JPS6296614A - Heat treatment of cr-mo steel having excellent hydrogen erosion resistant characteristic - Google Patents
Heat treatment of cr-mo steel having excellent hydrogen erosion resistant characteristicInfo
- Publication number
- JPS6296614A JPS6296614A JP23462885A JP23462885A JPS6296614A JP S6296614 A JPS6296614 A JP S6296614A JP 23462885 A JP23462885 A JP 23462885A JP 23462885 A JP23462885 A JP 23462885A JP S6296614 A JPS6296614 A JP S6296614A
- Authority
- JP
- Japan
- Prior art keywords
- steel
- treatment
- tempering
- relief annealing
- stress relief
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
Description
【発明の詳細な説明】 (産業上の利用分野) この発明は、耐水素侵食特性に優れるCr −M。[Detailed description of the invention] (Industrial application field) This invention uses Cr-M which has excellent hydrogen corrosion resistance.
鋼の熱処理方法に関し、特に高温高圧水素下で長期間操
業される圧力容器材料として好適に使用することのでき
る耐水素侵食特性に優れるCr −M。Regarding heat treatment methods for steel, Cr-M has excellent hydrogen attack resistance and can be suitably used as a material for pressure vessels operated for long periods of time under high temperature and high pressure hydrogen.
鋼の熱処理方法に関するものである。This invention relates to a method for heat treatment of steel.
(従来の技術)
石油精製工場9石油化学工場における各種圧力容器、石
炭の液化、ガス化プロセス等高温高圧水素下で長期間操
業される容器には水素侵食と呼ばれる材質の劣化現象が
発生することがある。この現象は容器材料鋼中の炭化物
と鋼中に侵入してきた水素が反応してメタンバブルが発
生する現象であり、材料鋼に特有な潜伏期が経過した後
急激に材質が劣化するという現象である。(Prior art) A phenomenon of material deterioration called hydrogen erosion occurs in various pressure vessels in petroleum refineries and petrochemical plants, and in vessels operated for long periods under high temperature and high pressure hydrogen, such as in coal liquefaction and gasification processes. There is. This phenomenon is a phenomenon in which methane bubbles are generated when the carbides in the steel container material react with hydrogen that has entered the steel, and the material deteriorates rapidly after the incubation period unique to the steel material has passed. .
従来、水素侵食に起因する事故を防止するため、実機に
おける事故例等の経験に基いて、容器材料鋼種毎に安全
操業が可能な温度および水素圧力の上限値を規定したネ
ルンン線図が作成されておυ、これに基いて圧力容器の
設計、操業の目安が定められている。%に石油精製工場
における重油脱硫装置、石炭液化装Wjtあるいは石炭
ガス化装置はその操業条件が苛酷であるため、2%Cr
−IMo鋼。In the past, in order to prevent accidents caused by hydrogen corrosion, a Nern diagram was created that stipulated the upper limits of temperature and hydrogen pressure that would allow safe operation for each steel type of container material, based on the experience of accidents in actual equipment. Based on this, guidelines for the design and operation of pressure vessels have been established. %Cr, heavy oil desulfurization equipment, coal liquefaction equipment, or coal gasification equipment in petroleum refineries have harsh operating conditions.
-IMo steel.
3 cr −I Mo鋼等のような水素侵食を受けにく
い高品質の材料が使用されている。High quality materials are used that are not susceptible to hydrogen attack, such as 3 cr -I Mo steel.
しかしながら近年操業の効率化を図るために、反応条件
は年々高温ならびに高圧化される趨勢にあり、従来の材
料を用いてはこのような苛酷な操業条件に対処すること
は困難になりつつある。However, in recent years, reaction conditions have tended to become higher in temperature and pressure year by year in order to improve operational efficiency, and it is becoming difficult to cope with such harsh operating conditions using conventional materials.
ところで、例えば特開昭59−219450号等により
材料の成分元素を適当にP1整することにより、材料の
耐水素侵食特性を向上させる技術が知られている。By the way, a technique is known, for example, as disclosed in Japanese Patent Laid-Open No. 59-219450, etc., in which the hydrogen corrosion resistance of a material is improved by appropriately adjusting the P1 of the constituent elements of the material.
(発明が解決しようとする問題点)
上記特開昭59−219450号等により化学成分を変
更した場合には、強度、靭性、溶接性、製造性等も変化
することになるため、必ずしも圧力容器材料に要求され
る材質特性を具備した材料が経済的に得られるとは限ら
ないという問題が残っていた。(Problems to be Solved by the Invention) If the chemical composition is changed according to the above-mentioned JP-A-59-219450, etc., the strength, toughness, weldability, manufacturability, etc. will also change. The problem remained that it was not always possible to economically obtain materials with the required material properties.
(問題点を解決するための手段)
この発明は、前記問題点を改善・除去する方法を提供す
ることを目的とするものであり、特許請求の範囲に記載
の方法を提供することによって前記目的を達成すること
ができる。すなわちこの発明は、c O,20%以下、
Si 0.60 %以下、Mn1.0チ以下、P0
.020%以下、 S O,010%以下、 Cr
2.0〜3.5 %、 Mo o、s〜1.6%を含み
、残部実質的にF8よりなるCr−Mo14に焼入れま
たは焼ならし処理を施した後、少なくとも1回の焼戻し
処理および/または応力除去焼なまし処理を、600〜
750Cの温度範囲内でかつ下記1)の場合には式(1
)より、下記2)の場合には式(2)より導かれるS値
が810以上になるような条件下で、施すことを特徴と
する耐水素侵食特性に優れるCr −Mo鋼の熱処理方
法に関するものである。(Means for Solving the Problems) The present invention aims to provide a method for improving and eliminating the above problems, and by providing the method described in the claims, the above object can be achieved. can be achieved. That is, this invention provides c O, 20% or less,
Si 0.60% or less, Mn 1.0% or less, P0
.. 020% or less, SO, 010% or less, Cr
After quenching or normalizing Cr-Mo14 containing 2.0 to 3.5%, Mo, s to 1.6%, and the remainder substantially consisting of F8, it is subjected to at least one tempering treatment and /or stress relief annealing treatment to 600~
Within the temperature range of 750C and in the case of 1) below, formula (1)
), in the case of 2) below, the present invention relates to a heat treatment method for Cr-Mo steel having excellent hydrogen corrosion resistance, characterized in that the heat treatment is performed under conditions such that the S value derived from formula (2) is 810 or more. It is something.
1)焼戻し処理および/またけ応力除去焼なまし処理が
1回だけ施される場合には、
S値、、 T + 7!M30g t ・・・・・・
(1)上記式(1)中、
T:焼戻し処理あるいは応力除去焼なまし処理温度(C
)、
t:焼戻し処理あるいは応力除去焼なまし処理時間(h
)。1) If the tempering treatment and/or straddle stress relief annealing treatment is applied only once, the S value, T + 7! M30g t・・・・・・
(1) In the above formula (1), T: tempering treatment or stress relief annealing treatment temperature (C
), t: Tempering treatment or stress relief annealing treatment time (h
).
2)焼戻し処理および/まだは応力除去焼なまし処理が
2回以上n回施される場合には
T1:上回口の焼戻し処理あるいは応力除去焼なまし処
理温度(C)、
tl:1回目の焼戻し処理あるいは応力除去焼な壕し処
理時間(h)。2) When tempering treatment and/or stress relief annealing treatment is performed two or more n times, T1: upper opening tempering treatment or stress relief annealing treatment temperature (C), tl: first time Tempering treatment or stress relief annealing treatment time (h).
次に本発明の詳細な説明する。Next, the present invention will be explained in detail.
従来2 % Cr −I Mo鋼あるい!23Cr−I
Mo鋼を用いて圧力容器等を製作する際には、焼入れあ
るいは焼ならし処理後、例えば650Cで6h程度の焼
戻し処理が施され、機械加工等に耐えることができる程
度の靭性が材料に付与された後に機械加工、溶接等が施
され、最後K 650〜690 t:で10〜25hの
焼戻し処理あるいは応力除去焼なまし処理が施されて最
終製品材料になされる。Conventional 2% Cr-I Mo steel! 23Cr-I
When manufacturing pressure vessels etc. using Mo steel, after quenching or normalizing treatment, tempering treatment is performed at, for example, 650C for about 6 hours, giving the material enough toughness to withstand machining etc. After that, it is subjected to machining, welding, etc., and finally subjected to tempering treatment or stress relief annealing treatment for 10 to 25 hours at K 650 to 690 t: to form the final product material.
本発明は従来の焼戻し処理あるいは応力除去焼なまし処
理(以下この処理なPWHTと略称する)を改変するこ
とにより、従来の熱処理方法におけるよりも優れた耐水
素侵食特性を材料に付与することを目的とするものであ
る。The present invention proposes to modify the conventional tempering treatment or stress relief annealing treatment (hereinafter referred to as PWHT) to impart superior hydrogen attack resistance properties to the material than in conventional heat treatment methods. This is the purpose.
本発明者等は従来のCr −Mo鋼の耐水素侵食性が十
分ではないのでこの点を改良すべく種々の研究を行なっ
た結果、2 y4Cr −I Mo鋼あるいは30r
−I Mo鋼にあっては焼戻し処理あるいはPWHT後
に存在する炭化物の種類が上記画処理の温度および/ま
たは時間に大きく依存することを新規に知見した。とこ
ろで、水素侵食は鋼中の炭化物と水素が反応してメタン
バブルが生じて材質が劣化する現象であることから、本
発明者等は安定な炭化物を析出させればメタン生成反応
が生じ難くなり、ひいては水素侵食による材質劣化が生
起し難くなるのではなかろうかとの想定に基いて研究し
た結果、本発明を完成した。The present inventors have conducted various studies to improve the hydrogen corrosion resistance of conventional Cr-Mo steel, and found that 2y4Cr-I Mo steel or 30r
-I It was newly discovered that the type of carbide present in Mo steel after tempering or PWHT largely depends on the temperature and/or time of the above-mentioned image treatment. By the way, hydrogen attack is a phenomenon in which carbides in steel react with hydrogen, producing methane bubbles and deteriorating the material.The inventors of the present invention have proposed that by precipitating stable carbides, the methane production reaction will be less likely to occur. The present invention was completed as a result of research based on the assumption that material deterioration due to hydrogen erosion would be less likely to occur.
従来のCr −Mo鋼を使用した圧力容器用材料を製造
する際の代表的熱処理条件、例えば材料を焼入れあるい
は暁ならし後650Cで6h程度の焼戻し処理後、機械
加工、溶接等により容器を製作した後、690Cで22
h程度のPWHTを施した最終製品のS値は793とな
る。しかし本発明者等は、通常の焼戻し処理あるいはP
WHTよりも処理温度を高く、あるいは処理時間を長く
してS値を810以上とiすと、水素侵食が著しく生起
し雛くなることを新規に知見したのである。Typical heat treatment conditions when manufacturing pressure vessel materials using conventional Cr-Mo steel, such as quenching or normalizing the material, tempering at 650C for about 6 hours, and then manufacturing the vessel by machining, welding, etc. After that, 22 at 690C
The S value of the final product subjected to PWHT of about h is 793. However, the present inventors have developed a method using normal tempering treatment or P.
It was newly discovered that when the S value is increased to 810 or more by increasing the treatment temperature or the treatment time higher than WHT, hydrogen attack occurs significantly and the chicks become unformed.
次に本発明により処理される2ACr−xMo鋼および
3 Gr −I Mo鋼の成分組成を限定する理由を説
明する。Next, the reason for limiting the composition of the 2ACr-xMo steel and 3Gr-IMo steel treated according to the present invention will be explained.
C:Cは強度の向上に寄与する元素であるが、0.20
%より多いと溶接性が劣化し、耐水素侵食特性も低下す
るので、Cは0.20%以下にする必要がある。C: C is an element that contributes to improving strength, but 0.20
If it exceeds 0.2%, weldability deteriorates and hydrogen corrosion resistance also deteriorates, so it is necessary to keep C at 0.20% or less.
Si : Siは脱酸ならびに強度の向上に寄与する元
素であるが、Slは0.60チより多いと焼戻し脆化、
水素侵食に対する感受性が増大し、クリープ破断強度も
低下するので、Slは0.60 %以下にする必要があ
る。Si: Si is an element that contributes to deoxidation and improvement of strength, but if the amount of Sl exceeds 0.60, tempering embrittlement occurs.
Sl should be kept below 0.60% because it increases susceptibility to hydrogen attack and reduces creep rupture strength.
Mn : Mnは強度の向上に寄与する元素である
が、1.0チより多いと焼戻し脆化感受性を高めるので
Mnは1.0%以下にする必要がある。Mn: Mn is an element that contributes to improving strength, but if it exceeds 1.0%, it increases the susceptibility to tempering embrittlement, so Mn needs to be 1.0% or less.
P:Pは結晶粒界に偏析して焼戻し脆化をひき起すので
、できるだけ低レベルに抑制することが望ましいが、実
操業による脱燐操作のためコストの上昇を招かずかつ焼
戻し脆化が生起しない上限である0、02096以下に
する必要がある。P: P segregates at grain boundaries and causes tempering embrittlement, so it is desirable to suppress it to as low a level as possible, but since the dephosphorization operation is performed in actual operation, it does not increase costs and does not cause tempering embrittlement. It is necessary to keep it below the upper limit of 0.02096.
S;Sは過剰に含まれた場合、靭性を劣化させまたSR
割れ感受性を増大させるのでSは0.010−以下にす
る必要がある。S: When S is contained in excess, it deteriorates toughness and increases SR.
Since it increases cracking susceptibility, S needs to be 0.010- or less.
Cr : Crは耐水素侵食特性1強度、靭性の向上に
寄与する元素であるが、2,01未満では本発明の目的
とするPWHTおよび焼戻し処理条件による耐水素侵食
特性の向上効果が十分には得られず、一方3.5チより
多1と同61にPWHT 、焼戻し条件?変えでも耐水
素侵食特性の変化が少なくなるので、Crは2.0〜3
.5−の範囲内にする必要がある。Cr: Cr is an element that contributes to improving hydrogen corrosion resistance 1 strength and toughness, but if it is less than 2.01, the effect of improving hydrogen corrosion resistance due to PWHT and tempering treatment conditions, which is the objective of the present invention, is not sufficient. On the other hand, if the PWHT is more than 1 and 61 than 3.5 inches, the tempering conditions? Cr is 2.0 to 3 because the change in hydrogen corrosion resistance properties will be less even if the change is made.
.. It must be within the range of 5-.
Mo : Moは強度、靭性、クリープ破断強度の向上
に寄与する元素であるが、0.8−未満では上記特性の
向上効果が十分には得られず、一方1.6%より多くて
も前記特性の向上効果は飽和して不経済であるので、M
oは0.8〜1.6%の範囲内にする必要がある。Mo: Mo is an element that contributes to improving strength, toughness, and creep rupture strength, but if it is less than 0.8%, the effect of improving the above properties cannot be obtained sufficiently, while if it is more than 1.6%, the above Since the effect of improving characteristics is saturated and uneconomical, M
o needs to be within the range of 0.8 to 1.6%.
次に本発明の熱処理条件を限定する理由を説明する。Next, the reason for limiting the heat treatment conditions of the present invention will be explained.
溶接後の熱応力の除去あるいは靭性の向上を目的として
PWHTあるいは焼戻し処理が施されるが、600C未
満の処理ではその効果が十分ではなく、一方750Cよ
り高い温度で処理した場合にはフェライトが形成されて
強度が低下するので、上記PWHTあるいは焼戻し処理
温度は600〜750Cの範囲内にする必要がある。PWHT or tempering treatment is performed for the purpose of removing thermal stress or improving toughness after welding, but the effect is not sufficient when treated at temperatures below 600C, while ferrite is formed when treated at temperatures higher than 750C. Therefore, the PWHT or tempering temperature must be within the range of 600 to 750C.
次に上記PWHTあるいは焼戻し処理温度を600〜7
50Cの範囲内で、かつS値を810以上にする理由に
ついて説明する。Next, increase the above PWHT or tempering temperature to 600-7
The reason why the S value is set within the range of 50C and at least 810 will be explained.
前記式(1)あるいは(2)により規定されるS値はG
r −Mo #の耐水素侵食特性に依存し、S値が81
0より少ないとPWHTあるいは焼戻し処理が施される
場合耐水素侵食特性が低下するので、S値は810以上
、なかでも815以上のとき上記特性が特に向上する。The S value defined by the above formula (1) or (2) is G
It depends on the hydrogen corrosion resistance property of r-Mo#, and the S value is 81
If the S value is less than 0, the hydrogen corrosion resistance will deteriorate when subjected to PWHT or tempering treatment, so when the S value is 810 or more, especially 815 or more, the above characteristics are particularly improved.
次に本発明を実施例について説明する。Next, the present invention will be explained with reference to examples.
実施例
第1表に示す成分組成よりなる2ACr −I Mo鋼
オヨび30r −I Moをそれぞれ950Cで2.5
hの焼入れ処理あるいは焼ならし処理後、23ACr
−I Mo鋼について第2表に、また3 Cr −IM
o鋼については第3表に示す条件で焼戻し処理および/
またはPWHTを施した。シャルピー衝撃試験片を切り
出し、2y4Cr −I Mo !14K ツvsては
600C,水素圧力300KPf/lL2テ、30r
−IMo鋼K ライては600C。Example 2ACr-IMo steel having the composition shown in Table 1 and 30r-IMo were each heated at 950C for 2.5
After quenching or normalizing treatment of h, 23ACr
-I Table 2 for Mo steel, and 3 Cr -IM
o Steel is tempered and/or treated under the conditions shown in Table 3.
Or PWHT was applied. A Charpy impact test piece was cut out and 2y4Cr-I Mo! 14K vs 600C, hydrogen pressure 300KPf/lL2te, 30r
-IMo Steel K is 600C.
水素圧力500に?f/cIL2で最高1000hの高
温高圧水素処理を行った後、OCで7ヤルピー衝撃試験
を行った。シャルピー吸収エネルギーの水素処理時間依
存性を測定し、吸収エネルギーの低下が始まる時間を水
素侵食の潜伏期と称することにする。Hydrogen pressure to 500? After performing high-temperature and high-pressure hydrogen treatment for a maximum of 1000 hours using f/cIL2, a 7 yalpy impact test was performed using OC. The dependence of Charpy absorbed energy on hydrogen treatment time is measured, and the time when the absorbed energy begins to decrease is referred to as the incubation period of hydrogen attack.
檀々の焼戻し処理および/またはPWHTを施した試料
のS値、水素侵食潜伏期を2y4Cr−IMo鋼につい
ては第2表に、3Cr−IMo鋼については第3表に示
す。The S value and hydrogen attack incubation period of the samples subjected to the tempering treatment and/or PWHT are shown in Table 2 for 2y4Cr-IMo steel, and in Table 3 for 3Cr-IMo steel.
@1表
これらの表より水素侵食の潜伏期IfiS値に依存し、
S値が810以上となる焼戻し処・理あるいはPWHT
f;r、vffAした場合には水素侵食の潜伏期が著
しく長くなり、水素侵食が生起しにくくなることがわか
る。@1 Table From these tables, the incubation period of hydrogen erosion depends on the IfiS value,
Tempering treatment or PWHT that results in an S value of 810 or more
It can be seen that when f;
(発明の効果)
以上示したように、本発明により製造され九Cr −M
o鋼は優れた耐水素侵食特性を示し、高瀉高圧水紫下で
操業される圧力容器用材料として最適であり、優れた工
業的価値を有する。(Effects of the Invention) As shown above, 9Cr-M produced by the present invention
O-steel exhibits excellent hydrogen corrosion resistance, is optimal as a material for pressure vessels operated under high pressure and high water pressure, and has excellent industrial value.
Claims (1)
0%以下、P0.020%以下、S0.010%以下、
Cr2.0〜3.5%、Mo0.8〜1.6%を含み、
残部実質的にFeよりなるCr−Mo鋼に焼入れまたは
焼ならし処理を施した後、少なくとも1回の焼戻し処理
および/または応力除去焼なまし処理を、600〜75
0℃の温度範囲内でかつ下記式(1)より導かれるS値
が810以上になるような条件下で、施すことを特徴と
する耐水素侵食特性に優れるCr−Mo鋼の熱処理方法
。 S値=Tn+75log(Σ^n_l_=_1ti・1
0^(^T^i^−^T^n^)^/^7^5)・・・
(1)上記式(1)中、 Ti:i回目の焼戻し処理あるいは応力除去焼なまし処
理温度(℃)、 ti:i回目の焼戻し処理あるいは応力除去焼なまし処
理時間(h)、 n:焼戻し処理および/または応力除去焼なまし処理回
数(n=1も含む)。[Claims] 1 C0.20% or less, Si 0.60% or less, Mn1.
0% or less, P 0.020% or less, S 0.010% or less,
Contains 2.0-3.5% Cr, 0.8-1.6% Mo,
After quenching or normalizing the Cr-Mo steel, the remainder of which is substantially composed of Fe, at least one tempering treatment and/or stress relief annealing treatment is performed at a temperature of 600 to 75
A method for heat treating Cr-Mo steel having excellent hydrogen corrosion resistance, characterized in that the heat treatment is performed within a temperature range of 0° C. and under conditions such that the S value derived from the following formula (1) is 810 or more. S value=Tn+75log(Σ^n_l_=_1ti・1
0^(^T^i^-^T^n^)^/^7^5)...
(1) In the above formula (1), Ti: i-th tempering treatment or stress-relief annealing treatment temperature (°C), ti: i-th tempering treatment or stress-relief annealing treatment time (h), n: Number of times of tempering treatment and/or stress relief annealing treatment (including n=1).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23462885A JPS6296614A (en) | 1985-10-22 | 1985-10-22 | Heat treatment of cr-mo steel having excellent hydrogen erosion resistant characteristic |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23462885A JPS6296614A (en) | 1985-10-22 | 1985-10-22 | Heat treatment of cr-mo steel having excellent hydrogen erosion resistant characteristic |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6296614A true JPS6296614A (en) | 1987-05-06 |
Family
ID=16974014
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP23462885A Pending JPS6296614A (en) | 1985-10-22 | 1985-10-22 | Heat treatment of cr-mo steel having excellent hydrogen erosion resistant characteristic |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6296614A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8821381B2 (en) | 2005-09-02 | 2014-09-02 | Olympus Medical Systems Corp. | Electronic endoscope |
-
1985
- 1985-10-22 JP JP23462885A patent/JPS6296614A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8821381B2 (en) | 2005-09-02 | 2014-09-02 | Olympus Medical Systems Corp. | Electronic endoscope |
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