US20040238375A1 - Method for the protection against corrosion of a steel part made of austentic or semi-austentic steel during the production of sulfuric acid - Google Patents

Method for the protection against corrosion of a steel part made of austentic or semi-austentic steel during the production of sulfuric acid Download PDF

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Publication number
US20040238375A1
US20040238375A1 US10/479,304 US47930404A US2004238375A1 US 20040238375 A1 US20040238375 A1 US 20040238375A1 US 47930404 A US47930404 A US 47930404A US 2004238375 A1 US2004238375 A1 US 2004238375A1
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US
United States
Prior art keywords
sulfuric acid
steel
austenitic
steel part
semi
Prior art date
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Abandoned
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US10/479,304
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English (en)
Inventor
Karl-Heinz Daum
Wolf-Christoph Rauser
Nikola Anastasijevic
Wolfram Schalk
Stephan Laibach
Herbert Schnaubelt
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Outokumpu Oyj
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Outokumpu Oyj
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Assigned to OUTOKUMPU OYJ reassignment OUTOKUMPU OYJ ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RAUSER, WOLF-CHRISTOPH, DAUM, KARL-HEINZ, ANASTASIJEVIC, NIKOLA, SCHALK, WOLFRAM, SCHNAUBELT, HERBERT, LAIBACH, STEFAN
Publication of US20040238375A1 publication Critical patent/US20040238375A1/en
Abandoned 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081—Heat exchange elements made from metals or metal alloys
    • F28F21/082—Heat exchange elements made from metals or metal alloys from steel or ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/005—Anodic protection
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/004—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using protective electric currents, voltages, cathodes, anodes, electric short-circuits

Definitions

  • This invention relates to a method for the protection against corrosion of steel parts made of austenitic or semi-austenitic steel during the production of sulfuric acid.
  • sulfuric acid is produced by the catalytic conversion of the SO 2 content of gases to obtain SO 3 and—in the case of dry gases—by the subsequent absorption of the SO 3 formed in concentrated sulfuric acid or—in the case of humid gases—by the subsequent condensation of the sulfuric acid formed.
  • the usual technical components such as drier, absorber, heat exchanger etc. get in contact with concentrated sulfuric acid starting at about 93 wt-% and an elevated temperature.
  • This sulfuric acid is extremely aggressive and exerts a fast and strong corrosion on the structural parts to be used. Therefore, the structural parts which get in contact with sulfuric acid must be made of corrosion-resistant materials.
  • the materials to be protected are coated with a metal oxide layer which prevents the corrosion attack.
  • exchangers, very thin-walled components are required, which need a high transfer of heat. In these components, the previous corrosion resistance no longer is sufficient.
  • These plants are usually operated with a sulfuric acid concentration ⁇ 93 wt-% to 100 wt-% and a temperature up to 140° C.
  • a known method of corrosion protection is the anodic corrosion protection. In this method, the materials to be protected are coated with a metal oxide layer which prevents the corrosion attack.
  • DE 38 30 365 describes the use of ferritic chromium-molybdenum steels which are resistant to sulfuric acid with a concentration from 94 wt-% onwards and with a temperature below the boiling point. These ferritic steels are very expensive and more difficult to process than austenitic steels. The corrosion resistance is not regarded as sufficient either.
  • this object is solved in the above-mentioned method in that at a sulfuric acid concentration of 93 wt-% up to 100 wt-% and a temperature of 140° C. up to the boiling point of the sulfuric acid, the steel part is made of austenitic or semi-austenitic steel which has a Cr content of 15 wt-% to 31 wt-% and an Ni content of 9 wt-% to 60 wt-%, and in which the ratio of the chemical elements (Cr+Si)/(Ni+Mo) lies in the range from 0.9 to 1.25, and in which the steel part has an anodic corrosion protection, wherein an anode, a cathode and a reference electrode are connected with a potentiostat which supplies an adjustable direct electric current, and wherein the cathode and the reference electrode are in contact with the sulfuric acid and the anode is in contact with the steel part.
  • the ratio is particularly favorable when molybdenum is present in a not too large amount of 0 wt-% to 2.5 wt-%.
  • austenitic or semi-austenitic steel parts with a molybdenum content of 2 wt-% to 2.5 wt-% can be used.
  • What is particularly critical for corrosion are those ranges in which the concentration of sulfuric acid is about 97 wt-% to 99 wt-% or the temperature of sulfuric acid is about 1 60° C. to 230° C.
  • heat exchangers such as e.g. plate-type heat exchangers or shell-and-tube heat exchangers, as well as the entire pipe system.
  • FIG. 1 shows the current density/potential curve of an austenitic material
  • FIG. 2 is a schematic representation of the anodic protection in a heat exchanger.
  • FIG. 1 shows the current density/potential curve of an austenitic material
  • FIG. 2 is a schematic representation of the anodic protection in a heat ex-changer.
  • FIG. 1 shows the current density/potential curve of a typical austenitic material containing 16.5 to 18.5 wt-% chromium, 11 to 14 wt-% nickel and 2 to 2.5 wt-% molybdenum.
  • sulfuric acid was used as medium with 98 wt-% at a temperature of 200° C.
  • cathode there was used a steel cathode made of 1.4404.
  • the potential is plotted in millivolt (mV) against a Hg/HgSO 4 reference electrode, and on the ordinate the current density is plotted in milliampere per square centimeter (mA/cm 2 ).
  • mV millivolt
  • Hg/HgSO 4 reference electrode there can also be used other reference electrodes, such as e.g. a calomel electrode or a cadmium bar.
  • the first part of the diagram in the range from 0 to 600 mV shows a peak which is referred to as active potential.
  • active potential In the range from 600 mV to 1800 mV then follows the saddle of the curve, the so-called passive potential.
  • passive potential The subsequent rise from 1800 mV is referred to as transpassive potential.
  • transpassive potential To achieve a corrosion protection as effective as possible in the anodic corrosion protection, the current density must lie within the range of the passive potential.
  • the values represented here are exemplary, as they are material- and temperature-dependent.
  • FIG. 2 shows the arrangement of the anodic corrosion protection in a shell-and-tube heat exchanger ( 1 ) for sulfuric acid.
  • cooling medium Via a connection ( 2 ), cooling medium is introduced into a first chamber ( 3 ) of a shell-and-tube heat exchanger ( 1 ). From there, the cooling medium is distributed and flows through individual tubes ( 4 ) into a second chamber ( 5 ), from which the cooling medium is discharged again.
  • the cooling medium is distributed and flows through individual tubes ( 4 ) into a second chamber ( 5 ), from which the cooling medium is discharged again.
  • only two tubes ( 4 ) are represented here.
  • connection ( 6 ) hot sulfuric acid ( 2 ) is introduced.
  • the sulfuric acid flows around the tubes ( 4 ) filled with cooling medium and is discharged again via the connection ( 7 ).
  • connection ( 7 ) When flowing around the tube bundles ( 4 ), the sulfuric acid is cooled.
  • a plurality of metal cathodes ( 8 ) are mounted between the tubes ( 4 ) in the shell-and-tube heat exchanger.
  • the representation shows a cathode ( 8 ) by way of example.
  • the number of cathodes ( 8 ) used depends on the size of the heat ex-changer and also on the temperature and the concentration of the sulfuric acid.
  • the cathode ( 8 ) is made of the material 1 . 4404 and is in permanent contact with the sulfuric acid.
  • the cathode ( 8 ) is connected with the negative pole of a potentiostat ( 9 ) by an electric line.
  • the potentiostat ( 9 ) is a d.c. voltage source whose positive pole ( 10 ) is connected with the parts of the shell-and-tube heat ex-changer ( 1 ) to be protected via an electric line.
  • a second reference electrode ( 11 ) is inserted in the shell-and-tube heat ex-changer via a seal and is connected with the potentiostat ( 9 ) via an electric line.
  • This reference electrode ( 11 ) likewise is permanently surrounded by the sulfuric acid and provides the measurement basis for the potentiostat ( 9 ).
  • the potential required for the corrosion protection is determined and adjusted at the potentiostat ( 9 ).

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Spark Plugs (AREA)
US10/479,304 2001-06-08 2002-05-28 Method for the protection against corrosion of a steel part made of austentic or semi-austentic steel during the production of sulfuric acid Abandoned US20040238375A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10128932.7 2001-06-08
DE10128032A DE10128032A1 (de) 2001-06-08 2001-06-08 Verfahren zum Schutz gegen Korrossion eines Stahlteils aus austenitischem oder halbaustenitischem Stahl bei der Herstellung von Schwefelsäure
PCT/EP2002/005842 WO2002101106A1 (en) 2001-06-08 2002-05-28 Method for the protection against corrosion of a steel part made of austenitic or semi-austenitic steel during the production of sulfuric acid

Publications (1)

Publication Number Publication Date
US20040238375A1 true US20040238375A1 (en) 2004-12-02

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US10/479,304 Abandoned US20040238375A1 (en) 2001-06-08 2002-05-28 Method for the protection against corrosion of a steel part made of austentic or semi-austentic steel during the production of sulfuric acid

Country Status (11)

Country Link
US (1) US20040238375A1 (es)
EP (1) EP1409756B1 (es)
JP (1) JP2004529274A (es)
KR (1) KR20040023612A (es)
AT (1) ATE340274T1 (es)
DE (2) DE10128032A1 (es)
EA (1) EA006778B1 (es)
ES (1) ES2272733T3 (es)
MX (1) MXPA03011234A (es)
PE (1) PE20030023A1 (es)
WO (1) WO2002101106A1 (es)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110041515A1 (en) * 2007-10-18 2011-02-24 Michael Lee Fraim High Efficiency, Corrosion Resistant Heat Exchanger and Method of Use Thereof
US8906133B2 (en) 2010-02-01 2014-12-09 Outotec Oyj Process and plant for cooling sulfuric acid

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4588022A (en) * 1982-01-21 1986-05-13 C-I-L Inc. Anodic protection system and method
US5028396A (en) * 1982-06-11 1991-07-02 Chemetics International Company, Ltd. Apparatus formed of high silicon chromium/nickel in steel in the manufacture of sulpheric acid
US5695716A (en) * 1993-12-10 1997-12-09 Bayer Aktiengesellschaft Austenitic alloys and use thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0018124A1 (en) * 1979-04-02 1980-10-29 Monsanto Company Anodically passivated vessel and method of passivating it
US4576813A (en) * 1983-07-05 1986-03-18 Monsanto Company Heat recovery from concentrated sulfuric acid
DE19807632A1 (de) * 1998-02-23 1999-09-02 Bayer Ag Vorrichtung zum Konzentrieren und Reinigen von Schwefelsäure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4588022A (en) * 1982-01-21 1986-05-13 C-I-L Inc. Anodic protection system and method
US5028396A (en) * 1982-06-11 1991-07-02 Chemetics International Company, Ltd. Apparatus formed of high silicon chromium/nickel in steel in the manufacture of sulpheric acid
US5695716A (en) * 1993-12-10 1997-12-09 Bayer Aktiengesellschaft Austenitic alloys and use thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110041515A1 (en) * 2007-10-18 2011-02-24 Michael Lee Fraim High Efficiency, Corrosion Resistant Heat Exchanger and Method of Use Thereof
US8906133B2 (en) 2010-02-01 2014-12-09 Outotec Oyj Process and plant for cooling sulfuric acid

Also Published As

Publication number Publication date
JP2004529274A (ja) 2004-09-24
ATE340274T1 (de) 2006-10-15
EP1409756A1 (en) 2004-04-21
DE10128032A1 (de) 2002-12-12
EA006778B1 (ru) 2006-04-28
PE20030023A1 (es) 2003-02-03
EP1409756B1 (en) 2006-09-20
DE60214859D1 (de) 2006-11-02
KR20040023612A (ko) 2004-03-18
MXPA03011234A (es) 2004-02-26
ES2272733T3 (es) 2007-05-01
WO2002101106A1 (en) 2002-12-19
DE60214859T2 (de) 2007-04-12
EA200400008A1 (ru) 2004-04-29

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Owner name: OUTOKUMPU OYJ, FINLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DAUM, KARL-HEINZ;RAUSER, WOLF-CHRISTOPH;ANASTASIJEVIC, NIKOLA;AND OTHERS;REEL/FRAME:015548/0533;SIGNING DATES FROM 20040617 TO 20040625

STCB Information on status: application discontinuation

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