CN108441703A - A kind of alkali corrosion resistance nickel-base alloy - Google Patents
A kind of alkali corrosion resistance nickel-base alloy Download PDFInfo
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- CN108441703A CN108441703A CN201810210111.3A CN201810210111A CN108441703A CN 108441703 A CN108441703 A CN 108441703A CN 201810210111 A CN201810210111 A CN 201810210111A CN 108441703 A CN108441703 A CN 108441703A
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- corrosion resistance
- alkali corrosion
- base alloy
- resistance nickel
- nickel
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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
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/22—Evaporating by bringing a thin layer of the liquid into contact with a heated surface
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- Mechanical Engineering (AREA)
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Abstract
The present invention provides a kind of alkali corrosion resistance nickel-base alloys, according to mass percent meter, including：C 0.01~0.03%；Si≤0.3%；Mn 0.3~0.7%；P≤0.008%；S≤0.005%；Cr 20.00~25.00%；Fe 24~34%；Mo 2.80~4.50%；Cu 1.80~3.50%；Ti 0.70~1.40%；N≤0.0120%；Remaining is Ni and inevitable impurity.The alkali corrosion resistance nickel-base alloy of the present invention can be used as kestner long-tube evaporator inner tube, and active time can be 2 to 3 times of current pure Ni pipes, and manufacturing cost can reduce by 30% to 40%.
Description
Technical field
The invention belongs to field of metallurgy, in particular it relates to a kind of alkali corrosion resistance nickel-base alloy.
Background technology
Caustic soda (NaOH) is the highly basic of solubility, is widely used in weaving, printing and dyeing, bleaching, papermaking, turpentole, smelting
The every profession and trades such as gold, chemistry.Caustic soda can be divided into piece alkali, solid caustic soda, grain alkali, wherein piece alkali yield highest according to form, and film-type evaporation
Device is one of the important equipment for producing piece alkali.Kestner long-tube evaporator is made of two layers of casing, and outer layer walks fused salt, and internal layer walks lye, and two
Kind liquid countercurrent conducts heat.Lye is heated (temperature after distributor enters every kestner long-tube evaporator by chuck fused salt
325-435 DEG C), then lye boiling, concentration and evaporation is detached through bottom gathering tube to gas-liquid separator.In production process
In, kestner long-tube evaporator inner tube corrosion failure is most commonly seen, to be seriously affected to product quality and production efficiency generation, and film
Formula evaporator procurement price is high.
Kestner long-tube evaporator inner tube generally uses the pure Ni pipes of military project grade at present, but in piece alkali production process, due to alkaline original
Unavoidably there is a small amount of complex corrosion element (such as ClO in lye in material or technological fluctuation problem-, [O] etc.), to cause
Pure Ni pipes local perforations and cracking failure, make active time shorten dramatically (most it is short be on active service more than 20 days i.e. perforation), equipment purchase at
Originally it sharply increases.
Invention content
The goal of the invention of the present invention is in view of the deficiencies in the prior art, to provide a kind of Ni-based conjunction of alkali corrosion resistance
Gold.
On the one hand, the present invention provides a kind of alkali corrosion resistance nickel-base alloys, according to mass percent meter, including as follows at
Point：C 0.01~0.03%；Si≤0.3%；Mn 0.3~0.7%；P≤0.008%；S≤0.005%；Cr 20.00~
25.00%；Fe 24~34%；Mo 2.80~4.50%；Cu 1.80~3.50%；Ti 0.70~1.40%；N≤
0.0120%；Remaining is Ni and inevitable impurity.
Alkali corrosion resistance nickel-base alloy above-mentioned, 62%≤Cr+Ni≤69%.
Alkali corrosion resistance nickel-base alloy above-mentioned, further includes Nb and/or Ta, and 0.2≤Nb+Ta≤2.00%.
Alkali corrosion resistance nickel-base alloy above-mentioned further includes Al 0.10~0.30%.
Alkali corrosion resistance nickel-base alloy above-mentioned, Ti/Al >=5.0.
Alkali corrosion resistance nickel-base alloy above-mentioned, according to mass percent meter, including following ingredient：C0.01~0.02%；Si
≤ 0.2%；Mn 0.4~0.6%；P≤0.008%；S≤0.002%；Cr21.00~23.00%；Fe 26~32%；Mo
2.80~3.50%；Cu 1.90~3.20%；Ti 0.70~1.00%；N≤0.005%；Remaining is for Ni and inevitably
Impurity.
On the other hand, the use the present invention provides alkali corrosion resistance nickel-base alloy above-mentioned in preparing kestner long-tube evaporator inner tube
On the way.
On the other hand, the present invention provides a kind of kestner long-tube evaporator inner tubes, using alkali corrosion resistance nickel-base alloy system above-mentioned
It is standby to obtain.
The alkali corrosion resistance nickel-base alloy of the present invention can be used as kestner long-tube evaporator inner tube, and active time can be current
2-3 times of pure Ni pipes, and manufacturing cost can reduce 30-40%.
Specific implementation mode
In order to fully understand the purpose of the present invention, feature and effect, by following specific implementation modes, the present invention is made detailed
It describes in detail bright.For the process of the present invention in addition to following the description, remaining is all made of the conventional method or device of this field.Following nouns
Term is unless otherwise stated, all have the normally understood meaning of those skilled in the art.
For existing kestner long-tube evaporator inner tube part easily perforation and cracking failure, active time is short, and equipment purchase is of high cost
The problems such as, the present inventor optimizes the element composition and proportioning of nickel-base alloy by research, to provide one
Kind alkali corrosion resistance nickel-base alloy.According to mass percent meter, alkali corrosion resistance nickel-base alloy of the invention includes：C 0.01~
0.03%；Si≤0.3%；Mn 0.3~0.7%；P≤0.008%；S≤0.005%；Cr 20.00~25.00%；Fe 24
~34%；Mo 2.80~4.50%；Cu 1.80~3.50%；Ti0.70~1.40%；N≤0.0120%；Remaining for Ni with
Inevitable impurity.
Preferably, in the alkali corrosion resistance nickel-base alloy of the present invention, the sum of the mass content of Cr and Ni are：62%≤Cr+
Ni≤69%.
Preferably, alkali corrosion resistance nickel-base alloy of the invention further includes Nb and/or Ta, and 0.2≤Nb+Ta≤
2.00%.
Preferably, alkali corrosion resistance nickel-base alloy of the invention further includes Al 0.10~0.30%.
Preferably, in the alkali corrosion resistance nickel-base alloy of the present invention, the mass ratio of Ti and Al meet Ti/Al >=5.0.
In a kind of preferred embodiment, according to mass percent meter, alkali corrosion resistance nickel-base alloy of the invention
Including：C 0.01~0.02%；Si≤0.2%；Mn 0.4~0.6%；P≤0.008%；S≤0.002%；Cr 21.00~
23.00%；Fe 26~32%；Mo 2.80~3.50%；Cu 1.90~3.20%；Ti 0.70~1.00%；N≤
0.005%；Remaining is Ni and inevitable impurity.
The present inventor integrates the advantage and disadvantage of existing nickel-base alloy, is formed on this basis to the element of nickel-base alloy
It is optimized with proportioning, to provide a kind of alkali corrosion resistance nickel-base alloy.Design through the invention, each element is according to this hair
Bright proportioning produces the effect of collaboration after being combined, effectively increase alkali corrosion resistance performance, specific as follows.
C primarily serves the effect of solution strengthening.(it is less than 0.01%) when C content is too low, invigoration effect is not notable.But
It is that the C content of addition is excessively high (i.e. more than 0.03%), on the one hand, C can be combined to be formed largely once with the Ti elements in alloy
TiC precipitates, to make reduced performance；On the other hand, excessively high C content can increase intercrystalline corrosion tendency, reduce alloy ductility.
Therefore, C content control is in 0.01~0.03%, preferably 0.01~0.02%.
Si belongs to harmful element in nickel-base alloy, harmful phase can be promoted to be precipitated.When Si contents are more than 0.3%, alloy
In certain temperature long service, crystal boundary can be precipitated and be harmful to precipitated phase containing Si, to weaken grain-boundary strength, cause to crack.Therefore,
Si contents are controlled≤0.3%, preferably≤0.2%.
Mn belongs to harmful element in the pure nickel based alloy without Fe, but in the nickel-base alloy containing a certain amount of Fe,
It can be properly added, play solution strengthening effect.(it is less than 0.3%) when Mn contents are too low, invigoration effect is not notable.But
It is that the Mn too high levels (i.e. more than 0.7%) of addition can be such that the thermoplasticity of alloy reduces, so as to cause forge crack.Therefore,
Mn contents are controlled in 0.3~0.7%, preferably 0.4~0.6%.
Cr is indispensable alloy element, plays solution strengthening, antioxidation.Cr is particularly significant in γ matrixes
Effect be to form Cr2O3Type oxidation film makes alloy have good anti-oxidant and corrosion resistance.Alkaline is steamed with membrane type
Device inner tube is sent out, main function is anti-free oxygen corrosion.When Cr contents are less than 20%, the anti-free oxygen corrosive nature of alloy is not
It can meet the requirements；But when Cr contents are higher than 25%, the Cr carbide of bulk can be formed in alloy, and manufacturing cost is made to increase,
And anti-oxidant contribution degree is not further added by.Therefore, the control of Cr contents 20.00~25.00%, preferably 21.00~
23.00%.
Mo is solution strengthening element, has anti-spot corrosion characteristic.When Mo contents are higher than 4.5%, alkaline is steamed with membrane type
The practical conventional working condition of device inner tube is sent out, corrosion resistance is superfluous.When Mo contents are less than 2.8%, anti-spot corrosion effect is not
It can play completely.Therefore, the control of Mo contents is in 2.80~4.50%, preferably 2.80~3.50%.
Cu has service hoisting alloy anti-oxidation characteristics.When Cu contents are higher than 3.5%, the hot-working character of alloy is notable
Deteriorate.When Cu contents are less than 1.8%, antioxidation cannot play completely.Therefore, the control of Cu contents 1.80~
3.50%, preferably 1.90~3.20%.
Al primarily serves faint antioxidation in this alloy, and main function is to prevent alloy in electroslag remelting mistake
The serious scaling loss of Ti in journey.If do not added Al elements, then the scaling loss of Ti can not accurately control, but when Al is higher than 0.30%,
Inclusion content in alloy can be increased.Therefore, Al content control is 0.10~0.30%.
Ti has certain solution strengthening effect, but Ti atoms can be combined with Ni elements, forms Ni3Ti is precipitated, and plays
Strong precipitation strength effect, and Ti can fix the C in alloy, prevent its alloy sensitization when certain temperature is on active service from losing
Effect.But when Ti too high levels (more than 1.4%), η harmful phases are easily generated；(it is less than when Ti contents are too low
0.7%), the above effect cannot give full play to.Therefore, the control of Ti contents is in 0.70~1.40%, preferably 0.70~1.00%.
Nb Ta atomic radiuses 15%-18% big compared with Ni atomic radiuses, and it is substantially reduced the stacking fault energy of matrix, it rises
Strong solution strengthening effect；On the one hand, Nb can be such that the precipitated phase in alloy more stablizes.But Nb constituent contents are excessively high
(being higher than 2%), it can be combined with the C in matrix, form the primary carbide and band tissue of bulk, and it is solderable to reduce alloy
Property.Therefore, the sum of Nb and Ta contents control are 0.20~2.00%.
It is rotten to improving alloy proof stress in high temperature NaOH solution when Fe contents are in 24~34% (preferably 26~32%)
Erosion cracking performance improves significantly.
S, P, N are harmful element in alloy, need stringent control as requested.
In addition to above-mentioned element, Ni is the main base element of alloy, has good caustic corrosion effect.The present invention's
In alkali corrosion resistance nickel-base alloy, Ni contents are controlled about 40%~45%.This is primarily due to：When Ni contents are less than 40%
When, alkali corrosion resistance effect can not play completely, and local failure during being on active service can be caused to fail；But when Ni contents are higher than 45%
When, other elements in alloy can be caused to reduce, can not accomplish acid and alkali resistance, oxidation active balance.
The alkali corrosion resistance nickel-base alloy of the present invention may be used conventional method and be produced, and production stage includes mainly：Very
Sky induction smelting, electroslag remelting, homogenize, forge, hot extrusion, cold rolling are pulled out, are heat-treated.In the actual production process, ability
Field technique personnel can select suitable production technology according to actual conditions for each step.
Embodiment
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
Product specification selects.
Embodiment 1
The composition of the alkali corrosion resistance nickel-base alloy of the present embodiment is as shown in table 1.
The alkali corrosion resistance nickel-base alloy of the present embodiment is after vacuum induction+electric slag refusion and smelting technique, obtained electroslag
Ingot actual weight is 930Kg.ESR ingot composition quality per distribution ratio is：
0.02%C；0.05%Si；0.51%Mn；0.005%P；0.001%S；22.11%Cr；28.65%Fe；
3.11%Mo；1.97%Cu；0.20%Al；1.15%Ti；0.15% (Nb+Ta)；0.0036%N；
Remaining is Ni and inevitable impurity.
Cr+Ni=64.18%；Ti/Al=5.75；
ESR ingot homogenize system be 1200 DEG C/for 24 hours, forging temperature section is 1200 DEG C -950 DEG C, and extrusion temperature is
1180 DEG C, tubing is through three passage cold rollings, cold-drawn etc., final solution treatment system：1020 DEG C/30min water coolings, final finished pipe
Size is：Long 6480mm, outer diameter φ 112mm, wall thickness 3.5mm.
Embodiment 2
The composition of the alkali corrosion resistance nickel-base alloy of the present embodiment is as shown in table 1.
The alkali corrosion resistance nickel-base alloy of the present embodiment is after vacuum induction+electric slag refusion and smelting technique, obtained electroslag
Ingot actual weight is 3350Kg.ESR ingot composition quality per distribution ratio is：
0.015%C；0.15%Si；0.55%Mn；0.006%P；0.001%S；22.51%Cr；28.12%Fe；
3.22%Mo；2.05%Cu；0.18%Al；1.21%Ti；0.10% (Nb+Ta)；0.0044%N；
Remaining is Ni and inevitable impurity.
Cr+Ni=64.39%；Ti/Al=6.72；
ESR ingot homogenizes system as 1200 DEG C/20h, and forging temperature section is 1200 DEG C -930 DEG C, and extrusion temperature is
1185 DEG C, tubing is through four-pass cold rolling, cold-drawn etc., final solution treatment system：1040 DEG C/25min water coolings, final finished pipe
Size is：Long 6480mm, outer diameter φ 112mm, wall thickness 3.5mm.
Embodiment 3
The composition of the alkali corrosion resistance nickel-base alloy of the present embodiment is as shown in table 1.
The alkali corrosion resistance nickel-base alloy of the present embodiment is after vacuum induction+electric slag refusion and smelting technique, obtained electroslag
Ingot actual weight is 4700Kg.ESR ingot composition quality per distribution ratio is：
0.011%C；0.18%Si；0.62%Mn；0.007%P；0.001%S；22.39%Cr；26.41%Fe；
3.12%Mo；2.25%Cu；0.21%Al；1.17%Ti；0.18% (Nb+Ta)；0.0042%N；
Remaining is Ni and inevitable impurity.
Cr+Ni=65.83%；Ti/Al=5.57；
ESR ingot homogenize system be 1200 DEG C/for 24 hours, forging temperature section is 1200 DEG C -940 DEG C, and extrusion temperature is
1180 DEG C, tubing is through four-pass cold rolling, cold-drawn etc., final solution treatment system：1040 DEG C/30min water coolings, final finished pipe
Size is：Long 6480mm, outer diameter φ 112mm, wall thickness 3.5mm.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| C | 0.02% | 0.015% | 0.011% |
| Si | 0.05% | 0.15% | 0.18% |
| Mn | 0.51% | 0.55% | 0.62% |
| P | 0.005% | 0.006% | 0.007% |
| S | 0.001% | 0.001% | 0.001% |
| Cr | 22.11% | 22.51% | 22.39% |
| Fe | 28.65% | 28.12% | 26.41% |
| Mo | 3.11% | 3.22% | 3.12% |
| Cu | 1.97% | 2.05% | 2.25% |
| Al | 0.20% | 0.18% | 0.21% |
| Ti | 1.15% | 1.21% | 1.17% |
| Nb+Ta | 0.15% | 0.10% | 0.18% |
| N | 0.0036% | 0.0044% | 0.0042% |
| Cr+Ni | 64.18% | 64.39% | 65.83% |
| Ti/Al | 5.75 | 6.72 | 5.57 |
Embodiment 4：Performance test
Production tube prepared by embodiment 1 to 3 manages (specification with the pure Ni of military project grade：Long 6480mm, outer diameter φ 112mm, wall thickness
Alkali corrosion resistance performance 3.5mm) is compared.Specific method is：The production tube 5 prepared respectively with embodiment 1 to embodiment 3
It is used for kestner long-tube evaporator with film supplying tube (i.e. one group is 10) is organized with 5 conducts of the pure Ni pipes of military project grade, under identical service state
It is used and is compared.The results are shown in Table 2.
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | The pure Ni pipes of military project grade | |
| Active time | 9 months | 8 months | 8 months | 3-4 months |
From table 2 it can be seen that kestner long-tube evaporator inner tube is made in the alkali corrosion resistance nickel-base alloy of the present invention in use, it takes
Use as a servant 2 to 3 times that the time can be current pure Ni pipes.
In addition, pure Ni pipes are with high costs, the present invention is usually prepared instead of part Ni Ni-based with the lower-cost member such as Fe, Cr
Alloy can make manufacturing cost that can reduce by 30% to 40%.
The above embodiment is a preferred embodiment of the present invention, but the embodiment of present aspect is not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by substitute, modification, combination, change, simplify
Deng should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of alkali corrosion resistance nickel-base alloy, which is characterized in that according to mass percent meter, including following ingredient：C 0.01~
0.03%；Si≤0.3%；Mn 0.3~0.7%；P≤0.008%；S≤0.005%；Cr 20.00~25.00%；Fe 24
~34%；Mo 2.80~4.50%；Cu 1.80~3.50%；Ti 0.70~1.40%；N≤0.0120%；Remaining for Ni with
Inevitable impurity.
2. alkali corrosion resistance nickel-base alloy according to claim 1, which is characterized in that 62%≤Cr+Ni≤69%.
3. alkali corrosion resistance nickel-base alloy according to claim 1, which is characterized in that further include Nb and/or Ta, and 0.2
≤ Nb+Ta≤2.00%.
4. alkali corrosion resistance nickel-base alloy according to claim 1, which is characterized in that further include Al 0.10~0.30%.
5. alkali corrosion resistance nickel-base alloy according to claim 4, which is characterized in that Ti/Al >=5.0.
6. according to claim 1-5 any one of them alkali corrosion resistance nickel-base alloys, which is characterized in that according to mass percent
Meter, including following ingredient：C 0.01~0.02%；Si≤0.2%；Mn 0.4~0.6%；P≤0.008%；S≤0.002%；
Cr 21.00~23.00%；Fe 26~32%；Mo 2.80~3.50%；Cu 1.90~3.20%；Ti 0.70~
1.00%；N≤0.005%；Remaining is Ni and inevitable impurity.
7. purposes of the claim 1-6 any one of them alkali corrosion resistance nickel-base alloys in preparing kestner long-tube evaporator inner tube.
8. a kind of kestner long-tube evaporator inner tube, which is characterized in that use the Ni-based conjunction of claim 1-6 any one of them alkali corrosion resistances
Gold is prepared.
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| CN201810210111.3A CN108441703B (en) | 2018-03-14 | 2018-03-14 | Alkali corrosion resistant nickel-based alloy |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109502579A (en) * | 2018-11-27 | 2019-03-22 | 苏州中材非金属矿工业设计研究院有限公司 | The technique of natural graphite alkali acid system purification |
| CN111991822A (en) * | 2020-06-29 | 2020-11-27 | 山西太钢工程技术有限公司 | Inner tube of falling film tube and replacing method thereof |
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| CN101139676A (en) * | 2006-09-08 | 2008-03-12 | 上海空间电源研究所 | Proton exchange film fuel cell flow field board corrosion resistant alloy material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109502579A (en) * | 2018-11-27 | 2019-03-22 | 苏州中材非金属矿工业设计研究院有限公司 | The technique of natural graphite alkali acid system purification |
| CN111991822A (en) * | 2020-06-29 | 2020-11-27 | 山西太钢工程技术有限公司 | Inner tube of falling film tube and replacing method thereof |
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| CN108441703B (en) | 2020-11-03 |
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