CN102471834B - Metallic nickel-based acid-resistant material - Google Patents

Metallic nickel-based acid-resistant material Download PDF

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CN102471834B
CN102471834B CN2010800322946A CN201080032294A CN102471834B CN 102471834 B CN102471834 B CN 102471834B CN 2010800322946 A CN2010800322946 A CN 2010800322946A CN 201080032294 A CN201080032294 A CN 201080032294A CN 102471834 B CN102471834 B CN 102471834B
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maximum
alloy
nickel
molybdenum
iron
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CN102471834A (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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  • Heat Treatment Of Steel (AREA)
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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 the concentrated sulfuric acid of moderate and hydrochloric acid soln, have the metallic substance of resistance.
Sulfuric acid is one of most important raw material in chemical industry.Sulfuric acid has wide spectrum of use while in chemical industry, in differing temps with different concns, using.It causes different corrosion loads for the metallic substance that uses for its operation.It generally raises and raises along with temperature, until erosion resistance finally no longer is provided.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 resistance of known metal material in bright sulfur acid is described (Metals Handbook, 9th Edition, Vol.13:Corrosion, ASM International, Metals Park, Ohio 44073,1987).As measuring of resistance, draw the corrosion line for the known metallic substance 0.5mm/ of difference-wait here.In this case, according to definition, what be in this line below is the resistance scope of affiliated material in every kind of situation.In Fig. 1, can draw, with the increase along with sulfuric acid concentration of the stainless resistance scope of type 316 expression, at first significantly reduce, thereby along with higher temperature is finally widened in the further increase of concentration again.In addition, for example C-276,625, G-3/G-30, alloy 20 and last nickel-molybdenum-alloy B/B-2 have significantly better resistance 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 described figure or operational conditions.On the one hand can replace corrosion line such as 0.5mm/-wait with corrosion line such as other ultimate value such as 0.1mm/-wait.The type of the hotchpotch that exists in sulfuric acid in operating practice on the other hand, and amount may have remarkably influenced to erosion resistance.But, by Fig. 1, be apparent that, to consider until, in the temperature range of 130 ℃, according to prior art, only have nickel-molybdenum-alloy B/B-2 to have enough erosion resistances in wide sulfuric acid concentration interval.According to the shortcoming of this nickel-molybdenum of prior art-alloy B/B-2, mainly be high material cost and therefore cause to a great extent the high metal price of the alloying element that is formed by nickel and molybdenum.
Therefore, at present to a great extent alloy B-2 commonly used according to UNS (Unified number system) N 10665 or EN (European standard) 2.4617 by following combining (quality %): 26 to 30% molybdenums, maximum 2% iron, maximum 1% chromium, maximum 1% manganese, maximum 0.08% silicon and maximum 0.01% carbon, surplus is mainly nickel.This means, the share of nickel be for example typically 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 of not too expensive alloy element Fe, chromium and manganese (data are in quality %) 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).
Precursor alloy B for previous routine provides the iron level of 4 to 6 quality % according to UNS N10001.
By US 3,649,255 known a kind of corrosion resistant nickel-molybdenums-alloy, 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 inevitable impurity.The average content of Mo should be 26 to 32%, Fe and should be until 7%.The exemplary Co that provides is 1.01%.
It is 26 to 30%, Fe to be 1 to 7%, Cr to be 0.4 to 1.5% that DE 42 10 997 relates to austenitic-molybdenum with following composition (quality %)-alloy: Mo, Mn is until 1.5%, Si is until 0.05%, Co is until 2.5%, P is until 0.04%, S is until 0.01%, Al is 0.1 to 0.5%, Mg to be until 0.1%, Cu is until 1.0%, C is until 0.01%, N is until 0.01%, surplus Fe.
The object of the invention is to, find a kind of metallic substance, it,, until in 20 to 80% sulfuric acid, be resistance under the high temperature of 130 ℃, also has enough resistances simultaneously with regard to cold water, with the metal alloy according to the prior art routine, compare particularly and significantly reduce aspect metal price.
Described purpose realizes by at high temperature reductant being had to the nickel-molybdenum of high resistance-alloy, and described 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, alloy according to the present invention can be used for reductant, particularly parts with high erosion resistance of the concentrated sulfuric acid of the moderate of heat and hydrochloric acid soln.
According to the preferred application area of alloy of the present invention, be the chemical devices field, because a large amount of situations of using reductant under comparatively high temps are arranged herein.
What it is contemplated that equally is to use described alloy as the scolder of the same type of linear structure and/or be used to welding nickel-molybdenum-alloy.
Can be for example as the wrought material of manufacturing sheet material, band, wire rod, bar, forging parts and tubing and as foundry goods according to alloy of the present invention.
Show astoundingly, when the sulfuric acid be used to operating heat uses the nickel-molybdenum provide previously-iron-alloy, can obviously alleviate the unfavorable situation of being brought by the prior art of the high metal price representative of nickel and molybdenum.The average content of nickel is advantageously between 61 and 63 quality %.This means, with respect to the exemplary prior art that provides of introductory song, mean that expensive alloying element nickel reduces by 6 to 7 quality %.The content of the Alloying Element Molybdenum of same costliness is on average between 24 and 26 quality %, remarkable nickel-molybdenum lower than the exemplary 27 or 28 quality % molybdenums that provide in prior art-alloy is (referring to Hochlegierte Werkstoffe, Korrosionsverhalten und Anwendung, TAW-Verlag, Wuppertal 2002, S.192).
Below will describe in detail.
Figure BDA0000131765010000051
Table 1: compare with the nickel-molybdenum of prior art according to data in literature-alloy B-2, the chemical constitution of nickel-molybdenum of checking when spectroscopic analysis is measured-iron-alloy is (referring to Hochlegierte Werkstoffe, Korrosionsverhalten und Anwendung, TAW-Verlag, Wuppertal 2002, S.192).
Table 1 illustrates the comparison according to nickel-molybdenum of the present invention-iron-alloy nickel-molybdenum outer with being in the scope of the invention-iron-alloy and the nickel-molybdenum that belongs to prior art-alloy B-2.Hotchpotch and impurity that more unlisted smeltings cause.Can find out, the exemplary iron level that provides with the alloy B-2 of prior art only 1.7 quality % is compared, and 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, be that 28 quality % compare, 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, be that 69 quality % compare, 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 table 1.
Figure BDA0000131765010000052
Table 2: nickel-molybdenum of checking-iron-alloy is according to embodiment of the present invention 50 and 44, corrosion-damaged in the concentrated sulfuric acid of the moderate of heat, with two be in the outer nickel-molybdenum of the scope of the invention-iron-alloy 51 and 45 relatively, and with the corresponding nickel-molybdenum of prior art-alloy B-2 relatively.
Table 2 illustrates, corrosion-damaged according in the concentrated sulfuric acid of embodiment of the present invention 50 and 44 moderates in heat of nickel-molybdenum of checking-iron-alloy, with two be in the outer nickel-molybdenum of the scope of the invention-iron-alloy 51 and 45 relatively, and with the nickel-molybdenum that belongs to prior art-alloy B-2 relatively.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 according to embodiment of the present invention 50 compound of nickel-molybdenum of checking-iron-alloy in the concentrated sulfuric acid (30 and 50%) of the moderate of heat is similar to the erosion resistance under welded condition not.
Nickel-molybdenum of checking-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 resistances.
The mechanical characteristics Rp according to embodiment of the present invention 44 of the nickel-molybdenum checked that at room temperature records in tensile test-iron-alloy 0.2>=350N/mm 2, Rp 1.0>=380N/mm 2, Rm>=760N/mm 2And A 5>=40%, its can be corresponding with prior art nickel-molybdenum-alloy B-2 compare (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 the outer nickel-molybdenum checked of the scope of the invention-iron-alloy does not reach mentioned intensity level.

Claims (8)

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 medal,
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 claim 1 alloy has (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 medal
Maximum 0.01% carbon
Maximum 0.1% silicon
Maximum 0.02% phosphorus
Maximum 0.01% sulphur
Maximum 1.0% cobalts.
3. according to claim 1 and 2 alloy has (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 medal
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 of one of according to claim 1 to 3 is for having the purposes of the parts of high erosion resistance to reductant.
5. the alloy of one of according to claim 1 to 3 has the purposes of the parts of high erosion resistance for the moderate to heat concentrated sulfuric acid and hydrochloric acid soln.
6. the alloy of one of according to claim 1 to 3 is for the purposes of the part of chemical devices.
7. the alloy of one of according to claim 1 to 3 is as scolder of the same type and be used to welding the purposes of nickel-molybdenum-alloy.
8. the alloy of one of according to claim 1 to 3 is as the wrought material of manufacturing 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 (2)

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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

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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
JPH07331367A (en) * 1994-06-03 1995-12-19 Mitsubishi Materials Corp Nickel-base alloy excellent in high temperature corrosion resistance and high temperature strength

Patent Citations (2)

* 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特开平7-331367A 1995.12.19

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DE102009034856B4 (en) 2012-04-19
US20170275737A1 (en) 2017-09-28
SI2459763T1 (en) 2014-01-31
EP2459763B1 (en) 2013-09-04
US20120114520A1 (en) 2012-05-10
EP2459763A1 (en) 2012-06-06
US20150344995A1 (en) 2015-12-03

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