EP0200862B1 - Use of an iron-chromium-nickel alloy resistant to highly concentrated sulfonic acid and to oleum - Google Patents
Use of an iron-chromium-nickel alloy resistant to highly concentrated sulfonic acid and to oleum Download PDFInfo
- Publication number
- EP0200862B1 EP0200862B1 EP86102555A EP86102555A EP0200862B1 EP 0200862 B1 EP0200862 B1 EP 0200862B1 EP 86102555 A EP86102555 A EP 86102555A EP 86102555 A EP86102555 A EP 86102555A EP 0200862 B1 EP0200862 B1 EP 0200862B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- sulfuric acid
- alloy
- resistant
- chromium
- 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
Links
Classifications
-
- 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
Definitions
- sulfuric acid generally takes place via the sulfur dioxide stage, from which sulfur trioxide is then formed by oxidation, which is then absorbed in concentrated sulfuric acid, where it reacts with water to form further sulfuric acid.
- Concentrated sulfuric acid and oleum are an extremely aggressive medium, especially in the higher temperature range. It is therefore highly desirable that all of the components of a sulfuric acid manufacturing plant, such as contact towers, heat exchangers, pipes, valves, pumps, distributors and the like, which come into contact with the sulfuric acid, are made of corrosion-resistant materials. Cast iron, brick, plastics and corrosion-resistant alloys are currently in use as such materials.
- the metallic components used are subject to considerably rapid corrosion. If no special precautions are taken or if they are not alloyed with high alloys, then they have a limited lifespan.
- the high-alloy materials and cast iron make processing difficult, which imposes restrictions on the shape of the deposits, and which requires more flanges, fittings and costs, and more spots of possible leakage.
- One way to reduce corrosion is to use anodic protection. Corrosion can be reduced considerably by the electrochemical formation of an oxide film. This means that stainless steels can also be used at acid temperatures above 120 ° C.
- anodic protection can be seen in the fact that it can only be used in devices with simple geometry. Corrosion cannot be avoided on special parts such as nozzles, pipe bends, flanges etc. by anodic protection. Furthermore, a large amount of control is required on an operational scale to ensure that the anode potentials are maintained. In the event of a business shutdown, the passivity must be partially rebuilt.
- tantalum for the production of corrosion-resistant materials (Chem. Ind. XXXV / 6, 1983, D.F. Lupton: special metals in chemical apparatus engineering) is countered by its high price, given the low availability.
- DE-PS 2 154 126 describes the use of a molybdenum-containing austenitic nickel alloy as a material resistant to hot concentrated sulfuric acid. However, due to the difficult processability, the use is limited to parts such as shafts, bearings, pumps, valves and the like.
- Silicon-containing steels are known from DE-OS 3 320 527. However, their disadvantage is their limited usability due to the difficult handling of the material.
- European patent application 1 30967 discloses 4 materials for use in hot, highly concentrated sulfuric acid, of which only the alloy 26-1 (material no. 1.4131, short name X1 CrMo 26 1) shows good corrosion resistance under the required conditions.
- a disadvantage of this material is its poor processability. Among other things, it requires particularly high requirements with regard to welding processing.
- chromium-containing alloys with chromium contents of 21 to 35% by weight which contain 30 to 70% by weight of iron and optionally nickel up to 40% by weight, meet these requirements in an outstanding manner.
- a particularly good corrosion resistance is achieved with alloys whose chromium content is 23 to 32% by weight.
- sulfuric acid-resistant alloys which have molybdenum contents in the range of at least 2% by weight.
- the alloys according to the invention are molybdenum-free. These are compared to the known molybdenum containing alloys, however, significantly improved in terms of their corrosion resistance.
- the alloys according to the invention are also less expensive than Mo-containing ones.
- the nickel content is jointly responsible for the good processability of the alloys according to the invention.
- This invention therefore also relates to the use according to the invention, according to which the material is resistant to sulfuric acid up to concentrations of 100, preferably between 98.0 and 99.5% by weight.
- the material is resistant to sulfuric acid at a concentration of 100 to 122.5% by weight (oleum). Due to its superior corrosion behavior, use in the oleum area is also recommended for economic and safety-related reasons.
- the unusual temperature behavior of the alloy according to the invention is of essential importance for use as a sulfur-resistant material.
- Materials made from it are resistant to sulfuric acids at temperatures up to 350 ° C, preferably from 50 to 250 ° C, but especially from 80 to 190 ° C.
- the alloy is in a ferritic, ferritic-austenitic or austenitic structure.
- the use of the other known materials according to the invention is superior. It is therefore ideally suited for the production of heat exchange devices, pipelines, pumps, pump parts, fittings, flanges, filter baskets, mist filters, droplet separators, devices for the absorption of gases containing SO 3 or for drying gases, provided that sulfuric acid is used as a drying agent , and for containers.
- the apparatus is manufactured using known techniques using the same or similar welding filler materials.
- temperatures above approx. 80 ° C. are aimed in particular in the area of intermediate and final absorption, with the heat exchange serving to preheat the feed water or at temperatures above 110 ° C. to produce low-pressure steam.
- the materials according to the invention are also very suitable for this.
- a further embodiment of the use according to the invention is that apparatus made from the alloy in the area of the intermediate and final absorption of sulfuric acid-producing plants at temperatures from 80 to 190 ° C. and sulfuric acid concentrations from 98.0 to 99.5% by weight H 2 SO 4 can be used.
- the duration of the experiment was 7 days.
- the removal rates were determined by gravimetric differential weighing and conversion to mm / a.
- the flow rate was approx. 1 m / sec, the test duration was 42-60 d.
- the amount of acid circulated was approx. 250 rn3 / h.
- the dimensions of the rectangular samples were 50x15x3 mm.
- the corrosion resistance in mm / a was determined by gravimetric weighing and conversion.
- a piece of pipe with a length of 80 cm (44.5x1.6 mm dimension) made of material 1.4335 was used in the bypass of the acid circuit of an intermediate absorber operated as a heat absorber and 56 days operated at 25-135 ° C and a sulfuric acid concentration of 98.5-99.5%.
- the flow rate was set to approximately 1 m / sec.
Abstract
Description
Die vorliegende Erfindung betrifft die Verwendung einer molybdänfreien, chromhaltigen Legierung, bestehend aus
- 21 bis 35 Gew.-% Chrom,
- 30 bis 70 Gew.-% Eisen,
- 2 bis 40 Gew.-% Nickel,
- 0 bis 20 Gew.-% Mangan
- 21 to 35% by weight of chromium,
- 30 to 70% by weight of iron,
- 2 to 40% by weight of nickel,
- 0 to 20% by weight of manganese
Die Herstellung von Schwefelsäure geschieht im allgemeinen über die Stufe des Schwefeldioxids, aus welchem dann durch Oxidation Schwefeltrioxid gebildet wird, das dann in konzentrierter Schwefelsäure absorbiert wird, wo es mit Wasser unter Bildung weiterer Schwefelsäure reagiert.The production of sulfuric acid generally takes place via the sulfur dioxide stage, from which sulfur trioxide is then formed by oxidation, which is then absorbed in concentrated sulfuric acid, where it reacts with water to form further sulfuric acid.
Wesentliche Operationen bei der Herstellung von Schwefelsäure sind Trocknen, Absorbieren und Kühlen. Bei diesen Operationen liegen die Schwefelsäurekonzentrationen im allgemeinen oberhalb 96%.Essential operations in the manufacture of sulfuric acid are drying, absorbing and cooling. In these operations, sulfuric acid levels are generally above 96%.
Konzentrierte Schwefelsäure und Oleum sind insbesondere im höheren Temperaturbereich ein äusserst aggressives Medium. Es ist daher äusserst wünschenswert, dass alle die Bauteile einer Schwefelsäureherstellungsanlage, wie zum Beispiel Kontakttürme, Wärmeaustauscher, Rohre, Ventile, Pumpen, Verteiler und dergleichen, die mit der Schwefelsäure in Berührung kommen, aus korrosionsbeständigen Materialien bestehen. Als solche Materialien sind derzeit Gusseisen, Ziegel, Kunststoffe sowie korrosionsbeständige Legierungen in Gebrauch.Concentrated sulfuric acid and oleum are an extremely aggressive medium, especially in the higher temperature range. It is therefore highly desirable that all of the components of a sulfuric acid manufacturing plant, such as contact towers, heat exchangers, pipes, valves, pumps, distributors and the like, which come into contact with the sulfuric acid, are made of corrosion-resistant materials. Cast iron, brick, plastics and corrosion-resistant alloys are currently in use as such materials.
Die verwendeten metallischen Bauteile unterliegen einer beträchtlich schnellen Korrosion. Wenn nicht besondere Vorkehrungen getroffen werden oder wenn sie nicht hoch legiert werden, dann besitzen sie eine beschränkte Lebensdauer.The metallic components used are subject to considerably rapid corrosion. If no special precautions are taken or if they are not alloyed with high alloys, then they have a limited lifespan.
Die hochlegierten Materialien und die Gusseisen machen bei der Verarbeitung Schwierigkeiten, wodurch sich Beschränkungen hinsichtlich der Form derAntage ergeben und wodurch mehr Flansche, Fittings und Kosten erforderlich sind und sich mehr Stellen möglicher Leckbildungen ergeben.The high-alloy materials and cast iron make processing difficult, which imposes restrictions on the shape of the deposits, and which requires more flanges, fittings and costs, and more spots of possible leakage.
Eine Möglichkeit zur Verringerung der Korrosion ist die Anwendung des anodischen Schutzes. Durch die elektrochemische Bildung eines Oxidfilms kann die Korrosion beträchtlich verringert werden. Somit können rostfreie Stähle auch bei Säuretemperaturen oberhalb 120°C eingesetzt werden.One way to reduce corrosion is to use anodic protection. Corrosion can be reduced considerably by the electrochemical formation of an oxide film. This means that stainless steels can also be used at acid temperatures above 120 ° C.
Die Nachteile des anodischen Schutzes sind darin zu sehen, dass dieser nur bei Apparaturen mit einfacher Geometrik anwendbar ist. An speziellen Teilen wie Düsen, Rohrbögen, Flanschen usw. kann daher durch anodischen Schutz die Korrosion nicht vermieden werden. Weiterhin ist im betrieblichen Massstab ein grosser Kontrollaufwand für die Einhaltung der Anodenpotentiale nötig. Im Falle eines Betriebsstillstandes muss die Passivität teilweise wieder neu aufgebaut werden.The disadvantages of anodic protection can be seen in the fact that it can only be used in devices with simple geometry. Corrosion cannot be avoided on special parts such as nozzles, pipe bends, flanges etc. by anodic protection. Furthermore, a large amount of control is required on an operational scale to ensure that the anode potentials are maintained. In the event of a business shutdown, the passivity must be partially rebuilt.
Dem Einsatz von Tantal zur Herstellung korrosionsresistenter Werkstoffe (Chem. Ind. XXXV/6, 1983, D.F. Lupton: Sondermetalle im chemischen Apparatebau) steht dessen hoher Preis, gegeben durch die geringe Verfügbarkeit, entgegen.The use of tantalum for the production of corrosion-resistant materials (Chem. Ind. XXXV / 6, 1983, D.F. Lupton: special metals in chemical apparatus engineering) is countered by its high price, given the low availability.
In der DE-PS 2 154 126 wird die Verwendung einer Molybdän-haltigen austenitischen Nickellegierung als gegen heisse konzentrierte Schwefelsäure beständiger Werkstoff beschrieben. Aufgrund der schwierigen Verarbeitbarkeit ist der Einsatz jedoch eingegrenzt auf Teile wie Wellen, Lager, Pumpen, Ventile und dergleichen.DE-PS 2 154 126 describes the use of a molybdenum-containing austenitic nickel alloy as a material resistant to hot concentrated sulfuric acid. However, due to the difficult processability, the use is limited to parts such as shafts, bearings, pumps, valves and the like.
Aus der DE-OS 3 320 527 sind Silicium-haltige Stähle bekannt. Deren Nachteil ist jedoch in ihrer eingeschränkten Verwertbarkeit aufgrund der erschwerten Handhabbarkeit des Materials zu sehen.Silicon-containing steels are known from DE-OS 3 320 527. However, their disadvantage is their limited usability due to the difficult handling of the material.
Schliesslich werden in der europäischen Patentanmeldung 1 30967 4 Werkstoffe für den Einsatz in heisser hochkonzentrierter Schwefelsäure offenbart, von denen aber nur das Alloy 26-1 (Werkstoff Nr. 1.4131, Kurzname X1 CrMo 26 1) unter den geforderten Bedingungen eine gute Korrosionsbeständigkeit zeigt. Nachteilig an derem Werkstoff sind dessen schlechte Verarbeitbarkeit. Es erfordert unter anderem besonders hohe Anforderungen bezüglich der schweisstechnischen Verarbeitung.Finally, European patent application 1 30967 discloses 4 materials for use in hot, highly concentrated sulfuric acid, of which only the alloy 26-1 (material no. 1.4131, short name X1 CrMo 26 1) shows good corrosion resistance under the required conditions. A disadvantage of this material is its poor processability. Among other things, it requires particularly high requirements with regard to welding processing.
Es ist also eine Aufgabe der vorliegenden Erfindung, ein kostengünstiges einfach handhabbares Material als Schwefelsäure-resistenten Werkstoff zur Verfügung zu stellen, welcher nicht die Nachteile der oben beschriebenen Legierungen aufweist.It is therefore an object of the present invention to provide an inexpensive, easy-to-handle material as a sulfuric acid-resistant material which does not have the disadvantages of the alloys described above.
Es wurde nun gefunden, dass chromhaltige Legierungen mit Chromgehalten von 21 bis 35 Gew.-%, die 30 bis 70 Gew.-% Eisen und gegebenenfalls Nickel bis zu 40 Gew.-% enthalten diese Anforderungen in hervorragender Weise erfüllen.It has now been found that chromium-containing alloys with chromium contents of 21 to 35% by weight, which contain 30 to 70% by weight of iron and optionally nickel up to 40% by weight, meet these requirements in an outstanding manner.
Der Gegenstand der vorliegenden Erfindung ist somit die Verwendung einer chromhaitigen Legierung, bestehend aus
- 21 bis 35 Gew.-% Chrom,
- 30 bis 70 Gew.-% Eisen,
- 2 bis 40 Gew.-% Nickel,
- 0 bis 20 Gew.-% Mangan
- 21 to 35% by weight of chromium,
- 30 to 70% by weight of iron,
- 2 to 40% by weight of nickel,
- 0 to 20% by weight of manganese
Eine besondere gute Korrosionsbeständigkeit wird mit Legierungen erreicht, deren Chromgehalt 23 bis 32 Gew.-% beträgt.A particularly good corrosion resistance is achieved with alloys whose chromium content is 23 to 32% by weight.
Als Schwefelsäure-resistente Legierungen werden nach dem Stand der Technik solche empfohlen, die Molybdängehalte im Bereich von mindestens 2 Gew.-% aufweisen. Die erfindungsgemässen Legierungen hingegen sind Molybdän-frei. Diese sind gegenüber den bekannten molybdän-haltigen Legierungen jedoch noch wesentlich verbessert bezüglich ihrer Korrosionsbeständigkeit. Die erfindungsgemässen Legierungen sind ausserdem preisgünstiger als Mo-haltige. Mitverantwortlich für die gute Verarbeitbarkeit der erfindungsgemässen Legierungen ist ein Gehalt an Nickel.According to the prior art, sulfuric acid-resistant alloys are recommended which have molybdenum contents in the range of at least 2% by weight. In contrast, the alloys according to the invention are molybdenum-free. These are compared to the known molybdenum containing alloys, however, significantly improved in terms of their corrosion resistance. The alloys according to the invention are also less expensive than Mo-containing ones. The nickel content is jointly responsible for the good processability of the alloys according to the invention.
Aus diesen Legierungen hergestellte Werkstoffe zeigen eine ausgesprochen gute Korrosionsbeständigkeit gegen hochkonzentrierte Schwefelsäuren. Gegenstand dieser Erfindung ist somit auch die erfindungsgemässe Verwendung, gemäss der der Werkstoff gegen Schwefelsäure bis zu Konzentrationen von 100, bevorzugt zwischen 98,0 und 99,5 Gew.-%, beständig ist.Materials made from these alloys show extremely good corrosion resistance against highly concentrated sulfuric acids. This invention therefore also relates to the use according to the invention, according to which the material is resistant to sulfuric acid up to concentrations of 100, preferably between 98.0 and 99.5% by weight.
Überraschenderweise zeigte sich aber auch, dass der Werkstoff gegen Schwefelsäure einer Konzentration von 100 bis 122,5 Gew.-% (Oleum) beständig ist. Auch im Oleum-Bereich ist aufgrund seines überlegenen Korrosionsverhaltens ein Einsatz aus wirtschaftlichen und sicherheitstechnischen Überlegungen empfehlenswert.Surprisingly, however, it was also found that the material is resistant to sulfuric acid at a concentration of 100 to 122.5% by weight (oleum). Due to its superior corrosion behavior, use in the oleum area is also recommended for economic and safety-related reasons.
Von wesentlicher Bedeutung für den Einsatz als Schwefelsäure-resistenter Werkstoff ist neben seinem konzentrationsabhängigen Korrosionsverhalten das ungewöhnliche Temperaturverhalten der erfindungsgemässen Legierung. Daraus hergestellte Werkstoffe sind gegen Schwefelsäuren von Temperaturen bis 350° C, bevorzugt von 50 bis 250° C, besonders aber von 80 bis 190° C, beständig.In addition to its concentration-dependent corrosion behavior, the unusual temperature behavior of the alloy according to the invention is of essential importance for use as a sulfur-resistant material. Materials made from it are resistant to sulfuric acids at temperatures up to 350 ° C, preferably from 50 to 250 ° C, but especially from 80 to 190 ° C.
Im Sinne dieser Erfindung ist es nicht von Bedeutung, ob die Legierung in ferritischer, ferritisch-austenitischer oder austenitischer Gefügeform vorliegt.In the sense of this invention it is not important whether the alloy is in a ferritic, ferritic-austenitic or austenitic structure.
Aufgrund der Summe der Eigenschaften ist die Verwendung der erfindungsgemässen anderen bekannten Materialien überlegen. Sie eignet sich somit hervorragend zur Herstellung von Apparaten zum Wärmeaustausch, von Rohrleitungen, Pumpen, Pumpenteilen, Armaturen, Flanschen, Filterkörben, von Nebelfiltern, Tropfenabscheidern, Apparaten zur Absorption S03-haltiger Gase bzw. Trocknung von Gasen, soweit Schwefelsäure als Trocknungsmittel verwendet wird, und für Behälter. Die Herstellung der Apparate erfolgt unter Zuhilfenahme bekannter Techniken unter Einsatz artgleicher oder artähnlicher Schweisszusatzwerkstoffe.Because of the sum of the properties, the use of the other known materials according to the invention is superior. It is therefore ideally suited for the production of heat exchange devices, pipelines, pumps, pump parts, fittings, flanges, filter baskets, mist filters, droplet separators, devices for the absorption of gases containing SO 3 or for drying gases, provided that sulfuric acid is used as a drying agent , and for containers. The apparatus is manufactured using known techniques using the same or similar welding filler materials.
Im Rahmen der Energiegewinnung bei der Schwefelsäureproduktion werden insbesondere im Bereich der Zwischen- und Endabsorption Temperaturen oberhalb ca. 80° C angestrebt, wobei der Wärmeaustausch der Speisewasservorwärmung oder bei Temperaturen oberhalb 110° C der Erzeugung von Niederdruckdampf dient. Auch hierfür eignen sich die erfindungsgemässen Werkstoffe sehr gut. Eine weitere Ausführung der erfindungsgemässen Verwendung besteht somit darin, dass aus der Legierung hergestellte Apparate im Bereich der Zwischen- und Endabsorption von Schwefelsäure-produzierenden Anlagen bei Temperaturen von 80 bis 190° C und Schwefelsäurekonzentrationen von 98,0 bis 99,5 Gew.-% H2SO4 eingesetzt werden.In the context of energy generation in the production of sulfuric acid, temperatures above approx. 80 ° C. are aimed in particular in the area of intermediate and final absorption, with the heat exchange serving to preheat the feed water or at temperatures above 110 ° C. to produce low-pressure steam. The materials according to the invention are also very suitable for this. A further embodiment of the use according to the invention is that apparatus made from the alloy in the area of the intermediate and final absorption of sulfuric acid-producing plants at temperatures from 80 to 190 ° C. and sulfuric acid concentrations from 98.0 to 99.5% by weight H 2 SO 4 can be used.
Im folgenden wird die Erfindung beispielhaft erläutert, ohne dass darin eine Einschränkung zu sehen ist.In the following, the invention is explained by way of example, without any limitation being seen therein.
Mit Hilfe der Methode der rotierenden Scheibe mit durchgehender Achse bei 2000 U/min wurden verschiedene Werkstoffe bei unterschiedlichen Temperaturen und Begasungsarten auf ihr Korrosionsverhalten in HSO, 99,03% untersucht (Heitz, E., Loss, C., Zum Mechanismus der Erosionskorrosion in schnell strömenden Flüssigkeiten, Werkstoffe und Korrosion, 24. Jahrgang, Heft 1 /73).Using the rotating disc method with a continuous axis at 2000 rpm, different materials at different temperatures and gassing types were examined for their corrosion behavior in HSO, 99.03% (Heitz, E., Loss, C., on the mechanism of erosion corrosion in fast flowing liquids, materials and corrosion, 24th year, issue 1/73).
Die Versuchsdauer betrug 7 Tage.The duration of the experiment was 7 days.
Die Abtragungsraten wurden durch gravimetrische Differenzwägung und Umrechnung auf mm/a bestimmt.The removal rates were determined by gravimetric differential weighing and conversion to mm / a.
Die untersuchten Werkstoffe sind der Tab. 1 zu entnehmen, die Ergebnisse des Beispiels 1 sind in der Tab. 2 aufgeführt.
In einer Doppelkontaktanlage auf Schwefelbrenner-Basis mit einer Kapazität von 500 tato S03 wurden im Säurekreislauf des Zwischenabsorbers vor Eintritt in den Säurekühler verschiedene Legierungen bei Temperaturen von 125-135° C und einer Schwefelsäurekonzentration von 98,5-99,5% eingesetzt.In a double contact system based on a sulfur burner with a capacity of 500 tpd SO 3 , various alloys were used in the acid circuit of the intermediate absorber before entering the acid cooler at temperatures of 125-135 ° C and a sulfuric acid concentration of 98.5-99.5%.
Die Strömungsgeschwindigkeit betrug ca. 1 m/ sec, die Versuchsdauer lag bei 42-60 d. Die umgewälzte Säuremenge lag bei ca. 250 rn3/h.The flow rate was approx. 1 m / sec, the test duration was 42-60 d. The amount of acid circulated was approx. 250 rn3 / h.
Die Ambessung der rechteckigen Proben betrug 50x15x3 mm.The dimensions of the rectangular samples were 50x15x3 mm.
Die Einzelproben (Schweissverbindung) waren untereinander durch Abstandshalter aus Teflon getrennt und gegen die Rohrwand isoliert.The individual samples (welded connection) were separated from each other by Teflon spacers and insulated against the pipe wall.
Die Korrosionsbeständigkeit in mm/a wurde durch gravimetrische Wägung und Umrechnung ermittelt.The corrosion resistance in mm / a was determined by gravimetric weighing and conversion.
Die Ergebnisse sind in der folgenden Tabelle 3 festgehalten.The results are shown in Table 3 below.
In einer Doppelkontaktanlage auf Schwefelbrenner-Basis mit einer Kapazität von 500 tato S03 wurde ein Rohrstück von 80 cm Länge (44,5x1,6 mm Abmessung) aus dem Werkstoff 1,4335 im Bypass des Säurekreislaufs eines als Heissabsorber betriebenen Zwischenabsorbers eingesetzt und 56 Tage bei 25-135° C und einer Schwefelsäurekonzentration von 98,5-99,5% betrieben. Die Strömungsgeschwindigkeit wurde auf ca. 1 m/sec eingestellt.In a double contact system based on a sulfur burner with a capacity of 500 tpd S0 3 , a piece of pipe with a length of 80 cm (44.5x1.6 mm dimension) made of material 1.4335 was used in the bypass of the acid circuit of an intermediate absorber operated as a heat absorber and 56 days operated at 25-135 ° C and a sulfuric acid concentration of 98.5-99.5%. The flow rate was set to approximately 1 m / sec.
Die produktberührten Innenoberflächen einschliesslich der Schweissnähte zeigten keinen nennenswerten Angriff.The inner surfaces in contact with the product, including the weld seams, showed no significant attack.
Nach der in Beispiel 1 beschriebenen Methode der rotierenden Scheibe wurden verschiedene Werkstoffe in Oleum untersucht. Die Versuchsergebnisse sind in Tabelle 4 aufgeführt.
Die folgenden Werkstoffe wurden 7 Tage in 99%iger H2SO4 bei verschiedenen Temperaturen gelagert. Dabei ergaben sich folgende Abtragsraten, gemessen in mm/a.The following materials were stored in 99% H 2 SO 4 at different temperatures for 7 days. This resulted in the following removal rates, measured in mm / a.
Der folgend Werkstoff wurde 7 Tage in 99%iger H2S04 bei verschiedenen Temperaturen gelagert. Dabei ergaben sich folgende Abtragsraten, gemessen in mm/a.The following material was stored in 99% H 2 S0 4 at different temperatures for 7 days. This resulted in the following removal rates, measured in mm / a.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86102555T ATE34779T1 (en) | 1985-03-09 | 1986-02-27 | USE OF AN IRON CHROMIC NICKEL ALLOY RESISTANT TO HIGHLY CONCENTRATED SULFURIC ACID AND OLEUM. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853508532 DE3508532A1 (en) | 1985-03-09 | 1985-03-09 | USE OF A CHROME ALLOY |
| DE3508532 | 1985-03-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0200862A1 EP0200862A1 (en) | 1986-11-12 |
| EP0200862B1 true EP0200862B1 (en) | 1988-06-01 |
Family
ID=6264782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86102555A Expired EP0200862B1 (en) | 1985-03-09 | 1986-02-27 | Use of an iron-chromium-nickel alloy resistant to highly concentrated sulfonic acid and to oleum |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0200862B1 (en) |
| JP (1) | JPS61207551A (en) |
| AT (1) | ATE34779T1 (en) |
| AU (1) | AU583898B2 (en) |
| CA (1) | CA1273230A (en) |
| DE (2) | DE3508532A1 (en) |
| ES (1) | ES8802377A1 (en) |
| FI (1) | FI80481C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3739903A1 (en) * | 1987-11-25 | 1989-06-08 | Bayer Ag | USE OF A CHROMIUM ALLOY |
| DE3830365C2 (en) * | 1988-09-07 | 1996-06-27 | Metallgesellschaft Ag | Use of ferritic chromium - molybdenum steels as a material resistant to concentrated sulfuric acid |
| DE4342188C2 (en) * | 1993-12-10 | 1998-06-04 | Bayer Ag | Austenitic alloys and their uses |
| FR2939052B1 (en) * | 2008-12-01 | 2010-12-10 | Rhodia Operations | INSTALLATION OF CRYSTALLIZATION OF ADIPIC ACID |
| US20210214825A1 (en) * | 2018-08-29 | 2021-07-15 | Chemetics Inc. | Austenitic stainless alloy with superior corrosion resistance |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0130967A1 (en) * | 1983-07-05 | 1985-01-09 | Monsanto Company | Heat recovery from concentrated sulfuric acid |
| EP0181313A2 (en) * | 1984-11-09 | 1986-05-14 | Monsanto Company | Heat recovery from concentrated sulfuric acid |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3649187A (en) * | 1970-02-09 | 1972-03-14 | Monsanto Co | Corrosion resistant apparatus |
| US3758296A (en) * | 1970-10-29 | 1973-09-11 | Lewis & Co Inc Charles | Corrosion resistant alloy |
| JPS5435171B2 (en) * | 1973-07-13 | 1979-10-31 | ||
| US3844774A (en) * | 1973-09-24 | 1974-10-29 | Carondelet Foundry Co | Corrosion-resistant alloys |
| US3947266A (en) * | 1974-05-17 | 1976-03-30 | Carondelet Foundry Company | Corrosion-resistant alloys |
| JPS5538957A (en) * | 1978-09-13 | 1980-03-18 | Japan Steel Works Ltd:The | Austenitic stainless cast steel |
| US4329173A (en) * | 1980-03-31 | 1982-05-11 | Carondelet Foundry Company | Alloy resistant to corrosion |
-
1985
- 1985-03-09 DE DE19853508532 patent/DE3508532A1/en not_active Withdrawn
-
1986
- 1986-02-27 EP EP86102555A patent/EP0200862B1/en not_active Expired
- 1986-02-27 AT AT86102555T patent/ATE34779T1/en not_active IP Right Cessation
- 1986-02-27 DE DE8686102555T patent/DE3660261D1/en not_active Expired
- 1986-03-06 FI FI860944A patent/FI80481C/en not_active IP Right Cessation
- 1986-03-07 JP JP61048722A patent/JPS61207551A/en active Pending
- 1986-03-07 CA CA000503590A patent/CA1273230A/en not_active Expired - Lifetime
- 1986-03-07 ES ES552799A patent/ES8802377A1/en not_active Expired
- 1986-03-07 AU AU54434/86A patent/AU583898B2/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0130967A1 (en) * | 1983-07-05 | 1985-01-09 | Monsanto Company | Heat recovery from concentrated sulfuric acid |
| EP0181313A2 (en) * | 1984-11-09 | 1986-05-14 | Monsanto Company | Heat recovery from concentrated sulfuric acid |
Non-Patent Citations (2)
| Title |
|---|
| Perry's Chemical Engineers Handbook, 6. Auflage, 1984, Seiten 23-44 * |
| Preisliste der Carpenter Technology Corporation, 14.Januar,1985 * |
Also Published As
| Publication number | Publication date |
|---|---|
| ES8802377A1 (en) | 1988-05-16 |
| FI860944A (en) | 1986-09-10 |
| AU583898B2 (en) | 1989-05-11 |
| CA1273230A (en) | 1990-08-28 |
| JPS61207551A (en) | 1986-09-13 |
| FI80481B (en) | 1990-02-28 |
| DE3508532A1 (en) | 1986-09-18 |
| AU5443486A (en) | 1986-09-11 |
| EP0200862A1 (en) | 1986-11-12 |
| FI860944A0 (en) | 1986-03-06 |
| ATE34779T1 (en) | 1988-06-15 |
| ES552799A0 (en) | 1988-05-16 |
| DE3660261D1 (en) | 1988-07-07 |
| FI80481C (en) | 1990-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3320527C2 (en) | Method and device for producing sulfuric acid | |
| DE4342188C2 (en) | Austenitic alloys and their uses | |
| EP0292061B1 (en) | Corrosion-resistant alloy | |
| EP0334410B1 (en) | Nickel chromium-molybdenum alloyd | |
| DE3300392C2 (en) | ||
| EP0991788B1 (en) | Nickel-chromium-molybdenum alloy | |
| EP0200862B1 (en) | Use of an iron-chromium-nickel alloy resistant to highly concentrated sulfonic acid and to oleum | |
| DE1608174A1 (en) | NICKEL-CHROME-MOLYBDAEN-STEEL ALLOY | |
| EP0249792B1 (en) | Use of a nickel alloy containing chromium | |
| DE3720055A1 (en) | CORROSION-RESISTANT AND WEAR-RESISTANT STEEL | |
| DE69923486T2 (en) | New use of a high strength stainless steel | |
| DE3311960A1 (en) | Copper alloy for radiators | |
| DE19963522B4 (en) | Alloy steel with superior corrosion resistance to molten salt containing alkali metal oxides | |
| DE2153186A1 (en) | Ferritic chromium steel - used as corrosion-resistant material in chemical appts mfr | |
| DE4118437A1 (en) | HIGH SILICON, CORROSION-RESISTANT, AUSTENITIC STEEL | |
| EP0361554B1 (en) | Use of ferritic chromium-molybdenum steels as materials resisting concentrated sulfuric acid | |
| EP0076367B1 (en) | Use of metal devices when converting or working with hydrofluoric and organic carboxylic acids or mixtures containing carbon monoxide | |
| EP0723029B1 (en) | Nickel alloy | |
| DE2807360C2 (en) | ||
| DE4308151C2 (en) | Use of kneading and casting materials as well as welding filler materials made of austenitic steel for components exposed to hot concentrated sulfuric acid or oleum | |
| CH630414A5 (en) | FERRITIC STEEL AND USE OF THE SAME FOR WELDED CONSTRUCTIONS. | |
| DE401779C (en) | Process to protect the inner walls of iron hollow bodies or vessels that are exposed to changing temperatures from rust | |
| EP0566950A1 (en) | Use of wrought and cast alloys and welding additives for parts contacted by oleum or concentrated hot sulphuric acid and process for the preparation of sulphuric acid | |
| DE2340603C3 (en) | Stainless steel with high chromium and low nickel content with high corrosion resistance and high tensile strength | |
| AT377534B (en) | HIGH CHROME NICKEL ALLOY |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19860227 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
| 17Q | First examination report despatched |
Effective date: 19871117 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| ITF | It: translation for a ep patent filed |
Owner name: SOCIETA' ITALIANA BREVETTI S.P.A. |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
| REF | Corresponds to: |
Ref document number: 34779 Country of ref document: AT Date of ref document: 19880615 Kind code of ref document: T |
|
| REF | Corresponds to: |
Ref document number: 3660261 Country of ref document: DE Date of ref document: 19880707 |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
| ET | Fr: translation filed | ||
| PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
| 26 | Opposition filed |
Opponent name: MONSANTO COMPANY Effective date: 19890222 |
|
| NLR1 | Nl: opposition has been filed with the epo |
Opponent name: MONSANTO COMPANY. |
|
| EAL | Se: european patent in force in sweden |
Ref document number: 86102555.9 |
|
| ITTA | It: last paid annual fee | ||
| APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
| APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19970115 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19970124 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19970129 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19970212 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19970219 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19970221 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19970228 Year of fee payment: 12 |
|
| APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
| PLAW | Interlocutory decision in opposition |
Free format text: ORIGINAL CODE: EPIDOS IDOP |
|
| RDAH | Patent revoked |
Free format text: ORIGINAL CODE: EPIDOS REVO |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19980223 Year of fee payment: 13 |
|
| RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
| 27W | Patent revoked |
Effective date: 19971206 |
|
| GBPR | Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state |
Free format text: 971206 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| NLR2 | Nl: decision of opposition | ||
| APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |