FR2562097A1 - Process for pickling alloy steels, copper, alloys of non-ferrous heavy metals, titanium, zirconium, tantalum and the like by means of nitric acid baths - Google Patents
Process for pickling alloy steels, copper, alloys of non-ferrous heavy metals, titanium, zirconium, tantalum and the like by means of nitric acid baths Download PDFInfo
- Publication number
- FR2562097A1 FR2562097A1 FR8404837A FR8404837A FR2562097A1 FR 2562097 A1 FR2562097 A1 FR 2562097A1 FR 8404837 A FR8404837 A FR 8404837A FR 8404837 A FR8404837 A FR 8404837A FR 2562097 A1 FR2562097 A1 FR 2562097A1
- Authority
- FR
- France
- Prior art keywords
- urea
- alloys
- pickling
- tantalum
- zirconium
- 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.)
- Pending
Links
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
- 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
- C23G1/08—Iron or steel
- C23G1/086—Iron or steel solutions containing HF
-
- 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
Landscapes
- 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)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
La présente invention est relative à un procédé pour le décapage d'aciers alliés de cuivre, d'alliages de métaux lourds non-ferreux, d'alliages spéciaux, de titane, de zirconium, de tantale, etc. au moyen de bains d'acide nitrique qui peuvent également contenir d'autres acides, par exemple de l'acide fluorhydrique. The present invention relates to a process for the pickling of copper alloy steels, non-ferrous heavy metal alloys, special alloys, titanium, zirconium, tantalum, etc. by means of nitric acid baths which may also contain other acids, for example hydrofluoric acid.
La pollution de l'environnement par les oxydes nitriques qui s'échappent sans contrôle particulier dans l'atmosphère, dégagés lors du décapage d'aciers alliés de cuivre, d'alliages de metaux lourds non-ferreux, d'alliages spéciaux, de titane, de zirconium, de tantale, etc. dans des acides nitriques en solution aqueuses ou des mélanges de solutions aqueuses d'acides contenant de l'acide nitrique, reste un vieux problème qui actuellement n'a pas encore été résolu de manière satisfaisante. Pollution of the environment by nitric oxides which escape without special control into the atmosphere, released during the pickling of copper alloy steels, non-ferrous heavy metal alloys, special alloys, titanium , zirconium, tantalum, etc. in nitric acids in aqueous solution or mixtures of aqueous solutions of acids containing nitric acid remains an old problem which at present has not yet been satisfactorily resolved.
La présente invention concerne un procédé selon lequel les quantités de NOX alors produites ne sont pas comme usuellement séparées des gaz qui s 'échappent après le décapage, mais dont la formation est déja diminuée a une fraction lors du décapage des métaux cités dans des solutions aqueuses d'acide nitrique.The present invention relates to a process according to which the quantities of NOX then produced are not as usually separated from the gases which escape after pickling, but the formation of which is already reduced to a fraction during the pickling of the metals cited in aqueous solutions nitric acid.
A cette fin, il a dejà été proposé d'ajouter du peroxyde d'hydrogène aux bains de décapage; il s'est cependant avéré qu'une partie si importante de cette substance coûteuse est décomposée par d'autres réactions que celles recherchées de sorte que le procédé est trop onéreux. To this end, it has already been proposed to add hydrogen peroxide to the pickling baths; however, it has been found that such a large part of this expensive substance is broken down by reactions other than those sought so that the process is too expensive.
Aussi l'addition d'urée a déjà été retenue pour le décapage de certains aciers à alliage. Sans tenir compte du fait que, selon l'état de la technique, cet additif est proposé à une autre fin que celle de l'objet de la présente invention, notamment pour améliorer les qualités de décapage et pour réduire le temps de décapage, cet etat de la technique ne présente aucun enseignement pour doser l'additif d'urée en tant que fonction de la concentration NO et encore moins en ce qui concerne un
x dosage surveillé d l'additif. Also, the addition of urea has already been retained for the pickling of certain alloy steels. Without taking into account the fact that, according to the state of the art, this additive is proposed for another purpose than that of the object of the present invention, in particular to improve the pickling qualities and to reduce the pickling time, this There is no teaching in the state of the art for determining the urea additive as a function of the NO concentration and even less as regards a
x monitored dosage of the additive.
Il s'est avéré maintenant qu'un apport réguJicr d'urée CO(NH2)2 sous folle solide ou dc solution aqueuse plus pratique, par exemple en tant que solution à 50 E, montre de façon beaucoup plus économique l'effet souhait. It has now been found that a regular supply of more practical urea CO (NH2) 2 under a solid or aqueous solution, for example as a 50 E solution, shows the desired effect much more economically.
Au total, la réaction principale ayant ainsi lieu peut s'exprimer par la formule suivante
CO(NH2)2 + N203 = 2 N2 + C02 + 2 H20
Ainsi, le procédé selon l'invention pour le décapage d'aciers alliés de cuivre, d'alliages de métaux lourds non-ferreux, d'alliages spéciaux, de titane, de zirconium, de tantale, etc. au moyen de bains d'acide nitrique qui peuvent également contenir d'autres acides, par exemple de l'acide fluorhydrique, bains additionnés d'urée ou d'une solution aqueuse d'urée est caractérisé en ce que l'apport d'urée est directement dosé par un détecteur de NOx travaillant en continu dans le conduit par lequel les gaz s'échappent et par un régulateur, par exemple un régulateur P.I.D., apport réglé à la concentration minimale désirée de NO dans les gaz qui s'échap pent. In total, the main reaction thus taking place can be expressed by the following formula
CO (NH2) 2 + N203 = 2 N2 + C02 + 2 H20
Thus, the method according to the invention for the pickling of copper alloyed steels, non-ferrous heavy metal alloys, special alloys, titanium, zirconium, tantalum, etc. by means of nitric acid baths which may also contain other acids, for example hydrofluoric acid, baths containing urea or an aqueous urea solution is characterized in that the supply of urea is directly dosed by a NOx detector working continuously in the conduit through which the gases escape and by a regulator, for example a PID regulator, supply adjusted to the minimum desired concentration of NO in the gases which escape.
Il est évident qu'avec une seule molécule d'urée par unité de N203 on ntobtient pas satisfaQtion,ainsi, par exemple, avec une molécule de NO et une molécule de N02 dont la formation est empêchée car d'autres reactions secondaires ont lieu. Suivant le type du métal décapé, des températures de décapage, etc., l'excès nécessaire est différent. Cependant, il s'est avéré que 130 à 160 % de la valeur théorique suffisent dans laplupartd~s cas et pourtant le développement de NO peut cotre diminué à un quart, parfois
x à 20 % de la quantité autrement développée.It is obvious that with a single molecule of urea per unit of N203 one does not obtain satisfaction, thus, for example, with a molecule of NO and a molecule of NO2 whose formation is prevented because other side reactions take place. Depending on the type of pickled metal, pickling temperatures, etc., the excess required is different. However, it turned out that 130 to 160% of the theoretical value is sufficient in most cases, and yet the development of NO can decrease to a quarter, sometimes
x 20% of the quantity otherwise developed.
Etant donne qu'en présence de conditions de décp- page identiques, une causalité existe entre la concentration de NO et l'addition d'urée, il s'est avéré très efficace d'utiliser l'analyse continue du NOx des gaz qui s'échappent par un régulateur P.I.D. (proportionnel intégral différentiel) pour doser la quantité d'urée. Bien entendu, il faut veiller en raison de la solubilité limitée de l'urée dans les solutions nitriques qu'une saturation d'urée soit élevée, c'est-à-dire que le seuil de solubilité du nitrate d'urée ne soit pas dépassé. Since in the presence of identical decanting conditions, a causality exists between the concentration of NO and the addition of urea, it has proven to be very effective to use the continuous analysis of the NOx of the gases which s escape by a PID regulator (proportional integral differential) to measure the amount of urea. Of course, due to the limited solubility of urea in nitric solutions, care must be taken to ensure that urea saturation is high, i.e. the solubility threshold for urea nitrate is not exceeded.
Ceci est cependant toujours possible comme cela est apparu lors du réglage des systèmes de dosage.This is however always possible as it appeared when setting the dosing systems.
Une forme de réalisation de l'objet de l'invention est illustrée à l'aide de l'exemple suivant. An embodiment of the object of the invention is illustrated with the aid of the following example.
Exemple : un traitement de recuit et de décapage d'une bande d'acier alliée laminée à chaud est inévitable pour produire des feuillards laminés à froid. Example: an annealing and pickling treatment of a hot rolled alloy steel strip is inevitable in order to produce cold rolled strips.
Le décapage est effectué sur une ligne de traitement continue. A cette fin, un mélange d'acide d'environ 15 % en poids d'HN03 et d'environ 2,5 % en poids d'HF est préparé pour l'austénité et pour la ferrite, un mélange d'acide d'environ 15 % en poids d'HN03 et d'environ 0,5 % en poids d'HF.Pickling is carried out on a continuous processing line. To this end, an acid mixture of about 15% by weight of HN03 and about 2.5% by weight of HF is prepared for austenity and for ferrite, a mixture of acid of about 15% by weight of HN03 and about 0.5% by weight of HF.
Afin d'empêcher que les vapeurs d'acide s'échap- pent dans la pièce, les bains de décapage sont recouverts et les vapeurs sont aspirées. Les gaz qui s'échappent sont conduits par un absorbeur à gaz et une cheminée dans l'atmosphère. In order to prevent acid vapors from escaping into the room, the pickling baths are covered and the vapors are drawn off. The escaping gases are led by a gas absorber and a chimney into the atmosphere.
Afin de diminuer la pollution de l'environnement par les émissions de N0x, de l'urée est ajoutée de manière appropriée dans la cuve de décapage. I1 s'est avéré que, lors du décapage d'austénité, la teneur en NOx des vapeurs aspirées a pu être réduite de 1200 ppm de NOx par lladdi- tion d'urée de 300 à 100 ppm de N0x. Lors du décapage de ferrite, la teneur en NOx des vapeurs aspirées a pu être réduite de 3000 ppm de NOx de 150 à 100 ppm NOx grâce à l'addition d'urée. In order to reduce pollution of the environment by N0x emissions, urea is appropriately added to the pickling tank. It has been found that, during austenity stripping, the NOx content of the aspirated vapors could be reduced by 1200 ppm of NOx by adding urea from 300 to 100 ppm of NOx. During the pickling of ferrite, the NOx content of the sucked vapors could be reduced by 3000 ppm of NOx from 150 to 100 ppm NOx thanks to the addition of urea.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8404837A FR2562097A1 (en) | 1984-03-28 | 1984-03-28 | Process for pickling alloy steels, copper, alloys of non-ferrous heavy metals, titanium, zirconium, tantalum and the like by means of nitric acid baths |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8404837A FR2562097A1 (en) | 1984-03-28 | 1984-03-28 | Process for pickling alloy steels, copper, alloys of non-ferrous heavy metals, titanium, zirconium, tantalum and the like by means of nitric acid baths |
Publications (1)
Publication Number | Publication Date |
---|---|
FR2562097A1 true FR2562097A1 (en) | 1985-10-04 |
Family
ID=9302556
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
FR8404837A Pending FR2562097A1 (en) | 1984-03-28 | 1984-03-28 | Process for pickling alloy steels, copper, alloys of non-ferrous heavy metals, titanium, zirconium, tantalum and the like by means of nitric acid baths |
Country Status (1)
Country | Link |
---|---|
FR (1) | FR2562097A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0267166A2 (en) * | 1986-09-11 | 1988-05-11 | Eka Nobel Aktiebolag | Method of reducing the emission of nitrogen oxides from a liquid containing nitric acid |
US6902627B2 (en) | 2002-11-25 | 2005-06-07 | Applied Materials, Inc. | Cleaning chamber surfaces to recover metal-containing compounds |
WO2005068681A2 (en) * | 2003-12-19 | 2005-07-28 | Applied Materials, Inc. | Cleaning tantalum-containing deposits from process chamber components |
US7762114B2 (en) | 2005-09-09 | 2010-07-27 | Applied Materials, Inc. | Flow-formed chamber component having a textured surface |
US7910218B2 (en) | 2003-10-22 | 2011-03-22 | Applied Materials, Inc. | Cleaning and refurbishing chamber components having metal coatings |
US7942969B2 (en) | 2007-05-30 | 2011-05-17 | Applied Materials, Inc. | Substrate cleaning chamber and components |
US7964085B1 (en) | 2002-11-25 | 2011-06-21 | Applied Materials, Inc. | Electrochemical removal of tantalum-containing materials |
US7981262B2 (en) | 2007-01-29 | 2011-07-19 | Applied Materials, Inc. | Process kit for substrate processing chamber |
US8021743B2 (en) | 2004-11-24 | 2011-09-20 | Applied Materials, Inc. | Process chamber component with layered coating and method |
US8617672B2 (en) | 2005-07-13 | 2013-12-31 | Applied Materials, Inc. | Localized surface annealing of components for substrate processing chambers |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1567825A (en) * | 1967-06-08 | 1969-05-16 | ||
AT377011B (en) * | 1982-06-28 | 1985-01-25 | Ruthner Industrieanlagen Ag | METHOD FOR TREATING STAINLESS STEELS, COPPER, COLORED METAL ALLOYS, SPECIAL ALLOYS, TITANIUM, ZIRCON OR TANTAL BY MEANS OF Nitric acid pickling bath |
-
1984
- 1984-03-28 FR FR8404837A patent/FR2562097A1/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1567825A (en) * | 1967-06-08 | 1969-05-16 | ||
AT377011B (en) * | 1982-06-28 | 1985-01-25 | Ruthner Industrieanlagen Ag | METHOD FOR TREATING STAINLESS STEELS, COPPER, COLORED METAL ALLOYS, SPECIAL ALLOYS, TITANIUM, ZIRCON OR TANTAL BY MEANS OF Nitric acid pickling bath |
Non-Patent Citations (1)
Title |
---|
ENVIRONMENTAL PROGRESS, vol. 3, no. 1, février 1984, pages 40-43; H.T. KARLSSON et al.: "Control of NOx in steel pickling" * |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0267166A3 (en) * | 1986-09-11 | 1989-02-15 | Eka Nobel Aktiebolag | Method of reducing the emission of nitrogen oxides from a liquid containing nitric acid |
EP0267166A2 (en) * | 1986-09-11 | 1988-05-11 | Eka Nobel Aktiebolag | Method of reducing the emission of nitrogen oxides from a liquid containing nitric acid |
US6902627B2 (en) | 2002-11-25 | 2005-06-07 | Applied Materials, Inc. | Cleaning chamber surfaces to recover metal-containing compounds |
US9068273B2 (en) | 2002-11-25 | 2015-06-30 | Quantum Global Technologies LLC | Electrochemical removal of tantalum-containing materials |
US7964085B1 (en) | 2002-11-25 | 2011-06-21 | Applied Materials, Inc. | Electrochemical removal of tantalum-containing materials |
US7910218B2 (en) | 2003-10-22 | 2011-03-22 | Applied Materials, Inc. | Cleaning and refurbishing chamber components having metal coatings |
WO2005068681A2 (en) * | 2003-12-19 | 2005-07-28 | Applied Materials, Inc. | Cleaning tantalum-containing deposits from process chamber components |
WO2005068681A3 (en) * | 2003-12-19 | 2005-09-15 | Applied Materials Inc | Cleaning tantalum-containing deposits from process chamber components |
US8021743B2 (en) | 2004-11-24 | 2011-09-20 | Applied Materials, Inc. | Process chamber component with layered coating and method |
US8617672B2 (en) | 2005-07-13 | 2013-12-31 | Applied Materials, Inc. | Localized surface annealing of components for substrate processing chambers |
US9481608B2 (en) | 2005-07-13 | 2016-11-01 | Applied Materials, Inc. | Surface annealing of components for substrate processing chambers |
US7762114B2 (en) | 2005-09-09 | 2010-07-27 | Applied Materials, Inc. | Flow-formed chamber component having a textured surface |
US7981262B2 (en) | 2007-01-29 | 2011-07-19 | Applied Materials, Inc. | Process kit for substrate processing chamber |
US7942969B2 (en) | 2007-05-30 | 2011-05-17 | Applied Materials, Inc. | Substrate cleaning chamber and components |
US8980045B2 (en) | 2007-05-30 | 2015-03-17 | Applied Materials, Inc. | Substrate cleaning chamber and components |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
FR2562097A1 (en) | Process for pickling alloy steels, copper, alloys of non-ferrous heavy metals, titanium, zirconium, tantalum and the like by means of nitric acid baths | |
US4938838A (en) | Method of reducing the emission of NOx gas from a liquid containing nitric acid | |
US3945865A (en) | Metal dissolution process | |
Doidge et al. | Hydride generation atomic absorption spectrometry with in situ pre-concentration in a graphite furnace in the presence of palladium | |
Kučera et al. | The distribution of redox equivalents in the anaerobic respiratory chain of Paracoccus denitrificans | |
JP5088998B2 (en) | Pickling agent containing urea and method for producing the same | |
ATE280851T1 (en) | METHOD FOR PICKLING STAINLESS STEEL WITHOUT NITRIC ACID AND IN THE PRESENCE OF CHLORIDE IONS | |
Duursma | Organic chelation of Co-60 and Zn-65 by leucine in relation to sorption by sediments | |
Hill et al. | Automated determination of sulfide as hydrogen sulfide in waste streams by gas-phase molecular absorption spectrometry | |
EP0415807B1 (en) | Acidic cleaning process for metal products containing titanium or a chemical element of the titanium family | |
Takahashi et al. | SOLVENT EXTRACTION OF CHROMIUM (Vl) BY 3-(4-PYRIDYL)-l, 5-DIPHENYL PENTANE | |
Singh et al. | Inhibition effect of sodium boro-gluconate on mild steel with and without nitrite ions in low chloride containing water | |
JPS602392B2 (en) | Pickling method for stainless steel that suppresses NOx generation | |
RU2090653C1 (en) | Solution for passivation of metal surface | |
Matsusaki et al. | Matrix modification with metal nitrates and organic compounds for the determination of germanium by graphite-furnace atomic absorption spectrometry | |
El-Cheikh et al. | New stoichiometry for copper dissolution in nitric acid | |
Korshunov et al. | Features of metal products treatment in nitric acid | |
JPS5839235B2 (en) | Pickling and descaling method for steel wire rod | |
Bermejo-Barrera et al. | Indirect determination of iodide, as an Hg x I y complex, by electrothermal atomic absorption spectrometry | |
Burke | Rapid combustion method for the determination of sulfur in nickel-, iron-, and copper-blase alloys | |
JPS59213492A (en) | Removal method of hard to decompose nitrogen compound in waste water | |
Kuldvere | Apparent and real reducing ability of polypropylene in cold-vapour atomic-absorption spectrophotometric determinations of mercury | |
SU433000A1 (en) | SUSPENSION FLUSH | |
Wasey et al. | Solid-liquid separation after liquid-liquid extraction: spectrophotometric determination of copper by extraction of its 1-phenyl-4, 4, 6-trimethyl-(1 H, 4 H)-pyrimidine-2-thiol into molten naphthalene | |
FR2460318A2 (en) | Soln. for destroying soot in chimneys - contg. potassium acetate and magnesium nitrate, and opt. magnesium acetate |