CN102644008A - High-temperature alloy super-heater pipe material for 700 DEG C ultra-supercritical fossil power generation unit and preparation method thereof - Google Patents
High-temperature alloy super-heater pipe material for 700 DEG C ultra-supercritical fossil power generation unit and preparation method thereof Download PDFInfo
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- CN102644008A CN102644008A CN2012100778381A CN201210077838A CN102644008A CN 102644008 A CN102644008 A CN 102644008A CN 2012100778381 A CN2012100778381 A CN 2012100778381A CN 201210077838 A CN201210077838 A CN 201210077838A CN 102644008 A CN102644008 A CN 102644008A
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Abstract
The invention relates to a high-temperature alloy super-heater pipe material for a 700 DEG C ultra-supercritical fossil power generation unit and a preparation method thereof. An alloy, comprising the components of 3% of w(C), 20% of w(Co), 0.5% of w(Mo), 2% of w(Nb), 1.8% of w(Ti), 0.9% of w(Al), 0.5% of w(Si), 0.3% of w(Mn), 0.7% of w(Fe), 0.5-2% of w(Sn), 23-24.5% of w(Cr) and a residual amount of w(Ni), is optimized to improve the machining properties of the alloy. Meanwhile, property requirements on the smoke resistance of a super-heater pipe material, and corrosion and anti-oxidation of deposited sulfates are met due to SnO2 with stable adhesiveness formed on the surface of the alloy. The high-temperature alloy super-heater pipe material has the advantage of wide application prospect.
Description
Technical field
The present invention relates to a kind of new superalloy superheater tubes material and preparation method thereof, particularly a kind of 700 ℃ of ultra supercritical thermal power station units belong to field of material preparation with superalloy superheater tubes material and preparation method thereof.
Background technology
Superheater tubes is the core material of 700 ℃ of ultra supercritical thermal power station units, the performance that depends primarily on superheater tubes work-ing life of 700 ℃ of ultra supercritical thermal power station units.Superheater tubes is life-time service under 700-750 ℃ of high temperature; Requirement has very high structure stability and creep rupture strength; Inside pipe wall is for a long time in the water vapor atmosphere of high pressure 30-40MPa; Be prone to pipe explosion accident takes place, this outer tube outer wall in atmosphere such as oxidation, sulfuration, very easily suffers thermal etching for a long time.In the highly developed epoch of current society,, the efficient of heat power station unit is also had higher requirement along with the important directions of the whole world urgent need solution energy and environment two large problems.As everyone knows, the erosion resistance of superheater tubes is good more, and work-ing life is long more, and the efficient of heat power station unit is just high more.At present; What common heat power station unit superheater tubes used is traditional ferritic, austenitic heat-resistance steel and nickel base superalloy; The superheater tubes of this quasi-tradition has higher strength and good oxidation-resistance property; Yet because Mo content is higher in these alloys, the ability of anti-flue gas corrosion and deposition sulphate corrosion very a little less than, and if be used for 700 ℃ of ultra supercritical thermal power station unit superheater tubes; Long service is in the high temperature more than 700 ℃, and its creep rupture strength can't satisfy condition.Present stage; Most 700 ℃ of ultra supercritical thermal power station unit superheater tubes adopt the Inconel740 alloy, and the Inconel740 alloy improves the massfraction of Cr in the common nickel base superalloy, and reduce the massfraction of Mo; Thereby its anti-steam and anti-flue gas corrosion ability have been improved; Form simultaneously the good Cr of adhesion, Al etc. and form and stablize sull, make that the diffusivity of the reactant in the oxidising process is very low, thereby improved its oxidation-resistance on its surface.But; Owing to improved the massfraction of Cr element in the Inconel740 alloy; Make the poor processability of alloy to be unfavorable for the moulding of superheater tubes, in the process of making this alloy large size thick-wall tube; Can occur the liquefaction tiny crack at welded heat affecting zone crystal boundary place, and in the process of 800 ℃ of long services, problem of unstable occur organizing owing to ag(e)ing process.These a series of problems to the Inconel740 alloy; The researcher of University of Science & Technology, Beijing passes through alloying constituent optimization on the basis of Inconel740 alloy; Invented the Inconel740H alloy; This research improves the massfraction of the Al element in the alloy simultaneously through reducing the massfraction of trace elements such as Nb, Ti, Si in the Inconel740 alloy, and this alloy has improved its surface-stable sull Al to a certain extent
2O
3Thickness; Thereby improved its oxidation-resistance; But its alloy processing characteristics does not improve, and the increase of superheater tubes interface dimensions and wall thickness makes the method for extrusion molding can't realize because of the restriction that receives maximum extrusion pressure, still need use the welding superheater tubes; Can occur the liquefaction tiny crack at welded heat affecting zone crystal boundary place, and in the process of 800 ℃ of long services, problem of unstable occur organizing owing to ag(e)ing process.
Though; Some 700 ℃ of ultra supercritical thermal power station units have been prepared at present with superalloy superheater tubes material; And had certain performance; But this can not satisfy the requirement of superheater tubes far away, and novel 700 ℃ of ultra supercritical thermal power stations of preparation unit has been imperative with the development and the exploitation of superalloy superheater tubes material.Therefore, seek and research and develop 700 ℃ of new ultra supercritical thermal power station units become this area with superalloy superheater tubes material subject matter.
Summary of the invention
The objective of the invention is to have poor processability, be unfavorable for problems such as superheater tube material forming, provide a kind of 700 ℃ of novel ultra supercritical thermal power station units with superalloy superheater tubes material and preparation method thereof to existing superheater tubes material.
The technical solution that realizes the object of the invention is: a kind of 700 ℃ of ultra supercritical thermal power station units are with superalloy superheater tubes material, and the alloying constituent of described pipe material is: w (C) is 3%, and w (Co) is 20%, and w (Mo) is 0.5%; W (Nb) is 2%, and w (Ti) is 1.8%, and w (Al) is 0.9%; W (Si) is 0.5%, and w (Mn) is 0.3%, and w (Fe) is 0.7%; W (Sn) is 0.5-2%, and w (Cr) is 23-24.5%, and all the other are w (Ni).
Above-mentioned superheater tubes material specifically may further comprise the steps by following method preparation:
Step 1, the Inconel740 alloy after will optimizing adopt vacuum induction melting method to be smelt the alloy spindle;
Step 2, the spindle in the step 1 is carried out remelting, obtain new alloy spindle with the vacuum arc melting method;
Step 3, new alloy spindle is carried out diffusion annealing;
Step 4, the alloy spindle after will annealing are processed into tubing;
Step 5, alloy pipe is being carried out the shrend solution treatment.
Inconel740 alloying constituent after optimizing described in the step 1 is that w (C) is 3%, and w (Co) is 20%, and w (Mo) is 0.5%; W (Nb) is 2%, and w (Ti) is 1.8%, and w (Al) is 0.9%; W (Si) is 0.5%, and w (Mn) is 0.3%, and w (Fe) is 0.7%; W (Sn) is 0.5-2%, and w (Cr) is 23-24.5%, and all the other are w (Ni).
Annealing temperature described in the step 3 is 1250-1300 ℃, and described annealing time is 15-18h.
Processing temperature in the step 4 is 1050-1100 ℃.
Treatment temp described in the step 5 is 1150 ℃, and the described treatment time is 1h.
Compared with prior art, of the present invention have a significant beneficial effect:
(1) 700 ℃ of ultra supercritical thermal power station units through the present invention preparation use superalloy superheater tubes material to contain Sn to measure and be 0.5-2%.
(2) 700 ℃ of ultra supercritical thermal power station units through the present invention preparation have good alloy processing characteristics with superalloy superheater tubes material, prepare superheater tubes and can use extrusion molding, need not welding fabrication.
(3) 700 ℃ of ultra supercritical thermal power station units through the present invention preparation have the anti-steam oxidation performance of excellence with superalloy superheater tubes material.
(4) 700 ℃ of ultra supercritical thermal power station units through the present invention preparation have excellent anti-flue gas and deposit the sulphate corrosion performance with superalloy superheater tubes material.
(5) 700 ℃ of ultra supercritical thermal power station units through the present invention preparation are with superalloy superheater tubes material, and its enduring quality is remarkable, can satisfy the working conditions of 700 ℃ of ultra supercritical units.
Embodiment
The superheater tubes of preparing among each embodiment among the present invention carries out 1000 ℃ of oxidation tests respectively and in the fluidizing air that contains 10% or 15% water vapour, carries out 800 ℃ of oxidation tests in still air, test its corrosion resistance nature.
Embodiment 1:
At first, the selection alloying constituent is that w (C) is 3%, and w (Cr) is 24.5%, and w (Co) is 20%, and w (Mo) is 0.5%, and w (Nb) is 2%, and w (Ti) is 1.8%, and w (Al) is 0.9%, and w (Si) is 0.5%, and w (Mn) is 0.3%, and w (Fe) is 0.7%, and w (Sn) is 0.5%, and all the other are w (Ni).
Secondly, above-mentioned alloy is carried out following processing:
Step 1, the Inconel740 alloy after will optimizing adopt vacuum induction melting method to be smelt the alloy spindle;
Step 2, the spindle in the step 1 is carried out remelting, obtain new alloy spindle with the vacuum arc melting method;
Step 3, with new alloy spindle 1300 ℃ of diffusion annealings of carrying out 15h;
Step 4, the alloy spindle after will annealing are processed into tubing under 1050 ℃;
Step 5, alloy pipe is being carried out making superheater tubes according to the invention after the 1h shrend solution treatment under 1150 ℃ of conditions.
The superheater tubes that makes is carried out oxidation test respectively and in flowing gas, carries out the steam oxidation test in still air; The result shows alloy No oxided film peeling phenomenon in 1000 ℃ of oxidation 220h; Under 800 ℃, contain oxidation in the air of 10% water vapour; At the oxidation initial stage, oxidation weight gain is very fast, and corrosion speed is slowed down and steadily subsequently.
Embodiment 2:
At first, the selection alloying constituent is that w (C) is 3%, and w (Cr) is 24%, and w (Co) is 20%, and w (Mo) is 0.5%, and w (Nb) is 2%, and w (Ti) is 1.8%, and w (Al) is 0.9%, and w (Si) is 0.5%, and w (Mn) is 0.3%, and w (Fe) is 0.7%, and w (Sn) is 1%, and all the other are w (Ni).
Secondly, above-mentioned alloy is carried out following processing:
Step 1, the Inconel740 alloy after will optimizing adopt vacuum induction melting method to be smelt the alloy spindle;
Step 2, the spindle in the step 1 is carried out remelting, obtain new alloy spindle with the vacuum arc melting method;
Step 3, with new alloy spindle 1250 ℃ of diffusion annealings of carrying out 16h;
Step 4, the alloy spindle after will annealing are processed into tubing under 1100 ℃;
Step 5, alloy pipe is being carried out making superheater tubes according to the invention after the 1h shrend solution treatment under 1150 ℃ of conditions.
The hot organ pipe material that makes is carried out oxidation test respectively and in flowing gas, carries out the steam oxidation test in still air; The result shows alloy No oxided film peeling phenomenon in 1000 ℃ of oxidation 250h; Under 800 ℃, contain oxidation in the air of 15% water vapour; At the oxidation initial stage, oxidation weight gain is very fast, and corrosion speed is slowed down and steadily subsequently.
Embodiment 3
At first, the selection alloying constituent is that w (C) is 3%, and w (Cr) is 23.5%, and w (Co) is 20%, and w (Mo) is 0.5%, and w (Nb) is 2%, and w (Ti) is 1.8%, and w (Al) is 0.9%, and w (Si) is 0.5%, and w (Mn) is 0.3%, and w (Fe) is 0.7%, and w (Sn) is 1.5%, and all the other are w (Ni).
Secondly, above-mentioned alloy is carried out following processing:
Step 1, the Inconel740 alloy after will optimizing adopt vacuum induction melting method to be smelt the alloy spindle;
Step 2, the spindle in the step 1 is carried out remelting, obtain new alloy spindle with the vacuum arc melting method;
Step 3, with new alloy spindle 1280 ℃ of diffusion annealings of carrying out 18h;
Step 4, the alloy spindle after will annealing are processed into tubing under 1080 ℃;
Step 5, alloy pipe is being carried out making superheater tubes according to the invention after the 1h shrend solution treatment under 1150 ℃ of conditions.
The hot organ pipe material that makes is carried out oxidation test respectively and in flowing gas, carries out the steam oxidation test in still air; The result shows alloy No oxided film peeling phenomenon in 1000 ℃ of oxidation 245h; Under 800 ℃, contain oxidation in the air of 10% water vapour; At the oxidation initial stage, oxidation weight gain is very fast, and corrosion speed is slowed down and steadily subsequently.
Embodiment 4
At first, the selection alloying constituent is that w (C) is 3%, and w (Cr) is 23%, and w (Co) is 20%, and w (Mo) is 0.5%, and w (Nb) is 2%, and w (Ti) is 1.8%, and w (Al) is 0.9%, and w (Si) is 0.5%, and w (Mn) is 0.3%, and w (Fe) is 0.7%, and w (Sn) is 2%, and all the other are w (Ni).
Secondly, above-mentioned alloy is carried out following processing:
Step 1, the Inconel740 alloy after will optimizing adopt vacuum induction melting method to be smelt the alloy spindle;
Step 2, the spindle in the step 1 is carried out remelting, obtain new alloy spindle with the vacuum arc melting method;
Step 3, with new alloy spindle 1300 ℃ of diffusion annealings of carrying out 18h;
Step 4, the alloy spindle after will annealing are processed into tubing under 1100 ℃;
Step 5, alloy pipe is being carried out making superheater tubes according to the invention after the 1h shrend solution treatment under 1150 ℃ of conditions.
The hot organ pipe material that makes is carried out oxidation test respectively and in flowing gas, carries out the steam oxidation test in still air; The result shows alloy No oxided film peeling phenomenon in 1000 ℃ of oxidation 230h; Under 800 ℃, contain oxidation in the air of 15% water vapour; At the oxidation initial stage, oxidation weight gain is very fast, and corrosion speed is slowed down and steadily subsequently.
Claims (8)
1. one kind 700 ℃ ultra supercritical thermal power station units is characterized in that with superalloy superheater tubes preparation methods the preparation method of said tubing may further comprise the steps:
Step 1, the Inconel740 alloy after will optimizing adopt vacuum induction melting method to be smelt the alloy spindle;
Step 2, the spindle in the step 1 is carried out remelting, obtain new alloy spindle with the vacuum arc melting method;
Step 3, new alloy spindle is carried out diffusion annealing;
Step 4, the alloy spindle after will annealing are processed into tubing;
Step 5, alloy pipe is being carried out the shrend solution treatment.
According to 700 ℃ of ultra supercritical thermal power station units described in the claim 1 with superalloy superheater tubes preparation methods, the composition of the Inconel740 alloy after it is characterized in that described in the step 1 optimizing is w (C): 3%, w (Co): 20%, w (Mo): 0.5%; W (Nb): 2%, w (Ti): 1.8%, w (Al): 0.9%; W (Si): 0.5%, w (Mn): 0.3%, w (Fe): 0.7%; W (Sn): 0.5-2%, w (Cr): 23-24.5%, all the other are w (Ni).
According to 700 ℃ of ultra supercritical thermal power station units described in the claim 1 with superalloy superheater tubes preparation methods, it is characterized in that the annealing temperature described in the step 3 is 1250-1300 ℃, described annealing time is 15-18h.
According to 700 ℃ of ultra supercritical thermal power station units described in the claim 1 with superalloy superheater tubes preparation methods, it is characterized in that the processing temperature in the step 4 is 1050-1100 ℃.
According to 700 ℃ of ultra supercritical thermal power station units described in the claim 1 with superalloy superheater tubes preparation methods, it is characterized in that the treatment temp described in the step 5 is 1150 ℃, the described treatment time is 1h.
6. one kind 700 ℃ ultra supercritical thermal power station units are with superalloy superheater tubes material, and it is characterized in that the alloying constituent of described pipe material is: w (C) is 3%, and w (Co) is 20%, and w (Mo) is 0.5%; W (Nb) is 2%, and w (Ti) is 1.8%, and w (Al) is 0.9%; W (Si) is 0.5%, and w (Mn) is 0.3%, and w (Fe) is 0.7%; W (Sn) is 0.5-2%, and w (Cr) is 23-24.5%, and all the other are w (Ni).
7. 700 ℃ of ultra supercritical thermal power station units according to claim 6 is characterized in that with superalloy superheater tubes material described pipe material prepares through following method:
Step 1, the Inconel740 alloy after will optimizing adopt vacuum induction melting method to be smelt the alloy spindle;
Step 2, the spindle in the step 1 is carried out remelting, obtain new alloy spindle with the vacuum arc melting method;
Step 3, new alloy spindle is carried out diffusion annealing;
Step 4, the alloy spindle after will annealing are processed into tubing;
Step 5, alloy pipe is being carried out the shrend solution treatment.
According to claim 6 or 7 described 700 ℃ of ultra supercritical thermal power station units with superalloy superheater tubes material, the Inconel740 alloying constituent after it is characterized in that optimizing described in the step 1 is that w (C) is 3%, w (Co) is 20%, w (Mo) is 0.5%; W (Nb) is 2%, and w (Ti) is 1.8%, and w (Al) is 0.9%; W (Si) is 0.5%, and w (Mn) is 0.3%, and w (Fe) is 0.7%; W (Sn) is 0.5-2%, and w (Cr) is 23-24.5%, and all the other are w (Ni); Annealing temperature described in the step 3 is 1250-1300 ℃, and described annealing time is 15-18h; Processing temperature in the step 4 is 1050-1100 ℃; Treatment temp described in the step 5 is 1150 ℃, and the described treatment time is 1h.
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| CN2012100778381A CN102644008A (en) | 2012-03-22 | 2012-03-22 | High-temperature alloy super-heater pipe material for 700 DEG C ultra-supercritical fossil power generation unit and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276251A (en) * | 2013-05-29 | 2013-09-04 | 钢铁研究总院 | Boiler tube for 700 DEG C steam parameter thermal power generating unit and preparation method thereof |
| CN105784772A (en) * | 2016-05-10 | 2016-07-20 | 华能国际电力股份有限公司 | System and method for real furnace verification on novel high-temperature alloy material and component |
| CN107513641A (en) * | 2017-08-11 | 2017-12-26 | 东北大学 | A kind of technique for preparing advanced ultra supercritical heat-resisting alloy |
| CN109190311A (en) * | 2018-10-29 | 2019-01-11 | 华能国际电力股份有限公司 | Ultra supercritical coal-fired unit austenitic heat-resistance steel spalling of oxide film prediction model |
-
2012
- 2012-03-22 CN CN2012100778381A patent/CN102644008A/en active Pending
Non-Patent Citations (2)
| Title |
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| 赵双群等: "Inconel 740合金在空气和含有水蒸气的空气中的氧化研究", 《动力工程学报》 * |
| 赵双群等: "新一代超级超临界锅炉过热器用管材Inconel 740", 《钢铁研究学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276251A (en) * | 2013-05-29 | 2013-09-04 | 钢铁研究总院 | Boiler tube for 700 DEG C steam parameter thermal power generating unit and preparation method thereof |
| CN103276251B (en) * | 2013-05-29 | 2015-04-29 | 钢铁研究总院 | Boiler tube for 700 DEG C steam parameter thermal power generating unit and preparation method thereof |
| CN105784772A (en) * | 2016-05-10 | 2016-07-20 | 华能国际电力股份有限公司 | System and method for real furnace verification on novel high-temperature alloy material and component |
| CN107513641A (en) * | 2017-08-11 | 2017-12-26 | 东北大学 | A kind of technique for preparing advanced ultra supercritical heat-resisting alloy |
| CN109190311A (en) * | 2018-10-29 | 2019-01-11 | 华能国际电力股份有限公司 | Ultra supercritical coal-fired unit austenitic heat-resistance steel spalling of oxide film prediction model |
| CN109190311B (en) * | 2018-10-29 | 2023-02-17 | 华能国际电力股份有限公司 | Method for predicting oxide film peeling of austenitic heat-resistant steel for ultra-supercritical thermal power generating unit |
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Application publication date: 20120822 |