EP0463905B1 - Verfahren zur Entfernung von Siliziumverbindungen aus Beizbädern und Einrichtung dafür - Google Patents

Verfahren zur Entfernung von Siliziumverbindungen aus Beizbädern und Einrichtung dafür Download PDF

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Publication number
EP0463905B1
EP0463905B1 EP91401525A EP91401525A EP0463905B1 EP 0463905 B1 EP0463905 B1 EP 0463905B1 EP 91401525 A EP91401525 A EP 91401525A EP 91401525 A EP91401525 A EP 91401525A EP 0463905 B1 EP0463905 B1 EP 0463905B1
Authority
EP
European Patent Office
Prior art keywords
cleaning bath
silicic compounds
pickling
bath
spent
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 - Lifetime
Application number
EP91401525A
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English (en)
French (fr)
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EP0463905A1 (de
Inventor
Lothaire Walter Scherer
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.)
Sollac SA
Original Assignee
Sollac SA
Lorraine de Laminage Continu SA SOLLAC
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Filing date
Publication date
Application filed by Sollac SA, Lorraine de Laminage Continu SA SOLLAC filed Critical Sollac SA
Publication of EP0463905A1 publication Critical patent/EP0463905A1/de
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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
    • 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 present invention relates to a process for the separation of silicic compounds from pickling baths containing iron ions and silicic compounds, as well as to a device for carrying out the process.
  • EP-0 141 034 discloses a process for separating a silicic compound from a spent pickling bath of steels.
  • the spent pickling bath passes through a filter made of a material adsorbing the silica compound.
  • Such a method has the drawback of requiring an operation for regenerating the adsorbent materials constituting the filter. In fact, during its use, the adsorbent filter becomes clogged and the flow and volume of the treated pickling bath gradually decreases.
  • Application JP-A-59162139 describes a process for treating spent pickling baths, comprising a concentration of the bath, followed by filtration to remove the insolubilized silicic compounds.
  • the pickling baths currently used for pickling steel substrates contain iron ions, essentially in the form of ferrous ions, as well as a certain proportion of silicic compounds formed from the silicon element coming from the substrate.
  • pickling baths after having been previously concentrated are thermally decomposed by known methods and are in particular calcined in an oven of the RUTHNER type, which makes it possible to recover iron oxides, essentially in Fe2O3 form.
  • Iron oxides which are sufficiently pure, can be used as colorants, for example in paints and cosmetic products, or as excipients in the pharmaceutical industry. They are also used in the manufacture of magnetic components or still in the manufacture of cements to improve their mechanical characteristics.
  • the silica content of the iron oxides currently recovered from the pickling baths is at least 350 ppm, while it would be desirable to lower it below 100 ppm for the applications mentioned above.
  • the object of the present invention is to provide a process which makes it possible to increase the purity of the iron oxides by lowering their content of residual silicic compounds.
  • the invention also relates to an installation comprising means for the regeneration of the pickling bath containing iron ions and silicic compounds, characterized in that the regeneration means include means for concentrating the spent pickling bath, at least one tank. for cooling the pickling bath and reheating it, at least one device for separating the precipitated silica compound (s) from the pickling bath and a device for thermally decomposing the pickling bath into iron oxides and vapor water and acid.
  • the separation device consists advantageously in a centrifuge device and / or a filtration device comprising filters with a porosity less than or equal to 20 ⁇ m.
  • FIG. 1 represents a diagram of an installation for pickling steel sheets.
  • the installation comprises a pickling unit 1 at the outlet of which the pickling bath containing water, hydrochloric acid, iron chlorides and one or more silicic compounds is depleted in acid and enriched in iron.
  • the bath temperature is around 90 ° C, it contains 30 to 60 g / l of hydrochloric acid and 90 to 140 g / l of iron ions, and optionally a compound preventing attack of the substrate.
  • the spent pickling bath is then directed to an evaporator 2 to be concentrated there.
  • the evaporator 2 consists of a liquid-gas exchanger supplied by hot gases leaving a device thermal 3 via a cyclone 4.
  • the evaporator 2 makes it possible to preheat the bath while concentrating it by evaporation of the water contained in it.
  • the concentrated spent bath recovered at the outlet of the evaporator 2 is directed to cooling and reheating tanks 5 and 6, where it is cooled to a temperature equal to or less than 60 ° C. preferably with a cooling rate about 2 ° C / min.
  • the pickling bath is then allowed to stabilize for a period of at least 2 hours, which makes it possible to create favorable conditions for the silicic compounds to crystallize in the form of relatively large particles.
  • the bath is heated so that the dissolution, in particular of the iron chloride, is sufficient and to obtain a viscosity of the bath allowing separation, for example by filtration of the silica compound (s).
  • the heating rate is not critical and can vary from a few minutes to several hours.
  • the pickling bath is advantageously centrifuged and / or filtered on the centrifugation and / or automatic filtration unit 7 which makes it possible to collect the precipitated silicic compound (s) and not redissolved.
  • the pickling bath depleted in silicic compounds is then directed towards the upper part of the thermal device 3 where it is treated to obtain iron oxide. Iron oxide is collected at the base of the thermal device 3.
  • the thermal device 3 known for the implementation for example of the RUTHNER process, the water and acid vapors produced containing a residual quantity of iron oxide are sent into a cyclone 4 which separates the iron oxide. The residual iron oxide thus separated is reintroduced into the thermal device 3.
  • the hot gases taken off at the head of the cyclone 4 are used for the operation of the evaporator 2.
  • the hot gases essentially comprising water vapor and hydrochloric acid pass through an absorber 8 supplied with water in its upper part by water coming from the rinsing unit 9 used for rinsing the substrates leaving the pickling unit 1.
  • the acid-depleted vapors exiting at the upper part of the absorber 8 are directed to a smoke washing device 10 supplied with water by an additional water 11.
  • the smoke washing water is added to the supplying water the absorber 8 from the rinsing unit 9.
  • a regenerated bath is collected containing a hydrochloric acid solution which can again be used for a second pickling and regeneration cycle.
  • the process and the device according to the invention for the substantial elimination of silicic compounds from pickling baths are easily transposable in an industrial environment and make it possible to obtain iron oxide, the silica content of which is less than 100 ppm.

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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)
  • Silicon Compounds (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Claims (8)

  1. Verfahren zur Entfernung von Siliziumverbindungen aus Stahlbeizbädern, die Eisenionen und Siliziumionen enthalten, bestehend aus den folgenden Verfahrensstufen:
    a) das gebrauchte Beizbad wird konzentriert,
    b) das gebrauchte konzentrierte Beizbad wird mit einer Geschwindigkeit zwischen 0,2 und 4°C/min bis auf eine Temperatur unterhalb 60°C derart abgekühlt, daß die Siliziumverbindungen ausfallen,
    c) die Temperatur des Beizbads wird 2 Stunden lang gehalten,
    d) das Beizbad wird wieder erwärmt,
    e) die gefällten Siliziumverbindungen werden aus dem Beizbad entfernt.
  2. Verfahren nach Anspruch 1, dadurch gekenzeichnet, daß die Abkühlgeschwindigkeit etwa 2°C/min beträgt.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das konzentrierte gebrauchte Beizbad auf eine Temperatur zwischen 20 und 40°C abgekühlt wird.
  4. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, daß die Wiedererwärmungstemperatur etwa 80°C beträgt.
  5. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennnzeichnet, daß die gefällten Siliziumverbindungen aus dem Beizbad durch Dekantieren, Zentrifugieren und/oder Filtrieren entfernt werden.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die gefällten Silciumverbindungen aus dem Beizbad durch Filtration über Filter mit einer Porengröße kleiner oder gleich 20 µm entfernt werden.
  7. Vorrichtung, die Mittel zur Regenierung eines gebrauchten, Eisenionen und Siliziumverbindungen enthaltenden Beizbads umfaßt, enthaltend:
    - Mittel (2) zum Konzentrieren des gebrauchten Beizbads,
    - mindestens ein Behältnis zum Abkühlen und Wiedererwärmen (5) (6),
    - mindestens eine Trenneinrichtung (7) zum Entfernen der gefällten Siliziumverbindungen ausgehend vom Beizbad und
    - eine Einrichtung (3) zur thermischen Zersetzung des Beizbads in Eisenoxide, Wasserdampf und Säure.
  8. Vorrichtung nach Anspruch 7, dadurch gekennzeichnet, daß die Trenneinrichtung (7) für die Siliziumverbindungen aus einer Einrichtung zum Zentrifugieren und/oder eine Einrichtung zum Filtrieren mit Filtern einer Porengröße kleiner oder gleich 20 µm besteht.
EP91401525A 1990-06-15 1991-06-10 Verfahren zur Entfernung von Siliziumverbindungen aus Beizbädern und Einrichtung dafür Expired - Lifetime EP0463905B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9007519 1990-06-15
FR9007519A FR2663344B1 (fr) 1990-06-15 1990-06-15 Procede de separation de composes siliciques des bains de decapage et installation pour sa mise en óoeuvre.

Publications (2)

Publication Number Publication Date
EP0463905A1 EP0463905A1 (de) 1992-01-02
EP0463905B1 true EP0463905B1 (de) 1994-09-07

Family

ID=9397677

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91401525A Expired - Lifetime EP0463905B1 (de) 1990-06-15 1991-06-10 Verfahren zur Entfernung von Siliziumverbindungen aus Beizbädern und Einrichtung dafür

Country Status (7)

Country Link
US (1) US5296001A (de)
EP (1) EP0463905B1 (de)
JP (1) JP3040201B2 (de)
AT (1) ATE111164T1 (de)
DE (1) DE69103825T2 (de)
ES (1) ES2063463T3 (de)
FR (1) FR2663344B1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4242619C2 (de) * 1992-12-14 1996-01-25 Mannesmann Ag Verfahren und Vorrichtung zur Säureentschlammung
AT403697B (de) * 1995-04-24 1998-04-27 Chemikalien & Tech Service Ges Verfahren zur entkieselung von wässrigen, sauren, vorzugsweise salzsauren lösungen sowie herstellung von kieselsäurearmem metalloxid
FR2916205A1 (fr) * 2007-05-16 2008-11-21 Siemens Vai Metals Tech Sas Installation et procede pour le traitement de solutions de decapage de bandes d'acier au silicium

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1432661A (fr) * 1965-02-09 1966-03-25 Loire Atel Forges Perfectionnements apportés au traitement des bains de décapage des aciers au silicium
US4184955A (en) * 1975-09-30 1980-01-22 Arvanitakis Kostas S Method and apparatus for clarifying liquids through settling
DE3019737C2 (de) * 1980-05-23 1982-09-02 Westfalia Separator Ag, 4740 Oelde Schleudertrommel zum Klären und Trennen von Schleuderflüssigkeiten
JPS59111930A (ja) * 1982-12-16 1984-06-28 Nippon Steel Corp 塩酸酸洗廃液から酸化鉄を製造する方法
JPS59169902A (ja) * 1983-03-14 1984-09-26 Tadayoshi Karasawa 廃酸精製処理工程の改良
US4636317A (en) * 1985-07-16 1987-01-13 Fluid Recycling Services, Inc. Recycling of metalworking fluids
JPS63144122A (ja) * 1986-12-03 1988-06-16 Sumitomo Metal Ind Ltd 塩酸酸洗廃液からけい素を除去する方法
JPS63144123A (ja) * 1986-12-08 1988-06-16 Sumitomo Metal Ind Ltd 鋼材の塩酸酸洗廃液中のけい素分の除去方法
JPS63242932A (ja) * 1987-03-30 1988-10-07 Sumitomo Metal Ind Ltd 鋼材の塩酸酸洗廃液中のけい素分の除去方法
JPH0742118B2 (ja) * 1987-12-10 1995-05-10 日本鋼管株式会社 第一鉄イオン含有酸溶液の精製方法

Also Published As

Publication number Publication date
JP3040201B2 (ja) 2000-05-15
ATE111164T1 (de) 1994-09-15
DE69103825D1 (de) 1994-10-13
JPH04231486A (ja) 1992-08-20
US5296001A (en) 1994-03-22
ES2063463T3 (es) 1995-01-01
DE69103825T2 (de) 1995-01-05
EP0463905A1 (de) 1992-01-02
FR2663344A1 (fr) 1991-12-20
FR2663344B1 (fr) 1992-10-09

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