CN102471834A - Metallic nickel-based acid-resistant material - Google Patents

Metallic nickel-based acid-resistant material Download PDF

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CN102471834A
CN102471834A CN2010800322946A CN201080032294A CN102471834A CN 102471834 A CN102471834 A CN 102471834A CN 2010800322946 A CN2010800322946 A CN 2010800322946A CN 201080032294 A CN201080032294 A CN 201080032294A CN 102471834 A CN102471834 A CN 102471834A
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maximum
alloy
nickel
molybdenum
iron
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CN102471834B (en
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R·贝伦斯
H·阿尔维斯
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VDM Metals GmbH
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ThyssenKrupp VDM GmbH
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Manufacture And Refinement Of Metals (AREA)
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  • Heat Treatment Of Steel (AREA)
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  • Powder Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

A nickel-molybdenum-iron alloy with high corrosion resistance with respect to reducing media at high temperatures, consisting of (in % by mass): 61 to 63% nickel, 24 to 26% molybdenum, 10 to 14% iron, 0.20 to 0.40% niobium, 0.1 to 0.3% aluminium, 0.01 to 1.0% chromium, 0.1 to 1.0% manganese, at most 0.5% copper, at most 0.01% carbon, at most 0.1% silicon, at most 0.02% phosphorus, at most 0.01% sulphur, at most 1.0% cobalt, and further smelting-related impurities.

Description

Metal acid resisting material based on nickel
The present invention relates at high temperature in spissated sulfuric acid of moderate and hydrochloric acid soln, have the metallic substance of resistency.
Sulfuric acid is one of most important material in the chemical industry.Sulfuric acid has wide spectrum of use when in chemical industry, using in differing temps with different concns.It causes different corrosion loads for operate employed metallic substance for it.Raise and raise along with temperature as the one of which, erosion resistance no longer is provided until at last.The respective application upper limit depends on sulfuric acid concentration and illustrates in so-called isocorrosion chart (Isokorrosionsdiagramm).
Fig. 1 illustrates this isocorrosion chart for example, comprises that the difference of the different resistency of known metal material in bright sulfur acid is described (Metals Handbook, 9th Edition; Vol.13:Corrosion, ASM International, Metals Park; Ohio 44073,1987).Draw corrosion line here as measuring of resistency for the known metallic substance 0.5mm/ of difference-wait.In this case, according to definition, what be in this line below is the resistency scope of affiliated material under every kind of situation.In Fig. 1, can draw, at first significantly reduce with the increase of the stainless resistency scope of type 316 expression along with sulfuric acid concentration, thereby along with higher temperature is widened in the further increase of concentration at last once more.In addition, for example C-276,625, G-3/G-30, alloy 20 and last nickel-molybdenum-alloy B/B-2 have significantly better resistency according to this diagram nickelalloy.
Isocorrosion chart as shown in Figure 1 is suitable for regard to the test conditions that is used for measuring said figure or operational conditions.On the one hand can with other ultimate value for example corrosion line such as 0.1mm/-wait replace corrosion line such as 0.5mm/-wait.The type of the hotchpotch that exists in the sulfuric acid in the operating practice on the other hand, possibly have remarkably influenced to erosion resistance with amount.But, be apparent that by Fig. 1, to consider in 130 ℃ TR, have only nickel-molybdenum-alloy B/B-2 to have enough erosion resistances at interval according to prior art at wide sulfuric acid concentration.Mainly be high material cost and the high metal price that therefore causes to a great extent the alloying element that constitutes by nickel and molybdenum according to the shortcoming of this nickel-molybdenum-alloy B/B-2 of prior art.
Therefore; Alloy B-2 commonly used to a great extent at present forms (quality %) according to UNS (unified numbering system) N 10665 or EN (European standard) 2.4617 by combination: 26 to 30% molybdenums, maximum 2% iron; Maximum 1% chromium; Maximum 1% manganese, maximum 0.08% silicon and maximum 0.01% carbon, surplus mainly is a nickel.This means, the share of nickel typically for example be 69 quality % (with reference to Hochlegierte Werkstoffe, Korrosionsverhalten und Anwendung, TAW-Verlag, Wuppertal 2002, S.192).
Come in, alloy such as B-3 (UNS N10675) are studied, the alloy content (data are in quality %) of not too expensive alloy element Fe, chromium and manganese is brought up to 1 to 3% iron; 1 to 3% chromium and maximum 3% manganese; Wherein provide exemplary nickel content 68 quality % (referring to Hochlegierte Werkstoffe, Korrosionsverhalten und Anwendung, TAW-Verlag; Wuppertal 2002, S.192).
Provide the iron level of 4 to 6 quality % according to UNS N10001 for the precursor alloy B of previous routine.
Through US 3,649,255 known a kind of corrosion resistant nickel-molybdenum-alloys, have (quality %): 20 to 40%Mo; Until 10%Fe, until 4%Co, until 5%Cr, until 2%Mn; Until 0.03%P, until 0.03%S, until 0.1%C, until 0.1%Si; 0.1 to 1.0%V, 0.001 to 0.035%B, 0.01 to 1%Zr, surplus Ni and unavoidable impurities.The average content of Mo should be 26 to 32%, and Fe should be until 7%.The exemplary Co that provides is 1.01%.
It is 26 to 30% that DE 42 10 997 relates to the austenitic-molybdenum-alloy with following composition (quality %): Mo, and Fe is 1 to 7%, and Cr is 0.4 to 1.5%, and Mn is until 1.5%; Si is until 0.05%, and Co is until 2.5%, and P is until 0.04%, and S is until 0.01%; Al is 0.1 to 0.5%, and Mg is until 0.1%, and Cu is until 1.0%; C is until 0.01%, and N is until 0.01%, surplus Fe.
The objective of the invention is to; Find a kind of metallic substance; It also has enough resistencys simultaneously until in 20 to 80% sulfuric acid, being resistency under 130 ℃ the high temperature with regard to cold water, significantly reduce aspect the metal price with comparing particularly according to the conventional metal alloy of prior art.
Said purpose realizes through at high temperature reductant being had the nickel-molybdenum of high resistency-alloy, and said alloy is by following the composition (quality %):
Ni 61 to 63%
Mo 24 to 26%
Fe 10 to 14%
Nb 0.20 to 0.40%
Al 0.1 to 0.3%
Cr 0.01 to 1.0%
Mn 0.1 to 1.0%
Cu maximum 0.5%
C maximum 0.01%
Si maximum 0.1%
P maximum 0.02%
S maximum 0.01%
Co maximum 1.0%
The impurity that causes with other smelting.
The favourable improvement project of alloy according to the present invention is drawn by dependent claims.
A kind of favourable alloy, it is by following the composition (quality %):
Ni 61.5 to 62.5%
Mo 24.5 to 26.0%
Fe 10.5 to 13.5%
Nb 0.2 to 0.4%
Al 0.1 to 0.3%
Cr 0.01 to 1.0%
Mn 0.1 to 0.8%
Cu maximum 0.5%
C maximum 0.01%
Si maximum 0.1%
P maximum 0.02%
S maximum 0.01%
Co maximum 1.0%.
Another kind of preferred alloy, it is by following the composition (quality %):
Ni 61.5 to 62.5%
Mo 24.8 to 26.0%
Fe 10.5 to 12.5%
Nb 0.2 to 0.4%
Al 0.1 to 0.3%
Cr 0.01 to 0.9%
Mn 0.1 to 0.5%
Cu maximum 0.3%
C maximum 0.008%
Si maximum 0.08%
P maximum 0.015%
S maximum 0.008%
Co maximum 1.0%.
Another theory of the present invention is that alloy according to the present invention can be used for reductant, the parts that particularly hot spissated sulfuric acid of moderate and hydrochloric acid soln have high erosion resistance.
Preferred application area according to alloy of the present invention is the chemical devices field, because a large amount of situation of under comparatively high temps, using reductant are arranged here.
What it is contemplated that equally is, uses said alloy as the scolder of the same type of linear structure and/or be used to weld nickel-molybdenum-alloy.
Can be according to alloy of the present invention for example as the wrought material of making sheet material, band, wire rod, bar, forging parts and tubing and as foundry goods.
Show astoundingly, when the sulfuric acid that is used to operate heat uses nickel-molybdenum-iron that the front provides-alloy, can obviously alleviate the unfavorable situation that the prior art represented by the high metal price of nickel and molybdenum is brought.The average content of nickel is advantageously between 61 and 63 quality %.This means,, mean that expensive alloying element nickel reduces by 6 to 7 quality % with respect to the exemplary prior art that provides of introductory song.The content of the alloying element molybdenum of same costliness is on average between 24 and 26 quality %; Nickel-molybdenum-the alloy that significantly is lower than the exemplary 27 or 28 quality % molybdenums that provide in the prior art is (referring to Hochlegierte Werkstoffe; Korrosionsverhalten und Anwendung; TAW-Verlag, Wuppertal 2002, S.192).
To describe in detail below.
Figure BDA0000131765010000051
Table 1: compare with nickel-molybdenum-alloy B-2 according to the prior art of data in literature; The chemical constitution of nickel-molybdenum-iron-alloy of being checked when spectroscopic analysis is measured is (referring to Hochlegierte Werkstoffe; Korrosionsverhalten und Anwendung; TAW-Verlag, Wuppertal 2002, S.192).
Table 1 illustrates according to nickel-molybdenum of the present invention-iron-alloy nickel-molybdenum-iron-alloy and the comparison that belong to the nickel-molybdenum-alloy B-2 of prior art outer with being in the scope of the invention.Hotchpotch and impurity that more unlisted smeltings cause.Can find out that the exemplary iron level that provides with the alloy B-2 of prior art only 1.7 quality % is compared, the test iron level is between 11 and 12 quality %, and the test iron level is 14.7 quality % in a kind of situation.With the exemplary molybdenum content that the alloy B-2 of prior art provides is that 28 quality % compare, and the molybdenum content of test is between 20.4 and 25.6 quality %.With the exemplary nickel content that the alloy B-2 of prior art provides is that 69 quality % compare, and the nickel content of test is between 60.1 and 63.3 quality %.
Table 2 illustrates the corrosion-damaged of the alloy that provides in the table 1.
Figure BDA0000131765010000052
Table 2: nickel-molybdenum of being checked-iron-alloy is according to embodiment of the present invention 50 and 44; Corrosion-damaged in the spissated sulfuric acid of the moderate of heat; Compare with two nickel-molybdenum-iron-alloys 51 and 45 that are in outside the scope of the invention, and compare with the corresponding nickel-molybdenum of prior art-alloy B-2.
Table 2 illustrates; Nickel-molybdenum of being checked-iron-alloy according to embodiment of the present invention 50 and 44 corrosion-damaged in the spissated sulfuric acid of the moderate of heat; Compare with two nickel-molybdenum-iron-alloys 51 and 45 that are in outside the scope of the invention, and compare with the nickel-molybdenum that belongs to prior art-alloy B-2.According to embodiment of the present invention 50 130 ℃ the time at 80% H 2SO 4In corrosion-damaged outside, corrosion-damaged below the corrosion lines such as 0.5mm/a-of Fig. 1 according to embodiment of the present invention 50 and 44.
The erosion resistance of welding compound in the spissated sulfuric acid of the moderate of heat (30 and 50%) according to embodiment of the present invention 50 of nickel-molybdenum of being checked-iron-alloy is similar to the erosion resistance under the welded condition not.
Nickel-molybdenum of being checked-iron-alloy according to embodiment of the present invention 50 in dip test in 4% salt solution 150 ℃ the time via showing the corrosion-damaged 0.08mm/a that is in 120 hours.This means, according to proposing of task, even with regard to cold water, in the cold water of muriate serious pollution, also have enough resistencys.
The mechanical characteristics Rp according to embodiment of the present invention 44 of nickel-molybdenum of the being checked-iron-alloy that at room temperature records in the tensile test 0.2>=350N/mm 2, Rp 1.0>=380N/mm 2, Rm>=760N/mm 2And A 5>=40%; It can the nickel-molybdenum-alloy B-2 corresponding with prior art be compared (referring to N ° of N of Sheet and Plate-High Performance Materials:Publication 554 98-10 der Krupp VDM GmbH; S.34/35), the embodiment 45 that is in outer nickel-molybdenum of the being checked-iron-alloy of the scope of the invention does not reach mentioned intensity level.

Claims (7)

1. nickel-molybdenum-iron-alloy, it at high temperature has high erosion resistance to reductant, by following the composition (quality %):
61 to 63% nickel,
24 to 26% molybdenums,
10 to 14% iron,
0.20 to 0.40% niobium,
0.1 to 0.3% aluminium,
0.01 to 1.0% chromium,
0.1 to 1.0% manganese,
Maximum 0.5% bronze medals,
Maximum 0.01% carbon,
Maximum 0.1% silicon,
Maximum 0.02% phosphorus,
Maximum 0.01% sulphur,
Maximum 1.0% cobalts,
The impurity that causes with other smelting.
2. according to the alloy of claim 1, have (quality %):
61.5 to 62.5% nickel
24.5 to 26.0% molybdenum
10.5 to 13.5% iron
0.2 to 0.4% niobium
0.1 to 0.3% aluminium
0.01 to 1.0% chromium
0.1 to 0.8% manganese
Maximum 0.5% bronze medals
Maximum 0.01% carbon
Maximum 0.1% silicon
Maximum 0.02% phosphorus
Maximum 0.01% sulphur
Maximum 1.0% cobalts.
3. according to the alloy of claim 1 or 2, have (quality %):
61.5 to 62.5% nickel
24.8 to 26.0% molybdenum
10.5 to 12.5% iron
0.2 to 0.4% niobium
0.1 to 0.3% aluminium
0.01 to 0.9% chromium
0.1 to 0.5% manganese
Maximum 0.3% bronze medals
Maximum 0.008% carbon
Maximum 0.08% silicon
Maximum 0.015% phosphorus
Maximum 0.008% sulphur
Maximum 0.02% nitrogen
Maximum 0.012% magnesium
Maximum 1.0% cobalts.
4. the alloy according to one of claim 1 to 3 is used for reductant, and particularly the spissated sulfuric acid of moderate and the hydrochloric acid soln of heat have the purposes of the parts of high erosion resistance.
5. the purposes that is used for the part of chemical devices according to the alloy of one of claim 1 to 3.
According to the alloy of one of claim 1 to 3 as scolder of the same type and the purposes that is used to weld nickel-molybdenum-alloy.
According to the alloy of one of claim 1 to 3 as the wrought material of making sheet material, band, wire rod, bar, forging parts and tubing and as the purposes of foundry goods.
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DE102009034856A DE102009034856B4 (en) 2009-07-27 2009-07-27 Use of a nickel-molybdenum-iron alloy
DE102009034856.5 2009-07-27
PCT/DE2010/000838 WO2011012109A1 (en) 2009-07-27 2010-07-19 Metallic nickel-based acid-resistant material

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CN111088447B (en) * 2020-03-12 2021-06-29 王军伟 Pre-oxidized Ni-Fe-Al series alloy used in molten chloride and pre-oxidation process

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3649255A (en) * 1970-05-25 1972-03-14 Cyclops Corp Universal Corrosion-resistant nickel-molybdenum alloys
CN1078267A (en) * 1992-04-02 1993-11-10 克鲁普德国联合金属制造有限公司 Austenitic molybdenum alloy
JPH07331367A (en) * 1994-06-03 1995-12-19 Mitsubishi Materials Corp Nickel-base alloy excellent in high temperature corrosion resistance and high temperature strength

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1134205B (en) * 1956-11-19 1962-08-02 Mond Nickel Co Ltd Use of a nickel-molybdenum-iron alloy for the production of objects resistant to hydrochloric acid by welding
DE2005371B2 (en) * 1970-02-06 1974-01-17 Fried. Krupp Gmbh, 4300 Essen Process for the production of magnetically soft iron-nickel alloys
US3844847A (en) * 1973-09-11 1974-10-29 Int Nickel Co Thermomechanical processing of mechanically alloyed materials
US4861550A (en) * 1983-07-25 1989-08-29 Mitsubishi Metal Corporation Of Tokyo Corrosion-resistant nickel-base alloy having high resistance to stress corrosion cracking
JPH0674473B2 (en) * 1986-01-07 1994-09-21 住友金属工業株式会社 High corrosion resistance Ni-based alloy

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3649255A (en) * 1970-05-25 1972-03-14 Cyclops Corp Universal Corrosion-resistant nickel-molybdenum alloys
CN1078267A (en) * 1992-04-02 1993-11-10 克鲁普德国联合金属制造有限公司 Austenitic molybdenum alloy
JPH07331367A (en) * 1994-06-03 1995-12-19 Mitsubishi Materials Corp Nickel-base alloy excellent in high temperature corrosion resistance and high temperature strength

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US20170275737A1 (en) 2017-09-28
SI2459763T1 (en) 2014-01-31
EP2459763B1 (en) 2013-09-04
US20120114520A1 (en) 2012-05-10
CN102471834B (en) 2013-11-20
EP2459763A1 (en) 2012-06-06
US20150344995A1 (en) 2015-12-03

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