JP3284794B2 - Heat transfer tubing for waste heat boilers utilizing refuse incineration exhaust gas with excellent high temperature corrosion resistance - Google Patents
Heat transfer tubing for waste heat boilers utilizing refuse incineration exhaust gas with excellent high temperature corrosion resistanceInfo
- Publication number
- JP3284794B2 JP3284794B2 JP28449494A JP28449494A JP3284794B2 JP 3284794 B2 JP3284794 B2 JP 3284794B2 JP 28449494 A JP28449494 A JP 28449494A JP 28449494 A JP28449494 A JP 28449494A JP 3284794 B2 JP3284794 B2 JP 3284794B2
- Authority
- JP
- Japan
- Prior art keywords
- corrosion resistance
- exhaust gas
- heat transfer
- temperature corrosion
- waste heat
- 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.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】この発明は、腐食性が強く、かつ
高温のごみ焼却排ガスに対して、すぐれた高温耐食性を
示すゴミ焼却排ガス利用廃熱ボイラの伝熱管材に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat transfer tube for a waste heat boiler utilizing refuse incineration exhaust gas, which is highly corrosive and exhibits excellent high-temperature corrosion resistance against high-temperature waste incineration exhaust gas.
【０００２】[0002]
【従来の技術】一般に、ごみ焼却施設には排ガスのもつ
高温潜熱を利用する目的で、廃熱ボイラが設置されてい
る。また、前記廃熱ボイラの構造部材である伝熱管材
は、腐食性の強いＨＣｌやＳＯ2 ガス、Ｎａ2 ＳＯ4 や
Ｃａ2 ＳＯ4 などの溶融硫酸塩、さらにＮａＣｌやＫＣ
ｌなどの溶融塩化物などの腐食性生成物を含有する高温
の排ガスにさらされ、かつ前記硫酸塩や塩化物などが表
面に堆積した環境下におかれることから、その製造には
高温耐食性のすぐれた各種の材料が用いられている。2. Description of the Related Art Generally, a waste heat boiler is installed in a refuse incineration plant for the purpose of utilizing high-temperature latent heat of exhaust gas. The heat transfer tube, which is a structural member of the waste heat boiler, is made of highly corrosive HCl or SO 2 gas, molten sulfate such as Na 2 SO 4 or Ca 2 SO 4 , NaCl or KC.
1) are exposed to high-temperature exhaust gas containing corrosive products such as molten chloride such as l, and are placed in an environment where the sulfates and chlorides are deposited on the surface. Various excellent materials are used.
【０００３】[0003]
【発明が解決しようとする課題】一方、近年の切迫した
エネルギー事情から、ごみ焼却による廃熱を最大限に利
用するために廃熱ボイラの蒸気条件も高温・高圧化する
傾向にある。これに伴ない、伝熱管の管壁温度はさらに
上昇し、かつごみの高カロリー化およびプラスチックの
増加により排ガスの腐食性も一段と激しさを増す状況に
あり、かかる点から廃熱ボイラの伝熱管材には、より一
層の高温耐食性が強く要求されているが、上記の各種従
来伝熱管材は、高温耐食性が不十分なために、これらの
要求に満足に対応することができないのが現状である。On the other hand, due to the urgent situation of energy in recent years, the steam condition of a waste heat boiler tends to be high temperature and high pressure in order to make maximum use of waste heat generated by incineration of waste. Along with this, the wall temperature of the heat transfer tubes further rises, and the corrosiveness of the exhaust gas is further increased due to the increase in the amount of calories and the amount of plastics in the garbage. Further high-temperature corrosion resistance is strongly demanded of pipe materials, but at present, the above-mentioned various conventional heat transfer tubes cannot satisfy these requirements satisfactorily due to insufficient high-temperature corrosion resistance. is there.
【０００４】[0004]
【課題を解決するための手段】そこで、本発明者等は、
上述のような観点から、より一段とすぐれた高温耐食性
を有するごみ焼却排ガス利用廃熱ボイラの伝熱管材を開
発すべく研究を行なった結果、上記伝熱管材を、重量％
（質量％）で［以下、％は重量％（質量％）を示す］、 Ｃｒ：２３〜２７％、 Ｍｏ：７〜１０％、 Ｎｂ：０．５〜５％、 Ｆｅ：０．０１〜７％、 Ｃ ：０．０５％以下、 Ｓｉ：０．１％以下、 Ｐ ：０．０３％以下、 Ｓ ：０．０３％以下、 を含有し、 Ｗ ：０．１〜２％、 を含有し、さらに、 希土類元素：０．００１〜０．１％、 Ｙ ：０．００１〜０．１％、 Ｚｒ：０．００１〜０．１％、 Ｈｆ：０．００１〜０．１％、 Ｂ ：０．００１〜０．０１％、 のうちの１種または２種以上、を含有し、残りがＮｉと
その他の不純物からなる組成を有するＮｉ基合金で構成
すると、この結果のＮｉ基合金製伝熱管材は、きわめて
苛酷な高温腐食環境下ですぐれた耐食性を示すという研
究結果を得たのである。Means for Solving the Problems Accordingly, the present inventors have
From the above-mentioned viewpoint, as a result of conducting research to develop a heat transfer tube for a waste heat boiler utilizing refuse incineration exhaust gas which has much higher high temperature corrosion resistance, the heat transfer tube was
(% Indicates weight% (mass%)), Cr: 23 to 27%, Mo: 7 to 10%, Nb: 0.5 to 5%, Fe: 0.01 to 7 %, C: 0.05% or less, Si: 0.1% or less, P: 0.03% or less, S: 0.03% or less, and W: 0.1 to 2%. Rare earth elements: 0.001 to 0.1%, Y: 0.001 to 0.1%, Zr: 0.001 to 0.1%, Hf: 0.001 to 0.1%, B: 0.001 to 0.01%, and the remainder is composed of a Ni-based alloy having a composition composed of Ni and other impurities. Research has shown that heat pipes exhibit excellent corrosion resistance in extremely harsh high-temperature corrosive environments.
【０００５】この発明は、上記の研究結果にもとづいて
なされたものであって、以下に伝熱管材を構成するＮｉ
基合金の成分組成を上記の通りに限定した理由を説明す
る。 （ａ） ＣｒおよびＭｏ これらの成分には、共存した状態で高温のごみ焼却排ガ
スに対する高温耐食性および高温耐酸化性を向上させる
作用があるが、その含有量がＣｒおよびＭｏのいずれか
でもＣｒ：２３％未満およびＭｏ：７％未満になると前
記作用に所望の効果が得られず、一方その含有量がＣ
ｒ：２７％およびＭｏ：１０％を越えても高温耐食性に
より一層の向上効果が現われないことから、その含有量
ををＣｒ：２３〜２７％、望ましくは２４〜２６％、Ｍ
ｏ：７〜１０％、望ましくは８．５〜１０％と定めた。[0005] The present invention has been made based on the above research results.
The reason why the component composition of the base alloy is limited as described above will be described. (A) Cr and Mo These components have an effect of improving high-temperature corrosion resistance and high-temperature oxidation resistance against high-temperature waste incineration exhaust gas in a coexisting state, and even if the content is either Cr or Mo, Cr: If the content is less than 23% and Mo: less than 7%, the desired effect cannot be obtained for the above-mentioned action, while the content is C
Even if r exceeds 27% and Mo exceeds 10%, no further improvement effect is exhibited by high-temperature corrosion resistance. Therefore, the content is set to Cr: 23 to 27%, desirably 24 to 26%, M
o: 7 to 10%, preferably 8.5 to 10%.
【０００６】 （ｂ） Ｎｂ Ｎｂ成分には、高温排ガス中の腐食性生成物である硫酸
塩や塩化物などに対する耐食性を向上させる作用がある
が、その含有量が０．５％未満では前記の高温耐食性に
所望の向上効果が得られず、一方その含有量が５％を越
えると曲げ加工性が低下するようになることから、その
含有量を０．５〜５％、望ましくは０．５〜２％と定め
た。(B) Nb The Nb component has an effect of improving corrosion resistance to sulfates, chlorides, and the like, which are corrosive products in high-temperature exhaust gas. The desired effect of improving the high-temperature corrosion resistance cannot be obtained. On the other hand, if the content exceeds 5%, the bending workability decreases, so that the content is 0.5 to 5%, preferably 0.5 to 0.5%. ２2%.
【０００７】 （ｃ） Ｆｅ Ｆｅ成分には熱間加工性を向上させる作用があるが、そ
の含有量が０．０１％未満では所望の熱間加工性を確保
することができず、一方その含有量が７％を越えると靭
性が低下するようになることから、その含有量を０．０
１〜７％、望ましくは１〜５％と定めた。(C) Fe The Fe component has an effect of improving hot workability, but if its content is less than 0.01%, desired hot workability cannot be ensured. If the amount exceeds 7%, the toughness will decrease.
1-7%, preferably 1-5%.
【０００８】 （ｄ） Ｃ 不純物としてのＣ成分の含有量が０．０５％を越える
と、粒界に存在する炭化物の量が増大するようになっ
て、特に高温排ガス中に含有する溶融塩化物による粒界
腐食の進行が促進されるようになることから、その含有
量を０．０５％以下と定めた。(D) When the content of the C component as the C impurity exceeds 0.05%, the amount of carbide present at the grain boundaries increases, and particularly the molten chloride contained in the high-temperature exhaust gas. Therefore, the content is determined to be 0.05% or less.
【０００９】 （ｅ） Ｓｉ Ｓｉ成分には脱酸作用があるので、溶湯の脱酸に用いる
場合があるが、この場合でもその含有量が０．１％を越
えると靭性が低下するようになることから、その含有量
を０．１％以下と定めた。(E) Si Since the Si component has a deoxidizing effect, it may be used for deoxidizing the molten metal. Even in this case, if the content exceeds 0.1%, the toughness decreases. Therefore, the content was determined to be 0.1% or less.
【００１０】 （ｆ） ＰおよびＳ 不純物としてのこれらの成分がそれぞれＰ：０．０３％
およびＳ：０．０３％を越えると、粒界に偏析するよう
になって熱間加工性を低下させ、かつ高温耐食性も低下
するようになることから、その含有量をＰ：０．０３％
以下およびＳ：０．０３％以下と定めた。(F) P and S These components as impurities are each P: 0.03%
And S: more than 0.03%, segregates at the grain boundaries, lowers hot workability, and also lowers high temperature corrosion resistance. Therefore, the content of P is set to 0.03%.
And S: 0.03% or less.
【００１１】 （ｇ） Ｗ Ｗ成分には、より一段と高温耐食性を向上させる作用が
あるが、その含有量が０．１％未満では前記作用に所望
の向上効果が得られず、一方その含有量が２％を越える
と曲げ加工性が低下するようになることから、その含有
量を０．１〜２％と定めた。(G) W The W component has a function of further improving the high-temperature corrosion resistance. However, if its content is less than 0.1%, a desired improvement effect cannot be obtained in the above-mentioned effect. Exceeds 2%, the bending workability deteriorates, so the content was determined to be 0.1 to 2%.
【００１２】 （ｈ） 希土類元素、Ｙ，Ｚｒ，Ｈｆ、およびＢ これらの成分には、いずれも管材表面に形成される保護
スケールの密着性を向上させ、よって高温耐食性の向上
に寄与する作用があるが、その含有量がいずれも０．０
０１％未満では前記作用に所望の効果が得られず、一方
その含有量が、Ｂ以外はいずれも０．１％、Ｂは０．０
１％を越えると熱間加工性が低下するようになることか
ら、その含有量を、それぞれＢ以外は０．００１〜０．
１％、Ｂは０．００１〜０．１％と定めた。(H) Rare earth elements, Y, Zr, Hf, and B These components all have the effect of improving the adhesion of the protective scale formed on the surface of the pipe material and contributing to the improvement of high-temperature corrosion resistance. However, the content is 0.0
If it is less than 01%, a desired effect cannot be obtained in the above-mentioned action.
If the content exceeds 1%, the hot workability is reduced, so that the content is 0.001 to 0.
1% and B were determined to be 0.001 to 0.1%.
【００１３】 （ｉ） その他不純物 その他不純物としてＭｎ，Ｔｉ、およびＡｌを含有する
場合があるが、これらの成分の含有量がそれぞれ０．４
％を越えると曲げ加工性が損なわれるようになることか
ら、その含有量をそれぞれ０．４％以下にとどめなけれ
ばならない。(I) Other impurities Mn, Ti, and Al may be contained as other impurities, and the content of each of these components is 0.4%.
%, The bending workability is impaired, so that their contents must each be kept to 0.4% or less.
【００１４】[0014]
【実施例】つぎに、この発明の伝熱管材を実施例により
具体的に説明する。通常の高周波溶解炉を用いて、表１
に示される成分組成をもったＮｉ基合金溶湯を調製し、
インゴットに鋳造し、このインゴットに１０００〜１２
５０℃の範囲内の所定温度で熱間鍛造を施して直径：５
５mmの丸棒材とし、ついでこの丸棒材から直径：５０mm
×肉厚：６mmの寸法に削り出すことにより本発明伝熱管
材１〜５をそれぞれ製造した。Next, the heat transfer tube of the present invention will be described in detail with reference to examples. Using a normal high-frequency melting furnace, Table 1
Prepare a Ni-base alloy melt having the component composition shown in
Cast into ingots and add 1000 to 12
Hot forging is performed at a predetermined temperature within the range of 50 ° C., and the diameter is 5
5mm round bar, then 50mm in diameter from this bar
× Wall thickness: Heat transfer tubes 1 to 5 of the present invention were manufactured by cutting to a size of 6 mm.
【００１５】ついで、この結果得られた伝熱管材を廃熱
ボイラに組み込み、この廃熱ボイラを処理能力：１５０
ton ／日のゴミ焼却施設に設置し、前記伝熱管材の表面
温度：４５０℃、排ガス温度：７００℃の条件で１００
０時間の操業を行ない、操業終了後伝熱管材を取り出
し、表面に付着した灰分や生成スケールを除去した状態
で周方向における肉厚を測定し、最大減肉量を求めると
共に、表面部の断面ミクロ組織を観察し、最大粒界腐食
長さを測定した。これらの測定結果を表２に示した。Then, the heat transfer tube obtained as a result is incorporated into a waste heat boiler, and the waste heat boiler is processed at a processing capacity of 150.
ton / day in a garbage incineration facility, where the surface temperature of the heat transfer tube is 450 ° C and the exhaust gas temperature is 100 ° C under the condition of 700 ° C.
After operating for 0 hours, take out the heat transfer tube after the operation is completed, measure the wall thickness in the circumferential direction with the ash attached to the surface and the generated scale removed, find the maximum wall thickness reduction, and cut the surface section The microstructure was observed and the maximum intergranular corrosion length was measured. Table 2 shows the results of these measurements.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【表２】 [Table 2]
【００１８】[0018]
【発明の効果】表１，２に示される結果から、本発明伝
熱管材１〜５は、いずれも高温のごみ焼却排ガス雰囲気
においてすぐれた高温耐食性を示すことが明らかであ
る。上述のように、この発明の伝熱管材は、高温のごみ
焼却排ガスに対してすぐれた高温耐食性を発揮するの
で、ごみ焼却施設の大型化および処理能力の向上に十分
満足に対応することができるのである。From the results shown in Tables 1 and 2, it is clear that the heat transfer tubes 1 to 5 of the present invention all show excellent high-temperature corrosion resistance in a high-temperature incineration exhaust gas atmosphere. As described above, since the heat transfer tube material of the present invention exhibits excellent high-temperature corrosion resistance against high-temperature waste incineration exhaust gas, it can sufficiently respond to an increase in the size of a waste incineration facility and an improvement in processing capacity. It is.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−188765（ＪＰ，Ａ) 特開 昭64−15353（ＪＰ，Ａ) 特開 昭57−203740（ＪＰ，Ａ) 特開 昭60−131958（ＪＰ，Ａ) 特開 昭63−213633（ＪＰ，Ａ) 特開 平５−59475（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C22C 19/05 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-188765 (JP, A) JP-A-64-15353 (JP, A) JP-A-57-203740 (JP, A) JP-A 60-88 131958 (JP, A) JP-A-63-213633 (JP, A) JP-A-5-59475 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C22C 19/05
Claims (1)
有するＮｉ基合金で構成したことを特徴とする高温耐食
性のすぐれたごみ焼却排ガス利用廃熱ボイラの伝熱管
材。1. In weight% (mass%), Cr: 23 to 27%, Mo: 7 to 10%, Nb: 0.5 to 5%, Fe: 0.01 to 7%, C: 0.05 %, Si: 0.1% or less, P: 0.03% or less, S: 0.03% or less, W: 0.1 to 2%, and Rare earth element: 0 0.001 to 0.1%, Y: 0.001 to 0.1%, Zr: 0.001 to 0.1%, Hf: 0.001 to 0.1%, B: 0.001 to 0.01 % Or more of the following, and the remainder is composed of a Ni-based alloy having a composition consisting of Ni and other impurities. Heat transfer tube for boiler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28449494A JP3284794B2 (en) | 1994-10-24 | 1994-10-24 | Heat transfer tubing for waste heat boilers utilizing refuse incineration exhaust gas with excellent high temperature corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28449494A JP3284794B2 (en) | 1994-10-24 | 1994-10-24 | Heat transfer tubing for waste heat boilers utilizing refuse incineration exhaust gas with excellent high temperature corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08120377A JPH08120377A (en) | 1996-05-14 |
| JP3284794B2 true JP3284794B2 (en) | 2002-05-20 |
Family
ID=17679251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28449494A Expired - Lifetime JP3284794B2 (en) | 1994-10-24 | 1994-10-24 | Heat transfer tubing for waste heat boilers utilizing refuse incineration exhaust gas with excellent high temperature corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3284794B2 (en) |
-
1994
- 1994-10-24 JP JP28449494A patent/JP3284794B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08120377A (en) | 1996-05-14 |
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