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 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
- 229910000990 Ni alloy Inorganic materials 0.000 title description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title 1
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 title 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000000956 alloy Substances 0.000 claims abstract description 27
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 239000011651 chromium Substances 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- 239000004411 aluminium Substances 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 239000010955 niobium Substances 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000002274 desiccant Substances 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 17
- 239000002253 acid Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- 241001295925 Gegenes Species 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910001149 41xx steel Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Luminescent Compositions (AREA)
- Plural Heterocyclic Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Pyrane Compounds (AREA)
- High-Tension Arc-Extinguishing Switches Without Spraying Means (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Secondary Cells (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Articles (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Glass Compositions (AREA)
Claims (7)
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)
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 |
MA53483A (fr) * | 2018-08-29 | 2021-12-08 | Chemetics Inc | Alliage inoxydable austénitique présentant une résistance à la corrosion supérieure |
Citations (2)
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)
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 |
-
1985
- 1985-03-09 DE DE19853508532 patent/DE3508532A1/de not_active Withdrawn
-
1986
- 1986-02-27 DE DE8686102555T patent/DE3660261D1/de not_active Expired
- 1986-02-27 AT AT86102555T patent/ATE34779T1/de not_active IP Right Cessation
- 1986-02-27 EP EP86102555A patent/EP0200862B1/fr not_active Expired
- 1986-03-06 FI FI860944A patent/FI80481C/fi not_active IP Right Cessation
- 1986-03-07 AU AU54434/86A patent/AU583898B2/en not_active Ceased
- 1986-03-07 ES ES552799A patent/ES8802377A1/es not_active Expired
- 1986-03-07 JP JP61048722A patent/JPS61207551A/ja active Pending
- 1986-03-07 CA CA000503590A patent/CA1273230A/fr not_active Expired - Lifetime
Patent Citations (2)
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)
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 |
JPS61207551A (ja) | 1986-09-13 |
ES8802377A1 (es) | 1988-05-16 |
EP0200862A1 (fr) | 1986-11-12 |
AU583898B2 (en) | 1989-05-11 |
DE3508532A1 (de) | 1986-09-18 |
FI860944A0 (fi) | 1986-03-06 |
CA1273230A (fr) | 1990-08-28 |
FI80481B (fi) | 1990-02-28 |
AU5443486A (en) | 1986-09-11 |
FI80481C (fi) | 1990-06-11 |
ATE34779T1 (de) | 1988-06-15 |
DE3660261D1 (en) | 1988-07-07 |
FI860944A (fi) | 1986-09-10 |
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