EP0331231A1 - Procédé pour régénérer des solutions de décapage contenant du ZrF4 - Google Patents

Procédé pour régénérer des solutions de décapage contenant du ZrF4 Download PDF

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Publication number
EP0331231A1
EP0331231A1 EP89200416A EP89200416A EP0331231A1 EP 0331231 A1 EP0331231 A1 EP 0331231A1 EP 89200416 A EP89200416 A EP 89200416A EP 89200416 A EP89200416 A EP 89200416A EP 0331231 A1 EP0331231 A1 EP 0331231A1
Authority
EP
European Patent Office
Prior art keywords
regenerated
pickling solution
compounds
content
nazrf
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.)
Granted
Application number
EP89200416A
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German (de)
English (en)
Other versions
EP0331231B1 (fr
Inventor
Wolfgang Fennemann
Erich Dr. Minzl
Horst Seidel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GEA Group AG
Original Assignee
Metallgesellschaft AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19883805654 external-priority patent/DE3805654A1/de
Priority claimed from DE19883826499 external-priority patent/DE3826499A1/de
Application filed by Metallgesellschaft AG filed Critical Metallgesellschaft AG
Publication of EP0331231A1 publication Critical patent/EP0331231A1/fr
Application granted granted Critical
Publication of EP0331231B1 publication Critical patent/EP0331231B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23G1/36—Regeneration of waste pickling liquors

Definitions

  • the invention relates to a method for regenerating pickling solutions containing ZrF4 5 to 60 g / l HF 150 to 400 g / l HNO3 0.06 to 1.0 g / l so what 5 to 50 g / l Zr by adding Na compounds, precipitation of NaZrF compounds, separating the NaZrF compounds and supplementing HF, HNO3 and possibly H2O.
  • the method according to the invention is based on various insights gained in the investigation of incidents of the previously known method.
  • NaZrF5 compounds does not necessarily lead to a poorly filterable gel and that one can control whether the predominantly NaZrF5 or Na2ZrF tries compounds are formed by adjusting the temperature and the Na: Zr molar ratio. As the temperature rises, NaZrF5 compounds predominantly precipitate out under the same conditions, while in the lower temperature range almost exclusively NA2ZrF6 compounds fail.
  • these two connections are not the only ones that form.
  • the Na-rich Compound Na2ZrF6 with a molar ratio of 2 and the low-Na compound NaZrF5 with a molar ratio of 1 form only partial complexes of the system.
  • the connection Na7Zr6F31 was demonstrated.
  • the various NaZrF compounds are subject to constant conversion or reorientation, which can explain the inertia observed during precipitation or the tendency to oversaturation.
  • a salt with the empirical formula Na 1.2 ZrF 5.2 is formed in two stages by the process according to the invention.
  • the lower Na content in the regenerated pickling solution also means that the Zr content is much higher than they were previously thought to be optimal.
  • the initial Zr content is less important than the dissolving capacity of the regenerated pickling solution, i.e. the difference between the Zr content after regeneration (Zr E ) and the Zr content after exhaustion regeneration (ZR A ).
  • the process according to the invention is advantageously carried out with significantly lower Na but with a correspondingly higher Zr level than that provided for example in European Patent 0 035 804.
  • the Zr dissolving capacity i.e. the difference between the values of FIGS. 1 and 2 is shown as a function of the Na content and the pickling temperature. It can be seen that in the preferred range from 0.1 to 0.6 g / l Na dissolving capacities from 4 to 30 g / l can be set, the regenerated pickling solution in any case containing less than 10 g / l Zr. In this way, the disadvantages of the known methods described at the outset can be overcome, i.e. on the one hand prevent uncontrolled precipitation during the pickling cycle and on the other hand work with a Na: Zr ratio that is only approx. 20% above the theoretical minimum of 1, which cannot be achieved for practical reasons.
  • the range from 0 to 5 is provided for B, and the specific value for a specific system or a specific procedure can be determined empirically.
  • the theoretical curve can be measured by appropriate measurements Fig. 2 can be replaced by one tailored to the specific case.
  • the first batch of used pickling solution was regenerated in a new system. This was naturally Na-free, was about 22 m3 and contained 39 g / l Zr, 250 g / l HNO3 and 5 g / l HF. It was strengthened with concentrated nitric acid, whereby 26.5 m3 of solution with 317 g / l HNO3, 4 g / l HF and 32 g / l Zr were obtained. This solution should be regenerated so that the Na content in the regenerated pickling solution is 0.1 g / l.
  • the fortification was increased to 8 g / l HF.
  • the pickling solution prepared in this way was heated to 55 ° C. before the calculated amount of sodium hydroxide solution was added with vigorous stirring, the Temperature rose to 67 ° C.
  • the mixture was then cooled to 35 ° C. with stirring and pumping over a heat exchanger and then filtered.
  • Example 4 The following precipitants were used instead of 45% sodium hydroxide solution: 15% sodium hydroxide solution 30% sodium hydroxide solution 45% aqueous NaNO3 solution fixed NaF solid Na2SO4 x 10 H2O. In all cases, comparable results were obtained with Example 4. 7. In a further case according to Example 4, the precipitation was carried out at 30 ° C., the temperature in the pickling solution rising to 38 ° C. A slimy salt was precipitated, which was difficult to filter and to drain. Heating the suspension to 60 ° C. and then cooling did not result in any improvement either. The removal of the salt by filtration required about 10 times the time and the filter cake obtained contained significantly more adhering moisture (about 60% instead of 35% before).
  • the pickling solution to be regenerated was heated to 75 ° C. before the precipitation, so that a temperature increase to approximately 85 ° C. resulted when sodium hydroxide solution was used as the precipitant. After the solution had been cooled to 39 ° C., positive results were achieved as in Example 4. 9.
  • the filtrate from Example 5 was used after replenishing HF and HNO3 as a regenerated pickling solution for pickling and was then used as a pickling solution of 29.0 m3 and the following composition: 41 g / l Zr 8th g / l HF 0.1 g / l N / A 316 g / l HNO3
  • the Na content should again be 0.1 g / l after regeneration.
  • a Na requirement of 8.6 g / l was calculated.
  • the resulting HF requirement was 7.5 g / l and was contained in the pickling solution to be regenerated, so that no addition was necessary. 964 kg of sodium hydroxide solution (45% strength) were added.

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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)
  • Separation Using Semi-Permeable Membranes (AREA)
EP89200416A 1988-02-24 1989-02-18 Procédé pour régénérer des solutions de décapage contenant du ZrF4 Expired - Lifetime EP0331231B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19883805654 DE3805654A1 (de) 1988-02-24 1988-02-24 Verfahren zum regenerieren von zrf(pfeil abwaerts)4(pfeil abwaerts) enthaltenden beizloesungen
DE3805654 1988-02-24
DE19883826499 DE3826499A1 (de) 1988-08-04 1988-08-04 Verfahren zum regenerieren von zrf(pfeil abwaerts)4(pfeil abwaerts) enthaltenden beizloesungen
DE3826499 1988-08-04

Publications (2)

Publication Number Publication Date
EP0331231A1 true EP0331231A1 (fr) 1989-09-06
EP0331231B1 EP0331231B1 (fr) 1991-10-16

Family

ID=25865125

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89200416A Expired - Lifetime EP0331231B1 (fr) 1988-02-24 1989-02-18 Procédé pour régénérer des solutions de décapage contenant du ZrF4

Country Status (3)

Country Link
US (1) US4937054A (fr)
EP (1) EP0331231B1 (fr)
DE (1) DE58900366D1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0723038A1 (fr) * 1995-01-24 1996-07-24 Zircotube Procédé et dispositif de régénération d'une solution usagée de décapage d'éléments en alliage de zirconium
WO2010139902A1 (fr) * 2009-06-05 2010-12-09 Airbus Operations (S.A.S) Procédé de régénération d'une solution de décapage ou d'usinage chimique de titane

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105469A (en) * 1977-02-11 1978-08-08 Teledyne Industries, Inc. Process for regenerating a pickle acid bath
DE2828547A1 (de) * 1978-06-29 1980-01-03 Didier Werke Ag Verfahren zur steuerung oder regelung der beizbadzusammensetzung einer beizanlage
EP0035804A1 (fr) * 1980-03-11 1981-09-16 Metallgesellschaft Ag Procédé pour régénérer des solutions de décapage contenant du ZrF6

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105469A (en) * 1977-02-11 1978-08-08 Teledyne Industries, Inc. Process for regenerating a pickle acid bath
DE2828547A1 (de) * 1978-06-29 1980-01-03 Didier Werke Ag Verfahren zur steuerung oder regelung der beizbadzusammensetzung einer beizanlage
EP0035804A1 (fr) * 1980-03-11 1981-09-16 Metallgesellschaft Ag Procédé pour régénérer des solutions de décapage contenant du ZrF6

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0723038A1 (fr) * 1995-01-24 1996-07-24 Zircotube Procédé et dispositif de régénération d'une solution usagée de décapage d'éléments en alliage de zirconium
FR2729676A1 (fr) * 1995-01-24 1996-07-26 Zircotube Procede et dispositif de regeneration d'une solution usagee de decapage d'elements en alliage de zirconium
US5788935A (en) * 1995-01-24 1998-08-04 Zircotube Process for the regeneration of a spent solution for pickling zirconium alloy elements
WO2010139902A1 (fr) * 2009-06-05 2010-12-09 Airbus Operations (S.A.S) Procédé de régénération d'une solution de décapage ou d'usinage chimique de titane
FR2946364A1 (fr) * 2009-06-05 2010-12-10 Airbus France Procede de regeneration d'une solution de decapage ou d'usinage chimique de titane

Also Published As

Publication number Publication date
EP0331231B1 (fr) 1991-10-16
US4937054A (en) 1990-06-26
DE58900366D1 (de) 1991-11-21

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