CN102747287A - High-temperature resistant pipe suitable for delayed coking process and producing method of high-temperature resistant pipe - Google Patents
High-temperature resistant pipe suitable for delayed coking process and producing method of high-temperature resistant pipe Download PDFInfo
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Abstract
Disclosed is a high-temperature resistant pipe suitable for a delayed coking process and a producing method of the high-temperature resistant pipe. The high-temperature resistant pipe comprises, by weight, no more than 0.20% of carbon, 0.05%-0.75% of silicon, 0.03%-0.80% of manganese, no more than 0.045% of phosphorus, no more than 0.045% of sulphur, 6.0%-12.0% of chromium, 0.60%-1.30% of molybdenum, 0.005%-0.50% of copper and the balance ferrum and unavoidable trace impurities. By the aid of adjustment of element types, restrict control of element content and a proper production and heating processing process, the high-temperature performance such as lasting creep strength and instant high-temperature strength can be achieved and the performance is higher than that of P/T9 required by American Society for Testing Material (ASTM)/American Society of Mechanical Engineers (ASME), requirements of current conventional outlet temperatures of 490 DEGC-500 DEG C of delayed coking are met and the pipe is suitable for an international trend that the output temperature is raised to 510 DEG C.
Description
Technical field
The invention belongs to metal material field, relate in particular to a kind of high temperature resistant tubing and method of manufacture thereof of suitable delay coking process.
Background technology
Delayed coking is the effective means that solves the diesel and gasoline ratio imbalance between supply and demand.Homemade crude oil is generally laid particular stress on, and wax content is high, and diesel yield causes year import about 80 * 10 than on average low 5～7 percentage points of external crude oil
4T diesel oil has to export 30 * 10 simultaneously
4T gasoline is in the hope of the domestic equilibrium of supply and demand.
Catalytic cracking is the main technique of China's oil refining enterprise secondary processing, and its diesel and gasoline ratio is merely 0.56, and delayed coking is the former 3.5 times up to 1.94, and therefore developing delayed coking is to solve diesel and gasoline ratio imbalance between supply and demand, the effective way of increasing output of diesel oil.Than hydrogen cracking, stability is poor although there are clean cargo in delayed coking, and its process cost only is 1/2～1/3 of hydrogen cracking, makes it have stronger competitive power.Therefore, because delayed coking has less investment, process cost is low; The depth of conversion advantages of higher; Developed into one of main working method of residual oil lighting, especially in present China financial strain, under the light oil products objective reality that especially the diesel and gasoline ratio imbalance between supply and demand is given prominence to; Delayed coking is to solve one of comparatively ideal means of this contradiction, and development is swift and violent.By the end of the year 2005, China Petrochemical Industry's about 25 covers of coker that put into operation, wherein precontract in 2000 15 covers are constructed and put into operation, and about 10 covers are constructed and put into operation after 2000, all have potential safety hazard in various degree.
Along with the rising of world's crude oil price and the lasting deterioration of former oil quality, processing heavy crude and crude oil with poor quality receive the attention of petrochemical industry day by day.Delayed coking unit is strong as a kind of flexibility, the residual oil complete processing of less investment, instant effect, is also increasingly adopted by many refinerys.For improving the flexibility of refinery processing heavy crude and crude oil with poor quality; Most of refinery is all at the machining load that increases coker; And the raw material that makes coker processing is heavier, sulphur content is higher, and existing equipment and pipe material are not suitable for the processing of high-sulfur raw material, seriously corroded; The particularly early stage coker that designs, many high-temperature pipes and valve remain carbon steel material.Therefore, the working conditions of equipment and pipeline changes, and expire the work-ing life of equipment and pipeline, but still exceeds the time limit to use, and has potential safety hazard.
Delayed coking unit is one of device of refinery hazardous; Only not external; Security incident more or less all took place in domestic every cover delayed coking unit; Wherein high-temperature sulfur corrosion, selection is unreasonable and the carbonization of coking boiler tube causes breaking etc. all once forced device to be stopped work, and furnace tube material is proposed higher performance requirement.
The temperature of reaction of delayed coking is by the control of furnace outlet temperature, when pressure and recycle ratio one timing, with respect to fresh feed; 5.6 ℃ of the every increases of temperature; Liquid yield can increase by 1.1%, and domestic selected heater outlet temperature is 490～500 ℃, then tends to bring up to 510 ℃ in the world; Improve 10 ℃ than common temperature out, can improve liquid yield greatly.
To the empyreumatic transformation of online high temperature, to the resistance to elevated temperatures of boiler tube, especially the TRANSIENT HIGH TEMPERATURE performance proposes harsher requirement by the traditional mechanical coke cleaning.Initial stage is many to be main with Cr5Mo, and existing overall trend is to substitute with Cr9Mo, rather than with more resistant to elevated temperatures stainless steel, because operation is bad during latter's blowing out, Jiao who ties in the boiler tube understands oneself and comes off, and influences that process furnace is empyreumatic to carry out.
Chinese patent CN200410069884.2 discloses a kind of stainless steel and stainless steel tube with anti-carburizing property and anti-coking property, and its alloy content only Cr mainly is applicable to cracking of ethylene technology just up to 20% ~ 35%.Japanese Patent JB19944027306 also is that cracking of ethylene is used heat resisting pipe, and its Cr content is also up to 30%.Japanese Patent JP2004256918 improves anti-coking property through increasing silicomanganese content, is conceived to prolong coke cleaning running period.
Summary of the invention
The object of the present invention is to provide a kind of high temperature resistant tubing and method of manufacture thereof of suitable delay coking process; Through the adjustment of element kind and the strictness control of content thereof; And suitable production and thermal treatment process, obtain the high-temperature behavior higher, like durable creeping intensity, TRANSIENT HIGH TEMPERATURE intensity etc. than the P/T9 of ASTM/ASME code requirement; Can not only satisfy the conventional temperature out requirement of 490～500 ℃ of present delayed cokings, can also adapt to temperature out and bring up to 510 ℃ international trend.
For achieving the above object, technical scheme of the present invention is:
A kind of high temperature resistant tubing of suitable delay coking process, its composition weight percent is: C≤0.20%, Si:0.05% ~ 0.75%; Mn:0.03% ~ 0.80%, P≤0.045%, S≤0.045%; Cr:6.0% ~ 12.0%; Mo:0.60% ~ 1.30%, Cu:0.005%～0.50%, all the other are Fe and inevitable impurity.
Preferably, high temperature resistant tubing composition weight percent is: C:0.01% ~ 0.17%, Si:0.10% ~ 0.60%, Mn:0.10% ~ 0.75%; P≤0.030%, S≤0.030%, Cr:7.0 ~ 11.0%; Mo:0.80% ~ 1.20%, Cu:0.01%～0.35%, all the other are Fe and inevitable impurity.
In composition design of the present invention:
C is the element that enlarges austenite region, can improve the intensity and the hardness of steel, reduces plasticity and toughness.Reduce carbon content and can obviously improve the anufacturability of steel pipe, increase C content, the resistance of steel is increased, thermal conductivity descends; The crackle tendency increases, and steel billet cutting and steel pipe welding property worsen, but can improve molten steel flow property, air-breathing property; Therefore, C content was difficult for low, can not be too high.C of the present invention≤0.20%, preferred 0.01%～0.17%.
Si is an austenite former, mainly is the intensity that improves steel through solution strengthening, makes the steel surface passivated membrane fine and close, improves the high-temperature oxidation resistance of steel.Si:0.05% of the present invention～0.75%, preferred 0.10%～0.60%.
Mn is an austenite former, can improve the intensity of steel, and during too high levels, microstructure segregation tendency increases the weight of, hydrogen-type corrosion can be in segregation line forming core on the carbide, crackle has along the trend of low-temperature transformation product (martensite or bainite) expansion.Si:0.03% of the present invention～0.80%, preferred 0.10%～0.75%.
Cr is the intensive carbide forming element, and the C in it and the steel generates stable carbide, and C is fixed in the carbide, make its at high temperature can not with medium hydrogen evolution methane, make steel have the performance of anti-hydrogen-type corrosion.Cr:6.0% of the present invention～12.00%, preferred 7.0%～11.00%.
Mo is the strong carbide forming element, improves the anti-hydrogen-type corrosion performance of steel.Very tiny because of its particle simultaneously, difficult gathering is grown up, and the precipitation strength that causes thus makes steel keep higher strength, and stops the recrystallize of α phase, plays solution strengthening.Mo:0.60% of the present invention～1.30%, preferred 0.80%～1.20%.
Cu is an austenite former, suppresses ferritic formation, improves hardenability; Suppress separating out of δ phase, impel to generate the ε phase, make full use of deposition precipitation strength effect, especially CuC, the Cu of copper-rich phase
2Precipitates such as C play Mo
2The equivalent strengthening effect of C, thus help improving high-temperature behavior, high-temperature and durable creeping performance etc. especially.But too much influence hot workability again, be unfavorable for poling and rolling, should be strict controlled in 0.005%～0.50%, preferred 0.01%～0.35%.
P and S are the residual harmful elements, implement and the raising overall performance for being easy to produce, and the present invention controls respectively and is lower than 0.045% and 0.045%, preferably is lower than 0.030% and 0.030% respectively.
The present invention is fit to the method for manufacture of the high temperature resistant tubing of delay coking process, comprises the steps:
1) press mentioned component and smelt, cast, the die casting demoulding or bloom cogging obtain steel ingot;
2) breaking down, the steel ingot heating, tandem rolling, annealing obtains pipe;
3) poling, heating of pipe blank, perforation obtains hollow forging;
4) finish rolling, hollow forging are heated to 1200～1300 ℃, are incubated after 10～30 minutes; Subtract at 1100～1200 ℃ of following skies, tandem rolling, postheating to 800～1000 ℃, soaking time 10～30 minutes; At 850～950 ℃ of following tension reducings, rolling, air cooling, obtain seamless tube;
5) thermal treatment,
Isothermal annealing, 650 ℃～800 ℃ of annealing temperatures are incubated >=30 minutes; Perhaps, normalizing+tempering, 900 ℃～1000 ℃ of normalizing temperatures are incubated >=30 minutes, and 600 ℃～700 ℃ following tempering of tempering temperature are incubated >=20 minutes.
By the high temperature resistant boiler tube of the present invention contain Cu composition system and content thereof, especially preferable range smelting, casting, breaking down gained pipe obtain seamless tube through poling, finish-rolling process; During this time need be through heating, insulation repeatedly; Especially last thermal treatment process, except make material softening, reduce hardness, the conventional effect such as eliminate stress, repeated heating and rolling; Not only refinement crystal grain, also impel tiny CuC, Cu
2Being uniformly distributed with nucleation, separating out the strengthening effect of this precipitate and Mo of compounds such as C
2The C equivalence, thus make high-temperature behavior be superior to the P/T9 boiler tube.
Beneficial effect of the present invention
The present invention passes through the adjustment of element kind as adding the Cu element; The strictness control of alloying constituent content, and suitable production and thermal treatment process obtain the better high-temperature behavior of generally using than in the delay coking process of ASTM/ASME P/T9; Like durable creeping intensity, TRANSIENT HIGH TEMPERATURE intensity etc.; Not only be higher than the permissible stress under the P/T9 corresponding temperature, the respective value of the P/T9 under the corresponding temperature also, i.e. permissible stress under the boiler tube corresponding temperature that the present invention is high temperature resistant can be higher than P/T9.Therefore; Be prerequisite for about 490～500 ℃ with the present conventional temperature out of delay coking stove of P/T9 of using; Steel grade of the present invention can make its temperature out bring up to 510 ℃, thereby increases diesel and gasoline ratio, optimizes the product ratio of petrochemical industry; Help reducing the imbalance between supply and demand of bavin gasoline, meet national economic development demand.
In addition, boiler tube resistance to elevated temperatures of the present invention improves, and the especially raising of TRANSIENT HIGH TEMPERATURE performance and high temperature oxidation resistance more helps adopting online high temperature to burn and replaces the traditional mechanical decoking process.The former when not only decoking is used compole short, also can omit machinery and remove and could recover the security measures of runing after the defocused equipment claimed pressure test.
Description of drawings
Fig. 1 is that TRANSIENT HIGH TEMPERATURE tensile strength is with the variation of temperature trend map.
Among the figure: σ
A-ASMEAnd σ
B-ASTMBe respectively ASME T/P9 permissible stress and moment high temperature tensile strength.
Fig. 2 is that the TRANSIENT HIGH TEMPERATURE ys is with the variation of temperature trend map.
Among the figure, σ
A-ASMEAnd σ
S-ASTMBe respectively ASME T/P9 permissible stress and moment high-temperature yield strength.
Fig. 3 is an embodiment of the invention steel isothermal annealing attitude creep rupture strength change curve in time.
Fig. 4 is isothermal annealing attitude creep rupture strength of the present invention and external contrast synoptic diagram.
Fig. 5 for the high-temperature oxidation resistance of steel of the present invention with temperature changing trend figure.
Fig. 6 is the comparison diagram of 600 ℃ of following oxidation-resistances of the present invention and import Cr5Mo and Cr9Mo.
Fig. 7 is the comparison diagram of 650 ℃ of following oxidation-resistances of the present invention and import Cr5Mo and Cr9Mo.
Fig. 8 is the comparison diagram of 700 ℃ of following oxidation-resistances of the present invention and import Cr5Mo and Cr9Mo.
Fig. 9 is the comparison diagram of 750 ℃ of following oxidation-resistances of the present invention and import Cr5Mo and Cr9Mo.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described further.
Embodiment of the invention composition is as shown in table 1, and surplus is Fe.Shown in table 2 and table 3, wherein embodiment 1～5th respectively for thermal treatment process and ambient temperature mechanical properties, and isothermal annealing is handled, and embodiment 6～10th, normalizing+temper.
Table 1 unit: weight percent
| Embodiment | C | Si | Mn | P | S | Cu | Cr | Mo |
| 1 | 0.118 | 0.750 | 0.619 | 0.0095 | 0.0034 | 0.095 | 6.670 | 1.125 |
| 2 | 0.170 | 0.601 | 0.466 | 0.0125 | 0.0016 | 0.311 | 11.002 | 1.024 |
| 3 | 0.199 | 0.268 | 0.750 | 0.0024 | 0.0028 | 0.407 | 8.752 | 0.600 |
| 4 | 0.021 | 0.461 | 0.552 | 0.0104 | 0.0022 | 0.009 | 9.807 | 0.721 |
| 5 | 0.008 | 0.696 | 0.229 | 0.0121 | 0.0028 | 0.011 | 7.010 | 1.242 |
| 6 | 0.003 | 0.101 | 0.703 | 0.0291 | 0.0019 | 0.273 | 10.536 | 1.300 |
| 7 | 0.043 | 0.148 | 0.100 | 0.0079 | 0.002 | 0.005 | 12.000 | 0.882 |
| 8 | 0.010 | 0.386 | 0.003 | 0.0277 | 0.0017 | 0.500 | 6.001 | 0.996 |
| 9 | 0.147 | 0.050 | 0.800 | 0.0138 | 0.003 | 0.183 | 10.081 | 1.198 |
| 10 | 0.083 | 0.537 | 0.310 | 0.0115 | 0.0019 | 0.348 | 11.466 | 0.801 |
Table 2 embodiment of the invention thermal treatment process
Table 3 embodiment of the invention mechanical property
| Embodiment | Ys/MPa | Tensile strength/MPa | Unit elongation/% | Yield tensile ratio/% |
| 1 | 515 | 665 | 31 | 77.44 |
| 2 | 379 | 630 | 29 | 60.16 |
| 3 | 500 | 670 | 30.5 | 74.63 |
| 4 | 489 | 660 | 33 | 74.09 |
| 5 | 492 | 645 | 30 | 76.28 |
| 6 | 291 | 525 | 35 | 55.43 |
| 7 | 266 | 505 | 30 | 62.86 |
| 8 | 265 | 555 | 31 | 47.75 |
| 9 | 264 | 525 | 44 | 50.29 |
| 10 | 309 | 530 | 37 | 58.3 |
It is to use on 510 ℃ the delayed coking unit that the high temperature resistant boiler tube of the present invention is fit to temperature out, and each item performance meets the demands fully, can increase economic efficiency.
The present invention's acquisition is explained with the performance of isothermal annealing attitude than the better high-temperature behavior of generally using in the delay coking process of ASTM/ASME P/T9 below:
(1) TRANSIENT HIGH TEMPERATURE tensile strength: as shown in Figure 1; Although the TRANSIENT HIGH TEMPERATURE tensile strength of boiler tube of the present invention reduces with the rising of temperature; Promptly with standard in the variation tendency of P/T9 be consistent; But the tensile strength values under the corresponding temperature is not only far above the permissible stress of P/T9 in the standard, also the TRANSIENT HIGH TEMPERATURE tensile strength of P/T9 in the standard.For example; TRANSIENT HIGH TEMPERATURE tensile strength of the present invention is compared the raising 9.29%, 11.13% and 14.45% of answering respectively when 300 ℃, 400 ℃ and 500 ℃; The high more relative raising rate of temperature is high more; In addition, taller than under 525 ℃ of standard T/P9 of the TRANSIENT HIGH TEMPERATURE tensile strength during 550 ℃ of the present invention, TRANSIENT HIGH TEMPERATURE tensile strength promptly of the present invention raises with temperature and reduction trend dies down.
(2) TRANSIENT HIGH TEMPERATURE ys: as shown in Figure 2; Although the TRANSIENT HIGH TEMPERATURE ys of boiler tube of the present invention reduces with the rising of temperature; Promptly with standard in the variation tendency of P/T9 be consistent; But the yield strength value under the corresponding temperature is not only far above the permissible stress of P/T9 in the standard, also the TRANSIENT HIGH TEMPERATURE ys of P/T9 in the standard.For example; TRANSIENT HIGH TEMPERATURE ys of the present invention is compared the raising 38.57%, 20.91% and 17.14% of answering respectively when 300 ℃, 400 ℃ and 500 ℃; The high more relative raising rate of temperature reduces; But, under 525 ℃ of the TRANSIENT HIGH TEMPERATURE yield strength ratio standard T/P9 during 600 ℃ of the present invention quite, TRANSIENT HIGH TEMPERATURE ys promptly of the present invention also is to raise and reduction trend dies down with temperature.
(3) creep rupture strength: ASME regulation; T/P9 is respectively 64.3MPa and 15.3MPa 550 ℃ and 650 ℃ of following 100,000 hours creep rupture strengths, and steel grade extrapolated value of the present invention is respectively 67.3MPa and 18.5MPa (Fig. 3), has all surpassed the permissible value scope of standard; Be respectively 4.7% and 20.9%; Be that temperature is high more, steel grade of the present invention with the obvious advantage, extrapolated value still remains on 9.1MPa during as 700 ℃.Fig. 4 is high temperature endurance performance of the present invention and standard P/T9 (import Cr9Mo) in the contrast of 550 ℃, 600 ℃, 650 ℃ and 700 ℃, and hence one can see that, and high temperature endurance performance of the present invention is superior to standard P/T9, especially at high temperature.
(4) high-temperature oxidation resistance: Fig. 5 is a boiler tube of the present invention in 600 ℃, 650 ℃, 700 ℃ and 750 ℃ of lower surfaces trend over time that increases weight.Generally speaking, parabola rule is obeyed in the oxidation of the present invention under 600 ℃～750 ℃, forms firm dense oxidation film.Specifically, when initial, temperature is high more, and surface oxidation is fast more, and oxidation further increases in time, but the weightening finish under the differing temps is tending towards identical after the LP oxidation, and explanation can form stable oxide film, and stops inner further oxidation weight gain.Fig. 6～Fig. 9 is respectively under 600 ℃, 650 ℃, 700 ℃ and 750 ℃, the high temperature oxidation resistance contrast of boiler tube of the present invention, standard P/T9 (import Cr9Mo) and standard P/T5 (import Cr5Mo) boiler tube.Hence one can see that, and the high temperature oxidation resistance of boiler tube of the present invention not only is superior to the Cr5Mo boiler tube, also is superior to the Cr9Mo boiler tube.
In a word, the present invention passes through the adjustment of element kind and the strictness control of content thereof, and suitable production and thermal treatment process, especially utilizes and adds the Cu element, and separate out sedimentary CuC, Cu in production and the final thermal treatment process
2Copper compounds such as C play Mo
2The equivalent strengthening effect of C; The high-temperature behavior that acquisition is higher than the P/T9 of ASTM/ASME code requirement; Like durable creeping intensity, TRANSIENT HIGH TEMPERATURE intensity etc.; Can not only satisfy the conventional temperature out requirement of 490～500 ℃ of present delayed cokings, can also adapt to temperature out and bring up to 510 ℃ international trend.
Claims (3)
1. the high temperature resistant tubing of a suitable delay coking process, its composition weight percent is: C≤0.20%, Si:0.05% ~ 0.75%; Mn:0.03% ~ 0.80%, P≤0.045%, S≤0.045%; Cr:6.0% ~ 12.0%; Mo:0.60% ~ 1.30%, Cu:0.005%～0.50%, all the other are Fe and inevitable impurity.
2. the high temperature resistant tubing of suitable delay coking process as claimed in claim 1 is characterized in that, its composition weight percent is: C:0.01% ~ 0.17%; Si:0.10% ~ 0.60%, Mn:0.10% ~ 0.75%, P≤0.030%; S≤0.030%, Cr:7.0 ~ 11.0%, Mo:0.80% ~ 1.20%; Cu:0.01%～0.35%, all the other are Fe and inevitable impurity.
3. according to claim 1 or claim 2 the method for manufacture of high temperature resistant boiler tube of suitable delay coking process comprises the steps:
1) press mentioned component and smelt, cast, the die casting demoulding or bloom cogging obtain steel ingot;
2) breaking down, the steel ingot heating, tandem rolling, annealing obtains pipe;
3) poling, heating of pipe blank, perforation obtains hollow forging;
4) finish rolling, hollow forging are heated to 1200～1300 ℃, are incubated after 10～30 minutes; Subtract at 1100～1200 ℃ of following skies, tandem rolling, postheating to 800～1000 ℃, soaking time 10～30 minutes; At 850～950 ℃ of following tension reducings, rolling, air cooling, obtain seamless tube;
5) thermal treatment,
Isothermal annealing, 650 ℃～800 ℃ of annealing temperatures are incubated >=30 minutes; Perhaps, normalizing+tempering, 900 ℃～1000 ℃ of normalizing temperatures are incubated >=30 minutes, and 600 ℃～700 ℃ following tempering of tempering temperature are incubated >=20 minutes.
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| CN107138876A (en) * | 2017-06-30 | 2017-09-08 | 武汉大学 | A kind of low nickel cupric type T/P92 steel wldings of high temperature creep-resisting |
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