CN105039827B - Microalloying 35Cr45NiNb alloy steel for ethylene cracking furnace pipe - Google Patents
Microalloying 35Cr45NiNb alloy steel for ethylene cracking furnace pipe Download PDFInfo
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Abstract
The invention discloses microalloyed 35Cr45NiNb alloy steel for an ethylene cracking furnace tube, which comprises the following components in percentage by mass: 0.40 to 0.50, Si: 1.20 to 1.80, Mn: 0.60 to 1.20, P: 0.001 to 0.020, S: 0.001 to 0.010, Cr: 35-36, Ni: 45-46, Nb: 0.80 to 1.50, W: 0.005 to 0.20, Mo: 0.005 to 0.20, Cu: 0.005 to 0.30, Al: 0.005 to 0.20, Ti: 0.05 to 0.10, Zr: 0.05-0.10, B: 0.0010 to 0.0050, As: 0-0.0020, Sn: 0-0.0020, Pb: 0 to 0.0020, Bi: 0 to 0.0001, and the balance Fe. The alloy steel requires that the percentage of columnar crystals in the wall thickness is more than 70 percent, and the grain size grade is 5-6 grade. The invention can effectively improve the high-temperature endurance of the ethylene cracking furnace tube, so that the requirement that the high-temperature endurance fracture time is more than 100 hours under the conditions of 1100 ℃ and 17MPa is met, and the aim of ensuring the long-period safe operation of an ethylene cracking furnace device is fulfilled.
Description
Technical field
The invention belongs to ethylene cracking tube field of material technology, and in particular to a kind of effective microalloying of ethane cracking furnace
35Cr45NiNb steel alloys.
Background technology
Ethylene cracking tube is widely used in the mainstay of the national economy such as petrochemical industry, electric power, metallurgy, combustion gas field, once hair
Raw failure will have a strong impact on the long period safe operation of package unit.In recent years, ethane cracking furnace is gradually to high parameter and large-scale
Change direction to develop, ethylene cracking tube military service operating mode is all the more complicated and harsh, the high-temperature behavior to ethylene cracking tube is proposed more
High requirement.The actual service life of the domestic ethylene cracking tube come into operation in the market is very different, the reality of a large amount of boiler tubes
Border service life even 1/3rd of only original projected life, failure accidents happen occasionally, and give petrochemical industry device for producing hydrogen
Long period safe operation bring very big hidden danger.Therefore, how to improve the high-temperature behavior of ethylene cracking tube turns at present urgently
Realistic problem to be solved.
HG/T2601-2011《High-temperature bearing centrifugal casting alloy furnace tubes by adopting》Middle regulation is to 35Cr45NiNb+ microalloy materials
The high temperature endurance performance of material is required as under the conditions of 1100 DEG C, 17MPa, high-temperature and durable rupture time is more than 100 hours.However, mesh
The high-temperature and durable rupture time of preceding domestic boiler tube can not still fully meet requirements above, cause boiler tube quality stability poor, frequency
Numerous generation initial failure, has a strong impact on device long period safe operation.
The content of the invention
There is provided a kind of high temperature of effective lifting ethylene cracking tube in order to overcome the above-mentioned deficiencies of the prior art by the present invention
Enduring quality and then the effective microalloying of ethane cracking furnace for ensureing cracking of ethylene furnace apparatus long period safe operation
35Cr45NiNb steel alloys.
To achieve the above object, present invention employs following technical scheme：
A kind of effective microalloying 35Cr45NiNb steel alloys of ethane cracking furnace, by percentage to the quality, contain C：0.40
~0.50, Si：1.20~1.80, Mn：0.60~1.20, P：0.001~0.020, S：0.001~0.010, Cr：35~36,
Ni：45~46, Nb：0.80~1.50, W：0.005~0.20, Mo：0.005~0.20, Cu：0.005~0.30, Al：0.005
~0.20, Ti：0.05~0.10, Zr：0.05~0.10, B：0.0010~0.0050, As：0~0.0020, Sn：0~
0.0020, Pb：0~0.0020, Bi：0~0.0001, surplus is Fe.
It is preferred that, column crystal accounts for wall thickness percentage more than 70%, and grain size number is 5~6 grades.
Shadow of the above-mentioned each element to the effective microalloying 35Cr45NiNb alloys steel high temperature resistant enduring quality of ethane cracking furnace
Sound is as follows：
1.C (0.40~0.50 mass %)
C and Cr, Mo, Ti, V, Nb etc. form primary carbide M7C3With NbC etc., improve material at high temperature intensity.In high temperature
During effect, the super saturated solid solution carbon in matrix is with the M of small and dispersed23C6Separate out, low-alloyed toughness can be dropped, deteriorate welding
Property, therefore, the phosphorus content in the material is 0.4~0.5 mass %.
2.Si (1.20~1.80 mass %)
Si is necessary deoxidier when smelting, and can improve mobility of the molten steel in casting.Si, which is dissolved in austenite, to be carried
The hardness and intensity of high material, meanwhile, in high temperature oxidative atmosphere, Si and O combines to form SiO2Film, improves the high temperature of boiler tube
Antioxygenic property.Si is easy to produce segregation in the higher environment of Ni contents, and Low melting point eutectic is formed on crystal boundary, is easily led
Welding hot crack tendency is caused, deteriorates the welding performance of material.Si is to promote σ phases to separate out element to exist, and addition excessively holds reduction
Long intensity.Therefore, the si content in the material is 1.2~1.8 mass %.
3.Mn (0.60~1.20 mass %)
Mn is to expand austenite phase p-block element p, and the MnS of nodularization is generated with S, S harm can be eliminated, can also improve weldability
Energy.But Mn elements promote σ phases to separate out, and low-alloyed antioxygenic property can excessively drop in addition.Therefore, the amount containing Mn in the material
For 0.6~1.2 mass %.
4.P (0.001~0.020 mass %)
P element is had a significant impact to creep rupture strength, with the increase of P element content, and creep rupture strength is reduced, due to
P element can produce segregation in heat treatment process, promote the forming core in cavity.Therefore, considering high-temperature and durable rupture time will
P content in summation financial cost factor, the material is 0.001~0.020 mass %.
5.S (0.001~0.010 mass %)
S constituent contents have a significant impact to high-temperature duration life, with the increase of S elements, creep rupture strength reduction.
This is due to that sulphur segregation is empty because the adhesion of sulfide and matrix is poor to crystal boundary formation sulfide in heat treatment process
Hole is easy to forming core, at high operating temperatures because stress raisers cause cavity connection so as to produce micro-crack, causes boiler tube
Rapid failure.Therefore, the requirement of high-temperature and durable rupture time and financial cost factor are considered, the amount containing S in the material is
0.001~0.010 mass %.
6.Cr (35~36 mass %)
Cr elements are main solution strengthening elements and carbide former in alloy.Cr elements are formed in material surface
Fine and close Cr2O3Diaphragm, can play a decisive role to the anti-oxidant of alloy, intensity, anti-carburizing.But Cr too high levels can be led
σ phases are caused to separate out, so as to drop low-alloyed intensity and toughness.Therefore, the amount containing Cr in the material is 35~36 mass %.
7.Ni (45~46 mass %)
Ni elements are to be formed and stable austenite, improve the essential element of impervious carbon, anti-oxidant, elevated temperature strength and toughness,
The intensity of material can be improved without significantly reducing its toughness, improve the processability and solderability of material.It is former that Ni atoms will reduce C
The solubility of son in the alloy, excessive add can cause the carbide of excess to separate out.Therefore, the ni content in the material is 45
~46 mass %.
8.Nb (0.80~1.50 mass %)
The NbC that Nb elements formation crystal boundary is separated out, effectively improves the intensity of material, while making crystal boundary chromium carbide even dispersion point
Cloth, postpones Carbide Coarsening process, so as to improve the elevated temperature strength of alloy.Therefore, the amount containing Nb in the material is 0.8~1.5
Quality %.
9.W (0.005~0.20 mass %)
W elements are solution strengthening elements, can improve the elevated temperature strength of alloy, suppress Carbon diffusion speed, but added
Amount can then influence the antioxygenic property of alloy, and promote σ phases to separate out, and drop low-alloyed intensity and toughness.Therefore, in the material
Amount containing W is 0.005~0.20 mass %.
10.Mo (0.005~0.20 mass %)
Mo elements are solution strengthening elements, can improve the elevated temperature strength of alloy, suppress Carbon diffusion speed, but added
Amount can then influence the antioxygenic property of alloy, and promote σ phases to separate out, and drop low-alloyed intensity and toughness.Therefore, in the material
Amount containing Mo is 0.005~0.20 mass %.
11.Cu (0.005~0.30 mass %)
Cu elements are the elements for expanding austenite phase field, improve the strength of materials and yield tensile ratio, but Cu constituent contents are too high
Copper brittleness is also easy to produce in hot procedure, causes cracking.Therefore, the amount containing Cu in the material is 0.005~0.30 mass %.
12.Al (0.005~0.20 mass %)
Al elements are used for deoxidation in casting process, while heat resistance can be improved with Ni formation compounds.But Al elements
Too high levels can promote σ phases during long-term creep to be formed and be roughened, and reduce creep life.Therefore, the amount containing Al in the material is
0.005~0.20 mass %.
13.Ti (0.05~0.10 mass %)
When Ti constituent contents are more than 0.10 mass %, the strength of materials can be improved in crystal boundary formation titanium carbide.Therefore, the material
Amount containing Ti in material is 0.05~0.10 mass %.
14.Zr (0.05~0.10 mass %)
Co elements can improve the antioxygenic property of material, while significantly improving the heat resistance and high temperature hardness of material.Therefore,
Amount containing Zr in the material is 0.05~0.10 mass %.
15.B (0.0010~0.0050 mass %)
B element has crystal grain thinning, improves grain morphology, and purification impurity etc. is acted on.The quenching degree of material can be improved simultaneously
And elevated temperature strength.B addition can not only play suppression S elements to the Free Surface segregation such as room formation sulfide, but also
The species and form of cemented zone carbide can be changed.Therefore, the amount containing B in the material is 0.0010~0.0050 mass %.
16.As (0~0.0020 mass %)
As elements are in the material often with Fe2As,Fe3As2, FeAs and solid solution thereof exist, easily occur segregation phenomena, make
The fragility increase of material, elongation percentage, the contraction percentage of area and impact flexibility reduction, and influence welding.Therefore, consider high temperature to hold
Amount containing As in long rupture time requirement and financial cost factor, the material is 0~0.0020 mass %.
17.Sn (0~0.0020 mass %)
Sn elements can substantially reduce the high-temperature mechanical property of alloy, and the processing characteristics to alloy is also extremely harmful.Therefore, it is comprehensive
It is 0~0.0020 mass % to close the amount containing Sn considered in the requirement of high-temperature and durable rupture time and financial cost factor, the material.
18.Pb (0~0.0020 mass %)
Pb elements are in the case of drawing by high temperature stress, to Grain Boundary Segregation, reduce surface energy, promote Creep hole
Germinating, ultimately results in the reduction of high temperature endurance performance.Therefore, consider the requirement of high-temperature and durable rupture time and financial cost because
Amount containing Pb in element, the material is 0~0.0020 mass %.
19.Bi (0~0.0001 mass %)
Bi elements are similar with Pb elements, and Bi elements reduce boundary surfaces energy to Grain Boundary Segregation, increase cavity nucleation rate.Cause
This, considers the requirement of high-temperature and durable rupture time and financial cost factor, and the amount containing Bi in the material is 0~0.0001 matter
Measure %.
20. column crystal accounts for wall thickness percentage more than 70%
The column crystal of furnace tube material in the present invention accounts for wall thickness percentage requirement more than 70%, can lift the high temperature of steel alloy
Performance.When column crystal account for wall thickness percentage it is higher when, primary carbide separate out form preferably (i.e. skeletal like form), warmly taken in height
On Dislocation Motion plays effectively pin effect in the case of labour, improves the high-temperature behavior of material.
21. grain size number is 5~6 grades
The grain size number area requirement of furnace tube material in the present invention is 5~6 grades, can effectively lift the height of steel alloy
Warm nature energy.The influence of grain size number is different mainly due to grain size, and the number of grain boundaries of unit area is different, the side of crystal boundary one
Face hinders the sliding of dislocation to play on invigoration effect, another aspect crystal boundary because diffusion carries out providing logical to dislocation climb rapidly
Road, promotes dislocation to play emollescence in climbing for its close region.Crystal grain is spent thick or meticulous is unfavorable for material at high temperature
Performance.
The beneficial effects of the present invention are：
The present invention proposes a kind of effective microalloying 35Cr45NiNb steel alloys of ethane cracking furnace, by various beneficial
Element carries out the mixing ratio of certain mass, is effectively improved the high-temperature and durable rupture time of ethylene cracking tube, has ensured dress
The long period safe operation put.
Embodiment
Below in conjunction with the subordinate list in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
It should be noted that the furnace tube material in the present invention uses customary preparation methods.
Embodiment 1
A kind of effective microalloying 35Cr45NiNb steel alloys of ethane cracking furnace, its chemical composition is shown in Table 1.
The effective microalloying 35Cr45NiNb alloy steel chemical compositions of the ethane cracking furnace of table 1
Note：In units of mass percent.
After tested, the column crystal after chloroazotic acid etch of the microalloying 25Cr35NiNb boiler tubes in the present embodiment accounts for wall thickness percentage
Than for 100%, it is 5.8 grades of level to evaluate its grain size number after the oxalic acid aqueous solution electro-etching for being 10% through volume fraction.
To with matched in table 1 the 35Cr45NiNb+ microalloy furnace tubes sample of making carry out respectively 3 times 1100 DEG C, 17MPa try
High temperature resistant creep rupture test under the conditions of testing, gained test result is as shown in table 2.
The microalloying 35Cr45NiNb furnace tube high temperature duration running results of table 2
From stress-rupture tester result, meet present component scope, column crystal and account for wall thickness percentage and grain size
The material at high temperature creep rupture strength of class requirement meets high-temperature and durable rupture time more than 100h.
Embodiment 2
A kind of effective microalloying 35Cr45NiNb alloy steel chemical compositions of ethane cracking furnace are shown in Table 3.
The effective microalloying 35Cr45NiNb alloy steel chemical compositions of the ethane cracking furnace of table 3
Note：In units of mass percent.
After tested, the column crystal after chloroazotic acid etch of the microalloying 25Cr35NiNb boiler tubes in the present embodiment accounts for wall thickness percentage
Than for 100%, it is 5.0 grades to evaluate its grain size number after the oxalic acid aqueous solution electro-etching for being 10% through volume fraction.
To with matched in table 3 the 35Cr45NiNb+ microalloy furnace tubes sample of making carry out respectively 3 times 1100 DEG C, 17MPa try
High temperature resistant creep rupture test under the conditions of testing, gained test result is as shown in table 4.
The 35Cr45NiNb+ microalloy furnace tube stress-rupture tester results of table 4
From stress-rupture tester result, meet present component scope, column crystal and account for wall thickness percentage and grain size
The material at high temperature creep rupture strength of class requirement meets high-temperature and durable rupture time more than 100h.
Comparative example 1
A kind of effective 35Cr45NiNb+ microalloys material of ethane cracking furnace, its chemical composition is shown in Table 5.
The effective microalloying 35Cr45NiNb alloy steel chemical compositions of the ethane cracking furnace of table 5
Note：In units of mass percent.
After tested, the column crystal after chloroazotic acid etch of the microalloying 25Cr35NiNb boiler tubes in the present embodiment accounts for wall thickness percentage
Than for 60%, it is 5.5 grades to evaluate its grain size number after the oxalic acid aqueous solution electro-etching for being 10% through volume fraction.
To with matched in table 5 the 35Cr45NiNb+ microalloy furnace tubes sample of making carry out respectively 3 times 1100 DEG C, 17MPa try
High temperature resistant creep rupture test under the conditions of testing, gained test result is as shown in table 6.
The 35Cr45NiNb+ microalloy furnace tube stress-rupture tester results of table 6
Al, Ti, Zr elemental composition do not provide material in the present invention in chemical composition result, the boiler tube composition
In composition range, and its column crystal accounts for the requirement that wall thickness percentage is unsatisfactory for being more than 70%, and its high-temperature and durable rupture time is less than
100h。
Comparative example 2
A kind of effective 35Cr45NiNb+ microalloys material of ethane cracking furnace, its chemical composition is shown in Table 7.
The effective microalloying 35Cr45NiNb alloy steel chemical compositions of the ethane cracking furnace of table 7
Note：In units of mass percent.
After tested, the column crystal after chloroazotic acid etch of the microalloying 25Cr35NiNb boiler tubes in the present embodiment accounts for wall thickness percentage
Than for 100%, it is 5.0 grades to evaluate its grain size number after the oxalic acid aqueous solution electro-etching for being 10% through volume fraction.
To with matched in table 7 the 35Cr45NiNb+ microalloy furnace tubes sample of making carry out respectively 3 times 1100 DEG C, 17MPa try
High temperature resistant creep rupture test under the conditions of testing, gained test result is as shown in table 8.
The 35Cr45NiNb+ microalloy furnace tube stress-rupture tester results of table 8
P, Cr, Ni, Al, Ti, Zr, Pb, Bi elemental composition is not at this in chemical composition result, the boiler tube composition
Invention is provided in the composition range of material, and its high-temperature and durable rupture time is less than 100h.
Claims (1)
1. a kind of effective microalloying 35Cr45NiNb steel alloys of ethane cracking furnace, it is characterised in that by percentage to the quality, contain
There is C：0.40~0.50, Si：1.20~1.80, Mn：0.60~1.20, P：0.001~0.020, S：0.001~0.010, Cr：
35~36, Ni：45~46, Nb：0.80~1.50, W：0.005~0.20, Mo：0.005~0.20, Cu：0.005~0.30,
Al：0.005~0.20, Ti：0.05~0.10, Zr：0.05~0.10, B：0.0010~0.0050, As：0.0008~
0.0020, Sn：0.0011~0.0020, Pb：0.0003~0.0020, Bi：0.00002~0.0001, surplus is Fe；
Column crystal accounts for wall thickness percentage more than 70%, and grain size number is 5~6 grades.
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| US7381369B2 (en) * | 1999-09-03 | 2008-06-03 | Kiyohito Ishida | Free cutting alloy |
| JP4506958B2 (en) * | 2004-08-02 | 2010-07-21 | 住友金属工業株式会社 | Welded joint and its welding material |
| CN102492895B (en) * | 2011-12-24 | 2013-02-13 | 王崇高 | Heat resistant steel for high temperature furnace tube |
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Address after: 230031 No. 888 Changjiang West Road, Shushan District, Anhui, Hefei Patentee after: HEFEI GENERAL MACHINERY RESEARCH INSTITUTE Co.,Ltd. Patentee after: Hefei General Machinery Research Institute special equipment inspection station Co., Ltd Address before: 230031 No. 888 Changjiang West Road, Shushan District, Anhui, Hefei Patentee before: HEFEI GENERAL MACHINERY Research Institute Patentee before: Special equipment inspection station of Hefei General Machinery Research Institute |