EP1409756B1 - Steel parts made of austenitic or semi-austenitic steel in a plant for producing sulfuric acid and method for the protection against corrosion - Google Patents
Steel parts made of austenitic or semi-austenitic steel in a plant for producing sulfuric acid and method for the protection against corrosion Download PDFInfo
- Publication number
- EP1409756B1 EP1409756B1 EP02743117A EP02743117A EP1409756B1 EP 1409756 B1 EP1409756 B1 EP 1409756B1 EP 02743117 A EP02743117 A EP 02743117A EP 02743117 A EP02743117 A EP 02743117A EP 1409756 B1 EP1409756 B1 EP 1409756B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sulfuric acid
- steel
- austenitic
- steel part
- content
- 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
Links
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 52
- 239000010959 steel Substances 0.000 title claims abstract description 52
- 238000005260 corrosion Methods 0.000 title claims abstract description 36
- 230000007797 corrosion Effects 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229910052729 chemical element Inorganic materials 0.000 claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 10
- 239000011651 chromium Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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
- 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 and to respective steel parts.
- 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 non-metallic materials generally have unfavorable mechanical properties and are difficult to process.
- the metallic materials have good mechanical properties, but their corrosion resistance is not sufficient, or the materials are very expensive.
- 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.
- US 5,028,396 proposes austenitic stainless steels with a relatively high silicon content consisting essentially of 17.5 % Cr, 17.5 % Ni, 4.6 to 5.8 % Si, the balance being Fe.
- US 5,695,716 discloses austenitic, corrosion resistant chromium, nickel iron alloys including at least 32 wt-% chromium.
- 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 160°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 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
- mA/cm 2 milliampere per square centimeter
- 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 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.
- only two tubes (4) are represented here.
- connection (6) hot sulfuric acid is introduced.
- the sulfuric acid flows around the tubes (4) filled with cooling medium and is discharged again via the connection (7).
- 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 exchanger 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 exchanger (1) to be protected via an electric line.
- a second reference electrode (11) is inserted in the shell-and-tube heat exchanger 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).
Landscapes
- 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)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10128032 | 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 (2)
Publication Number | Publication Date |
---|---|
EP1409756A1 EP1409756A1 (en) | 2004-04-21 |
EP1409756B1 true EP1409756B1 (en) | 2006-09-20 |
Family
ID=7687749
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02743117A Expired - Lifetime EP1409756B1 (en) | 2001-06-08 | 2002-05-28 | Steel parts made of austenitic or semi-austenitic steel in a plant for producing sulfuric acid and method for the protection against corrosion |
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) |
Families Citing this family (2)
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 |
DE102010006541B4 (de) * | 2010-02-01 | 2016-03-17 | Outotec Oyj | Verfahren und Anlage zum Abkühlen von Säure |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55134179A (en) * | 1979-04-02 | 1980-10-18 | Monsanto Co | Container and method for immobilizing anode |
CA1199305A (en) * | 1982-01-21 | 1986-01-14 | 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 |
US4576813A (en) * | 1983-07-05 | 1986-03-18 | Monsanto Company | Heat recovery from concentrated sulfuric acid |
DE4342188C2 (de) * | 1993-12-10 | 1998-06-04 | Bayer Ag | Austenitische Legierungen und deren Verwendung |
DE19807632A1 (de) * | 1998-02-23 | 1999-09-02 | Bayer Ag | Vorrichtung zum Konzentrieren und Reinigen von Schwefelsäure |
-
2001
- 2001-06-08 DE DE10128032A patent/DE10128032A1/de not_active Withdrawn
-
2002
- 2002-05-28 US US10/479,304 patent/US20040238375A1/en not_active Abandoned
- 2002-05-28 EA EA200400008A patent/EA006778B1/ru not_active IP Right Cessation
- 2002-05-28 MX MXPA03011234A patent/MXPA03011234A/es active IP Right Grant
- 2002-05-28 JP JP2003503852A patent/JP2004529274A/ja active Pending
- 2002-05-28 KR KR10-2003-7016039A patent/KR20040023612A/ko not_active Application Discontinuation
- 2002-05-28 ES ES02743117T patent/ES2272733T3/es not_active Expired - Lifetime
- 2002-05-28 AT AT02743117T patent/ATE340274T1/de not_active IP Right Cessation
- 2002-05-28 DE DE60214859T patent/DE60214859T2/de not_active Expired - Lifetime
- 2002-05-28 WO PCT/EP2002/005842 patent/WO2002101106A1/en active IP Right Grant
- 2002-05-28 EP EP02743117A patent/EP1409756B1/en not_active Expired - Lifetime
- 2002-06-07 PE PE2002000475A patent/PE20030023A1/es not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
EP1409756A1 (en) | 2004-04-21 |
EA200400008A1 (ru) | 2004-04-29 |
EA006778B1 (ru) | 2006-04-28 |
DE60214859D1 (de) | 2006-11-02 |
ATE340274T1 (de) | 2006-10-15 |
US20040238375A1 (en) | 2004-12-02 |
WO2002101106A1 (en) | 2002-12-19 |
PE20030023A1 (es) | 2003-02-03 |
JP2004529274A (ja) | 2004-09-24 |
KR20040023612A (ko) | 2004-03-18 |
DE10128032A1 (de) | 2002-12-12 |
MXPA03011234A (es) | 2004-02-26 |
ES2272733T3 (es) | 2007-05-01 |
DE60214859T2 (de) | 2007-04-12 |
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