CN108441703B - Alkali corrosion resistant nickel-based alloy - Google Patents
Alkali corrosion resistant nickel-based alloy Download PDFInfo
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- CN108441703B CN108441703B CN201810210111.3A CN201810210111A CN108441703B CN 108441703 B CN108441703 B CN 108441703B CN 201810210111 A CN201810210111 A CN 201810210111A CN 108441703 B CN108441703 B CN 108441703B
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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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Abstract
The invention provides an alkali corrosion resistant nickel-based alloy, which comprises the following components in percentage by mass: 0.01-0.03% of C; si is less than or equal to 0.3 percent; 0.3-0.7% of Mn; p is less than or equal to 0.008 percent; s is less than or equal to 0.005 percent; 20.00-25.00% of Cr; 24-34% of Fe; 2.80 to 4.50 percent of Mo; 1.80-3.50% of Cu; 0.70-1.40% of Ti; n is less than or equal to 0.0120 percent; the balance of Ni and inevitable impurities. The alkali corrosion resistant nickel-based alloy can be used as an inner pipe of a membrane evaporator, the service time of the alloy can be 2 to 3 times that of the prior pure Ni pipe, and the manufacturing cost can be reduced by 30 to 40 percent.
Description
Technical Field
The invention belongs to the field of metallurgy, and particularly relates to an alkali corrosion resistant nickel-based alloy.
Background
Caustic soda (NaOH) is a soluble strong base and is widely used in various industries such as textile, printing and dyeing, bleaching, papermaking, refined petroleum, metallurgy, chemistry and the like. Caustic soda can be divided into flake caustic soda, solid caustic soda and granular caustic soda according to forms, wherein the yield of flake caustic soda is highest, and a membrane evaporator is one of important devices for producing flake caustic soda. The membrane evaporator consists of two layers of sleeves, wherein the outer layer is filled with molten salt, the inner layer is filled with alkali liquor, and the two liquids are in countercurrent flow for heat transfer. After entering each membrane evaporator from the distributor, the alkali liquor is heated by jacket molten salt (temperature 325-. In the production process, the corrosion failure of the inner pipe of the membrane evaporator is the most common, so that the product quality and the production efficiency are seriously influenced, and the purchase price of the membrane evaporator is high.
The inner tube of the membrane evaporator is generally a military grade pure Ni tube at present, but in the production process of flake caustic soda, a small amount of complex corrosive elements (such as ClO) inevitably exist in the lye due to the fluctuation of the raw materials or the process for preparing the caustic soda-、[O]Etc.) to create a pure Ni tube sectionThe perforation and the crack are invalid, the service time is greatly shortened (the shortest service time is more than 20 days, namely perforation), and the equipment purchase cost is increased sharply.
Disclosure of Invention
The invention aims to provide an alkali corrosion resistant nickel-based alloy aiming at the defects in the prior art.
On one hand, the invention provides an alkali corrosion resistant nickel-based alloy which comprises the following components in percentage by mass: 0.01-0.03% of C; si is less than or equal to 0.3 percent; 0.3-0.7% of Mn; p is less than or equal to 0.008 percent; s is less than or equal to 0.005 percent; 20.00-25.00% of Cr; 24-34% of Fe; 2.80 to 4.50 percent of Mo; 1.80-3.50% of Cu; 0.70-1.40% of Ti; n is less than or equal to 0.0120 percent; the balance of Ni and inevitable impurities.
The alkali corrosion resistant nickel-based alloy has Cr + Ni of 62-69%.
The alkali corrosion resistant nickel-based alloy also comprises Nb and/or Ta, and Nb + Ta is more than or equal to 0.2 and less than or equal to 2.00 percent.
The alkali corrosion resistant nickel-based alloy further comprises 0.10-0.30% of Al.
In the alkali corrosion resistant nickel-based alloy, Ti/Al is more than or equal to 5.0.
The alkali corrosion resistant nickel-based alloy comprises the following components in percentage by mass: 0.01-0.02% of C; si is less than or equal to 0.2 percent; 0.4-0.6% of Mn; p is less than or equal to 0.008 percent; s is less than or equal to 0.002%; cr21.00-23.00%; 26-32% of Fe; mo2.80-3.50%; 1.90-3.20% of Cu; 0.70-1.00% of Ti; n is less than or equal to 0.005 percent; the balance of Ni and inevitable impurities.
In another aspect, the invention provides the use of the alkali corrosion resistant nickel-based alloy in the preparation of an inner tube of a membrane evaporator.
On the other hand, the invention provides a membrane evaporator inner tube which is prepared from the alkali corrosion resistant nickel-based alloy.
The alkali corrosion resistant nickel-based alloy can be used as an inner pipe of a membrane evaporator, the service time of the alloy can be 2-3 times that of the existing pure Ni pipe, and the manufacturing cost can be reduced by 30-40%.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention. The process of the present invention employs conventional methods or apparatus in the art, except as described below. The following noun terms have meanings commonly understood by those skilled in the art unless otherwise specified.
Aiming at the problems of local easy perforation and crack failure of the inner tube of the existing membrane evaporator, short service time, high equipment purchase cost and the like, the inventor of the invention optimizes the element composition and the proportion of the nickel-based alloy through research, thereby providing the alkali corrosion resistant nickel-based alloy. The alkali corrosion resistant nickel-based alloy comprises the following components in percentage by mass: 0.01-0.03% of C; si is less than or equal to 0.3 percent; 0.3-0.7% of Mn; p is less than or equal to 0.008 percent; s is less than or equal to 0.005 percent; 20.00-25.00% of Cr; 24-34% of Fe; 2.80 to 4.50 percent of Mo; 1.80-3.50% of Cu; 0.70-1.40% of Ti0.70; n is less than or equal to 0.0120 percent; the balance of Ni and inevitable impurities.
Preferably, in the alkali-corrosion-resistant nickel-based alloy of the present invention, the sum of the mass contents of Cr and Ni is: cr + Ni is more than or equal to 62% and less than or equal to 69%.
Preferably, the alkali corrosion resistant nickel-based alloy further comprises Nb and/or Ta, and 0.2 & lt Nb + Ta & lt 2.00%.
Preferably, the alkali corrosion resistant nickel-based alloy further comprises 0.10-0.30% of Al.
Preferably, in the alkali corrosion resistant nickel-based alloy, the mass ratio of Ti to Al satisfies that Ti/Al is more than or equal to 5.0.
In a preferred embodiment, the alkali-corrosion-resistant nickel-based alloy of the present invention comprises, in mass percent: 0.01-0.02% of C; si is less than or equal to 0.2 percent; 0.4-0.6% of Mn; p is less than or equal to 0.008 percent; s is less than or equal to 0.002%; 21.00-23.00% of Cr; 26-32% of Fe; 2.80 to 3.50 percent of Mo; 1.90-3.20% of Cu; 0.70-1.00% of Ti; n is less than or equal to 0.005 percent; the balance of Ni and inevitable impurities.
The inventor of the invention synthesizes the advantages and the disadvantages of the existing nickel-based alloy, optimizes the element composition and the proportion of the nickel-based alloy on the basis, and thereby provides the alkali corrosion resistant nickel-based alloy. Through the design of the invention, the elements are combined according to the proportion of the invention to generate a synergistic effect, and the alkali corrosion resistance is effectively improved, as follows.
C mainly plays a role in solid solution strengthening. When the C content is too low (i.e., less than 0.01%), the strengthening effect is insignificant. However, the content of C added is too high (i.e. more than 0.03%), on the one hand, C combines with Ti element in the alloy to form a large amount of primary TiC precipitates, thus degrading the performance; on the other hand, too high C content increases the intergranular corrosion tendency, decreasing the alloy toughness. Therefore, the C content is controlled to 0.01 to 0.03%, preferably 0.01 to 0.02%.
Si is a harmful element in the nickel-based alloy and can promote the precipitation of harmful phases. When the content of Si is more than 0.3 percent, harmful precipitated phases containing Si can be precipitated from grain boundaries when the alloy is in service at a certain temperature for a long time, so that the strength of the grain boundaries is weakened, and cracking is caused. Therefore, the Si content is controlled to 0.3% or less, preferably 0.2% or less.
Mn is a harmful element in pure Ni-based alloys containing no Fe, but can be added to Ni-based alloys containing a certain amount of Fe as appropriate to exert a solid solution strengthening effect. When the Mn content is too low (i.e., less than 0.3%), the strengthening effect is insignificant. However, the addition of Mn in an excessively high amount (i.e., more than 0.7%) causes the alloy to have reduced thermoplasticity, thereby causing forging cracks. Therefore, the Mn content is controlled to 0.3 to 0.7%, preferably 0.4 to 0.6%.
Cr is an indispensable alloying element and has the effects of solid solution strengthening and oxidation resistance. Cr plays an important role in forming Cr in a gamma matrix2O3The oxide film makes the alloy have good oxidation resistance and corrosion resistance. The inner tube of the membrane evaporator for alkali production mainly plays a role in resisting corrosion of free oxygen. When the Cr content is less than 20 percent, the free oxygen corrosion resistance of the alloy can not meet the requirement; however, when the Cr content is more than 25%, large Cr carbides are formed in the alloy, and the manufacturing cost is increased, and the contribution to oxidation resistance is not increased. Therefore, the Cr content is controlled to be 20.00-25.00%, preferably 21.00-23.00%.
Mo is a solid-solution strengthening element and has pitting corrosion resistance. When the Mo content is higher than 4.5%, the pitting corrosion resistance of the inner tube of the membrane evaporator for alkali production is excessive under the actual conventional working conditions. When the Mo content is less than 2.8%, the pitting corrosion resistance cannot be fully exerted. Therefore, the Mo content is controlled to be 2.80 to 4.50%, preferably 2.80 to 3.50%.
Cu has the characteristic of assisting in improving the oxidation resistance of the alloy. When the Cu content is more than 3.5%, the hot workability of the alloy is remarkably deteriorated. When the Cu content is less than 1.8%, the antioxidant effect thereof cannot be fully exerted. Therefore, the Cu content is controlled to be 1.80 to 3.50%, preferably 1.90 to 3.20%.
Al mainly plays a weak role in oxidation resistance in the alloy, and the main role of the Al is to prevent the serious burning loss of Ti in the electroslag remelting process of the alloy. If Al element is not added, the burning loss of Ti cannot be precisely controlled, but when Al is more than 0.30%, the inclusion content in the alloy increases. Therefore, the Al content is controlled to be 0.10 to 0.30%.
Ti has a certain solid solution strengthening effect, but Ti atoms can be combined with Ni element to form Ni3Ti is precipitated to play a strong precipitation strengthening role, and the Ti can fix C in the alloy and prevent the alloy from sensitization failure when the alloy is in service at a certain temperature. However, when the Ti content is too high (i.e., more than 1.4%), η harmful phase is easily generated; when the Ti content is too low (i.e., less than 0.7%), the above effect cannot be sufficiently exhibited. Therefore, the Ti content is controlled to 0.70 to 1.40%, preferably 0.70 to 1.00%.
The atomic radius of Nb or Ta is 15-18% larger than that of Ni, and the stacking fault energy of the matrix is obviously reduced, so that the strong solid solution strengthening effect is achieved; on the other hand, Nb can stabilize the precipitated phase in the alloy. However, an excessively high content of Nb element (i.e., greater than 2%) combines with C in the matrix, forming large primary carbides and a ribbon structure, and reducing the weldability of the alloy. Therefore, the sum of the Nb content and the Ta content is controlled to be 0.20-2.00%.
When the Fe content is 24-34% (preferably 26-32%), the stress corrosion cracking resistance of the alloy in a high-temperature NaOH solution is obviously improved.
S, P, N in the alloy is a harmful element and needs to be strictly controlled according to requirements.
In addition to the above elements, Ni is a main matrix element of the alloy, and has a good alkali corrosion effect. In the alkali corrosion resistant nickel-based alloy of the present invention, the Ni content is controlled to about 40% to 45%. This is mainly because: when the Ni content is lower than 40%, the alkali corrosion resistance of the alloy can not be fully exerted, and the local damage and failure in the service process can be caused; however, when the Ni content is higher than 45%, other elements in the alloy are reduced, and the effective balance of acid resistance, alkali resistance and oxidation cannot be achieved.
The alkali corrosion resistant nickel-based alloy can be produced by a conventional method, and the production steps mainly comprise: vacuum induction smelting, electroslag remelting, homogenization, forging, hot extrusion, cold rolling and drawing, heat treatment and the like. In the actual production process, a person skilled in the art can select a suitable production process for each step according to the actual situation.
Examples
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
The composition of the alkali-corrosion-resistant nickel-base alloy of the present example is shown in table 1.
The actual weight of the obtained electroslag ingot is 930Kg after the alkali corrosion resistant nickel-based alloy is subjected to vacuum induction and electroslag remelting smelting process. The electroslag ingot comprises the following components in percentage by mass:
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；
the balance of Ni and inevitable impurities.
Cr+Ni＝64.18％；Ti/Al＝5.75；
The electroslag ingot homogenization system is 1200 ℃/24h, the forging temperature interval is 1200-950 ℃, the hot extrusion temperature is 1180 ℃, the pipe is subjected to three times of cold rolling, cold drawing and the like, and the final solution treatment system is as follows: water cooling at 1020 ℃/30min, and the size of the final finished product pipe is as follows: the length is 6480mm, the outer diameter is 112mm, and the wall thickness is 3.5 mm.
Example 2
The composition of the alkali-corrosion-resistant nickel-base alloy of the present example is shown in table 1.
After the alkali corrosion resistant nickel-based alloy of the embodiment is subjected to vacuum induction and electroslag remelting smelting process, the actual weight of the obtained electroslag ingot is 3350 Kg. The electroslag ingot comprises the following components in percentage by mass:
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；
the balance of Ni and inevitable impurities.
Cr+Ni＝64.39％；Ti/Al＝6.72；
The electroslag ingot homogenization system is 1200 ℃/20h, the forging temperature interval is 1200-930 ℃, the hot extrusion temperature is 1185 ℃, the pipe is subjected to four-pass cold rolling, cold drawing and the like, and the final solution treatment system is as follows: water cooling at 1040 ℃/25min, and the size of the final finished product pipe is as follows: the length is 6480mm, the outer diameter is 112mm, and the wall thickness is 3.5 mm.
Example 3
The composition of the alkali-corrosion-resistant nickel-base alloy of the present example is shown in table 1.
After the alkali corrosion resistant nickel-based alloy of the embodiment is subjected to vacuum induction and electroslag remelting smelting process, the actual weight of the obtained electroslag ingot is 4700 Kg. The electroslag ingot comprises the following components in percentage by mass:
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；
the balance of Ni and inevitable impurities.
Cr+Ni＝65.83％；Ti/Al＝5.57；
The electroslag ingot homogenization system is 1200 ℃/24h, the forging temperature interval is 1200-940 ℃, the hot extrusion temperature is 1180 ℃, the pipe is subjected to four-pass cold rolling, cold drawing and the like, and the final solution treatment system is as follows: water cooling at 1040 ℃/30min, and the size of the final finished product pipe is as follows: the length is 6480mm, the outer diameter is 112mm, and the wall thickness is 3.5 mm.
TABLE 1
| Example 1 | Example 2 | Example 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 |
Example 4: performance testing
The finished pipes prepared in examples 1 to 3 were compared with military grade pure Ni pipes (specification: length 6480mm, external diameter. phi.112 mm, wall thickness 3.5mm) for their resistance to alkali corrosion. The specific method comprises the following steps: the finished tubes 5 prepared in examples 1 to 3 and the military grade pure Ni tubes 5 were used as the same group of falling film tubes (i.e., 10 tubes in one group) for the film evaporator, and were used in the same service condition and compared. The results are shown in Table 2.
TABLE 2
| Example 1 | Example 2 | Example 3 | Military grade pure Ni pipe | |
| Service time | 9 months old | 8 months old | 8 months old | 3-4 months |
As can be seen from Table 2, the service time of the inner tube of the membrane evaporator made of the alkali corrosion resistant nickel-based alloy can be 2 to 3 times that of the current pure Ni tube.
In addition, the cost of the pure Ni pipe is high, and the nickel-based alloy prepared by using elements with lower cost such as Fe, Cr and the like to replace partial Ni can reduce the manufacturing cost by 30 to 40 percent.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other substitutions, modifications, combinations, changes, simplifications, etc., which are made without departing from the spirit and principle of the present invention, should be regarded as equivalent substitutions, and are included in the scope of the present invention.
Claims (3)
1. The alkali corrosion resistant nickel-based alloy is characterized by comprising the following components in percentage by mass:
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; the balance of Ni and inevitable impurities.
2. Use of the alkali-corrosion resistant nickel-base alloy according to claim 1 for the production of an inner tube of a membrane evaporator.
3. A membrane evaporator inner tube, characterized in that it is made of the alkali-corrosion-resistant nickel-based alloy according to claim 1.
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| CN102744531A (en) * | 2012-07-31 | 2012-10-24 | 宝山钢铁股份有限公司 | Nickel-based alloy welding wire |
| JP2014040669A (en) * | 2013-10-10 | 2014-03-06 | Nippon Yakin Kogyo Co Ltd | High corrosion-resistant alloy excellent in intergranular corrosion resistance |
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| CN102744531A (en) * | 2012-07-31 | 2012-10-24 | 宝山钢铁股份有限公司 | Nickel-based alloy welding wire |
| JP2014040669A (en) * | 2013-10-10 | 2014-03-06 | Nippon Yakin Kogyo Co Ltd | High corrosion-resistant alloy excellent in intergranular corrosion resistance |
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