摻氫天然氣環境下管道鋼氫脆行為研究進展

張家軒，王財林，劉翠偉，胡其會，張睿，徐修賽，鞠世雄，李玉星

摻氫天然氣環境下管道鋼氫脆行為研究進展

張家軒1，王財林1，劉翠偉1，胡其會1，張睿1，徐修賽1，鞠世雄2，李玉星1

（1.中國石油大學（華東） 山東省油氣儲運安全省級重點實驗室，山東 青島 266580；2.國家石油天然氣管網集團有限公司油氣調控中心，北京 100020）

為推動我國摻氫天然氣管道的發展，綜述了目前含氫氣環境下管道鋼氫脆的研究成果，總結了溫度、壓力、摻氫比等運行條件對鋼材氫脆的影響，分析了鋼材強度、微觀組織、氫陷阱等材料性質與管道鋼氫脆行為之間的聯系，歸納了預防和抑制管道鋼氫脆行為的方法。筆者認為，當前亟待解決的科學技術問題包括進一步探究摻氫天然氣管道環境下不同運行條件對管道鋼氫脆行為的影響規律；確定摻氫天然氣管道的安全運行溫度、壓力、摻氫比等關鍵參數；建立不同服役條件下摻氫天然氣管道輸送的安全評價方法，完善摻氫天然氣管道與現役管道相容性評價體系；形成摻氫天然氣管道的設計規范和相關標準；開展氣體抑制劑和阻氫涂層等抗氫脆方法的評價。

摻氫天然氣；管道鋼；氫脆；機理；摻氫比；涂層

在化石能源日漸枯竭、全球氣候惡化的趨勢下，各國都在大力發展低碳可再生清潔能源[1-2]。我國國家發展改革委印發的《能源技術革命創新行動計劃（2016—2030年）》中，已將太陽能、風能、氫能等清潔能源的開發利用作為下一階段的重點任務，重點指出要大力發展氫氣的低成本制造、運輸以及儲存。由于可再生能源發電具有不穩定性，且電量供應受到市場供需的影響，造成了大量風電、光電的資源浪費[3-4]。將不穩定的風電、光電等通過電解制成氫氣后，再進行運輸和利用是解決以上問題的有效途徑[5-7]。然而，目前基礎設施、運輸方式等因素的限制，導致氫氣的運輸和儲存成本過高，成為氫氣在現有能源供應體系中未得到廣泛應用的重要原因[8]。目前，包括我國在內的很多國家都已經建立了大規模的天然氣輸送管道，利用現有的天然氣管道網絡，向天然氣中添加氫氣，并混合輸送，就可以在較低的成本下實現氫氣的大規模輸送[9-10]。截至目前，多個國家都已開展了摻氫天然氣管道示范工程[11]，表1匯總了近年來國內外主要的摻氫天然氣管道項目，圖1總結了摻氫天然氣管道所涉及的環節以及關鍵問題。從圖1和表1可以看出，氫氣的摻入一方面會引入氫氣摻混、液化及分離等新的工藝；另一方面，氫氣區別于天然氣的物理性質，也會對管道安全、管輸設備的相容性、管道的完整性等提出新的要求。與歐美發達國家相比，我國摻氫天然氣管道的發展目前仍處在起步階段，需要解決氫氣摻入所帶來的一系列關鍵問題，制定針對摻氫天然氣管道建設及運行的相關標準規范。

鋼材在氫氣環境下會產生氫損傷，包括氫脆、氫致裂紋、氫鼓泡等，此外在較高的溫度壓力下還會發生脫碳和氫蝕。其中氫脆是發展摻氫天然氣管道輸送技術的主要安全問題。當管道鋼處在富氫環境中時會發生氫脆現象，造成管道鋼延性和疲勞強度的降低，甚至導致管道開裂，引發嚴重的安全問題[20-21]。管道鋼在氫氣環境中發生氫脆的根本原因是氫原子對鋼材的滲透。氫原子滲透進入鋼材誘發氫脆并產生裂紋的過程為[9,22]：氫氣分子在與管道內壁碰撞的過程中吸附在管道鋼表面，并分解為吸附氫原子；吸附氫原子擴散到管道鋼內部成為溶解氫原子，并在鋼材內部遷移以及缺陷和微裂紋尖端聚集；當氫原子積累到一定程度后，會引起管道鋼脆化，并進一步產生氫致裂紋。目前氫氣加劇鋼材性能劣化的主流機理有：氫壓理論、氫致弱鍵理論以及氫致局部塑性變形理論等[23-28]。盡管目前國內外對氫脆機理已經進行了大量的研究，但針對不同的材料或外部條件，氫氣的影響機制不同[29]，同時某一特定氫脆現象可能受多種不同機制共同作用[30]，控制脆化現象和失效的實際微觀機制仍需進一步探索[31-32]。

本文對目前含氫氣環境下管道鋼氫脆研究進行了系統的綜述，總結分析了管道運行工況、鋼材性質等不同因素對管道鋼氫脆行為的影響，歸納了預防和抑制管道鋼氫脆行為的方法，并針對現有研究的不足，提出了當前亟待解決的科學技術問題和研究展望。

表1 國內外主要的摻氫天然氣輸送管道示范項目

Tab.1 Demonstration projects of hydrogen-blended natural gas pipelines at home and abroad

圖1 摻氫天然氣管道主要環節和涉及的關鍵問題

1 摻氫天然氣管道鋼氫脆行為影響因素

為保證摻氫天然氣管道的安全運行，需明確影響管材氫脆行為的主要因素。在高壓摻氫天然氣長輸管道中，管道運行工況（溫度、總壓、氫氣分壓）以及管材狀態（金相組織、析出物雜質、缺陷等），都會對氫氣與管道鋼之間的相互作用產生較大的影響[32-34]。

1.1 運行條件

1.1.1 溫度的影響

溫度的變化會影響氫原子的擴散和聚集，從而影響鋼材的氫脆行為。目前，幾乎沒有針對氣相環境下溫度對管道鋼氫脆行為影響的相關研究，但現有的其他鋼材在液相環境下的氫脆研究仍具有重要指導意義。Mehta等[35]在早期的研究中發現，當溫度從室溫上升到150 ℃后，氫原子擴散速率以及氫致裂紋的擴展速率會明顯加快。Doshida等[36]也得到了類似的結論，當溫度大于–30 ℃后，鋼的氫脆敏感性隨溫度的升高而增加。然而溫度對鋼材氫脆行為的影響還存在爭議。近期的研究中，Xing等[37]分別在模擬地層溶液環境和空氣環境中對X90鋼進行慢應變速率拉伸試驗，并發現X90鋼的氫脆行為存在溫度閾值，且氫脆敏感性不隨溫度單調變化。X90鋼在313 K下的氫脆敏感性最高；當溫度低于313 K時，氫脆效應隨溫度的升高而增強；超過313 K時，氫脆效應隨溫度的升高而減弱。Momotani等[38]研究了低碳馬氏體鋼氫脆敏感性在–100～100 ℃內隨溫度的變化情況，將試樣在液相環境中電化學充氫24 h后進行拉伸試驗。結果表明，在0 ～100 ℃內，含氫試樣的抗拉強度和伸長率隨溫度降低而降低；當溫度降到0 ℃以下時，抗拉強度和伸長率又逐漸增加。最終得出，當溫度處在室溫下時，低碳馬氏體鋼的氫脆的敏感性最大。

以上研究表明，溫度的變化可能對氫脆行為存在較為顯著的影響。從熱力學的角度分析，低溫環境會使得氫原子的滲透、擴散變慢，很難發生富集；在高溫條件下，氫原子的活化能和擴散速率高，使得氫原子不易在位錯、晶界等處富集，甚至發生熱解吸現象，使金屬內部氫原子濃度降低[38-39]，同時在高溫環境下金屬表面生成的氧化膜也會抑制氫脆行為[40]。總體上，目前關于溫度對常用管線鋼氫脆行為影響的研究還較少，尤其是在摻氫天然氣輸送環境下，不同季節管輸溫度變化對氫氣在管道鋼中擴散聚集的影響，以及不同鋼材的安全輸送溫度的確定都需要更進一步的研究。

1.1.2 壓力的影響

1）純氫環境下氫氣壓力的影響。近年來有很多研究者通過在純氫氣環境中進行試驗來探究氫氣壓力對管道鋼氫脆行為的影響。Amaro等[27,41]分別對X52鋼和X100鋼在氫氣環境下進行了拉伸試驗和疲勞裂紋擴展試驗。研究表明，與空氣環境下相比，13.8 MPa高壓氫氣環境下，2種鋼材拉伸試樣的伸長率都明顯減小，韌性損失顯著。在一定的應力強度因子范圍內，X52和X100鋼的疲勞裂紋擴展速率隨氫氣壓力的增加而增加。當氫氣壓力從1.72 MPa增加到20.68 MPa后，X100鋼的疲勞裂紋擴展速率提高2倍，甚至1個數量級。Stalheim等[42]和San等[43-44]評估了在5.5～ 21 MPa的氫氣環境下，不同種類的X60、X70、X80管道鋼的氫脆敏感性。研究結果表明，與空氣環境下相比，5.5 MPa氫氣環境下，每種管道鋼拉伸試樣的斷面收縮率和斷裂韌性都顯著減小，鋼材的氫脆程度增加，但隨著壓力的進一步增大至21 MPa，鋼材的斷面收縮率和斷裂韌性減小幅度較小。同時，在較大的強度因子范圍內（Δmax> 20 MPa·m1/2），當氫氣壓力從5.5 MPa增加至21 MPa后，試樣疲勞裂紋的擴速率變化不大。Andrew等[45]在1.7、7、21、48 MPa等4種氫力壓力下，對X52和X100管道鋼進行了疲勞裂紋擴展試驗。結果表明，X100和X52在氫氣環境下的疲勞裂紋擴展速率比在空氣中高出1～2個數量級，且在一定的強度因子范圍內，裂紋增長速率隨著氫氣壓力的增加而增大。

此外，還有研究表明，氫氣對管材的劣化影響并不會隨著壓力的升高而一直增大，而是存在一個臨界壓力值。Alvaro等[46]研究了X70鋼焊接熱影響區在20 ℃高壓氫氣環境下的氫脆敏感性，在不同氫壓力（0.1、0.6、10、40 MPa）下進行了單邊缺口試樣的拉伸試驗，同時對斷裂韌性進行了量化。結果表明，當氫氣壓力高于0.1 MPa時，試樣的斷裂韌性明顯降低；當氫壓力達到0.6 MPa以上后，斷裂韌性沒有繼續減小。他們進一步指出，X70鋼焊接熱影響區發生氫脆現象的臨界壓力在0.1～0.6 MPa。類似地，Moro等[47]在不同氫氣壓力下對X80鋼進行了拉伸試驗，并通過斷面收縮率對氫脆敏感性進行量化。結果表明，當氫氣壓力超過10 MPa后，X80鋼的氫脆敏感性將不再受到壓力升高的影響。

在氫氣環境中，氫原子在鐵等金屬中的溶解度與氫氣壓力的平方根成正比[48]。在一定范圍內，單位體積內壓力越高，氫氣分子的濃度越高，氫氣分子與管道內壁碰撞分解為氫原子的幾率就會增大，進而使得氫原子在管道鋼中的溶解度增大[47]，導致鋼材內部裂紋尖端具有更高的氫濃度[49]，促進脆化的發生。以上研究結果表明，對于不同的管道鋼材料，壓力對氫脆敏感性的影響規律，以及發生氫脆的臨界壓力閾值尚不明確，還需要進行進一步的研究。

2）摻氫環境下氫氣分壓的影響。在摻氫天然氣管道中，氫氣分壓可通過式（1）確定：

式中：H為氫氣分壓；為摻氫比例；為總壓。

顯然，摻氫比例和總壓的變化都會改變氫氣分壓的大小。張體明[50]測量了X80 鋼在12 MPa模擬煤制氣環境（0.25 MPa氫氣，0.20 MPa二氧化碳，其余為氮氣）中的氫滲透電流密度。結果表明，在反應釜中充入0.25 MPa的氫氣后，氫滲透電流迅速增大，電流穩定后再依次充入二氧化碳和氮氣將壓力逐級提高至12 MPa，這個過程中穩態電流基本不會變化，如圖2所示。張體明認為，氫滲透電流的大小僅與煤制氣中的氫分壓有關，與總壓關系不大。類似地，Nguyen等[51]在5、7、10 MPa等3種典型壓力下（摻氫比分別為0.1%、0.5%、1%、3%、5%、100%）的甲烷/氫氣混合氣體中對X70鋼的力學性能進行了測試。結果表明，X70鋼的力學性能下降主要受到氫氣分壓而非總壓的影響，如圖3所示。

圖2 X80鋼在模擬煤制氣環境中分段加壓過程中氫滲透曲線[50]

對于摻氫天然氣管道而言，在管輸壓力一定的情況下，氫氣在管道中的分壓是通過摻氫比來確定的。近年來也有學者在摻氫環境下對鋼材氫脆行為影響進行了相關研究。An等[52]通過低周疲勞試驗和裂紋擴展試驗探究了在總壓12 MPa摻氫環境下不同氫分壓對X80氫脆敏感性的影響。研究表明，隨著氫氣分壓的增加，X80缺口試樣的疲勞循環次數迅速減小，而緊湊拉伸試樣的裂紋擴展速率則急劇增加。與在氮氣環境中相比，0.2 MPa的氫氣分壓下，X80鋼的疲勞失效循環次數下降20%，疲勞裂紋擴展速率增加7倍；當氫氣分壓進一步增加至8 MPa后，失效循環次數的下降幅度達到90%，疲勞裂紋擴展速率增加2倍。An進一步指出，隨著氫氣壓力的增加，裂紋擴展速率增加是X80鋼疲勞壽命降低的主要原因。Meng等[53]研究了12 MPa下含0～50%（體積分數）氫氣的天然氣/氫氣混合氣體對X80管線鋼力學性能的影響。結果表明，隨著氫氣含量的增加，X80鋼的氫脆敏感性升高，疲勞裂紋擴展速率明顯加快。類似地，在最新的研究中，Nguyen等[51,54]同樣發現，在5～10 MPa的壓力下，X70鋼的氫脆敏感性隨著摻氫比的增大而增大，且氫氣的體積分數達到0.7%的時候，X70鋼的斷裂模式會由韌性斷裂向脆性斷裂 轉變。

盡管目前國內外學者的研究都表明氫氣分壓越高，鋼材的氫脆敏感性就越高，但是對于影響管道鋼安全運行的臨界氫氣分壓，目前尚沒有統一的定論。趙德輝等[55]將X70鋼和20#鋼的母材金相試樣和焊接區U彎試樣放置在總壓12 MPa的氮氣/氫氣混合環境中（其中氫氣分壓2 MPa）1個月后，未發現氫損傷和氫致開裂現象，同時外加恒載荷的試樣也未發生氫致開裂，并進一步得到X70鋼和20#鋼在煤制天然氣（總壓為12 MPa，氫氣分壓為0.72 MPa）中長期服役不會發生氫致開裂及氫損傷。關鴻鵬等[56]研究發現，X70鋼的母材和焊縫試樣在總壓為4 MPa、氫氣分壓為0.2 MPa的煤制氣環境下，沖擊性能、塑性及材料的損傷容限均未受到顯著影響。然而，同樣在12 MPa的總壓工況下，也有研究表明，當氫氣分壓分別為0.72 MPa[57]和0.96 MPa[58]時，X80鋼都表現出一定的氫脆敏感性。

此外，由于氫氣和甲烷的性質不同，天然氣摻氫后不僅會對管材性能產生影響，還會對管道的完整性、管輸設備以及下游用戶終端產生影響[59]。對于天然氣管道摻入氫氣而不影響管道安全和下游終端的臨界值，不同的研究給出了不同的結論，包括3%[12]、10%[21]、17%[60]、20%[13]，甚至50%[13]。國際能源署（IEA）在2020年更新了不同國家對天然摻氫比例的限制[61]，如圖4所示（特殊工況分別是，德國：未與管網連接的CNG加氣站；立陶宛：壓力大于1.6 MPa的天然氣管道；荷蘭：高熱值煤氣）。國外已有一些標準規范對特定情況下天然氣管道的摻氫比作出了限制，美國機械工程師協會頒布的ASME B31.12- 2014“Hydrogen Piping and Pipelines”適用于氫氣體積分數不小于10%的情況。標準指出，X60及以上管道的設計壓力不應大于10 MPa。當摻入10%以上的氫氣后，還需要根據標準中給出的校核方法重新計算最大操作壓力。除此之外，還有歐洲標準CGA-5.6“Hydrogen Pipeline System”，其中針對使用X52鋼的天然氣管道的摻氫比例限制為10%。

圖3 不同工況下氫氣分壓對X70鋼力學性能的影響[51]

圖4 國際能源署發布的不同國家對摻氫天然氣管道中氫氣含量的限制[61]

綜上所述，目前國內外雖然已開展摻氫天然氣管道的安全摻氫比研究，但仍缺乏一致的結論。對于在役的天然氣管道來說，受管道服役年限、材料的影響，不同研究所得出的安全摻氫比范圍有較大不同。國內尚缺乏摻氫天然氣管道的安全摻氫比標準規范，需確定在管輸壓力下不同摻氫比對管道力學性能的影響，同時結合管輸設備相容性、用戶需求及經濟性等多方面因素，確定適用于我國摻氫天然氣管道的安全摻氫比，填補相關規范標準的空白。

1.2 材料性質

1.2.1 強度的影響

目前，多數研究者認為，鋼材的氫脆敏感性會隨著強度的增大而增大[31]，對于抗拉強度小于700 MPa的鋼，幾乎不會出現嚴重的氫脆問題[62]。Nanninga等[49]和Hardie等[63]研究表明，不同管道鋼的氫脆敏感性隨著強度的增加而增大。Andrew等[45]也指出，相較于X52鋼，X100鋼疲勞裂紋的擴展速率和隨著氫氣壓力的增加而增大的現象更加明顯。Komatsuzaki等[64]指出，當碳鋼屈服強度由500 MPa升至1 400 MPa后，氫致斷裂的應力閾值顯著降低，最大降幅甚至達到70%。然而，Cabrini等[65]認為，當鋼材的極限抗拉強度超過700 MPa后，氫脆敏感性才會隨著極限抗拉強度的增大而增大；極限抗拉強度小于700 MPa時，鋼材的氫脆敏感性反而會隨著極限抗拉強度的增大而降低。一般認為，低級別強度的管道鋼的韌性相對較高，抗氫脆性能也較好。歐洲目前所建立的工業級口徑氫氣管道中，大部分都使用X42、X52、X56 等低強度管線鋼，ASME B31.12—2014也推薦采用X42、X52等低強度鋼[66]。

盡管目前大多數的研究表明強度的提升會增加鋼材的氫脆敏感性，但對于常用管道鋼氫脆敏感性與強度之間的定量關系尚不明確，還需結合金屬相態組成及晶粒大小等微觀因素進行分析。同時，摻氫比對管材強度與氫脆敏感性之間關系的影響也需要進一步的探究。

1.2.2 微觀組織的影響

鋼材的微觀金相組織是影響鋼材氫脆的關鍵因素[67]。目前，輸氣管道常用管道鋼（X70、X80等）的金相組成以鐵素體為主。Stalheim等[68]測試了X52、X60、X70、X80管道鋼在5.5、20.7 MPa氫氣環境中的斷裂韌性，結果表明，多邊形鐵素體/針狀鐵素體組織抗氫性能略優于多邊形鐵素體/上貝氏體–珠光體組織。類似地，Davani等[69]和Zhao等[67]也指出，X60、X80管線鋼中針狀鐵素體對氫致裂紋的敏感性較低。針狀鐵素體較好的抗氫脆性能，是由于其較高的韌性能夠抑制裂紋的擴展[70]。除了鐵素體外，在管道鋼的加工焊接等過程中，還會引入少量的馬氏體、貝氏體以及奧氏體等組織，這些相組織都會對鋼材的氫脆敏感性產生影響。其中，馬氏體對氫原子的捕獲能力最強，且馬氏體更容易受到氫脆的影響[71-72]，這歸根于馬氏體含有較多的位錯和邊界缺陷，會導致氫致裂紋的快速萌生和擴展[73]。此外，貝氏體對氫脆的敏感性也高于鐵素體[70,74]。奧氏體組織的氫脆敏感性最低，這是由于氫在奧氏體中溶解度高，且氫原子在奧氏體中的擴散速率比馬氏體慢3～4個數量級[75]。Tao等[76]研究指出，大多數氫致裂紋會在奧氏體處停止發展。然而，一直增加奧氏體的含量并不能提高鋼的抗氫脆性能，因為在高氫濃度和應力集中的耦合作用下，奧氏體會轉變為馬氏體，進而增加氫脆敏感性[77]。

長輸管道在焊接過程，較高的溫度造成焊接部位組織的不均勻分布，導致焊縫部位的氫脆敏感性更高。美國Sandia國家實驗室[78]測量了X52、X65、X70等鋼材在6.9 MPa的氫氣環境下的拉伸性能，結果表明，焊縫處塑性的劣化比母材更嚴重。張體明等[79]研究表明，X80鋼焊縫部分晶粒明顯長大，大角度晶界含量減少，氫的擴散速率及其在裂紋尖端的富集程度增加，導致焊縫部分的氫脆系數相較于母材明顯升高。

對于同種牌號的鋼，國內外對成分的控制以及熱加工工藝會有所差別，所以對于國外的實驗結果并不能盲目采用[80]，還需要進一步明確本土鋼材不同組織的抗氫脆性能，建立失效評價準則。

1.2.3 陷阱的影響

在鋼材的內部會不可避免地存在位錯、相界面、微孔以及各種雜質析出物，這些結構或者夾雜物的周圍會產生應力集中，從而誘導氫原子發生聚集[81]。這種可以吸附氫原子的結構或者夾雜物通常被稱為氫陷阱。根據其與氫原子之間結合能的大小，一般將結合能小于60 kJ/mol的氫陷阱定義為可逆氫陷阱。當氫原子進入可逆陷阱后，在一定的條件（高溫等）下，可以逃逸出來。結合能大于60 kJ/mol的氫陷阱為不可逆氫陷阱，一旦氫原子進入不可逆氫陷阱，將難以離開[82]。表2總結了一些常見的結構和雜質析出相與氫原子之間的結合能。

表2 金屬中不同結構/夾雜物與氫原子之間的結合能

Tab.2 The binding energy between structures/inclusions and hydrogen atoms in steel

氫陷阱對于鋼材氫脆行為的影響，學術界目前還沒有形成統一的結論。有研究表明，不可逆氫陷阱不僅可以束縛氫原子，還能阻礙位錯運動，從而抑制氫脆行為[91]；而可逆氫陷阱的存在，使得溶解在鋼中的可擴散氫濃度升高，會加劇鋼材的氫脆現象[77,82,92]。Huang等[93]和Nakatani等[94]則認為，被不可逆陷阱捕獲的氫原子會加劇高強度鋼力學性能的劣化。一方面，氫陷阱可以阻礙氫原子的滲透，降低氫脆敏感性；另一方面，氫陷阱附近也可能出現氫原子過多聚集，萌生裂紋[95]，且氫陷阱密度也會對鋼材氫脆敏感性產生較大的影響[96]。在不同的條件下，氫陷阱對鋼材氫脆行為的作用效果也會有所不同，需要進行進一步的研究。

除了鋼材本身的結構缺陷以外，鋼材中氧化物、鐵碳化物等析出夾雜物也是誘發氫脆的常見氫陷阱[97]。Xue等[81]發現，X80鋼中的氫致裂紋主要萌生在富Si、富Al的夾雜物附近。Escobar等[98]研究表明，MnS夾雜物會促進氫致裂紋的擴展，而MnS析出物是否會對鋼材的氫脆行為產生影響還存在爭議[99]。除此之外，管線鋼的氫脆敏感性還和C[100]、S[101]、V[102]等雜質有關。夾雜物的尺寸和分布也會對氫脆行為產生影響，一般來說，夾雜物的尺寸和分布面積越大，越容易萌生氫致裂紋[103-104]。

綜上所述，無論是結構缺陷，還是雜質析出相，氫陷阱對于鋼材氫脆敏感性的影響還存在一定爭議。同時，目前的研究大多數通過電化學液相充氫的方法來表征氫陷阱，對于將來的摻氫天然氣管道來說，高壓氣相環境下管線鋼中氫陷阱對氫脆行為的影響是否會發生變化，還需要更進一步的研究。

2 氫脆的預防措施分析

2.1 改變微觀相組織

由于不同微觀金相組織的氫脆敏感性差異較大，可以通過優化熱處理工藝和處理參數獲得理想的組織，晶粒細化工藝也可以提高鋼的抗氫脆性能[105]。Enyinnaya等[106]比較了2種不同相組織的X70管線鋼的抗氫脆性能，結果表明，含有更多馬氏體/殘余奧氏體成分的X70鋼具有更好的抗氫致裂紋的性能。類似地，Ohaeri等[107]將X70鋼進行了兩步退火處理后，產生了鐵素體–回火馬氏體雙相組織，雖然強度降低，但是由于回火馬氏體較小的晶粒尺寸減緩了氫在鋼中的遷移率，使得X70鋼的氫脆敏感性降低。Park等[70]評價了經過不同熱處理后X65鋼的抗氫脆性能，結果表明，針狀鐵素體的高韌性會阻止裂紋的擴展，鋼材的抗氫脆性能也會隨著針狀鐵素體含量的提升而提高。但改變相組織可能會導致部分材料力學性能下降，且控制工藝復雜，能耗大[108]，將來是否可以大規模應用于長輸管道鋼還有待進一步的驗證。

2.2 氣體抑制劑

氫氣環境中的某些氣體有抑制鋼材氫脆傾向的作用。Liu等[109]和Jacobs[110]等發現，SO2和CO2作為“毒化劑”可以抑制氫原子向鋼材內部的滲透，從而降低鋼材的氫脆程度。Deimel等[111]和Kussmaul等[112]發現了氫氣環境下O2的存在同樣會降低鋼的氫脆效應。Michler等[113]研究表明，O2對于氫脆的抑制作用是O2分壓的函數，同時抑制氫脆的O2分壓存在臨界值，根據鋼材等級和溫度變化，分壓臨界值可能相差3個數量級。這種現象是由于O2可以使得裂紋尖端鈍化，阻止氫原子滲透，但是隨著裂紋的擴展，新的裂紋尖端表面并不能被完全鈍化，從而導致O2對氫脆的抑制作用下降[114]。CO通過抑制鋼材表面的氫吸附，從而抑制管道鋼氫脆行為。李婷婷[115]研究發現，在10 MPa的氫氣環境下，添加0.01 MPa分壓的CO就使得X80鋼的氫脆指數降低95%以上。

在最新的研究中，Shang等[116]發現，CO2和H2會產生耦合作用，從而增加鋼的氫脆敏感性。除此之外，水蒸氣也會對促進鋼材的氫脆行為[117]，不僅如此，CO2[118]和H2S[119]等組分會和水共同形成酸性環境，也會對加劇管道鋼的氫脆現象。

就目前的研究來看，不同氣體對于鋼材氫脆行為的影響還存在爭議，其作用機理尚不完全明確，需要在摻氫天然氣管道實際工況條件下進一步探究不同氣體對于長輸氣體管道鋼氫脆行為的影響。同時，諸如分壓閾值、不同氣體之間的耦合作用等問題也都需要進一步的實驗來驗證，同時結合管道運行安全和管道下游需求，最終確定可以添加到管道中的氫脆氣體抑制劑，這將對摻氫天然氣管道的發展具有重要意義。

2.3 阻氫涂層

除了加入抑制氣體和改善管道鋼微觀組織結構之外，阻氫內涂層由于可以阻止氫原子的滲透，也成為預防管道鋼氫脆的新方法[9,20]。阻氫涂層大致上分為：金屬涂層、金屬氧化物涂層以及石墨烯等非金屬涂層。很早就有研究者發現，在鋼表面電鍍上Pt、Ni、Sn、Cd等金屬薄膜可以降低氫原子的滲透效率[120-121]，但是金屬涂層常常因為斷裂應變過低、附著力不足和涂層缺陷等問題使得涂層失效，需要進一步改進涂層工藝來改善涂層延性、附著力等性能[122]。

金屬涂層可以抑制氫原子滲透，一部分原因歸結于其表面的氧化層[123]，金屬氧化物也是一種有效的阻氫涂層。在金屬氧化物涂層中，Al2O3的阻氫效果較好，1 μm厚的Al2O3可以使氫滲透通量下降3～4個數量級，而且其在高溫下也具有較好的穩定性[124-125]。相較于單層的氧化物涂層，復合涂層具有更好的阻氫效果、更好的結合強度以及穩定性[126-127]。然而，并不是所有的氧化物都可以起到阻氫的作用，其對氫脆的影響在很大程度上取決于氧化物的深度分布，晶粒尺寸以及堆積方式，只有特定的氧化物層才有較好的阻氫效果[128]。

隨著石墨烯材料的興起，其阻氫性能的研究近年來也得到了廣泛關注。由于氫原子進入石墨烯涂層后，會形成C—H sp3鍵，從而阻礙了氫原子的滲透，在金屬表面覆蓋石墨烯涂層后，金屬內部的氫含量會顯著降低[129]。C—H的形成引起了石墨烯結構的變形，導致其阻氫能力降低。通過調整合成方式進一步減小晶粒尺寸，改善石墨烯結構以及多層石墨烯的研制可以進一步提升石墨烯涂層的抗變形能力[130]。

雖然涂層的阻氫效果好，但是由于涂層在加工過程中本身就會引入一些氫原子，而且其在破損后還會引發嚴重的局部腐蝕，再加上經濟性以及加工工藝的限制，導致阻氫涂層并不能大規模應用[108]。目前的研究多采用液相充氫實驗來衡量阻氫涂層的效果，并不能真實反映其在氫氣環境中的阻氫效果，還需要在高壓氣相環境中展開抗氫脆效果的評價研究。此外，新型涂層材料以及新型涂層制備工藝的效果評價也需進一步探究。

3 結語

基于以上綜述分析，現階段對于摻氫天然氣管道的氫脆行為研究較少，不同服役條件下摻氫天然氣管道的風險性、安全性和可靠性的變化規律尚不明確。針對當前的研究現狀，為推動將來摻氫天然氣管道的發展，提出以下建議及展望：

1）目前溫度變化對氫原子的擴散聚集以及常用管線鋼氫脆行為的影響規律尚無定量描述，需通過試驗明確不同鋼材在摻氫天然氣管道輸送環境下的安全輸送溫度。

2）摻氫天然氣管道的安全摻氫比缺乏一致的結論。需研究在管輸壓力下不同摻氫比對管道材料性能的影響，確定管材發生氫脆的臨界壓力閾值，同時結合管輸設備相容性、用戶需求及經濟因素等多方面條件，最終確定適用于我國摻氫天然氣管道的安全摻氫比。

3）改善微觀組織、在管道中添加氣體抑制劑、添加阻氫涂層等抑制管道鋼氫脆行為的方法需要進一步探索，尤其需要明確實際管輸溫度壓力、不同氣體相互作用等因素對阻氫效果的影響。

4）目前我國尚缺乏摻氫天然氣管道建設和安全運行的相關規范，應盡快建立不同服役條件下摻氫天然氣管道輸送的安全評價方法，形成相關標準規范，為摻氫天然氣管道的發展和大規模應用奠定基礎。此外，還需完善摻氫天然氣管道與現役天然氣管道相容性的評價方法和評價體系。

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Research Progress on Hydrogen Embrittlement Behavior of Pipeline Steel in the Environment of Hydrogen-Blended Natural Gas

1,1,1,1,1,1,2,1

(1. Shandong Provincial Key Laboratory of Oil & Gas Storage and Transportation Security, China University of Petroleum (East China), Shandong Qingdao 266580, China; 2. Pipe China Oil & Gas Pipeline Control Center, Beijing 100020, China)

Hydrogen energy has been vigorously developed in recent years, but excessive transportation and storage costs have become a key issue in restricting the development of hydrogen utilization. Blending H2into existing natural gas long- distance pipelines is the potential best way to transport hydrogen on a large scale, cost-effectively and efficiently. However, H2can induce hydrogen embrittlement of pipeline steel, which seriously restricts the safe operation of hydrogen-blended natural gas pipelines.

In order to promote the development of hydrogen-blended natural gas pipelines in China, this paper reviews the current research results of hydrogen embrittlement of pipeline steel in hydrogen-containing environment; summarizes the influence of operating conditions such as temperature, pressure, and hydrogen blending ratio on hydrogen embrittlement of steel; analyzes the relationship between the material properties and the hydrogen embrittlement behavior of pipeline steel, such as strength, microstructure organization, hydrogen traps; summarizes the methods to prevent and inhibit the hydrogen embrittlement behavior of pipeline steel.

For the high-pressure hydrogen-blended natural gas pipeline, the operating parameters such as temperature, pressure, and hydrogen-blending ratio have a great impact on the hydrogen embrittlement. At present, there are few studies focusing on the effect of temperature on the hydrogen embrittlement of pipeline steel. With the increase in hydrogen partial pressure, the hydrogen embrittlement susceptibility of pipeline steel increases. Affected by the service life and materials of the pipeline, the ranges of the safe hydrogen blending ratio obtained by different researches are quite different. It is necessary to determine the safe hydrogen blending ratio suitable for the hydrogen-blended natural gas pipelines in China, and formulate relevant standards and specifications.

Steel properties are also an important factor affecting the hydrogen embrittlement behavior. Most studies have shown that hydrogen embrittlement susceptibility of pipeline steel increased with strength, but the quantitative relationship is not clear. The different microstructures of steels can also lead to different hydrogen embrittlement susceptibilities, and particularly, there is a higher hydrogen embrittlement sensitivity for the welding area. In addition, under different conditions, the effects of hydrogen traps such as dislocations and grain boundaries on the hydrogen embrittlement behavior of steel are different, and further research is needed.

Finally, three methods for inhibiting hydrogen embrittlement of pipeline steel are summarized, including changing phase structure, blending protective gas, and hydrogen barrier coating. But all three methods have great limitations. Changing the phase structure may lead to the decline of the mechanical properties of some materials, and the energy consumption is large, so it is not suitable for large-scale application in long-distance pipeline steel. For blending protective gas, the influence of different gases on the hydrogen embrittlement behavior of steel is still controversial, and its mechanism of action is not completely clear. Moreover, blending other gases will have a greater impact on the safety of pipeline operation and downstream user terminals. The hydrogen barrier coating will cause severe local corrosion after damage. Due to the limitation of price and processing technology, the hydrogen barrier coating cannot be applied on a large scale.

In conclusion, the current scientific and technical issues that need to be solved include: further exploring the influence of different operating conditions on the hydrogen embrittlement behavior of pipeline steel under the environment of hydrogen- blended natural gas pipelines; determining the key parameters of hydrogen-blended natural gas pipelines such as the safe operating temperature, pressure and hydrogen blended ratio; establishing safety evaluation methods for hydrogen-blended natural gas pipeline transportation under different service conditions, and improving the compatibility evaluation system of hydrogen-blended natural gas pipelines and existing pipelines; forming design specifications and related standards for hydrogen-blended natural gas pipelines; carrying out evaluation of anti-hydrogen embrittlement methods such as gas inhibitors and hydrogen barrier coating.

hydrogen-blended natural gas; pipeline steel; hydrogen embrittlement; mechanism; hydrogen blending ratio; coating

TE88

A

1001-3660(2022)10-0076-13

10.16490/j.cnki.issn.1001-3660.2022.10.009

2021–08–18；

2022–01–19

2021-08-18；

2022-01-19

國家重點研發計劃“氫能技術”重點專項（2021YFB4001601）；山東省油氣儲運安全重點實驗室重點科研平臺基金開發課題（20CX02405A）

The National Key R & D Program of China (2021YFB4001601); The Fundamental Research Funds for the Central Universities and the Development Fund of Shandong Key Laboratory of Oil & Gas Storage and Transportation Safety (20CX02405A)

張家軒（1997—），男，碩士研究生，主要研究方向為管道鋼氫脆行為。

ZHANG Jia-xuan (1997-), Male, Postgraduate, Research focus: hydrogen embrittlement behavior of pipeline steel.

李玉星（1970—），男，博士，教授，主要研究方向為油氣及特殊氣體管輸技術。

LI Yu-xing (1970-), Male, Doctor, Professor, Research focus: oil-gas and special gas pipeline transportation technology

張家軒, 王財林, 劉翠偉, 等. 摻氫天然氣環境下管道鋼氫脆行為研究進展[J]. 表面技術, 2022, 51(10): 76-88.

ZHANG Jia-xuan, WANG Cai-lin, LIU Cui-wei, et al. Research Progress on Hydrogen Embrittlement Behavior of Pipeline Steel in The Environment of Hydrogen-Blended Natural Gas[J]. Surface Technology, 2022, 51(10): 76-88.

責任編輯：劉世忠