EP0843025A1 - Procédé de régénération de solutions de décapage usées - Google Patents

Procédé de régénération de solutions de décapage usées Download PDF

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Publication number
EP0843025A1
EP0843025A1 EP97119480A EP97119480A EP0843025A1 EP 0843025 A1 EP0843025 A1 EP 0843025A1 EP 97119480 A EP97119480 A EP 97119480A EP 97119480 A EP97119480 A EP 97119480A EP 0843025 A1 EP0843025 A1 EP 0843025A1
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EP
European Patent Office
Prior art keywords
metal
bed reactor
fluidized bed
acid
pickling solution
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.)
Ceased
Application number
EP97119480A
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German (de)
English (en)
Inventor
Frank H. Dr. Bärhold
Werner Engelhardt
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.)
Keramchemie GmbH
Original Assignee
Keramchemie GmbH
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 DE19747693A external-priority patent/DE19747693A1/de
Application filed by Keramchemie GmbH filed Critical Keramchemie GmbH
Publication of EP0843025A1 publication Critical patent/EP0843025A1/fr
Ceased 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/01—Waste acid containing iron

Definitions

  • the invention relates to a method for regeneration a used nitric and hydrofluoric acid and containing metal fluorides and metal nitrates Pickling solution in which the pickling solution is in a reactor heated about 300 - 1000 ° C, the metal fluorides and metal nitrates pyrohydrolysed and the resulting metal oxides are withdrawn as granules and in which the The resulting fluidized bed reactor is dedusted and cooled and is fed to an acid recovery unit.
  • DE-OS 43 15 551 describes a method for regeneration a used one consisting of nitric acid and hydrofluoric acid and containing metal fluorides and metal nitrates
  • Pickling solution known, after the used pickling solution a concentration, for example carried out in a cycle into a temperature of around 500 - 1000 ° C heated fluidized bed reactor is introduced in the for example, a fluidized bed is formed from iron oxide granules is.
  • the used pickling solution contained metal fluorides pyrohydrolysed. Subsequently becomes from the flue gas leaving the fluidized bed reactor by absorption of hydrogen fluoride and nitrogen oxides Acid recovered.
  • the nitrate reduced to nitric oxide, thereby recovering the nitric acid content is relatively expensive.
  • relatively expensive oxidizing agents are required.
  • the degree of recovery is still in need of improvement.
  • the invention is therefore based on the object, the known To further develop methods so that the efficiency in the used pickling solution or in the mixed acid contained nitrate and fluoride content in the form of free acid is improved and the recovery of the Nitric acid without the use of oxidizing agents and is therefore feasible while reducing operating costs.
  • the advantage should remain that the solved Metal ions into a dust-free, easy-to-treat, environmentally friendly and recyclable form can be transferred.
  • the invention proposed a method of the type described at the outset, that the used pickling solution initially in a separation process into a free acid and separated a partial stream enriched with metal salts and that the one enriched with free acid Partial stream of the acid recovery unit and with Partial stream enriched with metal salts to the fluidized bed reactor is fed.
  • This system is used to regenerate a used pickling solution consisting of nitric acid and hydrofluoric acid, referred to as mixed acid and containing metal fluorides and metal nitrates, which has the following composition at a density of approximately 1.180 kg / dm 3 : Iron 33.8 g / l Chrome (Cr) 7.65 g / l Nickel (Ni) 5.3 g / l total free acid 4.1 mol / l Residual water
  • This used pickling solution is used, for example, via a Line 1 first conveyed into a storage container 2, from which it has a pump, not shown, via a Line 3 arrives at a microfilter 4.
  • a line 5 of a washing stage for example a venturi scrubber 12.
  • the filtrate is removed from the microfilter 4 via a line 6 led to a separation stage, which in this example as Diffusion dialysis unit 7 is formed.
  • This separation stage can also from a crystallization or retardation plant consist.
  • a line 8 drawn off with a branch 9 rinse water from the pickling plant and also fed to the diffusion dialysis unit 7.
  • the filtrate from the microfilter 4 and Flushing water flow through the diffusion dialysis unit 7 in Countercurrent.
  • the free acids of the filtrate arrive due to the different concentrations of that Filtrate into the rinse water.
  • After flowing through the diffusion dialysis unit 7 is the diffusate from the rinse water - partial stream enriched with free acid - while the filtrate flowing in from the microfilter 4 now the dialysate - enriched with metal salts Partial flow - has become.
  • the diffusate flows out of the diffusion dialysis unit 7 via a line 10.
  • the dialysate leaves the diffusion dialysis unit 7 over a line 11 and will together with the rinse water from line 8 a venturi washer 12 supplied, the so-called Venturi circuit having.
  • the dialysate is in this cycle with the rinse water as a Venturi liquid and used for cooling purposes or heated, whereupon will be discussed below.
  • Part of the in the Venturi liquid hydrofluoric acid and the Nitric acid and water evaporated. A partial flow this so evaporated solution becomes the venturi circuit withdrawn and via a line 13 to a fluidized bed reactor 14 fed.
  • the fluidized bed reactor 14 is heated by a gas which is supplied via a line 15. Air enters the fluidized bed reactor 14 via a line 16 and burns there stoichiometrically with the gas. A temperature is sought which is approximately between 810 ° C and 870 ° C.
  • An iron oxide granulate with the following properties is supplied via a line 17 density 5080 kg / m 3 Bulk density 3050 kg / m 3 Grain size d 50 0.26 mm, consisting of 99% Fe 2 O 3 introduced into the fluidized bed reactor 14, which forms a fluidized bed or a fluidized bed there.
  • water and the free hydrofluoric acid evaporate from the partial stream supplied from the Venturi circuit.
  • the nitric acid and the metal fluorides and the metal nitrates react according to the following equations: 2FeF 3 + 3H 2 O Fe 2 O 3 + 6 HF 2CrF 3 + 3H 2 O Cr 2 O 3 + 6 HF NiF 2 + H 2 O NiO + 2 HF
  • This produces a granular metal oxide which is withdrawn from the fluidized bed reactor 14 via a line 18.
  • This granular metal oxide has a grain size of approximately 0.2 mm to 2.0 mm and replaces the iron oxide supplied when the fluidized bed reactor 14 is started up.
  • the specified grain size can be achieved by continuously withdrawing the metal oxide.
  • the hot flue gas which still contains dust-like metal oxides, leaves the fluidized bed reactor 14 above via a Line 19 and one of the same is designed as a cyclone Dust collector 20 supplied.
  • the one separated here Dust is returned to the fluidized bed reactor via a line 21 14 returned, while that largely from Dust-free flue gas is fed into the venturi scrubber via a line 22 12 is promoted. This is where the flue gas comes on cooled to a temperature of about 60 ° C to 100 ° C. At the same time becomes fine dust still in the flue gas deposited.
  • the venturi washer 12 therefore has the task to cool the flue gas, to separate the fine dust, the Concentrate used pickling solution and recover heat.
  • the dust-free and above all cooled flue gas is one of the Venturi scrubber 12 via a line 23 Absorption unit 24 fed.
  • Absorption unit 24 fed.
  • the mixed acid is recovered and over a line 27 is withdrawn.
  • the pre-cleaned gas or flue gas becomes from the absorption unit 24 for example through a fan a line 28 is withdrawn and to the gas scrubber already mentioned 26 funded.
  • a line 28 is withdrawn and to the gas scrubber already mentioned 26 funded.
  • possibly still existing ones Washed out residues of hydrofluoric acid.
  • As an absorption liquid is used in the scrubber 26 water, which the same is fed via a line 29. That from the Gas scrubber 26 will then drain, as already mentioned, the absorption unit 24 as an absorbent fed.
  • the gas, cleaned of hydrofluoric acid flows through a line 30 to a so-called DENOX unit 31.
  • DENOX unit 31 becomes Gas by combustion of one supplied via line 15 Heating gas heated.
  • Ammonia as a reducing agent They are still in the gas via line 32 existing nitrous components reduced to nitrogen.
  • the cleaned gas can then enter the chimney 33 Free are given.

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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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
EP97119480A 1996-11-15 1997-11-07 Procédé de régénération de solutions de décapage usées Ceased EP0843025A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19647196 1996-11-15
DE19647196 1996-11-15
DE19747693A DE19747693A1 (de) 1996-11-15 1997-10-29 Verfahren zur Regenerierung einer verbrauchten Beizlösung
DE19747693 1997-10-29

Publications (1)

Publication Number Publication Date
EP0843025A1 true EP0843025A1 (fr) 1998-05-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP97119480A Ceased EP0843025A1 (fr) 1996-11-15 1997-11-07 Procédé de régénération de solutions de décapage usées

Country Status (2)

Country Link
US (1) US6375915B1 (fr)
EP (1) EP0843025A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999014165A1 (fr) * 1997-09-12 1999-03-25 Steuler Industriewerke Gmbh Procede de regeneration de solutions acides metalliferes issues d'installations de traitement des surfaces
EP1038991A1 (fr) * 1999-03-22 2000-09-27 Andritz-Patentverwaltungs-Gesellschaft m.b.H. Procédé de récupération d' acides à partir de solutions métallifères de ces acides
WO2004007801A1 (fr) * 2002-07-10 2004-01-22 Uvk Engineering Gmbh Procede et dispositif pour recycler des bains de decapage de metaux

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT413697B (de) * 2001-11-07 2006-05-15 Andritz Ag Maschf Verfahren zur behandlung säurehältiger abwässer
CN101223293A (zh) * 2005-06-15 2008-07-16 澳斯特帕克资源公司 金属氯化物溶液的处理和直接还原铁的方法和装置
EP2784186A1 (fr) * 2013-03-27 2014-10-01 CMI UVK GmbH Procédé de récupération de particules d'oxyde métallique à partir d'une solution d'acide usé contenant des sels métalliques
EP2784185A1 (fr) * 2013-03-27 2014-10-01 CMI UVK GmbH Procédé de récupération d'acides à partir d'une solution d'acide usé contenant des sels métalliques
CN109553152B (zh) * 2018-11-30 2021-09-10 中冶南方工程技术有限公司 一种不锈钢混酸废液再生酸工艺
CN111732085B (zh) * 2020-05-14 2023-12-29 中冶南方工程技术有限公司 一种酸性污泥与废酸一体化回收装置及工艺

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2428207A1 (fr) * 1978-06-07 1980-01-04 Gueugnon Forges Procede et installation pour le traitement de bains fluonitriques uses
AT374508B (de) * 1982-07-01 1984-05-10 Ruthner Industrieanlagen Ag Verfahren zur aufarbeitung verbrauchter beizoder aetzloesungen auf der basis von salpeter-flussaeure
EP0296147A1 (fr) * 1987-06-16 1988-12-21 Maschinenfabrik Andritz Aktiengesellschaft Procédé d'extraction et/ou de récupération d'acides à partir de solutions métallifères de ces acides
EP0398863A1 (fr) * 1989-05-17 1990-11-22 BÖHLER Gesellschaft m.b.H. Procédé de récupération de métaux ou d'oxydes de métaux et des acides à partir de solutions salines, en particulier à partir d'acides ou mélanges d'acides de décapage
EP0463671A1 (fr) * 1990-06-28 1992-01-02 METALLGESELLSCHAFT Aktiengesellschaft Procédé de traitement de bains de décapage usés contenant des sels métalliques et des acides
DE4315551A1 (de) * 1993-05-10 1994-11-17 Gewerk Keramchemie Verfahren zur Regenerierung von verbrauchten, Metallsalze und/oder Metalloxide enthaltenden Lösungen, insbesondere Milchsäuren
WO1996027554A1 (fr) * 1995-03-07 1996-09-12 S.A.D. Edv-Systemanalyse Und -Systemdesign Gesellschaft Mbh Procede d'extraction ou de recuperation d'acides

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL132526C (fr) * 1965-04-17
DE1667195C3 (de) * 1968-01-31 1979-09-27 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur Herstellung von Halogenwasserstoffsäuren und von Metalloxiden
US3529931A (en) * 1968-07-12 1970-09-22 Nat Lead Co Regenerating hci from iron chloride solutions
US3658483A (en) * 1970-05-18 1972-04-25 Sued Chemie Ag Apparatus for the production of concentrated hydrohalogen acids and metal oxides
US5244551A (en) * 1990-06-28 1993-09-14 Metallgesellschaft Aktiengesellschaft Process of regenerating waste pickle which contains metal salts and acids
ATE155438T1 (de) * 1991-11-22 1997-08-15 Tech Resources Pty Ltd Regenerierung von salzsäure
JPH0657466A (ja) * 1992-08-07 1994-03-01 Kooe Eng Kk 酸洗廃液より硝酸と弗酸の混合酸又は硝酸、弗酸を回収する方法
DE4402028C2 (de) 1994-01-25 1996-11-28 Gewerk Keramchemie Verfahren zur Regenerierung einer verbrauchten, Flußsäure enthaltenden Prozeßlösung

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2428207A1 (fr) * 1978-06-07 1980-01-04 Gueugnon Forges Procede et installation pour le traitement de bains fluonitriques uses
AT374508B (de) * 1982-07-01 1984-05-10 Ruthner Industrieanlagen Ag Verfahren zur aufarbeitung verbrauchter beizoder aetzloesungen auf der basis von salpeter-flussaeure
EP0296147A1 (fr) * 1987-06-16 1988-12-21 Maschinenfabrik Andritz Aktiengesellschaft Procédé d'extraction et/ou de récupération d'acides à partir de solutions métallifères de ces acides
EP0398863A1 (fr) * 1989-05-17 1990-11-22 BÖHLER Gesellschaft m.b.H. Procédé de récupération de métaux ou d'oxydes de métaux et des acides à partir de solutions salines, en particulier à partir d'acides ou mélanges d'acides de décapage
EP0463671A1 (fr) * 1990-06-28 1992-01-02 METALLGESELLSCHAFT Aktiengesellschaft Procédé de traitement de bains de décapage usés contenant des sels métalliques et des acides
DE4315551A1 (de) * 1993-05-10 1994-11-17 Gewerk Keramchemie Verfahren zur Regenerierung von verbrauchten, Metallsalze und/oder Metalloxide enthaltenden Lösungen, insbesondere Milchsäuren
WO1996027554A1 (fr) * 1995-03-07 1996-09-12 S.A.D. Edv-Systemanalyse Und -Systemdesign Gesellschaft Mbh Procede d'extraction ou de recuperation d'acides

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999014165A1 (fr) * 1997-09-12 1999-03-25 Steuler Industriewerke Gmbh Procede de regeneration de solutions acides metalliferes issues d'installations de traitement des surfaces
EP1038991A1 (fr) * 1999-03-22 2000-09-27 Andritz-Patentverwaltungs-Gesellschaft m.b.H. Procédé de récupération d' acides à partir de solutions métallifères de ces acides
WO2004007801A1 (fr) * 2002-07-10 2004-01-22 Uvk Engineering Gmbh Procede et dispositif pour recycler des bains de decapage de metaux
DE10231308C5 (de) * 2002-07-10 2009-10-15 Cmi Uvk Gmbh Verfahren und Vorrichtung zum Recyceln von Edelstahl-Beizbädern
US9139916B2 (en) 2002-07-10 2015-09-22 Cmi Uvk Gmbh Method and device for recycling metal pickling baths

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US6375915B1 (en) 2002-04-23

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