EP0635586B1 - Verfahren zur Regenerierung von Salzsäure aus Beizanlagen - Google Patents

Verfahren zur Regenerierung von Salzsäure aus Beizanlagen Download PDF

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Publication number
EP0635586B1
EP0635586B1 EP94110417A EP94110417A EP0635586B1 EP 0635586 B1 EP0635586 B1 EP 0635586B1 EP 94110417 A EP94110417 A EP 94110417A EP 94110417 A EP94110417 A EP 94110417A EP 0635586 B1 EP0635586 B1 EP 0635586B1
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EP
European Patent Office
Prior art keywords
fact
process according
pickling
compound
acid
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
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EP94110417A
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German (de)
English (en)
French (fr)
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EP0635586A1 (de
Inventor
Wilhelm Dipl.-Ing. Dr. Techn. Karner
Dietfried Gamsriegler
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Andritz Patentverwaltungs GmbH
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Andritz Patentverwaltungs GmbH
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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 process for the regeneration of hydrochloric acid from pickling plants, comprising the thermal cleavage of iron chloride in the used pickling acid to iron oxide and gaseous hydrochloric acid, at least one reducing compound being admixed with the used pickling acid.
  • Pickling is an indispensable process step in metallurgical process engineering for the production of steel products.
  • Hydrochloric acid and sulfuric acid, as well as other acids and acid mixtures, are particularly suitable as the pickling medium. Due to various circumstances, partly due to the achievable quality of the end products and partly due to the fact that it can be completely regenerated, pickling with hydrochloric acid or mixtures containing it has become increasingly popular over the past 30 years.
  • the effect of the acid is to dissolve the layers of scale that form on the steel surface through previous processes such as rolling, annealing, etc. This happens after the following chemical reaction: (1) FeO + 2 HCI ⁇ FeCl 2nd + H 2nd O
  • the pickling process therefore consumes acid (HCl) to a point where the solution is saturated with iron chloride and can no longer be used for pickling.
  • These pollutants include the compounds NO and NO 2 (collectively referred to as nitrogen oxides, NO x ), which on the one hand can form themselves from the atmospheric nitrogen through the combustion process, and on the other hand can form nitrogen compounds, such as inhibitors, from the pickling bath.
  • NO x nitrogen oxides
  • Another pollutant is chlorine, which is formed in the form of elemental chlorine (Cl 2 ) in the above processes by oxidation of HCl according to the so-called Deacon equilibrium: (3) 2 HCl + 0.5 O 2nd ⁇ Cl 2nd + H 2nd O
  • the equilibrium constants of this homogeneous gas reaction are well known and are, for example, at Temperature (K) log Kp 500 0.9 600 - 0.7 700 - 1.9 800 - 2.8
  • the chlorine once formed can only be removed from the exhaust gases with difficulty, but this is unavoidable since, for example, the TA air only allows a content of 5 mg / m 3 .
  • laundry is part of the chlorine reduction State of the art with sodium thiosulfate: (4) Well 2nd S 2nd O 3rd + 4 cl 2nd + 5 h 2nd O ⁇ 2 NaHSO 4th + 8 HCl
  • the object of the present invention is to provide a method of the type mentioned in the introduction, in which the occurrence of the pollutants mentioned can be avoided in a simple and inexpensive manner in the recovery of hydrochloric acid from used pickling solutions.
  • At least one compound is added to the spent pickling acid which contains nitrogen with an oxidation number which has a reducing effect on NO, NO 2 and Cl 2 , such as, for example, ammonium compounds, ammonia, urea or amides.
  • the pollutants NO x and chlorine are oxidizing in relation to the added substances, so that they react in the following way, for example: (5) 3 NO + 2 NH 3rd ⁇ 2.5 N 2nd + 3 H 2nd O (5a) 3 NO 2nd + 4 NH 3rd ⁇ 3.5 N 2nd + 6 h 2nd O (6) 3 cl 2nd + 2 NH 3rd ⁇ 6 HCl + N 2nd
  • reaction (5) part of the reactor and the iron oxide in it take on the function of a catalytic converter.
  • the spent pickling acid together with at least one compound which contains nitrogen with an oxidation number which has a reducing effect on NO, NO 2 and Cl 2 , is fed into a venturi scrubber and then in one Reactor, which can be a spray roasting reactor or a fluidized bed reactor, is thermally split.
  • a venturi scrubber which can be a spray roasting reactor or a fluidized bed reactor, is thermally split.
  • the exhaust gas originating from the thermal decomposition is subjected to a wash, preferably with rinsing water from a rinsing system connected downstream of a pickling system, whereby the pollutant values in the exhaust gas can be reduced further.
  • FIG. 1 and 2 show schematically exemplary plants for carrying out the method according to the invention using a spray roasting reactor.
  • the spent pickling acid is introduced into a venturi scrubber 2 via a line 1.
  • the gases coming from the reactor 3, for example a spray roasting reactor, are fed into the venturi scrubber 2 via a line 4.
  • the aqueous solution from the venturi scrubber 2 is passed through the pump 6 via a line 5 to the spray device 7 of the reactor 3, to which gas and air for combustion and oxidation are fed via a line 8.
  • the oxide formed by the spray roasting process is via a line 9, preferably withdrawn from the reactor 3 by means of a rotary valve, not shown.
  • the exhaust gas from the reactor 3 is subsequently fed to a first column 10 and via line 23 to a second column 11 for further purification.
  • Both columns 10, 11 are preferably charged with water, to which chemicals can optionally be added to support the cleaning action, via lines 13 and the residual liquid is removed via lines 25.
  • the compound or the mixture of compounds containing nitrogen with a low oxidation number is fed into the supply line 1 for the used pickling acid to the venturi scrubber 2 via a line 16. It applies to the amount of nitrogen-containing compound (s) supplied that it must be admixed at least in a stoichiometric ratio to the pollutants contained, the lower the pollutant content in the exhaust gas, the greater the excess of the nitrogen-containing compound or the mixture thereof is. Depending on the initial values, at least five times, but preferably at least ten times, the amount is added instead of the stoichiometrically necessary amount for chlorine. For nitrogen oxides, the minimum addition amounts are twice, preferably three times, the stoichiometrically necessary amounts.
  • FIG. 2 is constructed similarly to that of FIG. 1, but no second column is provided.
  • a rinsing system 18 and the previous pickling system 19 are shown.
  • the rinsing system 18 is supplied with fresh water via a line 13, while its wastewater - with the residual content of pickling acid contained therein - is fed to the scrubber 12 via the line 20.
  • the nitrogen-containing compound or the mixture of such compounds is mixed with the water from the rinsing system 18 via a further line 17.
  • the cleaned exhaust gas is finally released into the atmosphere via a chimney 15.
  • the solution emerging from the first column 10 and containing the hydrochloric acid formed during the thermal cleavage is fed via line 21 to the pickling plant 19.
  • the pickling acid used in this process variant can also be mixed directly via line 16 with at least one compound containing nitrogen with a low oxidation number before the pickling acid enters the venturi scrubber 2.
  • the feed rate of the venturi washer was 16 l / h and that of the spray roasting reactor was 10 l / h.
  • the temperature in the burner level is 645 ° C and in the upper area of the reactor 389 ° C.
  • the amount of gas was 2.8 m 3 / h, the amount of air 28 m 3 / h and the O 2 content 5% (based on dry volume).
  • the NO x content in the chimney was measured and the averaging gave a value of 180 ppm consisting of 150 ppm NO and 30 ppm NO 2 . This corresponds to a total of 2.5 kg NO / h.

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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)
  • Treating Waste Gases (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
EP94110417A 1993-07-21 1994-07-05 Verfahren zur Regenerierung von Salzsäure aus Beizanlagen Expired - Lifetime EP0635586B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT1449/93 1993-07-21
AT0144993A AT399516B (de) 1993-07-21 1993-07-21 Verfahren zur regeneration von salzsäure aus beizanlagen

Publications (2)

Publication Number Publication Date
EP0635586A1 EP0635586A1 (de) 1995-01-25
EP0635586B1 true EP0635586B1 (de) 1996-06-12

Family

ID=3514134

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94110417A Expired - Lifetime EP0635586B1 (de) 1993-07-21 1994-07-05 Verfahren zur Regenerierung von Salzsäure aus Beizanlagen

Country Status (6)

Country Link
US (1) US6210650B1 (enrdf_load_stackoverflow)
EP (1) EP0635586B1 (enrdf_load_stackoverflow)
JP (1) JP3531840B2 (enrdf_load_stackoverflow)
AT (1) AT399516B (enrdf_load_stackoverflow)
DE (1) DE59400348D1 (enrdf_load_stackoverflow)
TW (1) TW265322B (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10006990B4 (de) * 1999-03-22 2006-05-04 Andritz-Patentverwaltungs-Ges.M.B.H. Anlage zur Rückgewinnung von Säuren aus metallhaltigen Lösungen dieser Säuren

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT403665B (de) * 1996-10-30 1998-04-27 Andritz Patentverwaltung Verfahren und anlage zur abscheidung feinster oxidteilchen
AT407757B (de) * 1999-03-22 2001-06-25 Andritz Patentverwaltung Verfahren zur rückgewinnung von säuren aus metallhaltigen lösungen dieser säuren
US6692719B1 (en) * 2000-11-08 2004-02-17 Hatch Ltd. Process for regeneration of acid halide solutions
WO2002083569A2 (de) * 2001-04-10 2002-10-24 Basf Aktiengesellschaft Eisenoxide mit höherem veredelungsgrad
AT413697B (de) 2001-11-07 2006-05-15 Andritz Ag Maschf Verfahren zur behandlung säurehältiger abwässer
JP4688399B2 (ja) * 2002-10-18 2011-05-25 富士工機株式会社 鉄塩酸処理廃液から塩酸を回収する方法
CN100434355C (zh) * 2005-05-20 2008-11-19 鞍钢股份有限公司 一种废盐酸再生除硅工艺及设备
DE102006023939A1 (de) * 2006-05-19 2007-11-22 Bayer Materialscience Ag Verfahren zur Absorption von Chlor aus einem Chlor- und Kohlendioxid-enthaltenden Gas
BRPI0914876B1 (pt) * 2008-06-19 2020-05-26 Sms Siemag Aktiengesellschaft Método de processamento de solução de cloreto de ferro residual
CN101376547B (zh) * 2008-10-10 2010-10-13 韩晓波 精苯酸洗液的回收处理方法
JP5405164B2 (ja) * 2009-03-24 2014-02-05 月島環境エンジニアリング株式会社 窒素成分を含む廃水の処理方法
RU2490374C1 (ru) * 2012-06-06 2013-08-20 Открытое акционерное общество "Северсталь" (ОАО "Северсталь") Установка для регенерации соляной кислоты из отработанного травильного раствора
TR201603891A2 (tr) * 2016-03-25 2017-10-23 Borcelik Celik San Tic A S Dekapaj çözelti̇leri̇nden saf demi̇r tozu üreti̇mi̇
AT526794A1 (de) 2022-12-20 2024-07-15 Andritz Ag Maschf Verfahren zur regeneration von saeure

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2838373A (en) * 1956-05-23 1958-06-10 United States Steel Corp Method for treatment of spent hydrochloric acid pickle liquor for the recovery of iron oxide, ammonium sulphate and hydrochloric acid
FR1309534A (fr) * 1960-12-10 1962-11-16 Otto Sauerebau Und Keramikwerk Dispositif et procédé pour la récupération de l'acide chlorhydrique dans les solutions de décapage
US3445284A (en) * 1963-11-18 1969-05-20 Dravo Corp Process for pickling of steel strip and regeneration of the contact acid
NL132526C (enrdf_load_stackoverflow) * 1965-04-17
US3443991A (en) * 1965-12-06 1969-05-13 Georges F Kremm Process for pickling metal
US3529931A (en) * 1968-07-12 1970-09-22 Nat Lead Co Regenerating hci from iron chloride solutions
US3682592A (en) * 1970-07-20 1972-08-08 Pori Inc Treatment of waste hci pickle liquor
US3755090A (en) * 1972-03-27 1973-08-28 British Steel Corp A method of providing a surface of a steel substrate with an aluminum coating
US4086321A (en) * 1976-06-21 1978-04-25 Carl A. Holley Producing pure iron oxides
US4397708A (en) * 1980-09-25 1983-08-09 Koltron Corporation Etching and etchant removal apparatus
SU1401014A1 (ru) * 1986-09-15 1988-06-07 Ужгородский Государственный Университет Способ окислени хлорида железа ( @ )
US4842834A (en) * 1987-02-02 1989-06-27 Fuel Tech, Inc. Process for reducing the concentration of pollutants in an effluent
JPH01129982A (ja) * 1987-11-13 1989-05-23 Hitachi Cable Ltd 塩化第２鉄エッチャントの再生方法とエッチング方法
US5098680A (en) * 1990-10-15 1992-03-24 Exxon Research & Engineering Company Aqueous ammonia injection scheme
JP3018018B2 (ja) * 1991-07-23 2000-03-13 株式会社アステック入江 金属塩化物の処理方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10006990B4 (de) * 1999-03-22 2006-05-04 Andritz-Patentverwaltungs-Ges.M.B.H. Anlage zur Rückgewinnung von Säuren aus metallhaltigen Lösungen dieser Säuren

Also Published As

Publication number Publication date
ATA144993A (de) 1994-10-15
JP3531840B2 (ja) 2004-05-31
US6210650B1 (en) 2001-04-03
DE59400348D1 (de) 1996-07-18
JPH07173657A (ja) 1995-07-11
AT399516B (de) 1995-05-26
TW265322B (enrdf_load_stackoverflow) 1995-12-11
EP0635586A1 (de) 1995-01-25

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