TW498348B - Method for relaxing stress corrosion cracking of structural member of nuclear reactor plant - Google Patents
Method for relaxing stress corrosion cracking of structural member of nuclear reactor plant Download PDFInfo
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- TW498348B TW498348B TW089117409A TW89117409A TW498348B TW 498348 B TW498348 B TW 498348B TW 089117409 A TW089117409 A TW 089117409A TW 89117409 A TW89117409 A TW 89117409A TW 498348 B TW498348 B TW 498348B
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498348498348
經濟部智慧財產局員工消費合作社印製 五、發明説明(i ) 發明背景 1.發明領域 本發明係有關一種緩和核子反應爐廠構造部件的應力 腐蝕裂化之方法且更特別有關適合用於具有沸水反應爐( 後文稱爲B W R )的核子反應爐廠之一種緩和核子反應爐 廠構造部件的應力腐蝕裂化之方法。 2 ·相關技藝之說明 B W R的核子反應爐構造材料(不鏽鋼、鎳族合金、 等)的應力腐蝕裂化(後文稱爲S C C )之產生可因爲材 料的改良而受到比先前更大的壓抑。再者,爲了壓抑 S C C的起始與擴張,乃注入氫。 氫注入係經由將氫注射到B W R的給水系統中,使氫 溶解在給水內,及將包括氫的給水導到核子反應爐內而進 行的。接著,要解說對應於氫注入的再結合反應。當將氫 加到核子反應爐的反應爐水內時,於核子反應爐中包圍反 應爐心的降流區中,氫會與氧和過氧化氫重組。當經由輻 射作用產生的反應性自由基種例如〇Η或其他者發出如同 催化劑般之作用時,此重組反應會快速進展。經由這種重 組反應,氧和過氧化氫在反應爐水中的濃度會降低。當氧 和過氧化氫的濃度降低時,核子反應爐構造材料的電化學 腐蝕電位也隨之降低。 隨者氫注入量的增加,反應爐水中的溶氧濃度會降低 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) — ^ 訂 . (請先閱讀背面之注意事項再填寫本頁) -4- 經濟部智慧財產局員工消費合作社印製 498348 A7 B7 五、發明說明(2 ) 。當反應爐水中的溶氧濃度降低到約1 0 p p b時, s C C的進展速率會降低到約1 / 1 〇。當隨著溶氧濃度 的降低使E C P降低到—2 3 0毫伏(m V ) V s SHE (•標準氫電極電位)或更低者時,S C C的產生會 受到額外地壓抑。不過,當將反應爐水的氫注入量增加以 期大幅地降低E C P時,溶於反應爐水內的輻射性氮1 6 會減少且會容易地移動到主蒸汽系統使得該主蒸汽系統的 劑量率增加。當給水中的氫濃度超過〇 · 4 p p m時,該 主蒸汽系統的劑量率即開始增加且再將該氫濃度增加時, 其劑量率會達到4或5倍。所以,爲了壓抑S C C的產生 ,從增加氫注入效應的觀點來看,有需要一種可以將 ECP降低到—2 3 0毫伏v s SHE或更低者而不會 增加主蒸汽系統的劑量率之技藝。 有關改良氫注入效應的第一種先前技藝係載於日本專 利2 8 1 8 9 4 3和日本專利申請公開 1 0 — 3 1 9 1 8 1之中者。此技藝係將氫加到反應爐水 中,將可加速氫對氧化劑的減少程序所用之鉑族高貴金屬 元素到該反應爐水中,及在構造材料的表面上形成一催化 劑層。 有關改良氫注入效應的第二種先前技藝係載於P C 丁 /J P/0 3 5 0 2之中者。此技藝係將鉑族高貴金屬元 素的氧化物或氫氧化物加到反應爐水中,及賦予構造材料 表面催化功能。 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (i) Background of the invention 1. Field of the invention The present invention relates to a method for mitigating stress corrosion cracking of structural components of a nuclear reactor plant and is more particularly suitable for use with boiling water A method for alleviating stress corrosion cracking of structural components of a nuclear reactor plant in a nuclear reactor plant of a reactor (hereinafter referred to as BWR). 2 · Explanation of related techniques The generation of stress corrosion cracking (hereinafter referred to as S C C) of nuclear reactor construction materials (stainless steel, nickel group alloys, etc.) of B W R can be more suppressed than before due to the improvement of materials. Moreover, in order to suppress the initiation and expansion of S C C, hydrogen was injected. Hydrogen injection is performed by injecting hydrogen into a BW R water supply system, dissolving hydrogen in the water, and introducing the water including hydrogen into a nuclear reactor. Next, a recombination reaction corresponding to hydrogen injection will be explained. When hydrogen is added to the reactor water of the nuclear reactor, hydrogen will recombine with oxygen and hydrogen peroxide in the downflow zone surrounding the reactor core in the nuclear reactor. This recombination reaction progresses rapidly when a reactive radical species, such as 〇Η or others, produced by radiation acts as a catalyst. Through this recombination reaction, the concentration of oxygen and hydrogen peroxide in the reactor water is reduced. When the concentration of oxygen and hydrogen peroxide decreases, the electrochemical corrosion potential of the nuclear reactor construction material also decreases. As the amount of hydrogen injected increases, the dissolved oxygen concentration in the reactor water will decrease. The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) — ^ Order. (Please read the precautions on the back before filling this page ) -4- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 498348 A7 B7 V. Invention Description (2). When the dissolved oxygen concentration in the reaction furnace water is reduced to about 10 p p b, the progress rate of s C C is reduced to about 1/10. When E C P is reduced to -230 millivolts (m V) V s SHE (• standard hydrogen electrode potential) or lower as the dissolved oxygen concentration decreases, the generation of S C C is additionally suppressed. However, when the amount of hydrogen injected into the reactor water is increased to significantly reduce the ECP, the radiant nitrogen 16 dissolved in the reactor water will be reduced and will easily move to the main steam system so that the dose rate of the main steam system increase. When the hydrogen concentration in the feedwater exceeds 0.4 p p m, the dose rate of the main steam system starts to increase, and when the hydrogen concentration is increased, the dose rate may reach 4 or 5 times. Therefore, in order to suppress the generation of SCC, from the viewpoint of increasing the effect of hydrogen injection, there is a need for a technique that can reduce the ECP to -230 mV vs SHE or lower without increasing the dose rate of the main steam system. . The first prior art regarding the improvement of the hydrogen injection effect is described in Japanese Patent No. 2 8 1 8 9 4 3 and Japanese Patent Application Laid-Open No. 10-3 1 9 1 8 1. This technique involves adding hydrogen to the reactor water, adding platinum group noble metal elements that can accelerate the reduction of hydrogen to oxidants, and forming a catalyst layer on the surface of the construction material. The second previous technique for improving the hydrogen injection effect is contained in PC D / J P / 0 3 5 0 2. This technique involves adding an oxide or hydroxide of a platinum group noble metal element to the reactor water, and imparting a catalytic function to the surface of the construction material. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)
498348498348
經濟部智慧財產局員工消費合作社印製 五、發明説明(3 ) 發明槪述 本發明的一項目地爲提出一種緩和核子反應爐廠構造 部件的應力腐蝕裂化之方法用以降低存在於反應爐水流速 低的部位中之核子反應爐廠構造部件所具電化學腐鈾電位 〇 用以完成上述目的之本發明特徵在於本發明包括下述 步驟:將鉑和鍺高貴金屬元素中的至少一種高貴金屬元素 之化合物和一種鈀化合物,注入核子反應爐的反應爐水內 及將鈀化合物注入核子反應爐的反應爐水內使得反應爐水 內的鈀莫耳數比反應爐水內的高貴金屬元素莫耳數較爲小 。經由注入前述高貴金屬元素和鈀的化合物到反應爐水中 ,可使存在於反應爐水流速低的部位中之核子反應爐廠構 造部件表面上產生的高貴金屬元素(於鉑和鍺中的至少一 金屬)沉積量增加且也使鈀沉積下來。其結果,該構造部 件的E C P會降低且於存在於反應爐水流速低的部位中之 核子反應爐廠構造部件內的S C C之起始與擴大也會被壓 抑。反應爐水流速低的部位爲反應爐水不會強力地流動且 產生因渦流所致流動。具體而言,核子反應爐壓力容器內 所裝噴嘴的熱套筒部分及在核子反應爐支撐板與爐心屏蔽 之間的狹窄部分即對應於彼等部位。 本發明不僅可應用於B W R廠而且可應用於壓水式核 子反應爐廠。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) I ^ 訂 . (請先閲讀背面之注意事項再填寫本頁) -6 - 498348 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明(4 ) 圖示之簡略說明 - 圖1爲顯示出用鉑沉積降低s U s 3 0 4電化學腐飽 電位的原理之闡示圖; 圖l·· ( a )爲顯示出沒有沉積鉑時的S U S 3 0 4電 化學腐蝕電位之闡示圖; 圖1 (b)爲顯示出有沉積鈾時的SUS304電化 學腐蝕電位之闡示圖; 圖2爲顯示出S U S 3 0 4表面上已於各種條件下有 沉積鉑和铑時,在室溫下對應地檢驗S U S 3 0 4電化學 腐蝕電位所得結果之圖式; 圖3爲顯示出鈀沉積速率與溫度之間的關係之特性圖 圖4爲顯示出室溫下氫對氧莫爾比例與試片電化學腐 蝕電位之間的關係之特性圖; 圖5爲將本發明第一具體實例緩和核子反應爐廠構造 部件的應力腐蝕裂化之方法應用於B W R廠之槪示圖; 圖6爲圖5中所示高貴金屬注射裝置的細部槪示圖; 圖7爲顯示出在該第一具體實例中所示每一種鈾、铑 和鈀化合物的注射時間之槪示圖; 圖8爲顯示出在該第一具體實例中的氫注射時間之槪 示圖; Η 9爲顯不出在本發明弟一*具體貫例緩和核子反應爐 廠構造部件的應力腐蝕裂化之方法中每一種鉑、铑和鈀化 合物的注射時間之槪示圖; 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) * (請先閱讀背面之注意事項再填寫本頁) .1 498348 A7 B7Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (3) Description of the Invention One project of the present invention is to propose a method for mitigating stress corrosion cracking of structural components of a nuclear reactor plant to reduce the water in the reactor. The electrochemical uranium decay potential possessed by the structural parts of the nuclear reactor plant in the part with a low flow rate. The present invention for accomplishing the above-mentioned object is characterized in that the present invention includes the following steps: at least one of the noble metals of platinum and germanium The compound of the element and a palladium compound are injected into the reactor water of the nuclear reactor and the palladium compound is injected into the reactor water of the nuclear reactor so that the palladium mole number in the reactor water is higher than that of the noble metal element in the reactor water Ears are relatively small. By injecting the compound of the noble metal element and palladium into the reactor water, the noble metal element (at least one of platinum and germanium) generated on the surface of a nuclear reactor plant structure part existing in the part where the water flow rate of the reactor is low Metal) deposition increases and also deposits palladium. As a result, the E C P of the structural member is reduced, and the initiation and expansion of the S C C in the nuclear reactor plant structural member existing in the portion where the water flow rate of the reactor is low is also suppressed. The part where the flow rate of the reactor water is low is that the reactor water does not flow strongly and a vortex flow is generated. Specifically, the thermal sleeve portion of the nozzle installed in the pressure vessel of the nuclear reactor and the narrow portion between the support plate of the nuclear reactor and the core shield correspond to those portions. The present invention can be applied not only to a BW R plant but also to a pressurized water nuclear reactor plant. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) I ^ order. (Please read the precautions on the back before filling out this page) -6-498348 Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention (4) Brief description of the diagram-Fig. 1 is an explanatory diagram showing the principle of reducing the electrochemical corrosion saturation potential of s U s 3 0 4 by platinum deposition; Fig. L (a) is a diagram showing An illustration of the electrochemical corrosion potential of SUS 3 0 4 without the deposition of platinum; Figure 1 (b) is an illustration of the electrochemical corrosion potential of SUS 304 with the deposition of uranium; Figure 2 is an illustration of SUS 3 0 4 When platinum and rhodium have been deposited on the surface under various conditions, the results obtained by correspondingly examining the electrochemical corrosion potential of SUS 3 0 4 at room temperature are shown; FIG. 3 shows the relationship between the palladium deposition rate and temperature. Characteristics FIG. 4 is a characteristic diagram showing the relationship between the hydrogen to oxygen moire ratio and the electrochemical corrosion potential of the test piece at room temperature. Corrosion cracking method applied to the BWR plant FIG. 6 is a detailed 槪 diagram of the noble metal injection device shown in FIG. 5; FIG. 7 is a 槪 diagram showing the injection time of each of the uranium, rhodium and palladium compounds shown in the first specific example; Fig. 8 is a diagram showing the hydrogen injection time in the first specific example; Fig. 9 is not shown in the method for mitigating the stress corrosion cracking of the structural parts of the nuclear reactor plant in the first embodiment of the present invention The time chart of the injection time of each platinum, rhodium and palladium compound; This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) * (Please read the precautions on the back before filling this page). 1 498348 A7 B7
五、發明説明(5 ) 圖1 0爲顯示出本發明第三具體實例緩和核子反應爐 廠構造部件的應力腐蝕裂化之方法應用於B W R廠之槪示 圖; 圖1 1爲顯示出在該第三具體實例中氫和鹼溶液的注 射時間之槪示圖。 主要元件對照表 1 2 3 4 5 6 7 8 9 10 經濟部智慧財產局員工消費合作社印製 4 7 再循環泵 飼水泵 反應爐壓力容器 再循環水系統管路 主蒸氣管 渦輪機 冷凝器 冷凝水泵 冷凝水除礦器 低壓給水加熱器 高壓給水加熱器 飼水泵 爐心 降流區 下部區間 排放管 反應爐水淸淨系統管 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(21〇 X 297公釐) -8- 498348 A7 B7 n 五、發明説明(6 ) 2 2 2 2 2 2 2 經濟部智慧財產局員工消費合作社印製 3 3 4 4 4 4 7 a 7 b 7 c 8 9, 〇, 4 5 6 7 8 9 〇 1 2 5 6 7, 2, 0, 1, 7, 3 再生型熱交換器 非再生型熱交換器 泵 除礦器 2 1,2 2,2 3 採樣管 2 0 a,b,c,d 水品質測量裝置 氫注入器 電化學腐蝕電位(E C P )感測器 劑量率監測器 蒸氣抽取器 廢氣系統管 氧注入器 再結合裝置 高貴金屬化合物 鹼注入器 包封容器 爐心側板 38 感應偶合電漿重量分析儀 4 6,5 0 閥 4 4,4 8 槽 4 5,4 9,5 2 管 4 3,5 1 泵 控制器 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -9- 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 498348 Α7 Β7 五、發明說明() 較佳實施例之說明 本案發明人曾多方探討以期更減低核子反應爐廠構造 部件的電化學腐蝕電位。其探討結果將在下文中詳細解說 出。 - 要用爲核子反應爐廠構造部件的構造材料之不鏽鋼在 與反應爐水接觸時的E C P,如圖1 ( a )所示者,係經 定義爲於整體氧化電流密度與在與氧(或過氧化氫)的還 原反應所產生的還原電流密度之間彼此平衡的條件下從金 屬表面流進和流出的電流密度明顯爲0時的電位。該整體 氧化電流密度係由氫的氧化反應所產生的電流密度和不鏽 鋼的腐蝕溶解產生的電流密度之和所定出者。 在接觸反應爐水的不鏽鋼表面上,氫的氧化反應沒有 如此高的活性,使得不鏽鋼的E C P幾乎由氧的還原反應 所產生的電流密度和不鏽鋼的腐蝕溶解產生的電流密度所 決定。所以,氫注入反應爐水中會經由氫與氧在輻射下的 重組反應而減低反應爐水內的氧濃度。其結果,氧的還原 電流密度會減低且因而使不鏽鋼的E C P降低。 同時,在經沉積在不鏽鋼表面上的鈾族高貴金屬元素 (後文稱爲高貴金屬元素)例如鉑、铑或鈀之表面上,經 由該高貴金屬元素所持有的對氫反應之催化性質,氫的氧 化還原反應所致交換電流密度會比不鏽鋼表面上所產生者 較大某些數位。該高貴金屬·元素的氧化還原電位高於該氧 產生電位,使得該高貴金屬元素本身的氧化溶解反應不會 產生。所以,如圖1 ( b )所示者,該高貴金屬(於此例 - (請先閱讀背面之注意事項再填寫本頁)V. Description of the invention (5) FIG. 10 is a diagram showing the application of the method for mitigating the stress corrosion cracking of the structural parts of the nuclear reactor plant in the third embodiment of the present invention, which is applied to the BWR plant; FIG. Time chart of injection time of hydrogen and alkali solution in three specific examples. Comparison table of main components 1 2 3 4 5 6 7 8 9 10 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 7 Recirculation pump Feed water pump Reactor furnace Pressure vessel Recirculation water system pipeline Main steam tube Turbine condenser Condensate pump condensation Water demineralizer low pressure feed water heater high pressure feed water heater feed water pump furnace core downflow zone lower section discharge pipe reactor furnace water purification system pipe (please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS) A4 specifications (21〇X 297 mm) -8- 498348 A7 B7 n V. Description of invention (6) 2 2 2 2 2 2 2 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 3 4 4 4 4 7 a 7 b 7 c 8 9, 0, 〇, 4 5 6 7 8 9 〇 1 2 5 6 7, 2, 0, 1, 7, 7, 3 regenerative heat exchanger non-regenerative heat exchanger pump demister 2 1 , 2 2, 2 3 Sampling tube 2 0 a, b, c, d Water quality measuring device Hydrogen injector Electrochemical corrosion potential (ECP) sensor Dose rate monitor Vapor extractor Exhaust system tube Oxygen injector recombination device Noble metal compound alkali injector encapsulating container furnace Side plate 38 Inductive coupling plasma weight analyzer 4 6, 5 0 Valve 4 4, 4 8 Slot 4 5, 4 9, 5 2 Tube 4 3, 5 1 Pump controller (Please read the precautions on the back before filling this page ) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). -9- Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economy This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 498348 Α7 Β7 V. Description of the invention () Description of the preferred embodiment The inventor of this case has explored in many ways with a view to further reducing the electrochemical corrosion potential of the structural components of the nuclear reactor plant. The results of this discussion are explained in detail below. -The ECP of stainless steel to be used as the structural material of the nuclear reactor plant when it is in contact with the reactor water, as shown in Figure 1 (a), is defined as the overall oxidation current density and the oxygen and (or The potential at which the current density flowing into and out of the metal surface under the condition that the reduction current density produced by the reduction reaction of hydrogen peroxide) is balanced with each other is obviously zero. The overall oxidation current density is determined by the sum of the current density generated by the oxidation reaction of hydrogen and the current density generated by the corrosion and dissolution of stainless steel. On the surface of stainless steel in contact with the furnace water, the oxidation reaction of hydrogen is not so active, so that the E C P of stainless steel is almost determined by the current density generated by the reduction reaction of oxygen and the current density generated by the corrosion and dissolution of stainless steel. Therefore, the injection of hydrogen into the reactor water will reduce the oxygen concentration in the reactor water through the recombination reaction of hydrogen and oxygen under radiation. As a result, the reduction current density of oxygen is reduced and the E C P of the stainless steel is lowered. At the same time, on the surface of the noble metal element of the uranium group (hereinafter referred to as noble metal element) deposited on the surface of stainless steel, such as platinum, rhodium or palladium, via the catalytic property of the noble metal element to the hydrogen reaction, The exchange current density caused by the redox reaction of hydrogen will be some digits larger than that produced on the stainless steel surface. The oxidation-reduction potential of the noble metal element is higher than the oxygen generation potential, so that the oxidation-dissolution reaction of the noble metal element itself does not occur. So, as shown in Figure 1 (b), the precious metal (in this example-(Please read the precautions on the back before filling this page)
經濟部智慧財產局員工消費合作社印製 498348 A7 B7 五、發明說明(8 ) 中爲鉑)的溶解可以忽略,使得鉛表面釣E C P係由氫與 氧的還原反應所決定。於此例中,氧的氧化反應所產生的 氧交換電流密度小於氫的氧化反應所產生的氫交換電流密 度且氧的過電壓大於氫的過電壓。所以,當氫超量時,氧 的還原電流密度係低於氫的交換電流密度,使得鉑表面的 電位與氫的氧化還原電位吻合。當B W R運轉時,於此種 情況中的電位會降低到約一 5 5 0毫伏v s S Η E,使 得促使S C C產生的低限電位値一 2 3 0毫伏ν s S Η Ε或更低者爲之達到。當不鏽鋼表面上沉積著铑或鈀 時也會產生前述現象。上述即爲經由沉積高貴金屬元素促 進氫注入效應之原理。 鉑係長久以來即爲人所熟知在電化學領域中作爲氫電 極時可使氫反應效率令人滿意者。铑係在電鍍領域經知悉 可形成具有高硬度且可慷據磨蝕的薄膜者,使得其經用於 構造材料的表面上時,可以預期有催化作用的耐久性。所 以,本案發明人於最初即考慮將這兩種高貴金屬元素沉積 在不鏽鋼304 (SUS304)的表面上。 所以,使用高貴金屬化合物N a 2 [ P t ( Ο Η ) 6 〕和Na3〔Rh (Ν〇2) 6〕作爲高貴金屬元素藥劑, 在1 2 0 °C下執行鉑和鍺在S U S 3 0 4表面上的沉積試 驗。將SU S 3 0 4浸漬在分別含有1 5 0 p p b這兩種 高貴金屬化合物的溶液中並將鉑和铑沉積在S U S 3 0 4 的表面上。於第一種情況中,係將S U S 3 0 4浸漬在靜 止狀態中的溶液內。於第二種情況中,係將S U S 3 0 4 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -ϋ 1_1 ϋ ·ϋ «ϋ ϋ ι «ϋ i«i ϋ mmmmw iae ββ§ ϋ ϊ— Mmmt ϋ —mm ι_1 ϋ ϋ I (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 498348 A7 B7 V. The dissolution of platinum in the description of the invention (8) can be ignored, so that the lead surface fishing E C P is determined by the reduction reaction of hydrogen and oxygen. In this example, the oxygen exchange current density produced by the oxidation reaction of oxygen is smaller than the hydrogen exchange current density produced by the oxidation reaction of hydrogen and the overvoltage of oxygen is greater than the overvoltage of hydrogen. Therefore, when the hydrogen is excessive, the reduction current density of oxygen is lower than the exchange current density of hydrogen, so that the potential on the platinum surface coincides with the redox potential of hydrogen. When BWR is running, the potential in this case will be reduced to about -550 mV vs S Η E, so that the lower limit potential that promotes SCC-230 mV ν s S Ε Ε or lower To achieve it. This phenomenon also occurs when rhodium or palladium is deposited on the stainless steel surface. The above is the principle of promoting the hydrogen injection effect by depositing noble metal elements. The platinum system has long been known for its satisfactory hydrogen reaction efficiency when used as a hydrogen electrode in the field of electrochemistry. The rhodium system is known in the field of electroplating to form a film with high hardness and abrasionable, so that it can be expected to have catalytic durability when used on the surface of construction materials. Therefore, the inventors of the present case considered depositing these two noble metal elements on the surface of stainless steel 304 (SUS304). Therefore, using the noble metal compounds Na 2 [P t (Ο Η) 6] and Na3 [Rh (NO 2) 6] as noble metal element agents, platinum and germanium were performed at 120 ° C at SUS 30. 4 Deposition test on the surface. SU S 3 0 4 was immersed in a solution containing two noble metal compounds of 150 p p b and platinum and rhodium were deposited on the surface of SU S 3 0 4. In the first case, S U S 3 0 4 is immersed in a solution in a stationary state. In the second case, the paper size of SUS 3 0 4 applies the Chinese National Standard (CNS) A4 (210 X 297 mm) -ϋ 1_1 ϋ · ϋ «ϋ ϋ ι« ϋ i «i ϋ mmmmw iae ββ§ ϋ ϊ— Mmmt ϋ —mm ι_1 ϋ ϋ I (Please read the notes on the back before filling this page)
498348 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(9 ) 浸漬在流動狀態中的溶液內。於該第一和第二兩種情況中 ,鉑和铑都經沉積在s U S 3 0 4表面上並接著探討在室 溫下電化學腐蝕電位相對於氫對氧莫耳比之關係。 如圖2中所示者,於第一種狀態中,隨著氫對氧莫耳 比的增加,表面上有沉積鈾和铑的S U S 3 0 4所具 E C P會比未接受沉積程序的S U S 3 0 4較爲低。所以 ,可以確定SU S 3 0 4表面上有沉積著鉑和铑。不過, 經發現該電位的減低仍小於鉑板的E C P,因此對於鉑和 铑在S U S 3 0 4上的沉積性質仍有尙待改良之處。 於第二種情況中,係在將含有前述兩種高貴金屬化合 物的溶液以0 · 1公分/秒的流速流經S U S 3 0 4試片 的情況下執行該試驗。該第二種情況所產生的結果爲表面 上有沉積鉑和鍺的S U S 3 0 4所具E C P之行爲類似於 鉑板所具者。其結果,在經由溶液的流動增加鉑和铑在 S U S 3 0 4表面上的進料速率且於初始高貴金屬沉積時 在金屬表面附近有高貴金屬化合物的分解產物等情況下’ 可以推測在高貴金屬元素的分解和沉積受到阻礙之後於 S U S 3 0 4表面上存在著不活性狀態。所以’乃於反應 爐水不充分流動的部位內之核子反應爐構造部件上充分地 沉積鉑和铑。 不過,於一核子反應爐中存在有反應爐水流速低的構 造部位。例如,有安裝在核子反應爐中的管噴嘴之熱套筒 部份及在核心支撐體與核心屏蔽之間和在頂部導件與核心 屏蔽之間的諸狹窄部位。於彼等反應爐水流速低的部位中 -12 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) ·'498348 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) Immersion in the solution in a flowing state. In both the first and second cases, platinum and rhodium were deposited on the surface of s U S 3 0 4 and then the relationship between the electrochemical corrosion potential and the hydrogen to oxygen mole ratio at room temperature was explored. As shown in FIG. 2, in the first state, as the hydrogen-to-oxygen molar ratio increases, SUS 3 0 with deposited uranium and rhodium on the surface has an ECP that is higher than that of SUS 3 without the deposition process. 0 4 is relatively low. Therefore, it was confirmed that platinum and rhodium were deposited on the surface of SU S 304. However, it has been found that the reduction of this potential is still smaller than the E C P of the platinum plate, so there is still room for improvement in the deposition properties of platinum and rhodium on SUS304. In the second case, the test is performed with a solution containing the two aforementioned noble metal compounds flowing through the SUS S304 test strip at a flow rate of 0.1 cm / sec. The result of this second case is that the E C P behavior of S U S 3 0 4 with platinum and germanium deposited on the surface is similar to that of a platinum plate. As a result, when the feed rate of platinum and rhodium on the surface of SUS 304 was increased through the flow of the solution, and there were decomposition products of noble metal compounds near the metal surface during the initial noble metal deposition, etc. After the decomposition and deposition of the elements are hindered, an inactive state exists on the surface of SUS 304. Therefore, 'platinum and rhodium are sufficiently deposited on the structural parts of the nuclear reactor in the part where the furnace water does not sufficiently flow. However, in the nuclear reactor, there are structures where the flow rate of the reactor water is low. For example, there are a thermal sleeve portion of a tube nozzle installed in a nuclear reactor and narrow portions between a core support and a core shield and between a top guide and the core shield. In the parts where the water flow rate of their reactors is low -12 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) · '
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498348 A7 B7 五、發明說明(1〇 ) S C C的發生機率高於其他反應爐水流速高的部位。 所以’本案發明人乃探討對於使核子反應爐中存在於 反應爐水流速低的部位中之構造材料增加其鉑和铑個別沉 積量的解決之道。首先,經由試驗確定出用硝酸鈀對受試 的s U S 3 0 4之鈀沉積特性。圖3顯示出試驗結果。鈀 即使在比較上較爲低的溫度下仍有高沉積速率。其沉積速 率在1 5 0°C附近達到最大且隨著溫度的上升,沉積速率 即降低。 其理由經認爲與S U S 3 0 4表面膜的安定性有關。 由於金屬表面在1 5 0°C附近最不安定,且金屬溶解經最 大化’且鈀在金屬表面上的沉積反應會隨著溫度上升而增 加,因此鈀沉積速率於約1 5 0 °C達到最大。當溫度再上 升時,經沉積的鈀之溶解速率會增加,使得鈀沉積速率相 對地降低。所以,當在8 0 °C至1 5 0 °C附近使用鈀時, 其可以最有效地沉積。前述溫度依賴性試驗顯示鈀具有容 易ί几積在金屬表面上及谷易從金屬表面上分開之性質。 其次,本案發名人執行另一試驗,其將SUS 3 0 4 浸漬在加有鈀、鉑和鍺的個別硝酸鹽化合物之溶液內並確 使鈀、鉑和铑沉積在S U S 3 0 4之上。使用鉑和铑的兩 種組合例如N a 2〔 P t (〇Η ) 6〕和498348 A7 B7 V. Description of the invention (10) The probability of occurrence of S C C is higher than that of other reactors where the water flow rate is high. Therefore, the inventor of the present case explored a solution to increase the individual deposition amount of platinum and rhodium in a nuclear reactor in which a structural material existing in a portion of the reactor where the water flow rate is low. First, the palladium deposition characteristics of the tested s U S 3 0 4 with palladium nitrate were determined through experiments. Figure 3 shows the test results. Palladium still has a high deposition rate even at relatively low temperatures. Its deposition rate reaches a maximum around 150 ° C and the deposition rate decreases as the temperature rises. The reason for this is thought to be related to the stability of the surface film of SU 304. Since the metal surface is the most unstable around 150 ° C, and the metal dissolution is maximized, and the deposition reaction of palladium on the metal surface will increase with temperature, the palladium deposition rate reaches about 150 ° C. maximum. When the temperature rises again, the dissolution rate of the deposited palladium increases, which causes the palladium deposition rate to decrease relatively. Therefore, it can be deposited most efficiently when used near 80 ° C to 150 ° C. The foregoing temperature-dependent test shows that palladium has a property of being easily accumulated on a metal surface and being easily separated from the metal surface. Second, the celebrity in this case performed another test, which immersed SUS 3 0 4 in a solution of individual nitrate compounds added with palladium, platinum, and germanium and indeed deposited palladium, platinum, and rhodium on SUS 3 0 4 . Use two combinations of platinum and rhodium such as Na 2 [P t (〇Η) 6] and
Na3〔Rh (Ν〇2) 6〕的組合與 [P t ( Ν Η 3 ) 4 ) (Ν〇3) 2 和 Rh (NO 3) 3 的組 合而對於鈀,則使用P d ( N〇3 ) 2。於該試驗中,首先 將SUS304試片浸漬在含有Na2〔Pt (〇H)6〕 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) (請先閱讀背面之注意事項再填寫本頁) 訂·"--------The combination of Na3 [Rh (Ν〇2) 6] and [P t (Ν 3) 4) (Ν〇3) 2 and Rh (NO 3) 3 ) 2. In this test, the SUS304 test piece was first immersed in a paper containing Na2 [Pt (〇H) 6]. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 x 297 mm). (Fill in this page) Order " --------
經濟部智慧財產局員工消費合作社印製 498348 A7 __ B7 五、發明說明(11 ) 和N a 3〔 R h ( N〇2 ) 6〕的溶液中及含有 〔Pt ( N Η 3 ) 4 ] (1^〇3)2和尺11(1^〇3)3的溶 液中並於每一試片上沉積鈾和铑。每一種溶液含有1 5 0 P P b枏應的鉑化合物和1 5 0 P P b相應的铑化合物。 每一溶液係呈靜止狀態,且溫度係保持在1 5 0 °C ’且每 一試片係浸漬在對應的溶液中4 8小時。即使是在兩種溶 液中,鉑和铑之間對於S U S 3 0 4試片的沉積特性也沒 有大幅差異。於確定好此項之後,將P d ( N〇3 ) 2加到 含有〔Pt ( N Η 3 ) 4 ] (1^〇3)2和11]1(1^〇3)3 的溶液中並將S U S 3 0 4試片浸漬在此溶液內。於此溶 液中含有lOOppb相應的鉑化合物,150ppb相 應的铑化合物和5 0 p p b相應的鈀化合物。該含有 P d ( N〇3 ) 2的溶液係呈靜滯狀態且溫度與試片浸漬時 間都與前述含有鉑和铑兩化合物的溶液相同。該鈾、铑和 鈀化合物會在溶液中分解並放出其個別的貴金屬離子。呈 離子狀態的鉑、铑和鈀會沉積在每一 s u s 3 〇 4試片的 表面上。當以硝酸鹽形式加入鈀時,爲了防止硝酸根離子 的影響,乃選擇呈硝酸鹽形式可溶於水中的銷和錢化核物 〇 圖4顯示出在前述試驗中於室溫下對有沉積舶和铑的 每一試片測量到的E C P結果及鉑板所具E c p。有沉積 鉛和铑的S U S 3 0 4所得E C P顯著地高於鉑板所具 E C P。鉑和铑在S U S 3 0 4上面的沉積係經由將 SU S 3 0 4浸漬在前述含有 _______U---- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) J---------_裝 (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 498348 A7 __ B7 V. Explanation of the invention (11) and Na 3 [R h (N〇2) 6] and the solution containing [Pt (N Η 3) 4] ( Uranium and rhodium were deposited in a solution of 1 ^ 3) 2 and 11 (1 ^ 03) 3 and each test piece was deposited. Each solution contains a platinum compound of 150 P P b and a corresponding rhodium compound of 150 P P b. Each solution was stationary, and the temperature was maintained at 150 ° C ', and each test piece was immersed in the corresponding solution for 48 hours. Even in the two solutions, there was no significant difference in the deposition characteristics between the platinum and rhodium for the SUS S304 test strip. After determining this, add P d (N〇3) 2 to a solution containing [Pt (NΗ3) 4] (1 ^ 〇3) 2 and 11] 1 (1 ^ 〇3) 3 and A SUS 3 0 4 test piece was immersed in this solution. This solution contained 100 ppb of the corresponding platinum compound, 150 ppb of the corresponding rhodium compound and 50 p p b of the corresponding palladium compound. The solution containing P d (No. 3) 2 was in a stagnant state, and the temperature and the test specimen immersion time were the same as those of the aforementioned solution containing two compounds of platinum and rhodium. The uranium, rhodium and palladium compounds decompose in solution and release their individual precious metal ions. Platinum, rhodium and palladium in an ionic state are deposited on the surface of each of the ss 304 test pieces. When palladium is added in the form of nitrate, in order to prevent the influence of nitrate ions, the pin and the nucleus which are soluble in water in the form of nitrate are selected. Figure 4 shows the deposition of The ECP results measured by each test piece of the ship and rhodium and the E cp possessed by the platinum plate. The E C P of S U S 3 0 4 with deposited lead and rhodium is significantly higher than that of platinum. The deposition of platinum and rhodium on SUS 3 0 4 is by dipping SU S 3 0 4 in the aforementioned containing _______ U ---- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) J- --------_ Loading (Please read the precautions on the back before filling this page)
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經濟部智慧財產局員工消費合作社印製 498348 B7 Λ2 五、發明說明( 〔P t ( Ν Η 3 ) 4 ] ( Ν 〇 3 ) 2 和 R h ( Ν 〇 3 ) 3 的溶 請 先 閱 讀 背 之 注 意 事 項 再 填 寫 本 頁 液中而進行的。沉積有鉑、铑和鈀的S U S 3 Ο 4所具 Ε C Ρ顯示出類似於鉛板Ε C Ρ的變化且在氫對氧莫耳比 幾乎爲3或更高時其會降低到鉑的E C Ρ水平。 經由使用鉑和铑的沉積程序處理過的S U S 3 0 4所 具E C Ρ高於鉑板E C Ρ之理由在於鉑和铑在 S U S 3 0 4上面的個別沉積量都是小者。亦即,單獨的 铑比鈾較難以沉積在S U S 3 0 4上面。即使其有沉積, 也難以使其呈可還原成金屬之狀態。另一方面,在將 S U S 3 0 4浸漬在含有铑化合物和鈷化合物的溶液中時 ,鉑沉積量會減少。雖然铑沉積量不變,铑會還原成金屬 。其原因在於共存在的鉑會將沉積的铑還原。基於前述理 由,難以在慢流速的系統內用足量的鉑和铑覆蓋 s U S 3 0 4。 經濟部智慧財產局員工消費合作社印製 在將S U S 3 0 4浸漬在含有鈀化合物、铑化合物和 鉑化合物的溶液中時,鈀會取代鉑而助成铑的還原。其結 果,可恢復鉑在S ϋ S 3 0 4上的沉積性質。铑會經由在 金屬表面上的還原作用從R h 3 +變成R h。鈀比鉑和铑更 容易沉積在S U S 3 0 4的表面上。其結果,鈀離子係先 沉積在S U S 3 0 4的表面上並在該金屬表面上還原成 P d金屬,然後爲鈀將鉛離子和R h 3 +取代並沉積在 SU S 3 0 4的表面上。金屬鈀會經由置換而將鉑離子和 铑離子還原成金屬狀態而金屬鈀本身則再度變成離子並從 S U S 3 0 4表面排放到水中。有一部分鈀會沉積在 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) 經濟部智慧財產局員工消費合作社印製 498348 A7 B7 Ή 五、發明說明() s U S 3 0 4表面上而不被鉛離子和R 11 3 +所置換。從金 屬排放出的鈀離子會與金屬表面附近經由鉑和铑化合物的 分解所產生和蓄積的分解產物組合而被帶離到水中。該等 分解產物係被快速流動處的水流所帶灕。從上述現象來看 ,沉積在S U S 3 0 4表面上的鉑和铑之量會增加,且還 原成金屬的铑量會增加,且鈀也會沉積一些,使得將 S U S 3 0 4試片浸漬在含有鈀化合物、铑化合物和鉑化 合物的溶液中時,試片的E C Ρ會顯著地減低。處於未被 還原成金屬的狀態下之铑經推斷係處於會緩慢地物理吸附 在金屬表面且容易從金屬表面分離的狀態之下。當其還原 成金屬铑時,表面上的安全性會增加並助成長時期的 E C Ρ減低。 即使是將S ϋ S 3 0 4試片浸漬在含有鉑化合物和鈀 化合物的溶液.中時,試片上的鉑沉積量會因爲鈀的運作而 比將S U S 3 0 4試片浸漬在含有鉑化合物的溶液中之情 況較爲增加。即使是將S U S 3 0 4試片浸漬在含有铑化 合物和鈀化合物的溶液中時,試片上的铑沉積量會因爲鈀 的運作而比將S U S 3 0 4試片浸漬在含有铑化合物的溶 液中之情況較爲增加。 從上述實驗結果看來,於使用含有鈾化合物和铑化合 物中至少一者的溶液時,必須添加鈀化合物以改良對應的 高貴金屬元素之沉積效應。 本案發明人基於前述探討結果發現宜於將鉑和铑高貴 金屬元素中至少一者的化合物與鈀化合物注射到核子反應 -- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) ---------訂----------Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 498348 B7 Λ2 V. Explanation of the invention (〔P t (Ν Η 3) 4] (Ν 〇3) 2 and Rh (Ν 〇3) 3 Note: It was performed by filling in the liquid on this page. SUS 3 〇4 with platinum, rhodium, and palladium deposited exhibits E C P similar to the change of lead plate E C P and almost has a hydrogen-to-oxygen molar ratio. At 3 or higher, it decreases to the EC P level of platinum. The reason why SUS 3 0 4 treated with a deposition process using platinum and rhodium has an EC P higher than that of the platinum plate EC P is that platinum and rhodium are at SUS 3 0 4 The individual deposition amounts above are small. That is, rhodium alone is more difficult to deposit on SUS 304 than uranium. Even if it is deposited, it is difficult to make it into a state that can be reduced to metal. On the other hand, When SUS 304 is immersed in a solution containing a rhodium compound and a cobalt compound, the amount of platinum deposited will decrease. Although the amount of rhodium is unchanged, rhodium will be reduced to metal. The reason is that co-existing platinum will deposit the rhodium Reduction. For the foregoing reasons, it is difficult to use in a slow flow system Sufficient amounts of platinum and rhodium cover US 3 04. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. When SUS 3 04 is immersed in a solution containing palladium, rhodium and platinum compounds, palladium will replace platinum and Facilitates the reduction of rhodium. As a result, the deposition properties of platinum on S ϋ S 3 0 4 can be restored. Rhodium will change from Rh 3 + to Rh through reduction on the metal surface. Palladium is easier to deposit than platinum and rhodium On the surface of SUS 3 0 4. As a result, palladium ions are first deposited on the surface of SUS 3 0 4 and reduced to P d metal on the metal surface, and then lead ions and Rh 3 + are substituted for palladium and It is deposited on the surface of SU S 304. Metal palladium will reduce platinum ions and rhodium ions to a metal state through replacement. Metal palladium itself will become ions again and be discharged into the water from the surface of SUS 304. Some palladium will Deposited on this paper scale applicable to China National Standard (CNS) A4 specifications (210 X 297 public love) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 498348 A7 B7 Ή 5. Description of the invention () s US 3 0 4 on the surface without By lead ions and R 11 3 + Replacement. The palladium ions discharged from the metal will be taken out of the water by combining with the decomposition products generated and accumulated near the surface of the metal through the decomposition of platinum and rhodium compounds. These decomposition products are carried away by the fast-flowing water From the above-mentioned phenomenon, the amount of platinum and rhodium deposited on the surface of SUS 304 will increase, and the amount of rhodium reduced to metal will increase, and palladium will also deposit some, so that the SUS 304 test piece is impregnated In a solution containing a palladium compound, a rhodium compound, and a platinum compound, the EC P of the test piece is significantly reduced. The rhodium in a state where it has not been reduced to metal is presumed to be in a state where it is slowly physically adsorbed on the metal surface and easily separated from the metal surface. When it is reduced to metal rhodium, the safety on the surface is increased and the E C P is reduced during the growth period. Even when the S ϋ S 3 0 4 test piece is immersed in a solution containing a platinum compound and a palladium compound, the amount of platinum deposited on the test piece will be lower than that of the SUS 3 0 4 test piece immersed in the platinum compound due to the operation of palladium. The situation in the solution was increased. Even when the SUS 304 test piece is immersed in a solution containing a rhodium compound and a palladium compound, the amount of rhodium deposited on the test piece due to the operation of palladium is greater than that when the SUS 304 test piece is immersed in a solution containing a rhodium compound. The situation has increased. From the above experimental results, when using a solution containing at least one of a uranium compound and a rhodium compound, a palladium compound must be added to improve the deposition effect of the corresponding noble metal element. Based on the results of the foregoing discussion, the inventor of the present case found that it is suitable to inject a compound of at least one of platinum and rhodium noble metal elements with a palladium compound into a nuclear reaction-the paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) ) (Please read the notes on the back before filling out this page) --------- Order ----------
498348498348
五、發明説明(14 ) (請先聞讀背面之注意事項再填寫本頁) 爐的反應爐水中且同時,將該高金屬化合物和鈀化合物注 射到反應爐水中到使得反應爐水內的鈀莫耳數比前述高貴 金屬元素在反應爐水中的莫耳數較爲小。經由如此般將高 貴金屬元素與鈀注射到反應爐水中,基於前述理由,高貴 金屬元素(鉑和鍺中至少一者)與鈀在存在於反應爐水流 速低的部位中之核子反應爐廠構造部件(用不鏽鋼製成者 )表面上的沉積量會增加。高貴金屬元素(鉑和铑中至少 一者)與JG在存在於反應爐水流速低的部位中之核子反應 爐廠構造部件上的沉積量當然也會增加。 在將鉑和鍺中至少一者的高貴金屬元素和鈀沉積在核 子反應爐廠構造部件的表面上之後,於B W R的運轉中, 要將電位減低到一 5 0 0毫伏v s S Η E所需的氫注入 量可設定到至少2 : 1 (莫耳比)的反應爐水中氫注入量 經濟部智慧財產局員工消費合作社印製 對溶氧濃度的化學計量比例。通常,在B W R核子反應爐 壓力容器內的溶氧濃度於沒有注入氫時爲2 0 0 P P b。 所以,在化學計量比例爲2時的氫濃度爲1 5 p p b。另 一方面,當給水中的氫濃度增加到0 _ 4 P P m時,主蒸 汽系統的輻射劑量率會增加,使得在考慮於給水流速對爐 心流速比例爲約1 5 %的情況例如1 1 〇 〇 〇 〇 〇仟瓦級 核子反應爐輸出的B W R和進步型B W R ( A B W R )時 ,反應爐水中的氫濃度爲6 0 P P b。所以’反應爐水中 的氫濃度可設定在1 5至6 0 P P b的範圔內。此對應於 給水中0 · 1至0 . 4 ρ p m的氫濃度。此種氫濃度設定 値可涵蓋具有不同核子反應爐輸出之B W R ° 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -17- 498348 A7 B7 五、發明說明(15 ) 或者,經由測量與反應爐水接觸的核子反應爐廠構造 部件所具E C P,可以控制氫注射量使得可以將E C P設 定在一 2 30毫伏v s SHE或更低者。通常,係事先 測量相對於氫注射量的核子反應爐廠構造部件所具E C P 之變化且由所測得値與分析結果來決定反應爐水中所需的 氫濃度。氫注射量係根據給水流速來控制以得到所決定的 氫濃度。 其次,要探討反應爐水p Η直對於E C P的影響。具 體而言,至此所考慮的氧和過氧化氫之還原反應可用下面 的式(1 )和(2 )表出。於式(1 )和(2 )的反應中 ,由於有質子(Η+)參與在左邊中: 〇2+4H + +4 6 +2Η2〇一一一一(1) Η2〇2+2Η + +2 e — + 2Η2〇——- (2) 因此彼等.反應決定於反應爐水P H。當反應爐水p Η 增加時,質子濃度減低,使得從左邊到右邊的反應受到壓 抑。氫的氧化反應係用式(3 )表出。不過,氫在高貴金 屬上顯示出可逆性: Η 2 ^ 2 Η + + 2 e ------(3) 此外,也會產生式(4 )的反應。這些反應都是平衡 系統且當P Η增加時: 2H + +2e— +Η2-----(4) 質子濃度會減低,使得式(4 )反應受到壓抑且使式 (3 )反應顯著地進展。其結果,於氫注入操作中將有高 貴金屬沉積著的核子反應爐廠構造部件表面放到鹼性環境 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ----;---------- (請先閱讀背面之注意事項再填寫本頁) — 訂-----------V. Description of the invention (14) (Please read the precautions on the reverse side before filling out this page) The reactor furnace water of the furnace and at the same time, the high metal compound and palladium compound are injected into the reactor furnace water to make the palladium in the reactor furnace water The molar number is smaller than the molar number of the noble metal element in the reactor water. By injecting noble metal elements and palladium into the reactor water in such a manner, for the foregoing reasons, the structure of a nuclear reactor plant where noble metal elements (at least one of platinum and germanium) and palladium exist in a part where the water flow rate of the reactor is low The amount of deposition on the surface of the component (made of stainless steel) will increase. Of course, the deposition amount of noble metal elements (at least one of platinum and rhodium) and JG on the nucleus reaction existing in the part where the water flow rate of the furnace is low will also increase. After depositing the noble metal elements of at least one of platinum and germanium and palladium on the surface of the structural parts of the nuclear reactor plant, during the operation of BWR, the potential should be reduced to 500 millivolts vs S Η E The required hydrogen injection amount can be set to at least 2: 1 (mole ratio) in the reactor water. The amount of hydrogen injected into the reactor is printed on the stoichiometric ratio of dissolved oxygen concentration by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Generally, the dissolved oxygen concentration in the pressure vessel of the B W R nuclear reactor is 2 0 P P b without hydrogen injection. Therefore, the hydrogen concentration at a stoichiometric ratio of 2 is 15 p p b. On the other hand, when the hydrogen concentration in the feedwater is increased to 0 _ 4 PP m, the radiation dose rate of the main steam system will increase, so that when the ratio of the feedwater flow rate to the core flow rate is about 15%, such as 1 1 In the case of BWR and progressive BWR (ABWR) output from a 0000-watt nuclear reactor, the hydrogen concentration in the reactor water was 60 PP b. Therefore, the hydrogen concentration in the reactor water can be set within the range of 15 to 60 P P b. This corresponds to a hydrogen concentration in the feedwater of from 0.1 · 0.4 to 0.4 p m. This hydrogen concentration setting can cover BWR with different nuclear reactor output. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -17- 498348 A7 B7 V. Description of invention (15) Or, via Measure the ECP of the nuclear reactor plant construction components in contact with the reactor water. The amount of hydrogen injected can be controlled so that the ECP can be set at 2 30 mV vs SHE or lower. Usually, the change in E C P of the nuclear reactor plant structural components relative to the amount of hydrogen injected is measured in advance, and the required hydrogen concentration in the reactor water is determined by the measured radon and the analysis results. The hydrogen injection amount is controlled according to the feed water flow rate to obtain the determined hydrogen concentration. Secondly, it is necessary to investigate the effect of the reactor water p Straightening on E C P. Specifically, the reduction reaction of oxygen and hydrogen peroxide considered so far can be expressed by the following formulae (1) and (2). In the reactions of formulas (1) and (2), there are protons (Η +) participating in the left side: 〇2 + 4H + +4 6 + 2Η2〇 one by one (1) Η2〇2 + 2Η + + 2 e — + 2Η2〇 ——- (2) So they. The reaction depends on the pH of the reactor water. When the reactor water p Η increases, the proton concentration decreases, so that the reaction from the left to the right is suppressed. The oxidation reaction of hydrogen is expressed by the formula (3). However, hydrogen shows reversibility on noble metals: Η 2 ^ 2 Η + + 2 e ------ (3) In addition, the reaction of formula (4) also occurs. These reactions are equilibrium systems and when PP is increased: 2H + + 2e— + Η2 ----- (4) The proton concentration will decrease, making the reaction of formula (4) suppressed and the reaction of formula (3) significantly progress. As a result, during the hydrogen injection operation, the surface of the structural parts of the nuclear reactor plant with noble metals deposited was placed in an alkaline environment. The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---- ; ---------- (Please read the notes on the back before filling this page) — Order -----------
經濟部智慧財產局員工消費合作社印製 498348 ^l -Ί 3 ^r· Β7 五、發明説明(16 ) (請先聞讀背面之注意事項再填寫本頁) 中時,氧的還原電流密度會更爲減低且氫的氧化電流密度 會更爲增加。所以,由圖1所示的關係,將核子反應爐廠 構造部件的電化學腐鈾電位減低所需的氫量可能比在中性 情況中較爲小。在沒有注入氫時,反應爐水中的溶氧濃度 爲約2 0 0 P P b。此時,於化學計量基礎上所需的氫量 爲1 5 P P b。由於在沒有注入氫時,反應爐水中的氫濃 度經測量爲約1 0 P P b,因此若將有沉積高貴金屬的表 面上之氧和過氧化氫的還原電流密度經由P Η控制壓低至 約2 / 3,則其電位只能由既存的氫予以減低到約 一 500毫伏vs SHE。一般而言,高溫水中的質子 濃度可以減低到1 X 1 0 ^ 6莫耳/升或更低者,使得宜於 將其P Η値控制到約爲8。即使加入只作用在氧和過氧化 氫的還原反應之元素且用相同的方式使還原反應減小,也 可以獲得相同的效應。 經濟部智慧財產局員工消費合作社印製 基於彼等結果,本案發明人的構想爲在將前述所選高 貴金屬元素的化合物和鈀化合物注射到反應爐水後的新操 作循環中,宜於將氫和鹼性物質給到反應爐水中。於氫注 入效應與弱鹼性水效應的組合中,核子反應爐廠構造部件 所具E C Ρ可更爲減低。 (第一實施例) 本發明一適當具體實例的緩和核子反應爐廠構造部件 的應力腐蝕裂化之方法要參照附圖予以解說。圖5顯示出 本實施例方法所要應用的B W R廠。 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) -19- 498348Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 498348 ^ l -Ί 3 ^ r · B7 V. Description of Invention (16) (Please read the precautions on the back before filling this page), the oxygen reduction current density will be It is further reduced and the oxidation current density of hydrogen is further increased. Therefore, from the relationship shown in Figure 1, the amount of hydrogen required to reduce the electrochemical uranium decay potential of the structural components of a nuclear reactor plant may be smaller than in the neutral case. In the absence of hydrogen injection, the dissolved oxygen concentration in the reactor water was about 200 P P b. At this time, the amount of hydrogen required on a stoichiometric basis is 15 P P b. Since the hydrogen concentration in the reactor water is measured to be about 10 PP b when no hydrogen is injected, if the reduction current density of oxygen and hydrogen peroxide on the surface where noble metals are deposited is reduced to about 2 via P Η control / 3, its potential can only be reduced by existing hydrogen to about 500 millivolts vs SHE. In general, the proton concentration in high temperature water can be reduced to 1 X 1 0 ^ 6 mol / L or lower, making it appropriate to control its P 到 to about 8. The same effect can be obtained even if an element that acts only on the reduction reaction of oxygen and hydrogen peroxide is added and the reduction reaction is reduced in the same manner. Based on their results, the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs based on their results. The inventor's idea for this case is to inject hydrogen in the new operation cycle after injecting the compound of the noble metal element and the palladium compound selected above into the reactor water. And alkaline substances into the reactor water. In the combination of the hydrogen injection effect and the weak alkaline water effect, the E C P of the structural components of the nuclear reactor plant can be further reduced. (First embodiment) A method for mitigating stress corrosion cracking of structural parts of a nuclear reactor plant in a suitable specific example of the present invention will be explained with reference to the drawings. Figure 5 shows the BW R plant to which the method of this embodiment is to be applied. This paper size applies to China National Standard (CNS) Α4 size (210X297 mm) -19- 498348
A7 B7 五、發明説明(17 ) (請先閲讀背面之注意事項再填寫本頁) 該BWR廠具有一反應爐壓力容器3和一渦輪機6。 該反應爐壓力容器3係安裝在一格納容器3 5內且其內部 具有一爐心1 3。於該反應爐壓力容器3之內’安裝著反 應爐內構造,例如包住爐心1 3的及一用以支撐該爐心屏 蔽3 6之屏蔽支撐體(圖中未顯示出)。於爐心1 3內部 裝有眾多燃料組s (圖中未顯示出)。 經濟部智慧財產局員工消費合作社印製 要給到爐心1 3中的反應爐水係經由燃料組s中所含 核分裂物質的核分裂予以加熱和蒸發。此蒸氣係經由主蒸 氣管5從反應爐壓力容器3導到渦輪機6。渦輪機6即被 驅動並轉動所連接的馬達(圖中未顯示出)。從渦輪機6 排出的蒸氣經由冷凝器7凝結後從給水管2以給水形式給 到反應爐壓力容器3內。此給水隨後會通過安裝在給水管 2中的一冷凝液栗8,一冷凝液脫礦質器9,一低壓給水 加熱器1 0,一給水泵1 2,及一高壓給水加熱器1 1。 給水係以反應爐水形式給到爐心1 3之中。反應爐水係被 循環栗1驅動向下移到位於爐心屏蔽3 6外面的下導管 1 4中,透過一循環系統管4到達下高壓室1 4,在導到 爐心1 3之內。 反應爐壓力容器3中的反應爐水係由泵1 7 c的驅動 而導到連接到循環系統管4的反應爐水淸淨系統管1 7。 在該反應爐水淸淨系統管1 7內安裝著一再生型熱交換器 17a ’該泵17c,一非再生型熱交換器17b,及一 脫礦質器1 8。該反應爐水淸淨系統管1 7內的反應爐水 會通過這些裝置,特別會被脫礦質器1 8所純化,並透過 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ------- -20- 498348 A7 __ B7 _ 五、發明說明(18 ) 給水管2回流到反應爐壓力容器3中。.在連接到該反應爐 水淸淨系統管1 7的一採樣管2 1中安裝著測量反應爐水 品質所用的水品質測量裝置2 0 a 。於下高壓室1 4中的 一部份反應爐水係由連接到反應爐壓力容器3底部的排管 1 6導到該反應爐水淸淨系統管1 7並由脫礦質器1 8予 以純化。於排管1 6安裝著測量反應爐水所具電化學腐蝕 電位所用的電化學腐蝕電位(E C P )感測器2 5。於連 接到排管1 6的採樣管2 2中安裝著測量反應爐水品質所 用的水品質測量裝置2 0 b。從採樣管2 1和2 2採取所 得反應爐水的品質(溶氧濃度、溶氫濃度、P Η、傳導係 數、等)係在將反應爐水解壓與冷卻之後用水品質測量裝 置2 0 a和2 0 b線上測量的。與流經排管1 6內部的反 應爐水接觸之構造材料所具E C P係用E C P感測器2 5 測量的。如此一來,可以測得反應爐水的氧濃度與過氧化 氫濃度。 從給水管2透過採樣管1 9採到的給水樣鎖具品質( 溶氧濃度、溶氫濃度、P Η、傳導係數、等)係係在將給 水解壓與冷卻之後用水品質測量裝置2 0 c線上測量的。 此外,有一水品質測量裝置2 0 d透過採樣管2 3連接到 主蒸氣管5。該水品質測量裝置2 0 d將抽取自採樣管 2 3的蒸氣凝結,將此凝結水解壓與冷卻,然後線上測量 該凝結水的品質。於該主蒸氣管5上安裝有測量主蒸氣系 統的輻射劑量率所用之劑量率監測器2 6 ° 該等水品質測量裝置2 0 a至2 〇 d係將目標水&壓 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁)A7 B7 V. Description of the invention (17) (Please read the notes on the back before filling this page) The BWR plant has a reactor pressure vessel 3 and a turbine 6. The reactor pressure vessel 3 is installed in a Gner vessel 35 and has a furnace core 13 inside. Inside the reaction vessel pressure vessel 3, a reaction vessel structure is installed, such as a furnace core 13 and a shield support (not shown) for supporting the furnace core shield 36. Inside the furnace core 1 3 there are a number of fuel groups s (not shown). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The reactor water system in the furnace core 13 is heated and evaporated by the nuclear fission contained in the fuel group s. This steam is guided from the reactor pressure vessel 3 to the turbine 6 via the main steam pipe 5. The turbine 6 is driven and rotates the connected motor (not shown). The steam discharged from the turbine 6 is condensed through a condenser 7 and is fed into the reactor pressure vessel 3 from the water supply pipe 2 as feed water. The feedwater then passes through a condensate pump 8, a condensate demineralizer 9, a low-pressure feedwater heater 10, a feedwater pump 12, and a high-pressure feedwater heater 11 installed in the feedwater pipe 2. The water supply system is supplied to the furnace core 13 in the form of reaction furnace water. The water system of the reaction furnace is driven down by the circulating pump 1 into the lower duct 14 located outside the furnace core shield 3 6 and passes through a circulation system pipe 4 to reach the lower high pressure chamber 14 and is guided to the furnace core 13. The reactor water in the reactor pressure vessel 3 is driven by a pump 17c to the reactor water purification system pipe 17 connected to the circulation system pipe 4. A regenerative heat exchanger 17a ', a pump 17c, a non-regenerative heat exchanger 17b, and a demineralizer 18 are installed in the reactor water purification system pipe 17. The reactor furnace water in the reactor water purification system tube 17 will pass through these devices, especially purified by the demineralizer 18, and apply the Chinese National Standard (CNS) A4 specification (210X297 mm) through this paper size. ------- -20- 498348 A7 __ B7 _ V. Description of the invention (18) The feed water pipe 2 is refluxed into the pressure vessel 3 of the reaction furnace. A water quality measuring device 20 a for measuring the water quality of the reaction furnace is installed in a sampling tube 21 connected to the reactor water purification system tube 17. A part of the reaction furnace water in the lower high-pressure chamber 14 is led by a pipe 16 connected to the bottom of the reactor pressure vessel 3 to the reactor water purification system pipe 17 and purified by a demineralizer 18 . An electrochemical corrosion potential (E C P) sensor 25 for measuring the electrochemical corrosion potential of the reactor water is installed on the row of pipes 16. A water quality measuring device 2 0 b for measuring the water quality of the reaction furnace is installed in the sampling tube 22 connected to the row 16. The quality of the reaction furnace water (dissolved oxygen concentration, dissolved hydrogen concentration, P Η, conductivity coefficient, etc.) taken from the sampling tubes 2 1 and 2 2 is obtained by using a water quality measuring device 20 a and 2 0 b Measured on line. The E C P of the construction material that is in contact with the reactor furnace water flowing through the inside of the discharge pipe 16 is measured with an E C P sensor 2 5. In this way, the oxygen concentration and hydrogen peroxide concentration of the reactor water can be measured. The quality of the water supply sample lock (dissolved oxygen concentration, dissolved hydrogen concentration, P Η, conductivity coefficient, etc.) obtained from the water supply pipe 2 through the sampling pipe 19 is connected to the water quality measuring device 20 c line after the water supply pressure is cooled and cooled. measured. In addition, a water quality measuring device 20 d is connected to the main steam pipe 5 through a sampling pipe 2 3. The water quality measuring device 20 d condenses the steam extracted from the sampling tube 23, hydrolyzes and condenses the condensate, and then measures the quality of the condensed water online. A dose rate monitor 2 6 ° for measuring the radiation dose rate of the main steam system is installed on the main steam pipe 5. The water quality measuring devices 20 a to 20 d are the target water & China National Standard (CNS) A4 Specification (210 X 297 mm) (Please read the notes on the back before filling this page)
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經濟部智慧財產局員工消費合作社印製 498348 A7 __B7 五、發明說明(9 ) I (請先閱讀背面之注意事項再填寫本頁) 與冷卻之後在室溫至約5 〇 t:及1至約5大氣壓的條件下 測量水的品質。該等水品質測量裝置2 〇 a至2 0 d所得 溶氧濃度、溶氫濃度、p Η、傳導係數和其他者之測量結 果係在顯示裝置(圖中未顯示出)上顯示與監測。反應爐 水的ρ Η係保持在5 · 3至8 · 6的範圍內而反應爐水的 傳導係數係經保持在1 〇 # s / c m或更低者。 於循環系統管4連接有一高貴金屬化合物注入器3 1 。對於在低壓給水加熱器1 〇與給水泵1 2之間的給水管 連接著一氫注入器2 4。 在冷凝器7上連接著一廢氣系統管2 8。對該廢氣系 統管2 8安裝著一蒸氣抽取器2 7和一(重組裝置3 0。對 於在冷凝器7與蒸氣抽取器2 7之間的廢氣系統管2 8連 接著一氧注入器2 9。 經濟部智慧財產局員工消費合作社印製 本具體實例在具有上述構成的BWR廠內緩和應力腐 鈾裂化之方法要參照圖7予以解說。於圖7中,水平軸指 該B W R廠的運轉時間而垂直軸指反應爐水的溫度及反應 爐水中的高貴金屬元素濃度。圖7槪示出在一運轉循環週 期內的反應爐停機運轉中應爐水的溫度及反應爐水中的高 貴金屬元素濃度之變化。於此情況中,一運轉循環意指從 核子反應爐啓動到核子反應爐停機以交換燃料組s之期間 且其包括核子反應爐的啓動操作,核子反應爐的額定輸出 操作(額定操作),及核子反應爐的停止操作。於一運轉 循環過去之後會將裝在爐心1 3中的一部份燃料組s從爐 心1 3取出並換上新的燃料組s。 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 498348 A7 - ___ B7Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 498348 A7 __B7 V. Description of the invention (9) I (Please read the precautions on the back before filling this page) and cool at room temperature to about 5 0t: and 1 to about Water quality was measured at 5 atmospheres. The measurement results of the dissolved oxygen concentration, dissolved hydrogen concentration, pΗ, conductivity, and others obtained by the water quality measuring devices 20a to 20d are displayed and monitored on a display device (not shown in the figure). The ρ Η of the reactor water is kept in the range of 5 · 3 to 8 · 6 while the conductivity of the reactor water is kept at 10 # s / cm or lower. A noble metal compound injector 3 1 is connected to the circulation system pipe 4. A hydrogen injector 24 is connected to the water supply pipe between the low-pressure water supply heater 10 and the water supply pump 12. An exhaust system pipe 28 is connected to the condenser 7. A steam extractor 27 and a (recombination device 30) are installed to the exhaust system pipe 28. An oxygen injector 2 9 is connected to the exhaust system pipe 2 8 between the condenser 7 and the steam extractor 27. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The specific method for mitigating stress cracking uranium cracking in a BWR plant with the above structure shall be explained with reference to Fig. 7. In Fig. 7, the horizontal axis indicates the operating time of the BWR plant. The vertical axis refers to the temperature of the reaction furnace water and the concentration of the noble metal elements in the reaction furnace water. Figure 7 槪 shows the temperature of the furnace water and the concentration of the noble metal elements in the reaction furnace water during a shutdown cycle of the reaction furnace. In this case, an operating cycle means the period from the start of the nuclear reactor to the shutdown of the nuclear reactor to exchange the fuel group s and it includes the startup operation of the nuclear reactor, the rated output operation of the nuclear reactor (rated operation ), And the stop operation of the nuclear reactor. After a cycle of operation has passed, a part of the fuel group s contained in the furnace core 13 is taken out of the furnace core 13 and replaced with a new fuel group s . This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 498348 A7-___ B7
Of) 五、發明說明() 根據此具體實例,於核子反應爐停.止運轉減低核子反 應爐輸出之中,在反應爐水溫度到達1 5 0 °C之前(如當 該溫度減低到1 7 0 °C時)立即從高貴金屬化合物注入器 (請先閲讀背面之注意事項再填寫本頁) 3 1將鈀化合物、鉑化合物和铑化合物開始注射到在循環 管4內部流動的反應爐水中。當反應爐水溫度到達8 〇 °c 時即停止注入彼等化合物。於1 7 0 °C至8 0 t之間的期 間爲高貴金屬注入期間(圖7 )。於此期間,係將前述三 種化合物注入。將個別化合物導到反應爐壓力容器3的下 高壓室1 5中。這些化合物從高貴金屬化合物注入器3 1 的進料起始與進料停止係經由將安裝在高貴金屬化合物注 入器3 1中的閥4 2,4 6和5 0打開和關閉而進行的。 該高貴金屬化合物注入器31具有一裝塡著鈀化合物 溶液的槽4 0,一裝塡著鉑化合物溶液的槽4 4及一裝塡 著铑化合物溶液的槽4 8。各槽都透過個別的管4 1, 經濟部智慧財產局員工消費合作社印製 4 5和4 9連接到一經連接到循環系統管4的管5 2。閥 4 2和泵4 3係經安裝到管4 1 ,閥4 6和泵4 7係經安 裝到管4 5,且閥5 0和泵5 1係經安裝到管4 9。鈀化 合物、鉛化合物和铑化合物的注入量可分別調整。亦即, 一控制器5 3可以經由使用由感應偶合電漿重量分析儀 3 8 (或感應偶合電漿重量分析儀3 7 )測得的反應爐水 中鈀、鉑和铑個別濃度測量値而個別地控制閥4 2,4 6 和5 0的打開。各化合物溶液注入量的此種調整係非常有 利者,係因爲各高貴金屬元素在構造部件表面上的沉積速 率互不相同且各高貴金屬元素在反應爐水中的濃度之變化 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 498348 Α7 __ Β7 91 五、發明說明() 速率也不相同之故。 於此具體實例中,係使用P d ( N〇3 ) 2作爲鈀化合 物,使用〔P t ( Ν Η 3 ) 4〕 ( Ν〇3 ) 2作爲鉑化合物和 使用R h ( Ν〇3 ) 3作爲铑化合物。彼等化合物都是溶解 在反應爐水中且鈀,鉑和铑都是以離子狀態存在於反應爐 水中。要將反應爐水中的鈀濃度調定在5 0 p p b,將鉑 濃度調定在1 0 0 p p b及將铑濃度調定在1 〇 〇 p p b ,每一化合物在反應爐水中的注入量係經由調整相應閥的 開放予以控制。於前述高貴金屬注入期中,於反應爐水溫 度爲1 5 0至8 0 C之期間’將’鉛和錶的個別濃度分 別控制到前述設定濃度。鈀,鉑和铑的個別濃度係用感應 偶合電漿重量分析儀3 7或3 8測量者,將於後面說明之 。基於這些測量値,調整對應的閥並控制反應爐水中的個 別濃度。反應爐水中的鈀,鉑和铑諸離子會沉積在B W R 廠與反應爐水接觸的構造部件表面上。於該構造部件表面 上經由沉積鈀,鉑和鍺而形成彼等混合金屬的膜。在加入 鈀化合物時,鉛和铑在構造部件表面上的個別沉積量會增 加。再者,鉑和铑在存在於反應爐水流速低的部位中之構 造部件表面上的個別沉積量也會增加。在8 0至1 5 0 °C 的反應爐水溫度範圍內,鉑和铑在核子反應爐廠構造部件 上的個別沉積量會增加。 取代P d ( N〇3 ) 2者,可以使用 [P d ( Ν Η 3 ) 4 ] (Ν〇3)2 或 〔P d ( Ν 〇 2 ) 2〕 ( Ν Η 3 ) 2。取代 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) d丨訂: 經濟部智慧財產局員工消費合作社印製 24 498348 Α7 _______ Β7 五、發明說明() (請先閱讀背面之注意事項再填寫本頁) [P d ( Ν Η 3 ) 4 ] (NO 3) 2 者,可以使用 〔P t ( Ν Η 3 ) 4 ](〇Η) 2。取代 Rh (Ν〇3 ) 3 者 ,可以使用〔Rh (ΝΗ3) 5 (Η2〇)〕(Ν〇3) 3。 有關前述三種高貴金屬元素的個別化合物,係選用每一種 化合物分解時產生銨離子和硝酸根離子的化合物。這兩種 離子極少影響核子反應爐廠構造部件的腐蝕。反應爐水的 ρ Η會因爲氨的緩衝作用(cushioning effect )而不容易大 幅地改變。 經濟部智慧財產局員工消費合作社印製 該感應偶合電漿重量分析儀3 7和3 8係經安裝到採 樣管2 1和2 2。每一種高貴金屬元素在反應爐水中的濃 度可以經由定期地(或視需要地)用該感應偶合電漿重量 分析儀3 7和3 8測量該等採樣管2 1和2 2所採取的反 應爐水予以確定。取代該感應偶合電漿重量分析儀者,可 以使用無焰式原子吸收分析儀。再者,當採樣管2 1和 2 2有安裝反應爐水傳導係數計(或ρ η計)時,可以用 該反應爐水傳導係數計來監測每一種高貴金屬元素在反應 爐水中的濃度。亦即,在沒有採取反應爐水樣之下使用反 應爐水傳導係數計(或ρ Η計)來監測高貴金屬元素在反 應爐水中的濃度改變所引起的反應爐水傳導係數(或ρ Η )之變化。 當構造部件表面上的沉積被消除掉且鈾,铑和鈀等離 子被反應爐水淸淨系統的脫礦質器1 8所分別脫除時,鉑 ’铑和鈀在反應爐水中的個別量即減低。於高貴金屬注射 期間從高貴金屬化合物注入器3 1注入每一種鉑,铑和銷 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 498348 A7 r———_ B7 五、發明說明() 化合物之舉係經進行以彌補被脫礦質器i 8脫除掉的個別 里。於局貴金屬注射期間終止後,鉑,铑和銷在反應爐7jC 中的個別濃度會因脫礦質器1 8的脫除操作而減低。 於經由注入個別鈾,铑和鈀化合物所進行的鈾,铑和 鈀在核子反應爐廠構造部件上的沉積程序完成之後,即停 止B W R廠的運轉。於隨後的定期檢查期中,係執行燃料 組s的交換和廠,的定期檢查。於定期檢查結束之後,在 B W R廠啓動時,如圖7中所示者,係啓動控制棒從爐心 的拉出操作。於反應爐水溫度到達額定溫度(約2 8 0 °C )且核子反應爐壓力到達設定壓力(7 0大氣壓)後,即 將核子反應爐輸出增加到1 0 0 %。 在給水泵1 2被驅動時,即打開氫注入器2 4的閥( 圖中未顯示出)並將氫注射到給水管2之中。包括著氫的 給水係經導到反應爐壓力容器3之內。於此情況中,係在 根據氫注入量有效率地減低E C P和驗證E C P的回應之 後決定在反應爐壓力容器3內部反應爐水中的氫濃度。該 氫濃度較佳者爲在反應爐水中的2 0至6 0 P P b。不過 ,由於反應爐水中的氫濃度會隨著反應爐壓力容器在反應 爐水中的位置和核子反應爐的運轉條件而變異,因此氫注 入量要控制以使給水中的氫濃度調定在0 · 1至0 · 4 p p m範圍內。於此實施例中,反應爐水中的氫濃度,如 圖8中所示者,係經控制到2 5 p p b。當S C C預防標 的部件處的E C P可以直接測量或可以經由計算來估計時 ,可以控制來自氫注入器2 4的氫注入量以使該部件處的 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 7丨訂‘ 經濟部智慧財產局員Η消費合作社印製 498348 經濟部智慧財產局員工消費合作社印製 A7 B7___ 24 五、發明說明() ECP調定在一 230毫伏v s SHE或更低者。 經由沉積在核子反應爐廠構造部件表面上的鉑、铑和 鈀所具催化作用,注入的氫與包括在反應爐水內的氧之間 的反應會被促進並產生水。如此,氫可助成在核子反應爐 廠構造部件附近的反應爐水內所含溶氧之還原。所以’在 反應爐壓力容器3內的核子反應爐廠構造部件所具E C P 會減低且使該構造部件的S C C受到極端地壓抑。特別者 ,也在與反應爐水流速低的反應爐水部位接觸之核子反應 爐廠構造部件表面上沉積鉑,铑和鈀,使得該接觸反應爐 水部位之構造部件所具E C P降低到一 2 3 0毫伏v s SHE或更低者,如圖4中黑方形標誌()所示者。 該接觸反應爐水部位的構造部件之S C C也受到顯著地壓 抑。由於利用到鉑,铑和鈀的催化作用,因此與溶氧反應 所需的氫量即顯著地減低。所以’雖然溶氧還原效應係大 者,氮1 6的產生量仍會顯著地減少。由於蒸氣系統例如 主蒸氣管5和渦輪機6的表面劑量率沒有增加,彼等的維 修和檢查可以容易地實施且該維修和檢查所需的時間得以 縮短。 根據此實施例,反應爐水中的鈀濃度等於反應爐水中 的鉑濃度和铑濃度,使得鈀濃度低於鉑濃度和铑濃度。亦 即,鈀的莫耳數小於鉛和铑的莫耳數。如此一來,鉑和铑 的個別沉積量會增加。當鈀的莫耳數大於鉑和铑的莫耳數 時,鉑和鍺在構造部件上的沉積會被遏止且彼等的個別沉 積量會減少。其原因在於容易沉積的鈀之沉積量增加之故 __- -_ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) J丨訂, 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 498348 A7 _____ B7 五、發明說明(25 ) 。鈀係容易沉積者,雖則其反而比鉑和i老更容易離子化且 對應於此其會容易地從其所沉積的構造部件表面上溶解到 反應爐水中。其結果,鉑和铑個別沉積量的增加會使在構 造部件表面附近的反應爐水中之溶氧濃度於長期間內遠更 爲減低且使核子反應爐廠構造部件的E C P爲之減低。 (第二實施例) 本發明另一具體實例的緩和核子反應爐廠構造部件的 應力腐蝕裂化之方法要參照圖9予以解說。本實施例所用 B W R廠的構造係相同於參照圖5說明過的第一實施例所 用的B W R廠所具構造。根據此實施例,係於核子反應爐 停止運轉中反應爐水溫度從1 7 0 t降低到8 0 °C之時, 即將鈀化合物(P d ( N〇3 ) 2 ),鉑化合物 ([P t ( Ν Η 3 ) 4 ] ( Ν〇3 ) 2 )和铑化合物 (R h ( Ν〇3 ) 3 )注射到反應爐水中。不過,根據此實 施例,即使在1 5 0至2 0 0 °C的溫度範圍內,鈀也會容 易地沉積在構造部件上,使得如圖9中所示者,鈀化合物 係在比鈾化合物和铑化合物更早的高溫時點注射。此實施 例係控制到使反應爐水中的鈀濃度經調定成1 0 5 p p b 並將鉑和铑的個別濃度調定成1 2 5 P P b。此外,於此 實施例中,鈀在反應爐水中的莫耳數小於鉑和铑的個別莫 耳數。根據此實施例,鈀會較早沉積在核子反應爐廠構造 部件上,然後爲鉑和铑沉積在該構造部件上。 此實施例可以產生與第一實施例所產生者相同之效應 (請先閱讀背面之注意事項再填寫本頁)Of) 5. Description of the invention () According to this specific example, the nuclear reactor is stopped. Stopping operation to reduce the output of the nuclear reactor, before the temperature of the reactor water reaches 150 ° C (such as when the temperature is reduced to 1 7 At 0 ° C) Immediately from the noble metal compound injector (please read the precautions on the back before filling out this page) 3 1Inject the palladium compound, platinum compound, and rhodium compound into the reactor furnace water flowing inside the circulation tube 4. When the temperature of the reactor water reached 80 ° C, the injection of their compounds was stopped. The period between 170 ° C and 80 t is the period of noble metal implantation (Figure 7). During this period, the aforementioned three compounds were injected. Individual compounds are introduced into the lower pressure chamber 15 of the pressure vessel 3 of the reaction furnace. The starting and stopping of the feeding of these compounds from the noble metal compound injector 31 is performed by opening and closing the valves 4 2, 4 6 and 50 installed in the noble metal compound injector 31. The noble metal compound injector 31 has a tank 40 filled with a palladium compound solution, a tank 44 filled with a platinum compound solution, and a tank 48 filled with a rhodium compound solution. Each tank is connected to a tube 5 2 which is connected to the circulation system tube 4 through an individual tube 41, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 5 and 4 9. Valve 4 2 and pump 4 3 are mounted to pipe 41, valve 4 6 and pump 4 7 are mounted to pipe 4 5 and valve 50 and pump 51 are mounted to pipe 49. The injection amounts of the palladium compound, lead compound and rhodium compound can be adjusted individually. That is, a controller 5 3 can be individually measured by measuring the individual concentrations of palladium, platinum, and rhodium in the reactor water measured by the inductively coupled plasma weight analyzer 38 (or the inductively coupled plasma weight analyzer 37). The ground control valves 4 2, 4 6 and 50 are opened. This adjustment of the injection amount of each compound solution is very advantageous because the deposition rates of the noble metal elements on the surface of the structural component are different from each other and the concentration of each noble metal element in the reaction furnace water varies. Standard (CNS) A4 specification (210 X 297 mm) 498348 Α7 __ B7 91 V. Description of the invention () The speed is not the same. In this specific example, P d (No 3) 2 is used as the palladium compound, [P t (Ν 3) 4] (No 3) 2 is used as the platinum compound, and Rh (Ν〇 3) 3 is used As a rhodium compound. These compounds are all dissolved in the reactor water and palladium, platinum and rhodium are all present in the reactor water in an ionic state. To adjust the palladium concentration in the reactor water to 50 ppb, the platinum concentration to 100 ppb and the rhodium concentration to 1000 ppb, the injection amount of each compound in the reactor water was adjusted. The opening of the corresponding valve is controlled. In the aforementioned noble metal injection period, the individual concentrations of the lead and the meter are controlled to the aforementioned set concentrations during the period when the temperature of the reactor water is 150 to 80 ° C. Individual concentrations of palladium, platinum, and rhodium are measured with an inductively coupled plasma weight analyzer 37 or 38, which will be described later. Based on these measurements, adjust the corresponding valves and control the individual concentrations in the reactor water. The palladium, platinum and rhodium ions in the reactor water are deposited on the surface of the structural parts of the BWR plant that is in contact with the reactor water. A film of these mixed metals is formed on the surface of the structural member by depositing palladium, platinum, and germanium. When palladium compounds are added, individual deposits of lead and rhodium on the surface of the construction component increase. Furthermore, the amount of individual deposition of platinum and rhodium on the surface of the structural member existing in the portion where the flow velocity of the reactor water is low also increases. Within the reactor water temperature range of 80 to 150 ° C, individual deposits of platinum and rhodium on structural parts of nuclear reactor plants increase. In place of P d (No. 3) 2, [P d (No. 3) 4] (No. 3) 2 or [Pd (No. 2) 2] (N. 3) 2 can be used. Instead of this paper size, apply Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page) d 丨 Subscribe: Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives 24 498348 Α7 _______ Β7 V. Description of the invention () (Please read the notes on the back before filling this page) [P d (Ν Η 3) 4] (NO 3) 2 For those who can use [P t (Ν Η 3) 4] (〇Η) 2. Instead of Rh (Ν〇3) 3, [Rh (ΝΗ3) 5 (Η2〇)] (Ν〇3) 3 can be used. As for the individual compounds of the aforementioned three noble metal elements, those compounds which produce ammonium ions and nitrate ions when each compound is decomposed are selected. These two ions rarely affect the corrosion of structural components in a nuclear reactor plant. The ρ Η of the reactor water is not easily changed greatly due to the cushioning effect of ammonia. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The inductively coupled plasma weight analyzers 37 and 38 are installed in the sampling tubes 21 and 22. The concentration of each noble metal element in the reactor water can be measured periodically (or as needed) by using the inductively coupled plasma weight analyzer 3 7 and 3 8 to measure the reactors taken by the sampling tubes 2 1 and 2 2 Water is OK. Instead of this inductively coupled plasma weight analyzer, a flameless atomic absorption analyzer can be used. Furthermore, when the sampling tube 2 1 and 2 2 are equipped with a reactor water conductivity meter (or ρ η meter), the reactor water conductivity meter can be used to monitor the concentration of each noble metal element in the reactor water. That is, the reactor water conductivity coefficient meter (or ρ Η meter) is used to monitor the reactor water conductivity coefficient (or ρ Η) caused by the change in the concentration of noble metal elements in the reactor water without taking the reactor water sample. The change. When the deposition on the surface of the structural part is eliminated and the uranium, rhodium and palladium plasmas are removed by the demineralizer 18 of the reactor water purification system, the individual amounts of platinum'rhodium and palladium in the reactor water are reduced. . During the noble metal injection period, each kind of platinum, rhodium and pins are injected from the noble metal compound injector 31. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 498348 A7 r ———_ B7 V. Description of the invention () The compound is carried out to make up for the individual removed by the demineralizer i 8. After the termination of the local precious metal injection period, individual concentrations of platinum, rhodium and pins in the reactor 7jC will be reduced by the demineralizer 18 removal operation. After the deposition of uranium, rhodium and palladium on the structural components of the nuclear reactor plant by injection of individual uranium, rhodium and palladium compounds was completed, the operation of the BW R plant was stopped. During the subsequent periodic inspection period, the exchange of fuel group s and the regular inspection of the plant are performed. After the periodic inspection is completed, when the B W R plant is started, as shown in FIG. 7, the pulling operation of the control rod from the furnace core is started. After the temperature of the reactor water reaches the rated temperature (about 280 ° C) and the pressure of the nuclear reactor reaches the set pressure (70 atmospheres), the output of the nuclear reactor is increased to 100%. When the feed water pump 12 is driven, the valve (not shown in the figure) of the hydrogen injector 24 is opened and hydrogen is injected into the feed water pipe 2. The feedwater system including hydrogen is guided into the pressure vessel 3 of the reaction furnace. In this case, the hydrogen concentration in the reactor water in the reactor pressure vessel 3 is determined after the E C P is effectively reduced and the response of the E C P is verified according to the amount of hydrogen injected. The hydrogen concentration is preferably 20 to 60 P P b in the reactor water. However, since the hydrogen concentration in the reactor water varies with the position of the reactor pressure vessel in the reactor water and the operating conditions of the nuclear reactor, the amount of hydrogen injected should be controlled so that the hydrogen concentration in the feed water is set to 0. Within the range of 1 to 0 · 4 ppm. In this embodiment, the hydrogen concentration in the reaction furnace water, as shown in Fig. 8, is controlled to 2 5 p p b. When the ECP at the SCC prevention target component can be directly measured or can be estimated by calculation, the amount of hydrogen injection from the hydrogen injector 24 can be controlled so that the paper size at the component applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) (Please read the precautions on the back before filling out this page) 7 丨 Order 'Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperative 498348 Printed by the Consumer Cooperatives of the Intelligent Property Bureau of the Ministry of Economic Affairs A7 B7___ 24 V. Invention Explanation () ECP is set at 230 mV vs SHE or lower. Through the catalytic action of platinum, rhodium, and palladium deposited on the surface of nuclear reactor plant construction components, the reaction between the injected hydrogen and the oxygen contained in the reactor water is promoted and water is produced. In this way, hydrogen can assist in the reduction of dissolved oxygen contained in the reactor water near the structural components of the nuclear reactor plant. Therefore, the E C P possessed by the structural components of the nuclear reactor plant in the reactor pressure vessel 3 is reduced and the S C C of the structural component is extremely suppressed. In particular, platinum, rhodium, and palladium were also deposited on the surface of the nuclear reactor plant structural parts that are in contact with the reactor water site where the water flow rate of the reactor is low, so that the ECP of the structural parts contacting the reactor water site was reduced to 2 30 millivolts vs SHE or lower, as shown by the black square mark () in Figure 4. The S C C of the structural member in contact with the water portion of the reaction furnace is also significantly suppressed. Due to the catalysis of platinum, rhodium and palladium, the amount of hydrogen required to react with dissolved oxygen is significantly reduced. Therefore, although the dissolved oxygen reduction effect is large, the amount of nitrogen 16 produced will still be significantly reduced. Since the surface dose rate of the steam system such as the main steam pipe 5 and the turbine 6 is not increased, their maintenance and inspection can be easily performed and the time required for the maintenance and inspection is shortened. According to this embodiment, the palladium concentration in the reaction furnace water is equal to the platinum concentration and the rhodium concentration in the reaction furnace water, so that the palladium concentration is lower than the platinum concentration and the rhodium concentration. That is, the molar number of palladium is smaller than that of lead and rhodium. As a result, individual deposits of platinum and rhodium increase. When the molar number of palladium is greater than the molar number of platinum and rhodium, the deposition of platinum and germanium on the structural part will be suppressed and their individual deposition amount will be reduced. The reason is that the amount of palladium that is easy to deposit increases. __- -_ This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) J 丨, printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, the paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 498348 A7 _____ B7 5. Description of the invention (25). Palladium is easy to deposit, although it is easier to ionize than platinum and iodide, and correspondingly, it will easily dissolve into the reactor water from the surface of the structural component on which it is deposited. As a result, an increase in the individual deposition amount of platinum and rhodium will reduce the dissolved oxygen concentration in the reactor furnace water near the surface of the structural component for a long period of time and reduce the E C P of the structural component of the nuclear reactor plant. (Second Embodiment) A method for mitigating stress corrosion cracking of structural components of a nuclear reactor plant according to another embodiment of the present invention will be described with reference to FIG. 9. The structure of the BW R plant used in this embodiment is the same as that of the BW R plant used in the first embodiment explained with reference to FIG. According to this embodiment, when the temperature of the reactor water is reduced from 170 t to 80 ° C when the nuclear reactor is stopped, that is, a palladium compound (P d (No 3) 2), a platinum compound ([P t (ΝΗ3) 4] (Ν〇3) 2) and a rhodium compound (Rh (NO3) 3) were injected into the reactor water. However, according to this embodiment, even in a temperature range of 150 to 200 ° C, palladium is easily deposited on the structural member, so that, as shown in FIG. 9, the palladium compound is more specific than the uranium compound. And rhodium compounds are injected at an earlier high temperature. This embodiment is controlled so that the palladium concentration in the reaction furnace water is adjusted to 105 p p b and the individual concentrations of platinum and rhodium are adjusted to 1 2 5 p p b. In addition, in this example, the molar number of palladium in the reaction furnace water is smaller than the individual molar numbers of platinum and rhodium. According to this embodiment, palladium is deposited on the nuclear reactor plant construction member earlier, and then platinum and rhodium are deposited on the construction member. This embodiment can have the same effect as that produced by the first embodiment (please read the precautions on the back before filling this page)
498348 A7 __B7___ 五、發明說明(26 ) (請先閱讀背面之注意事項再填寫本頁) 。於此實施例中,由於鈀係先沉積在構.造部件上者,因此 可以在將鈀濃度增加到對反應爐水的傳導係數和P Η沒有 影響的範圍內之後才注入鈀。鈾和铑也可以在將個別濃度 對應於鈀的不存在予以增加之後才注入。其結果,鉑和铑 在核子反應爐廠構造部件上的個別沉積量可以比第一實施 例中者更爲增加。 (第三實施例) 下文要解說本發明另一具體實例的緩和核子反應爐廠 構造部件的應力腐蝕裂化之方法。本實施例所用B W R廠 的構成,如圖1 0所示者,爲在圖5所示構成中加入一鹼 注入器3 2之構成。該鹼注入器3 2係連接到在低壓給水 加熱器1 0的下游側的給水管2。 經濟部智慧財產局員工消費合作社印製 此外,於此實施例中,以和第一實施例相同的方式, 注入鉑化合物,铑化合物和鈀化合物並在核子反應爐廠構 造部件表面沉積鉛,铑和鈀。於此實施例緩和應力腐蝕裂 化之方法中,係在鉑,铑和鈀沉積操作完成後的次一運轉 循環中打開鹼注入器3 2的閥並將鹼性溶液注射到給水中 。鹼性溶液的注入,如圖1 1中所示者,係在從B W R廠 啓動拉出控制棒的起始點到該核子反應爐運轉停止之過程 中進行的。在將包括鹼的給水給入反應爐壓力容器3內之 時,·反應爐水的Ρ Η係保持在約8之下其在運轉循_環中係 呈弱鹼性。反應爐水的Ρ Η係使用水品質測量裝置2 0 a 或2 0 b測量的。基於測得的p Η値,調整鹼注入器3 2 ---2Θ--- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 498348 Α7 Β7 97 五、發明說明() 的閥之開放並控制反應爐水的p Η。關於該鹼性溶液,係 使用N a〇Η溶液。不過,也可以使用L i〇Η溶液,氨 水,或含有碳酸氫鈉或碳酸鈉之溶液做爲該鹼性溶液。 (請先閱讀背面之注意事項再填寫本頁) 本實施例可以得到在第一實施例中所產生的結果。由 於此實施例將反應爐水控制到弱鹼性,因此核子反應爐廠 構造部件的裂化尖端(crack Up )所具ρ Η可偏移到鹼性 邊。其結果,可以將構造部件裂化的進展有效地壓制。由 於可以經由反應爐水的弱鹼控制減低氫注射量,因此可以 將反應爐水中的氫濃度減低到約1 7 p p b。其結果,氮 1 6的產生量可以比第一實施例中者更爲減低。 於運轉循環中,宜於將室溫下反應爐水的p Η控制在 7至8 · 5的範圍內。也宜於將運轉循環中的反應爐水氫 濃度控制在1 5至6 0 P P b的範圍內。當室溫ρ η和氫 濃度都控制在.前述範圍內時,配合氫注入效應和弱鹼水品 質效應,可以用較少的氫注入量將構造部件的E C Ρ減低 到約—5 0 0毫伏ν s SHE。 經濟部智慧財產局員工消費合作社印製 於此實施例中,反應爐水的Ρ Η調整有可以經由將塡 充在冷凝液脫礦質器9或脫礦質器18中的一部份Η型陽 離子樹脂改變成鹼性型陽離子樹脂例如N a型者而不必使 用鹼注入器3 2來進行。於使用N a型陽離子樹脂時,從 該N a型陽離子樹脂流出的N a離子會注入到反應爐水中 ,使得反應爐水的Ρ Η可控制到弱鹼性。有關鹼性型陽離 子樹脂,除了 N a型者之外’也可以使用Κ型,L i型, 或Ν Η 4 +型。於使用鹼性型陽離子樹脂時,即不需要鹼注 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 498348 A7 _____ B7 五、發明說明(28 ) 入器3 2且B W R廠的構成可以簡化。 於該第一、第二和第三實施例中,係注入鈾化合物和 铑化合物以使反應爐水中鉑的莫耳數等於铑的莫耳數。不 過,可以將鉑化合物和铑化合物注入成使得反應爐水中鉑 和铑中有一者的莫耳數小於另一者的莫耳數。於此種情況 中,將鈀化合物注入使得反應爐水中的鈀莫耳數比鉑和铑 中較小的莫耳數更小。例如,於圖5所示構成中,爲了將 反應爐水中的鉑濃度調定成5 0 p p b,铑濃度爲1 〇 〇 P p b ’且鈀濃度爲1 〇 p p b,乃將鉑化合物,鍺化合 物和鈀化合物從高貴金屬注入器3 1注射到反應爐水內。 由於鈀莫耳數比鉑和铑中較小的莫耳數更小,因此鈀的功 能爲促進鉑和铑在核子反應爐廠構造部件表面上的沉積。 當鉑濃度爲5 0 p p b且铑濃度爲1 〇 〇 p p b的條件下 之鈀濃度小於5 0 p p b時此功能即可應驗。當鈀莫耳數 比鉑和铑中較小的莫耳數更大時,鈀的功能爲壓制鉑和铑 的沉積。 反之’當反應爐水中铑的莫耳數小於鉑的莫耳數時, 要將鈀化合物注射到反應爐水中使反應爐水中鈀的莫耳數 小於铑的莫耳數。其原因在於使鈀實現前述鈾和铑的沉積 促進功能。 也可以考慮將鉑和铑中之一者的化合物與紀化合物注 射到反應爐水中。於此情況中,係將鈀化合物注射到反應 爐水中使得鈀的莫耳數小於鉑(或铑)的莫耳數。經由此 舉,鈾(或铑)的沉積即獲得促進。即使在注入兩種化合 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) J丨訂· •線」 498348 A7 _ B7 五、發明說明f ) 物例如鉑化合物與鈀化合物(或铑化合.物與鈀化合物)時 ,也可以得到注入三種化合物例如一鉑化合物,一铑化合 物與一鈀化合物,所產生的效應。 於前述諸實施例中,高貴金屬化合物注入器3 1係連 接到循環系統管4。不過,該高貴金屬化合物注入器3 1 也可以連接到反應爐水淸淨系統管1 7下游側(較佳者於 泵1 7 c的下游側)或冷凝液脫礦質器9下游側之給水管 2。該高貴金屬化合物注入器3 1可以連接到殘熱脫除系 統管(圖中未示出),該管係在核子反應爐停機時給入反 應爐水。該殘熱脫除系統管則連接到循環系統管4和反應 爐壓力容器3。 鉑和錢在核子反應爐廠構造部件表面上的沉積係在 8 0至1 5 0 °C的反應爐水溫度範圍內進行的。當反應爐 水溫度滿足此條件時,於核子反應爐停機中(例如,在定 期檢查期間)或在核子反應爐啓動時而非核子反應爐停止 運轉中’即可注入銷,舶和錢的個別化合物。於前述諸實 施例中,係經由將反應爐水溫度從1 5 〇降低至8 〇 t, 即注入上述各化合物。不過,也可以經由將反應爐水溫度 保持在上述溫度範圍內的某一溫度(例如,1 5 〇 t )之 下,即將上述各化合物注入。 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁)498348 A7 __B7___ 5. Description of the Invention (26) (Please read the notes on the back before filling this page). In this embodiment, since palladium is first deposited on the fabricating member, palladium can be injected after the palladium concentration is increased to a range that does not affect the conductivity of the reactor water and P Η. Uranium and rhodium can also be injected after individual concentrations have been increased corresponding to the absence of palladium. As a result, the individual deposition amount of platinum and rhodium on the structural parts of the nuclear reactor plant can be increased more than that in the first embodiment. (Third Embodiment) A method for mitigating stress corrosion cracking of structural components in a nuclear reactor plant according to another embodiment of the present invention will be described below. The configuration of the BW R plant used in this embodiment, as shown in FIG. 10, is a configuration in which an alkali injector 32 is added to the configuration shown in FIG. The alkali injector 32 is connected to a water supply pipe 2 on the downstream side of the low-pressure feed water heater 10. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, in this example, platinum compounds, rhodium compounds, and palladium compounds were injected in the same manner as in the first embodiment, and lead and rhodium were deposited on the surface of the nuclear reactor plant construction components And palladium. In the method for mitigating stress corrosion cracking in this embodiment, the valve of the alkali injector 32 is opened and the alkaline solution is injected into the feed water in the next operation cycle after the platinum, rhodium and palladium deposition operations are completed. The injection of the alkaline solution, as shown in FIG. 11, is performed from the starting point of the pull-out of the control rod in the BW R plant to the stop of the operation of the nuclear reactor. When feed water including alkali is fed into the reactor pressure vessel 3, the P , system of the reactor water is kept below about 8 and it is weakly alkaline in the operation cycle. The pH of the reactor water is measured using a water quality measuring device 20a or 20b. Based on the measured p Η 値, adjust the alkali injector 3 2 --- 2Θ --- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 498348 Α7 Β7 97 5. Description of the invention () The valve opens and controls the p 炉 of the reactor water. For this alkaline solution, a NaOH solution was used. However, it is also possible to use a solution of Li 〇Η, ammonia, or a solution containing sodium bicarbonate or sodium carbonate as the alkaline solution. (Please read the notes on the back before filling out this page) This embodiment can get the results produced in the first embodiment. Since the reactor water is controlled to be weakly alkaline in this embodiment, the ρ Η of the crack up point of the structural components of the nuclear reactor plant can be shifted to the alkaline side. As a result, the progress of cracking of the structural member can be effectively suppressed. Since the injection amount of hydrogen can be reduced through the weak base of the reactor water, the hydrogen concentration in the reactor water can be reduced to about 17 p p b. As a result, the amount of nitrogen 16 produced can be reduced more than that in the first embodiment. In the operation cycle, it is appropriate to control the p Η of the reactor furnace water at a room temperature of 7 to 8 · 5. It is also suitable to control the hydrogen concentration of the reactor water in the operation cycle in the range of 15 to 60 P P b. When the room temperature ρ η and the hydrogen concentration are both controlled within the foregoing ranges, combined with the hydrogen injection effect and the weak alkaline water quality effect, the EC P of the structural component can be reduced to about -50 0 millimeters with a smaller hydrogen injection amount. Vol ν s SHE. Printed in this embodiment by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The pH of the reactor furnace water is adjusted to include a part of Η-type cationic resin that can be charged in the condensate demineralizer 9 or demineralizer 18 Changing to a basic type cationic resin such as Na type is performed without using an alkali injector 32. When a Na-type cationic resin is used, Na ions flowing out of the Na-type cationic resin are injected into the reaction furnace water, so that the pH of the reaction furnace water can be controlled to be weakly alkaline. As for the basic cation resin, in addition to the Na type, a K type, a Li type, or an NΝ 4 + type may be used. When alkaline type cationic resin is used, no alkaline injection is required. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 498348 A7 _____ B7 V. Invention It is explained that (28) the inlet 32 and the structure of the BWR plant can be simplified. In the first, second and third embodiments, the uranium compound and the rhodium compound are injected so that the molar number of platinum in the reaction furnace water is equal to the molar number of rhodium. However, the platinum compound and the rhodium compound may be injected so that the molar number of one of the platinum and rhodium in the reaction furnace water is smaller than that of the other. In this case, the injection of a palladium compound results in a smaller mol number of palladium in the reaction furnace water than smaller mol numbers of platinum and rhodium. For example, in the configuration shown in FIG. 5, in order to adjust the platinum concentration in the reaction furnace water to 50 ppb, the rhodium concentration to 1000P pb 'and the palladium concentration to 10ppb, the platinum compound, germanium compound and The palladium compound is injected from the noble metal injector 31 into the reactor water. Since the palladium mole number is smaller than the smaller mole numbers of platinum and rhodium, the function of palladium is to promote the deposition of platinum and rhodium on the surface of structural parts of nuclear reactor plants. When the platinum concentration is 50 p p b and the rhodium concentration is 100 p p b, the palladium concentration is less than 50 p p b. When the palladium mole number is larger than the smaller mole numbers of platinum and rhodium, the function of palladium is to suppress the deposition of platinum and rhodium. Conversely, when the molar number of rhodium in the reaction furnace water is smaller than the molar number of platinum, the palladium compound is injected into the reaction furnace water so that the molar number of palladium in the reaction furnace water is smaller than that of rhodium. The reason for this is to make palladium perform the aforementioned functions of promoting the deposition of uranium and rhodium. It is also conceivable to inject a compound of one of platinum and rhodium into the reactor water. In this case, the palladium compound is injected into the reaction furnace water so that the molar number of palladium is smaller than the molar number of platinum (or rhodium). By doing so, the deposition of uranium (or rhodium) is promoted. Even if two paper sizes are injected, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) applies (please read the precautions on the back before filling this page) J 丨 Order · • Line "498348 A7 _ B7 5 2. Description of the invention When f) such as a platinum compound and a palladium compound (or a rhodium compound and a palladium compound), three kinds of compounds such as a platinum compound, a rhodium compound and a palladium compound can be injected to obtain the effect. In the foregoing embodiments, the noble metal compound injector 31 is connected to the circulation system pipe 4. However, the noble metal compound injector 3 1 can also be connected to the downstream side of the reactor furnace water purification system pipe 17 (preferably downstream of the pump 17 c) or the water supply pipe of the condensate demineralizer 9 downstream. 2. The noble metal compound injector 31 can be connected to a residual heat removal system pipe (not shown in the figure), which is fed with reactor water when the nuclear reactor is shut down. The residual heat removal system tube is connected to the circulation system tube 4 and the reactor pressure vessel 3. The deposition of platinum and money on the surface of the structural parts of the nuclear reactor plant was carried out in the reactor water temperature range of 80 to 150 ° C. When the reactor water temperature meets this condition, the nuclear reactor can be shut down (for example, during periodic inspections) or when the nuclear reactor is started instead of the nuclear reactor stopped. Compound. In the foregoing embodiments, each of the above compounds was injected by reducing the temperature of the water in the reaction furnace from 150 to 80 t. However, the above-mentioned compounds may be injected by keeping the temperature of the reaction furnace water at a certain temperature (for example, 150 ° t) within the above-mentioned temperature range. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)
-(ϋ ϋ ϋ ϋ κ ϋ 一一<»Jy i^i I ί ϋ n ϋ ·ϋ I-(ϋ ϋ ϋ ϋ κ ϋ 一一 < »Jy i ^ i I ί ϋ n ϋ · ϋ I
經濟部智慧財產局員工消費合作社印製Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
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PCT/JP2000/000563 WO2001057879A1 (en) | 2000-02-02 | 2000-02-02 | Method for mitigating stress corrosion cracking of structural member of atomic reactor plant |
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JP (1) | JP3941503B2 (en) |
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WO (1) | WO2001057879A1 (en) |
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JP4349956B2 (en) * | 2004-03-29 | 2009-10-21 | 日立Geニュークリア・エナジー株式会社 | Operation method of residual heat removal system |
JP4518984B2 (en) * | 2005-03-11 | 2010-08-04 | 中国電力株式会社 | Hydrogen injection method for nuclear power plant |
JP2007232432A (en) * | 2006-02-28 | 2007-09-13 | Hitachi Ltd | Chimney of natural circulation type boiling water reactor |
JP6446384B2 (en) * | 2016-03-31 | 2018-12-26 | 日立Geニュークリア・エナジー株式会社 | Nuclear power plant and method for injecting precious metal thereof |
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JPH05209992A (en) * | 1992-01-31 | 1993-08-20 | Hitachi Ltd | Method for restraining shift of radioactive nitrogen to gaseous phase in primary cooling water system of direct cycle type reactor |
US5448605A (en) * | 1993-10-29 | 1995-09-05 | General Electric Company | Palladium acetylacetonate solution and related method of manufacture |
US5581588A (en) * | 1995-06-23 | 1996-12-03 | General Electric Company | Insulated protective coating doped with a noble metal for mitigation of stress corrosion cracking |
JPH10160892A (en) * | 1996-11-27 | 1998-06-19 | Hitachi Ltd | Method and device for treatment of carbon steel part in reactor power plant |
JPH10186085A (en) * | 1996-12-20 | 1998-07-14 | Toshiba Corp | Device and method for sticking noble metal to nuclear reactor structural material |
JPH1184075A (en) * | 1997-09-12 | 1999-03-26 | Hitachi Ltd | Anticorrosion method for atomic reactor |
JP2946207B2 (en) * | 1998-04-06 | 1999-09-06 | 株式会社日立製作所 | Nuclear power plant and water quality control method and apparatus therefor |
JPH11295480A (en) * | 1998-04-13 | 1999-10-29 | Hitachi Ltd | Method for forming catalyst surface |
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