TW554347B - Method to protect the component of the primary system of a boiling-water reactor especially from stress-crack corrosion - Google Patents

Method to protect the component of the primary system of a boiling-water reactor especially from stress-crack corrosion Download PDF

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TW554347B
TW554347B TW091109880A TW91109880A TW554347B TW 554347 B TW554347 B TW 554347B TW 091109880 A TW091109880 A TW 091109880A TW 91109880 A TW91109880 A TW 91109880A TW 554347 B TW554347 B TW 554347B
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component
stress
water reactor
hydrogen
patent application
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TW091109880A
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Bernhard Stellwag
Wilfried Ruehle
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Framatome Anp Gmbh
Enbw Kraftwerke Ag
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/122—Alcohols; Aldehydes; Ketones
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C15/00—Cooling arrangements within the pressure vessel containing the core; Selection of specific coolants
    • G21C15/28—Selection of specific coolants ; Additions to the reactor coolants, e.g. against moderator corrosion
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C17/00—Monitoring; Testing ; Maintaining
    • G21C17/02—Devices or arrangements for monitoring coolant or moderator
    • G21C17/022—Devices or arrangements for monitoring coolant or moderator for monitoring liquid coolants or moderators
    • G21C17/0225—Chemical surface treatment, e.g. corrosion
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C19/00—Arrangements for treating, for handling, or for facilitating the handling of, fuel or other materials which are used within the reactor, e.g. within its pressure vessel
    • G21C19/28—Arrangements for introducing fluent material into the reactor core; Arrangements for removing fluent material from the reactor core
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C19/00—Arrangements for treating, for handling, or for facilitating the handling of, fuel or other materials which are used within the reactor, e.g. within its pressure vessel
    • G21C19/28—Arrangements for introducing fluent material into the reactor core; Arrangements for removing fluent material from the reactor core
    • G21C19/30—Arrangements for introducing fluent material into the reactor core; Arrangements for removing fluent material from the reactor core with continuous purification of circulating fluent material, e.g. by extraction of fission products deterioration or corrosion products, impurities, e.g. by cold traps
    • G21C19/307—Arrangements for introducing fluent material into the reactor core; Arrangements for removing fluent material from the reactor core with continuous purification of circulating fluent material, e.g. by extraction of fission products deterioration or corrosion products, impurities, e.g. by cold traps specially adapted for liquids
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Plasma & Fusion (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Catalysts (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Description

554347 五、發明說明（1) 本發明涉及一種保護沸水式反應器之主系統組件使特別 不受應力之撕裂侵蝕所用之方法。在沸水式反應器中，冷 卻劑（其與反應器核心相接觸），主冷卻劑及承受該主冷卻 劑之組件及管路稱爲主系統。沸水式反應器主系統除了反 應器壓力容器之外另包含管路系統以及各種組件及泵。這 些組件通常由不銹綱（例如，CrNi鋼）或由Ni爲主之合金 (例如，Inconel 600)所構成。在沸水式反應器中，藉由主 冷卻劑之輻射分解另外可形成各種反應產物，例如，過氧 化氫，氧及氫。由於氧化劑之過剩所形成之可氧化之各種 條件會造成侵蝕現象，特別是使各組件會受到應力之撕裂 侵蝕。爲了進行補救，則已知之方式是使氫混合至主冷卻 劑。氫與主冷卻劑中所含有之氧化劑相結合而使組件表面 之電化學電位偏移至負値。此種傳統方法之缺點是：需要 較大量之氫，以確保能達成一種足夠大之侵蝕保護作用。 大量之氫需求（其與成本有關）特別是由下述事實所造成： 以氧化物層覆蓋之組件表面上之氫之電化學氧化作用會受到 一種大的反應性阻礙，這必須藉由較高之氫濃度來補償。此 外，其它缺點是氣體形式之氫之劑量分配所需之設備費用。 由EP 073 6878中已知一種方法，其中主系統中組件表面之 氧化物層以貴金屬來摻雜，這樣可使所使用之氫含量較少。 在DE 1 00 3 0726A1中描述一種方法，其中氫及貴金屬之含 量以下述方式而降低：組件表面塗佈一種含有光催化作用 之物質。光催化作用之物質（較佳是使用Ti02及Zr02)是η 型半導體，其藉由反應器中存在之Cherenkov-輻射而被激發 554347 五、發明說明（2) ，此時此種物質使組件表面之侵鈾電位偏移至負値。 本發明之目的建議另一種方法來保護沸水式反應器之主 系統組件，本方法在較少之材料費及較少之時間耗費下可 確保一種有效之侵蝕保護作用。 此目的以申請專利範圍第1項之方法來達成。一種在反 應系統中所存在之各條件下可氧化之醇類（alc〇h〇l)(較佳 是液體形式）饋入主冷卻劑中以取代氫，其中組件表面是 空著的（blank)或只塗佈一特定之氧化物層。特定之氧化物 層是一種氧化物層，其在反應器操作期間或氧化之預處理 期間在儲存外來金屬或外來金屬氧化物時藉由組件材料之 侵蝕而形成。已顯示之事實是：上述形式之醇類劑量之添 加作爲唯一之措施即已足夠使組件表面之侵蝕電位下降至 小於-230mv之値，此時特別是不必以光催化作用之物質 來進行昂貴之塗層。作爲還原劑時醇類相對於水所具有之 優點是：其可以液體形式或作爲溶液而進行劑量之添加。 以設備技術上之觀點而言液體較氣體形式之物質更容易饋 入主冷卻劑中。此外，上述之化合物在操控及儲存時具有 優點。最後，上述之化合物較氫還便宜，同樣可使設備操 作成本下降。在較佳之另一種方法中，組件表面以貴金屬 (例如，鉑）來摻雜，這樣可使主冷卻劑中所需之醇類濃度 較小。較佳是使主冷卻劑中醇類之濃度介於〇. 1和 300gm〇l/kg之間。適當之方式是醇類饋入冷凝液系統中或 給水系統中。因此須測定該劑量之添加量，以調整沸水式 反應器之下降空間中上述之濃度。下降空間是反應器壓力 554347 五、發明說明（3) 容器中饋入管之注入口向下延伸之此種區域。較佳是使用 甲醇，乙醇（ethanol)及丙醇。但較適當的是使用甲酸，甲 醛及縮醛。 本發明以下將依據附圖來詳述。圖式簡單說明= 第1圖 沸水式反應器之縱切面。 第2圖 在出現CH3OH或氫作爲還原劑時CrNi鋼及 Pt之電位。 第1圖是已簡化之沸水式反應器，其壓力容器1中有燃 料元件2。上述形式之醇類（較佳是甲醇）注入該供路管路 3中作爲侵蝕之保護之用且特別是作爲應力之撕裂侵蝕 (IGSCC)之保護之用，管路3在壓力容器中以環形之分佈 管路之形式而延伸。反應器處於操作狀態中，其中反應器 之組件（即，壓力容器1及核心柵格（未顯示），其通常由 CrNi鋼或Ni爲主之合金所構成）是空著的（blank)或只塗 佈特定之氧化物層。第一種情況（即，空著的）例如發生於 一系列之修改過程中當氧化物層由組件表面去除時。須測 定此注入該供給管路3中之數量，使向下緊鄰之下降空間 4中醇類（特別是甲醇）之濃度可由Ο.ΐμιηοΐ/kg調整至 30(^mol/kg。醇類之最佳濃度是與各種不同之因素（例如 ，組件材料，貴金屬摻雜物之存在等等）有關且因此各別 之反應器須各別地之決定。 爲了測試所建議之方法之有效性。則以pt-及CrNi-鋼-電 極來進行硏究。由CrNi鋼所構成之電極在28 0°C及一種 對應於反應器中之使用條件之水化學劑中預氧化500小時 五、發明說明（4) 。這樣所預處處之CrNi鋼電極或Pt電極配置在一種280°C 之熱水所流經之高壓鍋中。已翻轉之水化學劑依據比例而 放入沸水式反應器中。氧含量保持在0.2及2 p p m之間。 甲醇作爲還原劑且添加氫以進行比較。電極之電位値作爲 甲醇含量或氫含量之函數且在第2圖中以甲醇/氧或氫/氧 之摩爾比（mole ratio)作爲橫軸。第2圖中之CrNi表示 CrNi鋼。可辨認的是：甲醇劑量顯示一可與氫劑量相比 較之保護作用。在此二種情況中，Pt電位在保護電位下方 下降-2 3 Omv。在未摻雜之CrNi鋼電極中，可觀察到甲醇 及氫中同樣可比較之電化學活性（activity)。此處爲了下降 至保護電位，則須設定大很多之摩爾比。須以較小之氧含 量或以過量之還原劑來進行處理。在氧含量小於lOppb且 甲醇含量是2ppm( = 62.5umol/kg)時，則所測得之電位是 -500mv 〇 氫及甲醇或其它醇類（特別是乙醇或丙醇）各具有一可與 氫相比較之電化學活性，但其活性在輻射分解時對由水所 形成之具強烈氧化作用之OH基而言是較大的。本方法之 其它優點由醇類之小很多之揮發性而得。當已添加之氫之 大部份轉換成氣相，藉由氣相而分送且以不可冷凝之氣體 在反應器之廢氣設備中在添加化學計量之氧數量之情況下 利用催化劑而被氧化時，醇類中已轉換成氣相之成份較少 。此外，以氣相來分送之醇類成份實際上可完全冷凝而可 輸送回到反應器中。化學劑，裝置及控制技術上之措施之 費用因此較傳統之方法還低。 554347 五、發明說明（5) 符號之說明 1 壓力容器 2 燃料元侔 3 供給管路 4 下降空間

Claims (1)

  1. 554347 六、申請專利範圍 第91 101966號「保護沸水式反應器之主系統組件使特別不受 應力之撕裂侵蝕所用之方法」專利案 (91年8月修正） 六申請專利範圍 1· ·一種保護沸水式反應器之主系統組件使特別不受應力之 撕裂侵蝕所用之方法，主冷卻劑中饋入一種在主系統之 條件下可氧化之醇類，其特徵爲：組件之表面是空著的 或只塗佈特定之氧化物層。 2·如申請專利範圍第1項之方法，其中該主冷卻劑中乙醇 之濃度調整至0.1至30(^mol/kg之値。 3··如申請專利範圍第1或2項之方法，其中醇類饋入冷凝 液系統中或給水系統中且利用該給水（feed-water)而供應 至主系統中。 4·如申請專利範圍第1或2項之方法，其中醇類由甲醇， 乙醇及丙醇所形成之組中選取。 5·如申請專利範圍第3項之方法，其中醇類由甲醇，乙醇 及丙醇所形成之組中選取。
TW091109880A 2001-05-15 2002-05-13 Method to protect the component of the primary system of a boiling-water reactor especially from stress-crack corrosion TW554347B (en)

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DE10123690A DE10123690A1 (de) 2001-05-15 2001-05-15 Verfahren zum Schutz der Bauteile des Primärsystems eines Siedewasserreaktors insbesondere vor Spannungsrisskorrosion

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US (3) US20050135542A1 (zh)
EP (1) EP1388151B1 (zh)
JP (1) JP3970182B2 (zh)
DE (2) DE10123690A1 (zh)
ES (1) ES2334647T3 (zh)
TW (1) TW554347B (zh)
WO (1) WO2002093586A2 (zh)

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DE10123690A1 (de) 2002-12-05
JP3970182B2 (ja) 2007-09-05
EP1388151A2 (de) 2004-02-11
US20050135542A1 (en) 2005-06-23
ES2334647T3 (es) 2010-03-15
JP2005504265A (ja) 2005-02-10
US20130272476A1 (en) 2013-10-17
WO2002093586A3 (de) 2003-02-20
WO2002093586A2 (de) 2002-11-21
US20070263761A1 (en) 2007-11-15
EP1388151B1 (de) 2009-11-11
DE50213991D1 (de) 2009-12-24

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