JP2003027259A - Surface modification method for imparting corrosion resistance to member of supercritical water treatment apparatus - Google Patents
Surface modification method for imparting corrosion resistance to member of supercritical water treatment apparatusInfo
- Publication number
- JP2003027259A JP2003027259A JP2001218929A JP2001218929A JP2003027259A JP 2003027259 A JP2003027259 A JP 2003027259A JP 2001218929 A JP2001218929 A JP 2001218929A JP 2001218929 A JP2001218929 A JP 2001218929A JP 2003027259 A JP2003027259 A JP 2003027259A
- Authority
- JP
- Japan
- Prior art keywords
- supercritical water
- corrosion resistance
- coating layer
- metallic
- modifying
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ハロゲン系，硫黄
系，リン系あるいは金属系の化合物を含む固体，液体あ
るいは気体の有機物質或いは無機物質を、超臨界水環境
下で処理する装置に係る。本発明は、前記装置部材の耐
食性を高めるための表面改質方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for treating a solid, liquid or gaseous organic substance or inorganic substance containing a halogen-based, sulfur-based, phosphorus-based or metal-based compound in a supercritical water environment. . The present invention relates to a surface modification method for increasing the corrosion resistance of the device member.
【０００２】[0002]
【従来の技術】現在、超臨界水環境を利用して有機物質
あるいは無機物質を処理する装置部位用材料（以下、装
置部材という）としてＮｉ基合金，純Ｔｉ，Ｔｉ基合金
あるいは貴金属（白金など）が使われている。また、非
金属性（セラミックス）材料も部材として適用されてい
る。2. Description of the Related Art At present, Ni-based alloys, pure Ti, Ti-based alloys or precious metals (such as platinum) are used as materials for equipment parts (hereinafter referred to as equipment members) for treating organic substances or inorganic substances by utilizing a supercritical water environment. ) Is used. In addition, non-metallic (ceramics) materials are also applied as members.
【０００３】「まてりあ」第３９巻第４号（２０００）
第３２０頁ないし第３２４頁には、超臨界環境における
金属材料の腐食について記載されている。"Materia" Vol. 39, No. 4 (2000)
Pages 320 to 324 describe corrosion of metallic materials in a supercritical environment.
【０００４】[0004]
【発明が解決しようとする課題】超臨界水は、有害かつ
難分解性多種有機物質あるいは無機物質の処理プロセス
環境として注目を集めている。Supercritical water has been attracting attention as a treatment process environment for harmful and hardly decomposable multi-organic substances or inorganic substances.
【０００５】しかし、そういう物質を超臨界水環境下で
処理するときに発生する固体，液体あるいは気体反応生
成物は、処理装置部材に対して厳しい腐食環境である。
高温高圧のこの環境では、多くの金属材料は十分な耐食
性を示さない。非金属性（セラミックス）材料は金属材
料より耐食性に優れているが、機械的性質及び加工性に
制約があるため、装置部位をセラミックス材料で作製す
ることは困難である。However, the solid, liquid or gas reaction product generated when such a substance is processed in a supercritical water environment is a severe corrosive environment for processing equipment members.
In this environment of high temperature and high pressure, many metallic materials do not show sufficient corrosion resistance. Although non-metallic (ceramics) materials have better corrosion resistance than metallic materials, it is difficult to fabricate device parts with ceramics materials because of limitations in mechanical properties and workability.
【０００６】本発明の目的は、表面改質によって超臨界
水利用装置用金属材料の耐食性を向上することにある。An object of the present invention is to improve the corrosion resistance of metallic materials for supercritical water utilization devices by surface modification.
【０００７】[0007]
【課題を解決するための手段】本発明は、腐食性のハロ
ゲン系，硫黄系，リン系あるいは金属系化合物を含む超
臨界水環境に使用する前に、Ｆｅ，ＮｉあるいはＣｏ基
金属材料からなる処理装置部材の表面にＣｒ，Ａｌ，Ｓ
ｉ，Ｔｉ，Ｍｏ，Ｚｒ，ＩｒあるいはＰｔの１種、ある
いはそれらの組合せ主体の金属性コーティング層を形成
し、耐食性を高めることを特徴とする。The present invention comprises a Fe, Ni or Co based metallic material prior to use in a supercritical water environment containing corrosive halogen-based, sulfur-based, phosphorus-based or metal-based compounds. Cr, Al, S on the surface of the processing equipment member
One of i, Ti, Mo, Zr, Ir, or Pt, or a metallic coating layer mainly composed of a combination thereof is formed to enhance corrosion resistance.
【０００８】この金属性コーティング層は、拡散処理法
（パック コーティング），高温ディップコーティング
法，ＣＶＤ法，溶射法，肉盛溶接法あるいは塗布法を適
用することによって作製することが好ましい。This metallic coating layer is preferably produced by applying a diffusion treatment method (pack coating), a high temperature dip coating method, a CVD method, a thermal spraying method, a overlay welding method or a coating method.
【０００９】そうした金属材料をそのままあるいはさら
に耐食性を向上するために金属性コーティング層を低酸
素分圧雰囲気中で、３００〜８５０℃の温度で予備酸化
しても良い。The metallic coating layer may be pre-oxidized at a temperature of 300 to 850 ° C. in a low oxygen partial pressure atmosphere as it is or in order to further improve the corrosion resistance.
【００１０】[0010]
【発明の実施の形態】以下、本発明の実施例を腐食試験
の結果を用いて説明する。表１に試験供試材として用い
たＳＵＳ３０４鋼の化学成分を示す。この鋼から寸法１
５×１０×３mmの三つの試験片（＃１，＃２及び＃３）
を加工し、アセトン洗浄の後、試験片全面に機械研磨し
た。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below by using results of a corrosion test. Table 1 shows the chemical composition of SUS304 steel used as a test sample material. Dimension 1 from this steel
Three test pieces of 5 × 10 × 3 mm (# 1, # 2 and # 3)
Was processed, washed with acetone, and mechanically polished on the entire surface of the test piece.
【００１１】[0011]
【表１】 [Table 1]
【００１２】機械研磨した二つの試験片（＃２及び＃
３）の表面に、図１に模式図を示す拡散処理法（パック
コーティング）によってＡｌ主体のコーティング層を
作製した。拡散処理は８００℃以上，５０時間で行い、
拡散パック原料としてＡｌ粉末，ＡｌＦ3 粉末及びＡｌ
2Ｏ3粉末を使用した。試験片１をパック原料粉末中に挿
入して、前記した条件で処理した。Two mechanically polished specimens (# 2 and #
On the surface of 3), an Al-based coating layer was prepared by a diffusion treatment method (pack coating) whose schematic diagram is shown in FIG. Diffusion treatment is performed at 800 ℃ or more for 50 hours,
Al powder, AlF 3 powder and Al as diffusion pack raw material
2 O 3 powder was used. The test piece 1 was inserted into the pack raw material powder and treated under the above-mentioned conditions.
【００１３】表面にＡｌ主体のコーティング層を作製し
た二つの試験片のうち一つの試験片（＃３）を、７５０
℃，Ｈ2 −Ｈ2Ｏ（酸素分圧〜１０-40Ｐａ）混合ガス中
で３時間予備酸化した。One of the two test pieces (# 3) having the Al-based coating layer formed on the surface was replaced with 750
Preoxidation was performed in a mixed gas of H 2 —H 2 O (oxygen partial pressure: 10 −40 Pa) for 3 hours.
【００１４】バッチ式超臨界水試験装置を利用し機械研
磨したままの試験片（＃１）及び表面改質した試験片
（＃２及び ＃３）の腐食試験を実施した。試験は５０
０℃，２５ＭＰａの超臨界水環境下で１０時間行った。
超臨界水試験では添加剤としてハロゲン化合物（ＮａＣ
ｌ）を使用した。A batch type supercritical water test apparatus was used to carry out a corrosion test on the test pieces as they were mechanically polished (# 1) and the surface-modified test pieces (# 2 and # 3). 50 tests
It was carried out for 10 hours in a supercritical water environment of 0 ° C. and 25 MPa.
In the supercritical water test, halogen compounds (NaC
1) was used.
【００１５】腐食試験中には研磨したままの試験片（＃
１）の表面にＣｒ2Ｏ3を含む酸化皮膜が生成したが、Ｓ
ＵＳ３０４鋼のＣｒ含有量は低い（２０mass％以下）た
め酸化皮膜は不連続の形態であり母材（ＳＵＳ３０４
鋼）に対して保護性ではなかった。During the corrosion test, the as-polished test piece (#
An oxide film containing Cr 2 O 3 was formed on the surface of 1), but S
Since the Cr content of US304 steel is low (20 mass% or less), the oxide film has a discontinuous form, and the base material (SUS304
It was not protective against steel).
【００１６】そして、表面にＡｌ主体のコーティング層
を作製したままの試験片（＃２）の場合、表面にＡｌ2
Ｏ3を含む酸化皮膜が生成した。この皮膜は母材の腐食
を抑制したが酸化皮膜の保護性は必ずしも十分ではなか
った。これの原因としてコーティング層のＡｌ成分と添
加剤からなるＨＣｌガスとの高温化学反応が指摘され
る。この反応によってコーティング層のＡｌ濃度が減
り、試験片（＃２）表面に成長したＡｌ2Ｏ3酸化皮膜の
機能が低下したものと推測される。Then, in the case of the test piece (# 2) in which the coating layer mainly composed of Al was formed on the surface, Al 2 was formed on the surface.
An oxide film containing O 3 was formed. This film suppressed the corrosion of the base material, but the protective property of the oxide film was not always sufficient. It is pointed out that the high temperature chemical reaction between the Al component of the coating layer and the HCl gas composed of the additive is the cause of this. It is presumed that this reaction reduced the Al concentration in the coating layer and reduced the function of the Al 2 O 3 oxide film grown on the surface of the test piece (# 2).
【００１７】この腐食試験では、表面にＡｌ主体のコー
ティング層を作製した後７５０℃，Ｈ2 −Ｈ2Ｏ混合ガ
ス中で予備酸化した試験片（＃３）が最も耐食性に優れ
た。これの理由として予備酸化による試験片（＃３）表
面に成長したＡｌ2Ｏ3主体の酸化皮膜は腐食性のＨＣｌ
ガスに対して保護性であることが考えられる。In this corrosion test, the test piece (# 3), which was prepared by forming a coating layer mainly composed of Al on the surface and then pre-oxidized in a H 2 —H 2 O mixed gas at 750 ° C., had the best corrosion resistance. The reason for this is that the oxide film mainly composed of Al 2 O 3 grown on the surface of the test piece (# 3) by pre-oxidation is corrosive HCl.
It is considered to be protective against gas.
【００１８】表２ではコーティング層のＡｌ成分とＨＣ
ｌガス及びＡｌ2Ｏ3予備酸化皮膜とＨＣｌガスとの化学
反応式を示す。In Table 2, Al component and HC of the coating layer
1 shows the chemical reaction formulas of 1 gas and Al 2 O 3 pre-oxidized film and HCl gas.
【００１９】[0019]
【表２】 [Table 2]
【００２０】Ａｌ−Ａｌ2Ｏ3−ＨＣｌシステムの熱力学
データを利用して、これらの反応で発生するＡｌ塩化物
ガスの平衡濃度（分圧）を計算した。表３に示すように
試験片の表面にＡｌ2Ｏ3皮膜がある場合（試験片＃
３）、Ａｌ塩化物の分圧は非常に低い。Using the thermodynamic data of the Al-Al 2 O 3 -HCl system, the equilibrium concentration (partial pressure) of Al chloride gas generated in these reactions was calculated. As shown in Table 3, when there is an Al 2 O 3 film on the surface of the test piece (test piece #
3), the partial pressure of Al chloride is very low.
【００２１】[0021]
【表３】 [Table 3]
【００２２】従って、供試材表面にＡｌ主体のコーティ
ング層を作製した後、この層の予備酸化により表面に成
長するＡｌ2Ｏ3皮膜は、供試材の超臨界水環境下での耐
食性を向上した。Therefore, the Al 2 O 3 film that grows on the surface of the test material after the Al-based coating layer is formed on the surface of the test material by the pre-oxidation of this layer has a corrosion resistance in the supercritical water environment. Improved.
【００２３】[0023]
【発明の効果】本発明によれば、超臨界水環境におい
て、装置部材を腐食環境から保護することができる。According to the present invention, the device member can be protected from the corrosive environment in the supercritical water environment.
【図１】拡散処理法の模式図。FIG. 1 is a schematic diagram of a diffusion processing method.
１…試験片。 1 ... Test piece.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２３Ｃ 10/50 Ｃ２３Ｃ 10/50 (72)発明者 土井 裕之 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 Ｆターム(参考） 4K044 AA02 AA06 BA02 BA08 BA10 BA12 BA19 BB03 BC02 CA11 CA12 CA14 CA62 Front page continuation (51) Int.Cl. 7 Identification code FI theme code (reference) C23C 10/50 C23C 10/50 (72) Inventor Hiroyuki Doi 7-1 Omika-cho, Hitachi-shi, Ibaraki Stock company Hitachi, Ltd. Hitachi Research Laboratory F-term (reference) 4K044 AA02 AA06 BA02 BA08 BA10 BA12 BA19 BB03 BC02 CA11 CA12 CA14 CA62
Claims (4)
系の化合物を含む固体，液体あるいは気体の有機物質或
いは無機物質を超臨界水環境下で処理する装置におい
て、前記装置部料に使用されるＦｅ基，Ｎｉ基或いはＣ
ｏ基金属材料の表面に該金属材料よりも耐食性の高い表
面層を形成することを特徴とする超臨界水処理装置部材
の耐食性表面改質方法。1. An apparatus for treating a solid, liquid or gaseous organic substance or inorganic substance containing a halogen-based, sulfur-based, phosphorus-based or metal-based compound in a supercritical water environment, which is used as the above-mentioned apparatus component. Fe group, Ni group or C
A method of modifying the surface of a supercritical water treatment device for corrosion resistance, which comprises forming a surface layer having higher corrosion resistance than the metal material on the surface of the o-based metal material.
境下で使用する前に前記金属材料の表面にＣｒ，Ａｌ，
Ｓｉ，Ｔｉ，Ｍｏ，Ｚｒ，ＩｒあるいはＰｔの１種、あ
るいはそれらの組合せ主体の金属性コーティング層を形
成することを特徴とする超臨界水処理装置部材の耐食性
表面改質方法。2. The method according to claim 1, wherein before the metallic material is used in the environment, Cr, Al,
A method for modifying the corrosion-resistant surface of a supercritical water treatment device member, which comprises forming a metallic coating layer mainly composed of one of Si, Ti, Mo, Zr, Ir or Pt, or a combination thereof.
前記金属性コーティング層を形成した後、水蒸気，純
水，超臨界水あるいは酸素を含む混合ガスからなる低酸
素分圧の雰囲気中で、３００〜８５０℃の温度で予備酸
化することを特徴とする超臨界水処理装置部材の耐食性
表面改質方法。3. The low oxygen partial pressure atmosphere according to claim 2, wherein the metallic coating layer is formed on the surface of the metallic material, and the mixed gas contains water vapor, pure water, supercritical water or oxygen. , Pre-oxidizing at a temperature of 300 to 850 [deg.] C., a method for modifying the surface of a supercritical water treatment device having corrosion resistance.
前記金属性コーティング層を形成するために、拡散処理
法（パック コーティング），高温ディップコーティン
グ法，ＣＶＤ法，溶射法，肉盛溶接法あるいは塗布法か
ら選ばれた方法を適用することを特徴とする超臨界水装
置部材の耐食性表面改質方法。4. The diffusion treatment method (pack coating), high temperature dip coating method, CVD method, thermal spraying method, build-up welding method according to claim 2, for forming the metallic coating layer on the surface of the metallic material. Alternatively, a method of modifying the corrosion resistance surface of a supercritical water device member, characterized by applying a method selected from coating methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001218929A JP2003027259A (en) | 2001-07-19 | 2001-07-19 | Surface modification method for imparting corrosion resistance to member of supercritical water treatment apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001218929A JP2003027259A (en) | 2001-07-19 | 2001-07-19 | Surface modification method for imparting corrosion resistance to member of supercritical water treatment apparatus |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003027259A true JP2003027259A (en) | 2003-01-29 |
Family
ID=19053026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001218929A Pending JP2003027259A (en) | 2001-07-19 | 2001-07-19 | Surface modification method for imparting corrosion resistance to member of supercritical water treatment apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003027259A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005154818A (en) * | 2003-11-25 | 2005-06-16 | Furuya Kinzoku:Kk | Corrosion resistant material, and its production method |
| JP2006009094A (en) * | 2004-06-25 | 2006-01-12 | Furuya Kinzoku:Kk | Corrosion-resistant material and its manufacturing method |
| JP2012221986A (en) * | 2011-04-04 | 2012-11-12 | Toshiba Corp | Supercritical drying method and apparatus of semiconductor substrate |
| WO2022202740A1 (en) * | 2021-03-26 | 2022-09-29 | 国立研究開発法人物質・材料研究機構 | Titanium alloy for supercritical water utilization device |
-
2001
- 2001-07-19 JP JP2001218929A patent/JP2003027259A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005154818A (en) * | 2003-11-25 | 2005-06-16 | Furuya Kinzoku:Kk | Corrosion resistant material, and its production method |
| JP4615847B2 (en) * | 2003-11-25 | 2011-01-19 | 株式会社フルヤ金属 | Corrosion resistant material and method for producing the same |
| JP2006009094A (en) * | 2004-06-25 | 2006-01-12 | Furuya Kinzoku:Kk | Corrosion-resistant material and its manufacturing method |
| JP4615909B2 (en) * | 2004-06-25 | 2011-01-19 | 株式会社フルヤ金属 | Corrosion resistant material and method for producing the same |
| JP2012221986A (en) * | 2011-04-04 | 2012-11-12 | Toshiba Corp | Supercritical drying method and apparatus of semiconductor substrate |
| WO2022202740A1 (en) * | 2021-03-26 | 2022-09-29 | 国立研究開発法人物質・材料研究機構 | Titanium alloy for supercritical water utilization device |
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