EP0200862B1 - Application d'un alliage fer-chrome-nickel résistant à l'acide sulfurique hautement concentré et à l'oléum - Google Patents

Application d'un alliage fer-chrome-nickel résistant à l'acide sulfurique hautement concentré et à l'oléum Download PDF

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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
Application number
EP86102555A
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German (de)
English (en)
Other versions
EP0200862A1 (fr
Inventor
Helmut Dipl.-Ing. Diekmann
Günter Pütz
Klaus-Peter Grabowski
Kurt Wilhelm Dr. Eichenhofer
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.)
Bayer AG
Original Assignee
Bayer AG
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Publication date
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Application filed by Bayer AG filed Critical Bayer AG
Priority to AT86102555T priority Critical patent/ATE34779T1/de
Publication of EP0200862A1 publication Critical patent/EP0200862A1/fr
Application granted granted Critical
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Expired legal-status Critical Current

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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.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Catalysts (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Pyrane Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Luminescent Compositions (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Heat Treatment Of Articles (AREA)
  • Heat Treatment Of Steel (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • High-Tension Arc-Extinguishing Switches Without Spraying Means (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Glass Compositions (AREA)
  • Secondary Cells (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Claims (7)

1. Utilisation d'un alliage contenant du chrome et exempt de molybdène, consistant en
21 à 35% en poids de chrome,
_ 30 à 70% en poids de fer,
2 à 40% en poids de nickel,
9 à 20% en poids de manganèse,
de même qu'en les éléments d'accompagnement usuels comme le carbone, le silicium, le phosphore, le soufre, l'azote, l'aluminium, le cuivre, le vanadium, le titane, le tantale et le niobium, comme matériau pour objets qui sont stables envers l'acide sulfurique à une concentration supérieure à 96%.
2. Utilisation de l'alliage selon la revendication 1, caractérisée en ce que la teneur en chrome est de 23 à 32% en poids.
3. Utilisation de l'alliage selon l'une des revendications 1 ou 2, caractérisée en ce que le matériau est résistant à l'acide sulfurique jusqu'à des concentrations de 100, de préférence entre 98,0 et 99,5% en poids.
4. Utilisation de l'alliage selon l'une des revendications 1 à 3, caractérisée en ce que le matériau est résistant à l'acide sulfurique à une concentration de 100 à 122,5% en poids (oléum).
5. Utilisation de l'alliage selon l'une des revendications 1 à 4, caractérisée en ce que les matériaux fabriqués à partir de celui-ci sont résistants aux acides sulfuriques aux températures allant jusqu'à 350° C, de préférence de 50 à 250° C et particulièrement de 80 à 190° C.
6. Utilisation de l'alliage selon l'une des revendications 1 à 5, caractérisée en ce qu'on utilise celui-ci pour la fabrication d'appareils d'échange de chaleur, de conduites tubulaires, de pompes, d'é)éments de pompes, d'armatures, de brides, de paniers de filtration, de filtres à brouillard, de séparateurs de gouttes, d'appareils d'absorbtion des gaz contenant du S03 ou de séchage des gaz, pour autant que l'on utilise de l'acide sulfurique comme agent exsiccateur, et pour des récipients.
7. Utilisation de l'alliage selon l'une des revendications 1 à 6, caractérisée en ce que les appareils fabriqués à partir de celui-ci sont utilisés dans le domaine de l'absorption intermédiaire et finale des installations de production d'acide sulfurique à des températures de 80 à 190° C et à des concentrations d'acide sulfurique de 98,0 à 99,5% en poids de HZSO4.
EP86102555A 1985-03-09 1986-02-27 Application d'un alliage fer-chrome-nickel résistant à l'acide sulfurique hautement concentré et à l'oléum Expired EP0200862B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86102555T ATE34779T1 (de) 1985-03-09 1986-02-27 Verwendung einer gegen hochkonzentrierte schwefelsaeure und oleum bestaendigen eisen-chrom- nickel-legierung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3508532 1985-03-09
DE19853508532 DE3508532A1 (de) 1985-03-09 1985-03-09 Verwendung einer chromhaltigen legierung

Publications (2)

Publication Number Publication Date
EP0200862A1 EP0200862A1 (fr) 1986-11-12
EP0200862B1 true EP0200862B1 (fr) 1988-06-01

Family

ID=6264782

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86102555A Expired EP0200862B1 (fr) 1985-03-09 1986-02-27 Application d'un alliage fer-chrome-nickel résistant à l'acide sulfurique hautement concentré et à l'oléum

Country Status (8)

Country Link
EP (1) EP0200862B1 (fr)
JP (1) JPS61207551A (fr)
AT (1) ATE34779T1 (fr)
AU (1) AU583898B2 (fr)
CA (1) CA1273230A (fr)
DE (2) DE3508532A1 (fr)
ES (1) ES8802377A1 (fr)
FI (1) FI80481C (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3739903A1 (de) * 1987-11-25 1989-06-08 Bayer Ag Verwendung einer chromhaltigen legierung
DE3830365C2 (de) * 1988-09-07 1996-06-27 Metallgesellschaft Ag Verwendung von ferritischen Chrom - Molybdän-Stählen als gegen konzentrierte Schwefelsäure beständigem Werkstoff
DE4342188C2 (de) * 1993-12-10 1998-06-04 Bayer Ag Austenitische Legierungen und deren Verwendung
FR2939052B1 (fr) * 2008-12-01 2010-12-10 Rhodia Operations Installation de cristallisation d'acide adipique
CA3108890A1 (fr) * 2018-08-29 2020-03-05 Chemetics Inc. Alliage inoxydable austenitique presentant une resistance a la corrosion superieure

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0130967A1 (fr) * 1983-07-05 1985-01-09 Monsanto Company Récupération de la chaleur de l'acide sulfurique concentré
EP0181313A2 (fr) * 1984-11-09 1986-05-14 Monsanto Company Récupération de chaleur d'acide sulfurique concentré

Family Cites Families (7)

* Cited by examiner, † Cited by third party
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 (fr) * 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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0130967A1 (fr) * 1983-07-05 1985-01-09 Monsanto Company Récupération de la chaleur de l'acide sulfurique concentré
EP0181313A2 (fr) * 1984-11-09 1986-05-14 Monsanto Company Récupération de chaleur d'acide sulfurique concentré

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
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
ES552799A0 (es) 1988-05-16
ES8802377A1 (es) 1988-05-16
FI80481B (fi) 1990-02-28
FI860944A (fi) 1986-09-10
EP0200862A1 (fr) 1986-11-12
AU583898B2 (en) 1989-05-11
JPS61207551A (ja) 1986-09-13
FI80481C (fi) 1990-06-11
AU5443486A (en) 1986-09-11
ATE34779T1 (de) 1988-06-15
FI860944A0 (fi) 1986-03-06
DE3508532A1 (de) 1986-09-18
CA1273230A (fr) 1990-08-28
DE3660261D1 (en) 1988-07-07

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