and rinsed off after 5 minutes of exposure.
- the washing liquid obtained had a pH of 7.2 and a fluoride content of 20 mg / l. Without further treatment, i. H. be drained into the sewage system only after decantation of the water-insoluble components.
- Example 3 was repeated with the variant that the application quantity was doubled to 200 g / m weld seam.
- washing liquid was also obtained here, the pH of which was only 7.8 and the fluoride content was 16 mg / l and which, as in the case of Example 3, could be drained into the sewage system.
Abstract
Description
Die Erfindung betrifft ein Verfahren zum Überführen von auf Metalloberflächen befindlichen abgearbeiteten, fluoridhaltigen Beizpasten in umweltverträgliche Produkte.The invention relates to a method for converting processed, fluoride-containing pickling pastes located on metal surfaces into environmentally compatible products.
Es ist üblich, von Metalloberflächen, z. B. aus Stahl und/oder Aluminium und deren Legierung, unansehnliche und korrosionsfördernde Oxidschichten, wie sie z. B. bei der Wärmebehandlung von Metallen (Schweißen) oder durch Wirkung der Umgebung entstehen, zu beseitigen. Dies geschieht überwiegend mit Säurelösungen z. B. auf Basis Salzsäure, Schwefelsäure, Phosphorsäure oder auch Flußsäure.It is common for metal surfaces, e.g. B. of steel and / or aluminum and their alloy, unsightly and corrosion-promoting oxide layers, such as z. B. in the heat treatment of metals (welding) or caused by the effect of the environment. This is mainly done with acid solutions such. B. based on hydrochloric acid, sulfuric acid, phosphoric acid or hydrofluoric acid.
Insbesondere bei großen Teilen oder örtlicher Oxidbildung können auf die zu reinigenden Stellen auch säurehaltige Pasten aufgebracht werden. Dadurch wird ein Teil der Oxide und das mit ihnen verhaftete Grundmetall aufgelöst, so daß die Oxide die Haftung zur Metalloberfläche verlieren. Sie werden nach angemessener Zeit mit Wasser abgespült bzw. durch Bürsten entfernt.Acid-containing pastes can also be applied to the areas to be cleaned, especially for large parts or local oxide formation. This dissolves part of the oxides and the base metal attached to them, so that the oxides lose their adhesion to the metal surface. After an appropriate time, they are rinsed off with water or removed by brushing.
Eine derartige Beiz- oder Entrostungspaste auf Basis Phosphorsäure enthält z. B. als Verdickungsmittel verseifbares Öl oder eine in eine Seife überführbare Fettsäure (DE-AS 10 82 475).Such pickling or rust removal paste based on phosphoric acid contains z. B. as a thickener saponifiable oil or a convertible fatty acid into a soap (DE-AS 10 82 475).
Ein anderes bekanntes Reinigungs- und Ätzmittel besteht aus Flußsäure, einer Magnesiumverbindung, mindestens einer Säure aus der Gruppe Salpetersäure, Phosphorsäure und Schwefelsäure in Form von freier Säure oder in Form ihrer Salze sowie einer bestimmten Sulfonsäure (DE-AS 19 50 560).Another known cleaning and etching agent consists of hydrofluoric acid, a magnesium compound, at least one acid from the group consisting of nitric acid, phosphoric acid and sulfuric acid in the form of free acid or in the form of their salts and a certain sulfonic acid (DE-AS 19 50 560).
Schließlich sind Beiz- und Entrostungspasten vorgeschlagen worden, die neben Fluoridionen eine Mischung von Verbindungen des Calciums sowie des dreiwertigen Eisens und/oder Aluminiums enthalten und eine Acidität entsprechend wenigstens 10 Gew.-% freier Säure (berechnet als 100 %iges HF) aufweist (DE-OS 31 505 508). Derartige Beizpasten sind vornehmlich zur Behandlung von legierten Stählen vorgesehen.Finally, pickling and rust removal pastes have been proposed which, in addition to fluoride ions, contain a mixture of compounds of calcium and of trivalent iron and / or aluminum and have an acidity corresponding to at least 10% by weight of free acid (calculated as 100% HF) (DE -OS 31 505 508). Such pickling pastes are primarily intended for the treatment of alloyed steels.
Im Unterschied zur Verwendung von Beizflüssigkeiten tritt beim Einsatz von fluoridhaltigen Beizpasten insofern ein besonderes Problem auf, als einerseits die sonst üblichen Spülbehälter in der Regel nicht zur Verfügung stehen und andererseits die beim Abspülen der abgearbeiteten Beizpasten gebildeten stark sauren fluoridhaltigen Abwässer nicht ohne weitere Nachbehandlung abgelassen oder anderweitig verworfen werden dürfen.In contrast to the use of pickling liquids, a particular problem arises when using fluoride-containing pickling pastes in that, on the one hand, the otherwise usual rinsing containers are generally not available and, on the other hand, the strongly acidic fluoride-containing waste water formed when the processed pickling pastes are rinsed off is not drained off without further after-treatment or may otherwise be discarded.
Soweit möglich, ist es allgemein üblich, derartige Abwässer zu sammeln und mit Calciumhydroxid auf einen pH-Wert von 6,5 bis 9,5 einzustellen. Bei der Reaktion entstehen unlösliche Calciumfluoride, die abgeschieden werden können, während die klare Flüssigkeit abgelassen wird.As far as possible, it is common practice to collect such wastewater and adjust it to a pH of 6.5 to 9.5 with calcium hydroxide. The reaction produces insoluble calcium fluorides that can be separated while the clear liquid is being drained.
Schwierigkeiten ergeben sich hierbei insofern, als Lösungen bzw. Aufschlämmungen von Calciumhydroxid bzw. Kalkmilch oft nachreagieren, so daß es zu einer Überdosierung mit der Folge eines erneuten pH-Wert-Anstieges über die zugelassene Grenze hinaus kommen kann. Die Behandlung der Abwässer bedarf daher einer genauen Prüfung der Alkalität und einer oft zeitraubenden Einstellung mit mehreren Kontrollen.Difficulties arise in that solutions or slurries of calcium hydroxide or lime milk often react further, so that an overdose with the result of a renewed rise in pH can occur beyond the permitted limit. The treatment of the waste water therefore requires a precise check of the alkalinity and an often time-consuming adjustment with several controls.
Andere Vorschläge, die fluoridhaltigen sauren Abwässer über granuliertes Calciumcarbonat, z. B. Marmor, fließen zu lassen, sind schon deswegen wenig brauchbar, als sich die Calciumcarbonat-Oberfläche schnell mit unlöslichem Calciumfluorid bedeckt und so dem weiteren Reaktionsablauf entzogen ist.Other suggestions that the acidic wastewater containing fluoride over granulated calcium carbonate, e.g. B. marble, to flow, are of little use because the calcium carbonate surface quickly covered with insoluble calcium fluoride and is thus withdrawn from the further course of the reaction.
Aufgabe der Erfindung ist es, ein Verfahren zum Überführen von auf Metalloberflächen befindlichen abgearbeiteten fluoridhaltigen Beizpasten bereitzustellen, das die Nachteile der bekannten Verfahren vermeidet und dennoch einfach und ohne kostenmäßigen Aufwand durchführbar ist.The object of the invention is to provide a method for transferring processed fluoride-containing pickling pastes located on metal surfaces, which avoids the disadvantages of the known methods and yet can be carried out simply and without cost.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man auf die abgearbeitete fluoridhaltige Beizpaste eine wäßrige, Calciumcarbonat mit einer Partikelgröße von max. 5 Km sowie Alkalihydrogencarbonat enthaltende Paste mit einem pH-Wert von max. 9,5 aufbringt.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that an aqueous, calcium carbonate with a particle size of max. 5 km and paste containing alkali hydrogen carbonate with a pH value of max. 9.5 applies.
Die Menge der angebotenen Calciumionen muß so hoch sein, daß die Fluoridionen der abgearbeiteten Beizpaste durch das Calcium in unlösliches Calciumfluorid überführt werden können. Die gleichzeitige Gegenwart von Alkalihydrogencarbonat wirkt neutralisierend, wobei der pH-Wert in wäßriger Lösung - auch bei Überdosierung - nicht über 8,4 steigt (gemessen als 1 %ige Natriumbicarbonatlösung).The amount of calcium ions offered must be so high that the fluoride ions of the processed pickling paste can be converted into insoluble calcium fluoride by the calcium. The simultaneous presence of alkali hydrogen carbonate has a neutralizing effect, the pH in aqueous solution - even when overdosed - not exceeding 8.4 (measured as a 1% sodium bicarbonate solution).
Durch einen geringfügigen Zusatz alkalischer Verbindungen, z. B. von Natriumcarbonat, kann im Bedarfsfall der pH-Wert auf max. 9,5 erhöht werden.With a slight addition of alkaline compounds, e.g. B. of sodium carbonate, if necessary, the pH to max. 9.5 can be increased.
Die Partikelgröße des Calciumcarbonats spielt insofern eine Rolle, als Partikeln, die größer als 5 Am sind, nur noch unvollkommen reagieren. Durch Bildung einer äußeren Calciumfluorid-Schicht wird das innere Calciumcarbonat einer weiteren Reaktion mit Fluoridionen oder Säure entzogen. Mit zunehmender Feinheit des Calciumcarbonats wird die Vollständigkeit der Umsetzung, aber auch die Geschwindigkeit der Reaktion vergrößert. Zusätzlich verbessert sich die Streichfähigkeit der Paste.The particle size of the calcium carbonate plays a role in that particles larger than 5 Am react only imperfectly. By forming an outer layer of calcium fluoride, the inner calcium carbonate is removed from a further reaction with fluoride ions or acid. With increasing fineness of the calcium carbonate, the completeness of the implementation, but also the speed of the reaction, is increased. In addition, the spreadability of the paste improves.
Eine bevorzugte Ausgestaltung der Erfindung sieht daher vor, eine Paste aufzubringen, deren Calciumcarbonat-Komponente eine Partikeigröße unterhalb 2µm, vorzugsweise unterhalb 1 µm, aufweist.A preferred embodiment of the invention therefore provides to apply a paste whose calcium carbonate component has a particle size below 2 μm, preferably below 1 μm.
Besonders zweckmäßig ist der Einsatz von durch einen Fällungsprozeß gebildetem Calciumcarbonat.The use of calcium carbonate formed by a precipitation process is particularly expedient.
Eine weitere, besonders vorteilhafte Ausgestaltung der Erfindung besteht darin, auf dieA further, particularly advantageous embodiment of the invention is based on the
abgearbeitete Beizpaste eine Paste aufzubringen, die Calciumcarbonat in einer Menge von 20 bis 50 Gew.-%, vorzugsweise 30 bis 40 Gew.-%, und Alkalihydrogencarbonat in einer Menge von 20 bis 50 Gew.-%, vorzugsweise 30 bis 40 Gew.-% (berechnet als NaHCO3), enthält.processed pickling paste to apply a paste containing calcium carbonate in an amount of 20 to 50% by weight, preferably 30 to 40% by weight, and alkali hydrogen carbonate in an amount of 20 to 50% by weight, preferably 30 to 40% by weight % (calculated as NaHCO 3 ).
Einen besonders guten Verlauf der Paste und eine weitere Beschleunigung der Reaktion läßt sich erzielen, wenn man in weitereer zweckmäßiger Ausgestaltung des Verfahrens eine Paste aufbringt, die Tensid in einer Menge von 0,1 bis 10 g/kg Paste, vorzugsweise 0,3 bis 3 g/kg Paste, enthält. Als Tenside sind besonders geeignet nichtionogene oder anionaktive Tenside, insbesondere äthoxylierte Alkylphenole.A particularly good course of the paste and a further acceleration of the reaction can be achieved if a paste is applied in a further expedient embodiment of the method, the surfactant in an amount of 0.1 to 10 g / kg paste, preferably 0.3 to 3 g / kg paste. Particularly suitable surfactants are nonionic or anionic surfactants, in particular ethoxylated alkylphenols.
Je nach den bestehenden Vorschriften hinsichtlich Abwasserbeschaffenheit kann es weiterhin zweckmäßig sein, eine Paste aufzubringen, deren pH-Wert 8 bis 9 beträgt.Depending on the existing regulations regarding the quality of wastewater, it may also be expedient to apply a paste whose pH is 8 to 9.
Die Aufbringung der Paste erfolgt üblicherweise durch Pinselauftrag. Insbesondere bei geringer eingestellter Viskosität ist jedoch auch die Aufbringung im Spritzverfahren möglich. Die jeweils aufzubringende Menge sollte mindestens ebenso groß sein wie die Menge aufgebrachter Beizpaste. Ein Überschuß ist wegen der Umweltverträglichkeit absolut problemlos.The paste is usually applied by brush application. However, spray application is also possible, especially if the viscosity is set to a low level. The amount to be applied should be at least as large as the amount of pickling paste applied. A surplus is absolutely no problem because of the environmental compatibility.
Die Überführung der abgearbeiteten Beizpaste in umweltfreundliche Produkte ist mit einer Kohlendioxidgasentwicklung verbunden, deren Abschluß gleichzeitig das Ende der Reaktion anzeigt. Eine Beobachtung des Reaktionsablaufes, etwa durch die Messung des pH-Wertes, ist daher entbehrlich. Die Dauer der Umsetzung liegt im allgemeinen innerhalb von 1 bis 5 min.The conversion of the processed pickling paste into environmentally friendly products is associated with a carbon dioxide gas evolution, the completion of which simultaneously indicates the end of the reaction. It is therefore not necessary to observe the course of the reaction, for example by measuring the pH. The duration of the reaction is generally from 1 to 5 minutes.
Nach dem Abschluß der Reaktion werden die auf der Metalloberfläche befindlichen Umsetzungsprodukte am zweckmäßigsten mit Wasser entfernt. Je nach Beschaffenheit der behandelten Metalloberfläche kann dies durch Abbürsten oder Abspritzen erfolgen. Sofern die Möglichkeit gegeben ist, kann die Waschflüssigkeit durch Filtrieren oder Dekantieren von unlöslichen Bestandteilen befreit und die wäßrige Phase in die Kanalisation abgelassen werden.After the completion of the reaction, the reaction products on the metal surface are most conveniently removed with water. Depending on the nature of the treated metal surface, this can be done by brushing or spraying. Insofar as this is possible, the washing liquid can be freed from insoluble constituents by filtering or decanting and the aqueous phase can be drained into the sewage system.
Die herausragendsten Vorteile des erfindungsgemäßen Verfahrens sind, daß die zur Formulierung der Paste erforderlichen Chemikalien preisgünstig sind, daß die Paste eine hohe Lagerfähigkeit aufweist und der Umgang mit ihr keine besonderen Vorsichtsmaßnahmen erfordert. Ein wesentlicher weiterer Vorteil ist, daß die Dosierung keine Schwierigkeiten bereitet, insbesondere selbst eine erhebliche Überdosierung keinerlei Sondermaßnahmen erforderlich macht. Schließlich sind auch die erhaltenen Umsetzungsprodukte ohne besondere Maßnahmen deponierbar bzw. ihre wäßrige Phase in eine gegebenenfalls vorhandene Kanalisation ableitbar.The most outstanding advantages of the method according to the invention are that the chemicals required for formulating the paste are inexpensive, that the paste has a long shelf life and that handling it requires no special precautionary measures. A significant further advantage is that the metering presents no difficulties, in particular even a considerable overdosing does not require any special measures. Finally, the reaction products obtained can also be deposited without special measures or their aqueous phase can be discharged into a sewage system which may be present.
Die Erfindung wird im folgenden näher und beispielsweise erläutert.The invention is explained in more detail below and for example.
Zur Vorbereitung der Versuche wurde auf verschiedene, mit einer Schweißnaht versehene Rohrabschnitte aus Chromnickelstahl eine Beizpaste in einer Menge von 100 g/m Schweißnaht aufgebracht. Die Beizpaste bestand ausTo prepare the tests, a pickling paste was applied in a quantity of 100 g / m weld seam to various pipe sections made of chromium-nickel steel with a weld seam. The pickling paste consisted of
Die Einwirkungsdauer war auf 15 min eingestellt.The exposure time was set to 15 minutes.
Zum Vergleich wurde auf eine Teilchengröße von 10 bis 15 IJ.m aufgemahlenes Calciumcarbonat mit Wasser zu einer Paste mit einem Feststoffgehalt von 40 Gew.-% (pH-Wert 8,5) vermischt und in einer Menge von 100 g/m Schweißnaht auf die abgearbeitete Beizpaste aufgebracht. Nach einer Einwirkungszeit von 5 min und Abspülen der Umsetzungsprodukte wurde eine Waschflüssigkeit mit einem pH-Wert von 4,0 und einem Gehalt von 180 mg/I Fluoridionen erhalten. Die Waschflüssigkeit konnte ohne eine pH-Wert-Korrektur nicht abgelassen werden.For comparison, calcium carbonate ground to a particle size of 10 to 15 IJ.m was mixed with water to form a paste with a solids content of 40% by weight (pH 8.5) and applied in an amount of 100 g / m of weld processed pickling paste applied. After an exposure time of 5 min and rinsing off the reaction products, a washing liquid with a pH of 4.0 and a content of 180 mg / l of fluoride ions was obtained. The washing liquid could not be drained without a pH correction.
Auch eine Verdoppelung der auf die Beizpaste aufgebrachten Pastenmenge und damit eine beträchtliche Erhöhung des Calcium-Angebotes veränderte das Ergebnis nur unwesentlich. Es wurde eine Waschflüssigkeit mit einem pH-Wert von 5,0 und einem Fluoridgehalt von 140 mg/I erhalten, die wiederum in unbehandelter Form nicht deponierbar bzw. ablaßbar war.A doubling of the amount of paste applied to the pickling paste and thus a considerable increase in the calcium supply changed the result only insignificantly. A washing liquid with a pH of 5.0 and a fluoride content of 140 mg / l was obtained, which in turn could not be deposited or drained in the untreated form.
Ebenfalls zum Vergleich wurde aus gefälltem Calciumcarbonat mit einer Partikelgröße von ca. 1 IJ.m eine Paste von ebenfalls 40 Gew.-% Feststoffanteil (pH-Wert 8,5) angesetzt und in einer Menge von 100 g/m Schweißnaht auf die abgearbeitete Beizpaste aufgebracht.Also for comparison, a paste of likewise 40% by weight solids content (pH 8.5) was made from precipitated calcium carbonate with a particle size of about 1 IJ.m and in a quantity of 100 g / m weld seam on the processed pickling paste upset.
Nach einer Einwirkungszeit von 5 min wurden die Umsetzungsprodukte abgespült und eine Waschflüssigkeit mit einem pH-Wert von 5,4 und einem Fluoridgehalt von 70 mg/I erhalten. Auch sie durfte ohne pH-Wert-Korrektur nicht abgelassen werden.After an exposure time of 5 minutes, the reaction products were rinsed off and a washing liquid with a pH of 5.4 and a fluoride content of 70 mg / l was obtained. It too could not be drained without a pH correction.
Zur Durchführung des erfindungsgemäßen Verfahrens wurde eine Paste hergestellt, die aus
Die erhaltene Waschflüssigkeit besaß einen pH-Wert von 7,2 und einen Fluoridgehalt von 20 mg/I. Sie konnte ohne weitere Behandlung, d. h. lediglich nach Dekantation der wasserunlöslichen Bestandteile, in die Kanalisation abgelassen werden.The washing liquid obtained had a pH of 7.2 and a fluoride content of 20 mg / l. Without further treatment, i. H. be drained into the sewage system only after decantation of the water-insoluble components.
Das Beispiel 3 wurde wiederholt mit der Variante, daß die Auftragsmenge auf 200 g/m Schweißnaht verdoppelt wurde.Example 3 was repeated with the variant that the application quantity was doubled to 200 g / m weld seam.
Trotz des erheblichen Überschusses wurde auch hierbei eine Waschflüssigkeit erhalten, deren pH-Wert nur 7,8 und deren Fluoridgehalt 16 mg/l betrug und die, wie im Falle des Beispiels 3, in die Kanalisation abgelassen werden konnte.Despite the considerable excess, a washing liquid was also obtained here, the pH of which was only 7.8 and the fluoride content was 16 mg / l and which, as in the case of Example 3, could be drained into the sewage system.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83201149T ATE19661T1 (en) | 1982-08-18 | 1983-08-03 | PROCESS FOR TREATMENT OF WORK-OFF STAIN PASTE. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3230603 | 1982-08-18 | ||
| DE19823230603 DE3230603A1 (en) | 1982-08-18 | 1982-08-18 | METHOD FOR TREATING PREPARED MAKING PASTE |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0101126A2 EP0101126A2 (en) | 1984-02-22 |
| EP0101126A3 EP0101126A3 (en) | 1984-03-21 |
| EP0101126B1 true EP0101126B1 (en) | 1986-05-07 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83201149A Expired EP0101126B1 (en) | 1982-08-18 | 1983-08-03 | Process for treating waste pickling pastes |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4478647A (en) |
| EP (1) | EP0101126B1 (en) |
| JP (2) | JPS5956585A (en) |
| AT (1) | ATE19661T1 (en) |
| DE (2) | DE3230603A1 (en) |
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| US4847818A (en) * | 1988-10-31 | 1989-07-11 | Timex Corporation | Wristwatch radiotelephone |
| JP2576323B2 (en) * | 1991-10-03 | 1997-01-29 | カシオ計算機株式会社 | Performance recording and playback device |
| US5467324A (en) * | 1994-11-23 | 1995-11-14 | Timex Corporation | Wristwatch radiotelephone with deployable voice port |
| FI120742B (en) * | 2006-05-10 | 2010-02-15 | Outokumpu Oy | Method in connection with steel production |
| GB201312158D0 (en) * | 2013-07-05 | 2013-08-21 | Xeros Ltd | Method of treating a metal substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB843100A (en) * | 1956-01-14 | 1960-08-04 | Geigy Co Ltd | Improvements in the cleaning of metal surfaces |
| CH359950A (en) * | 1956-04-12 | 1962-01-31 | Parker Ste Continentale | Rust removal paste, process for its manufacture and use thereof |
| GB1067293A (en) * | 1964-09-28 | 1967-05-03 | Ici Ltd | Treatment of waste liquor from pickling of ferrous metals |
| SE351444B (en) * | 1970-11-03 | 1972-11-27 | Nordstjernan Rederi Ab | |
| US3959132A (en) * | 1974-10-25 | 1976-05-25 | Galson Technical Services, Inc. | Methods for removing fluoborates from aqueous media |
| US4045339A (en) * | 1975-08-05 | 1977-08-30 | Dart Industries Inc. | Waste treatment of fluoroborate solutions |
| US4032466A (en) * | 1976-04-16 | 1977-06-28 | Basf Wyandotte Corporation | Acid cleaner and process for disposal thereof |
| AT348947B (en) * | 1977-03-02 | 1979-03-12 | Voest Ag | PROCEDURE FOR NEUTRALIZING ACID RINSING WATERS OR USED PICKLING ACIDS FROM METAL PICKLING |
| DE3105508A1 (en) * | 1981-02-14 | 1982-09-02 | Metallgesellschaft Ag, 6000 Frankfurt | Stain and rust removal paste for metals |
-
1982
- 1982-08-18 DE DE19823230603 patent/DE3230603A1/en not_active Withdrawn
-
1983
- 1983-08-03 AT AT83201149T patent/ATE19661T1/en not_active IP Right Cessation
- 1983-08-03 EP EP83201149A patent/EP0101126B1/en not_active Expired
- 1983-08-03 DE DE8383201149T patent/DE3363397D1/en not_active Expired
- 1983-08-15 JP JP58149101A patent/JPS5956585A/en active Pending
- 1983-08-18 US US06/524,503 patent/US4478647A/en not_active Expired - Fee Related
- 1983-08-18 JP JP58150894A patent/JPS5956586A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US4478647A (en) | 1984-10-23 |
| EP0101126A2 (en) | 1984-02-22 |
| DE3230603A1 (en) | 1984-02-23 |
| DE3363397D1 (en) | 1986-06-12 |
| ATE19661T1 (en) | 1986-05-15 |
| EP0101126A3 (en) | 1984-03-21 |
| JPS5956586A (en) | 1984-04-02 |
| JPS5956585A (en) | 1984-04-02 |
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