EP0035804B1 - Verfahren zum Regenerieren von ZrF4 enthaltenden Beizlösungen - Google Patents

Verfahren zum Regenerieren von ZrF4 enthaltenden Beizlösungen Download PDF

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Publication number
EP0035804B1
EP0035804B1 EP81200113A EP81200113A EP0035804B1 EP 0035804 B1 EP0035804 B1 EP 0035804B1 EP 81200113 A EP81200113 A EP 81200113A EP 81200113 A EP81200113 A EP 81200113A EP 0035804 B1 EP0035804 B1 EP 0035804B1
Authority
EP
European Patent Office
Prior art keywords
pickle
zrf
process according
naoh
hno
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.)
Expired
Application number
EP81200113A
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German (de)
English (en)
French (fr)
Other versions
EP0035804A1 (de
Inventor
Wolfgang Fennemann
Jürgen Haldorn
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
Application filed by Metallgesellschaft AG filed Critical Metallgesellschaft AG
Publication of EP0035804A1 publication Critical patent/EP0035804A1/de
Application granted granted Critical
Publication of EP0035804B1 publication Critical patent/EP0035804B1/de
Expired legal-status Critical Current

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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
    • C23G1/36—Regeneration of waste pickling liquors

Definitions

  • the invention relates to a process for the regeneration of ZrF 4- containing HF-HNO 3 pickling solutions by precipitation of ZrF 4 in the form of Na 2 ZrF 6 and separation of the precipitated Na 2 ZrF 6 and addition of HF, HNO 3 and possibly H 2 O.
  • NaF is a relatively expensive precipitant.
  • the process is also sensitive to overdosing or underdosing of the precipitant. If the residual NaF content is too high after the regeneration is over due to an overdosing of the precipitant, precipitation of Na 2 ZrF 6 is already initiated there when it is returned to the pickling bath, as a result of which the pickling process is impaired. For safety reasons, zirconium can only be precipitated in the regenerated pickling solution to a content of 3 to 7 g / l in the known processes.
  • under-dosing forms gel-like NaZrF 5 ⁇ H 2 O, which is difficult to filter.
  • the invention has for its object to propose a method of the type mentioned, which is less complex and easier to use and in which the disadvantages described are avoided.
  • the used pickling solution is first heated to above 40 ° C. and then dissolved NaOH is added and that after cooling to below 20 ° C. the precipitated Na 2 ZrF 6 is separated off by filtration.
  • HNO 3 before the precipitation and HF and possibly H 2 0 after the separation are added.
  • NaOH is preferably added at a temperature of 50 to 60 ° C.
  • the removal is expediently carried out at a temperature of -20 to + 10 ° C.
  • the NaOH addition is preferably dimensioned such that the completely regenerated pickling solution has a Na content of 1 to 3 g / l and a Zr content of 1.5 to 2.5 g / l.
  • the Na content in the completely regenerated pickling solution is preferably set to 1.5 to 2.5 g / l.
  • the process can be carried out in such a way that continuously removed pickling solution is withdrawn from a pickling plant and is continuously fed back to the pickling plant after regeneration.
  • the pickling solution contents of HF, HNO 3 and Na can be measured continuously and the measured values can be used for automatic control of the addition of NaOH, HNO 3 and HF and, if necessary, H 2 0.
  • the heating and cooling of the pickling solution is carried out with a circulating heat transfer medium having a suitable boiling temperature.
  • NaOH is about 12 times as soluble as NaF, it can be added in solution without significantly disturbing the water balance.
  • the expenditure of NaOH + H F for the regeneration of a certain amount of pickling solution is nevertheless only about 50% of the costs compared to the addition of NaF according to the known process.
  • the addition of NaOH as a solution makes dosing easier.
  • the heating of the used pickling solution according to the invention has the purpose of avoiding the formation of NaZrF 5 .H 2 O. It has been found that this gel-like compound, which is therefore difficult to filter, does not form, regardless of a sufficient dosage with NaOH, if the precipitation is initiated at an elevated temperature.
  • the necessary heating and cooling of the pickling solution can be carried out with a minimum of energy if the amount of heat extracted from the pickling agent stream during cooling is used for heating, whereby a heat transfer medium circuit with a heat pump can be used for the required temperature increase.
  • the used pickling solution is fed into the heat exchanger 5 by means of the pump 3 via the line 2, after 3 HNO 3 had been added beforehand.
  • the pickling solution is heated to above 40 ° C., then the precipitant NaOH is fed in at 6 and the precipitation of the ZrF 4 is initiated.
  • the pickling solution then reaches the heat exchanger 8 via the line 7, where it is cooled to below 20 ° C. and the precipitation is completed.
  • the pickling solution is then fed via line 9 to the filter 10, from which the precipitated Na 2 ZrF 6 is removed at 11.
  • the pickling solution is then fed via line 13 to H 2 0 at 15 and HF at 16 into heat exchanger 14, where it is brought back to the pickling bath temperature and then fed back to the pickling bath via line 17.
  • the circuit of the heat transfer medium essentially consists of the compressor 18 and the lines 19, 20 and 21. From the heat exchanger 8, vaporous heat transfer medium is sucked off, compressed in the compressor 18 and liquefied after cooling in the heat exchangers 5 and 14 before it is again via a throttle point is introduced into the heat exchanger 8, where it evaporates again while absorbing heat.

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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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
EP81200113A 1980-03-11 1981-01-30 Verfahren zum Regenerieren von ZrF4 enthaltenden Beizlösungen Expired EP0035804B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3009265 1980-03-11
DE19803009265 DE3009265A1 (de) 1980-03-11 1980-03-11 Verfahren zum regenerieren von zrf (pfeil abwaerts)4(pfeil abwaerts) enthaltenden beizloesungen

Publications (2)

Publication Number Publication Date
EP0035804A1 EP0035804A1 (de) 1981-09-16
EP0035804B1 true EP0035804B1 (de) 1983-09-21

Family

ID=6096846

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81200113A Expired EP0035804B1 (de) 1980-03-11 1981-01-30 Verfahren zum Regenerieren von ZrF4 enthaltenden Beizlösungen

Country Status (4)

Country Link
US (1) US4330342A (enrdf_load_stackoverflow)
EP (1) EP0035804B1 (enrdf_load_stackoverflow)
JP (1) JPS56136983A (enrdf_load_stackoverflow)
DE (2) DE3009265A1 (enrdf_load_stackoverflow)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4572824A (en) * 1984-11-01 1986-02-25 General Electric Company Process for recovery of zirconium and acid from spent etching solutions
DE58900366D1 (de) * 1988-02-24 1991-11-21 Metallgesellschaft Ag Verfahren zum regenerieren von zrf4 enthaltenden beizloesungen.
US4943419A (en) * 1988-05-24 1990-07-24 Megy Joseph A Process for recovering alkali metal titanium fluoride salts from titanium pickle acid baths
US5076884A (en) * 1990-07-19 1991-12-31 Westinghouse Electric Corp. Process of precipitating zirconium or hafnium from spent pickling solutions
US5082523A (en) * 1990-11-19 1992-01-21 Westinghouse Electric Corp. Process of regenerating spent HF-HNO3 pickle acid containing (ZrF6-2
US5232460A (en) * 1991-07-12 1993-08-03 W. R. Grace & Co.-Conn. System and process for recycling aqueous cleaners
US5256313A (en) * 1992-12-21 1993-10-26 Heritage Environmental Services, Inc. System and process for treatment of cyanide-containing waste
FR2729676B1 (fr) * 1995-01-24 1997-04-11 Zircotube Procede et dispositif de regeneration d'une solution usagee de decapage d'elements en alliage de zirconium
RU2124589C1 (ru) * 1996-12-03 1999-01-10 Открытое акционерное общество "Чепецкий механический завод" Способ переработки отработанных кислых электролитов, содержащих цирконий и медь
RU2120497C1 (ru) * 1997-03-20 1998-10-20 Открытое акционерное общество "Чепецкий механический завод" Способ регенерации нитрато-фторидных травильных растворов, содержащих цирконий
GB2350543B (en) * 1999-05-29 2001-05-09 Graham Edward Burden Tine mountings for agricultural equipment
MY167700A (en) * 2011-04-08 2018-09-21 Shinetsu Chemical Co Preparation of complex fluoride and complex fluoride phosphor

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2828547A1 (de) * 1978-06-29 1980-01-03 Didier Werke Ag Verfahren zur steuerung oder regelung der beizbadzusammensetzung einer beizanlage

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2743160A (en) * 1952-01-31 1956-04-24 Wainer Eugene Preparation of alkali metal double fluorides of zirconium and hafnium
US2812237A (en) * 1952-01-31 1957-11-05 Horizons Titanium Corp Preparation of alkali metal fluotitanates
US3048503A (en) * 1958-06-19 1962-08-07 Crucible Steel Co America Pickling apparatus and method
US4105469A (en) * 1977-02-11 1978-08-08 Teledyne Industries, Inc. Process for regenerating a pickle acid bath

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2828547A1 (de) * 1978-06-29 1980-01-03 Didier Werke Ag Verfahren zur steuerung oder regelung der beizbadzusammensetzung einer beizanlage

Also Published As

Publication number Publication date
DE3009265A1 (de) 1981-09-24
US4330342A (en) 1982-05-18
JPS6254195B2 (enrdf_load_stackoverflow) 1987-11-13
DE3160900D1 (en) 1983-10-27
EP0035804A1 (de) 1981-09-16
JPS56136983A (en) 1981-10-26

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