TWI408220B - 高溫腐蝕抑制劑 - Google Patents

高溫腐蝕抑制劑 Download PDF

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TWI408220B
TWI408220B TW094138495A TW94138495A TWI408220B TW I408220 B TWI408220 B TW I408220B TW 094138495 A TW094138495 A TW 094138495A TW 94138495 A TW94138495 A TW 94138495A TW I408220 B TWI408220 B TW I408220B
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corrosion inhibitor
corrosion
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crude oil
acid
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TW200632089A (en
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Scott E Lehrer
S Blake Pruett
Liliana V Minevski
James G Edmondson
Alan E Goliaszewski
Feng Shao
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Gen Electric
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Description

高溫腐蝕抑制劑
本發明大體言之係關於在精煉操作中抑制腐蝕之方法。本發明特定言之係關於抑制由存在於原油中之環烷酸引起之腐蝕。
認識到在石油精煉操作中與原油中環烷酸組份相關之腐蝕問題已有多年。該腐蝕在介於約350℉與790℉之間之溫度下的常壓及真空蒸餾單元中尤其嚴重。造成含有環烷酸之原油之腐蝕性的其他因素包括環烷酸之存在量、含硫化合物之濃度、單元中流動流之速度與湍流度及在單元中之位置(例如液體/蒸氣介面)。
在原油之蒸餾精煉中，原油連續通過熔爐及一或多個分餾器(諸如常壓塔及真空塔)。大多數操作中，在低於約350℉之溫度下環烷酸腐蝕並非問題。傳統以氮為主之薄膜化腐蝕抑制劑在高於350℉之溫度下為無效，且防止環烷酸腐蝕之其他方法(例如中和)係存在操作問題或為無效。
應注意術語"環烷酸"包括一元及二元羧酸，且通常構成原油中全部酸性組份之50重量%。許多環烷酸可由下式表示： 其中R為烷基或環烷基且n通常在2至10之範圍內。
此結構及分子量可能有許多變化。一些實施者將烷基有機酸包括於環烷酸之類別中。
環烷酸在約350℉(180℃)至約790℉(420℃)之範圍之間為腐蝕性的。在更高溫度下，環烷酸呈氣相且脫羧速率增加。在較低溫度下，腐蝕率不嚴重。原油及餾出物之腐蝕性亦受硫化物化合物的存在影響，諸如硫化氫、硫醇、元素硫、硫化物、二硫化物、多硫化物及硫酚。歸因於含硫化合物之腐蝕在溫度低至450℉時變得顯著。已確認藉由熱分解硫醇而催化產生硫化氫為硫化物腐蝕之誘因。
使環烷酸腐蝕降至最低或防止環烷酸腐蝕之努力包括以下方法：a)將環烷酸含量較高之油與環烷酸含量低之油摻合；b)自原油中中和並移除環烷酸；及c)使用腐蝕抑制劑。
因為此等方法並非完全令人滿意，所以工業中可接受之方法為以耐蝕金屬(諸如高品質不銹鋼或含有較高量之鉻及鉬之合金)建構蒸餾單元或曝露於環烷酸腐蝕之部分。然而，在並非如此建構之單元中，需要提供對抗此類型腐蝕之抑制處理。先前技術之環烷酸環境之腐蝕抑制劑包括以氮為主之薄膜化腐蝕抑制劑。然而，此等腐蝕抑制劑在環烷酸油之高溫環境中相對無效。
在加工某些原油時，常壓及真空蒸餾系統經受環烷酸腐蝕。當前使用之處理在使用溫度下具有熱反應性。在磷基抑制劑之狀況下，認為此等抑制劑導致比鋼基更耐環烷酸腐蝕之金屬磷酸鹽表面薄膜。此等抑制劑具有相對揮發性且展示相當狹窄之蒸餾範圍。將它們饋至視溫度範圍而高於或低於腐蝕點之管柱中。多硫化物抑制劑分解為較高及較低多硫化物與可能之元素硫及硫醇之複雜混合物。因此，揮發性及所提供之保護無法預測。
本發明提供抑制在加工原油或自其衍生之高溫石油餾出物中使用之裝置之內金屬表面腐蝕的方法。其包含向原油或餾出物中添加足以抑制腐蝕之有效量之四官能性經取代芳族化合物(I)及/或苯偏三酸酯或苯偏三酸酐(II)。
以上所定義之四官能性經取代芳族化合物(I)可由以下通式表示： 其中W、X、Y及Z皆存在且可能相同或不同，且係獨立選自由(OH)、(COOH)及COOR1 組成之群，其限制條件為W、X、Y、Z之相鄰對可為 即酐官能基。該式中之R1 為具有約1至約16個碳原子之烷基部分；Ar為芳族部分。
苯偏三酸之酯或酐(II)由式(II)表示： 其中R2 及R3 為或，其限制條件為當R2 或R3 為或時，則另一為或，從而足以形成酐基，即連接芳族部分上1及2位置之；R2 及R3 亦可為COOR5 ，其中每一R5 係獨立選自具有約1至約16個碳原子之烷基。R4 為COOR6 ，其中R6 為C1 －C1 6 烷基。
屬於上式I之代表性化合物包括沒食子酸丙酯、沒食子酸、苯均四酸(即1,2,4,5－苯四甲酸)、1,2,4,5－苯四甲酸二酐、沒食子酸辛酯及苯均四酸四辛酯。目前苯均四酸為較佳。
關於上式(II)所涵蓋之化合物，可提及1,2,4－苯三甲酸酐及苯偏三酸三辛酯。
根據本發明之一態樣，處理物(即上述化合物I及/或II)可直接饋至原油進料且(例如)在下部原油塔及真空管柱中提供保護。反之，抑制處理物將於任何位置饋至製程流，其中其將與製程介質(例如原油或其餾出餾份)接觸。
根據本發明待使用之腐蝕抑制劑之最有效量可視局部操作條件及所加工之特定碳氫化合物而變化。因此，酸腐蝕系統之溫度及其他特徵可對待使用之抑制劑或抑制劑混合物之量具有影響。在操作溫度及/或酸濃度較高時，通常需要成比例之較高量之腐蝕抑制劑。已發現添加至原油中之腐蝕抑制劑之濃度以體積計可能在約1 ppm至5000 ppm之範圍內。亦已發現，以相對較高之2000至3000 ppm之初始劑量率添加抑制劑且維持此含量相對短之時間直至抑制劑之存在促使金屬表面上建立腐蝕保護塗層是較佳的。可添加純的或經稀釋的腐蝕抑制劑。保護表面一旦建立，維持該保護所需之劑量率可降至約100至1500 ppm之正常操作範圍而無實質之保護犧牲。
實例
現在將結合以下實例進一步描述本發明，該等實例基於說明目的提供且不意欲作為本發明之限制。
使用重量損失試樣高壓釜測試來評估用於環烷酸腐蝕之化合物。測試樣本為具備玻璃珠表面修整之清潔的預稱重之軟鋼或5Cr腐蝕試樣。石蠟烴油與環烷酸一起配料以提供6.0之總酸數目(Total Acid Number)，並將其置於測試高壓釜中。將在室溫下為固態之候選處理物添加至高壓釜中並混合。以氬將油脫氣。在一些實驗中，藉由添加導致彼等實驗中0.5%之硫化物之含硫化合物(即，在實例2中為正十二烷基甲硫醚且在實例5中為二丁硫醚)來測定硫化物對腐蝕及抑制之效應。將高壓釜加熱至600℉或500℉之所要測試溫度。曝露20小時之後，將試樣移除、清潔並重新稱重。測試結果如下所示。在具有正十二烷基甲硫醚之實驗中，因為5Cr試樣之腐蝕率相當低(<10 mpy)，因此僅測定軟鋼試樣之腐蝕抑制率。
實例1
316C，不添加硫化物未處理之腐蝕率：軟鋼＝108.2 MPY，5Cr＝153.9 MPY
實例2
316C，添加正十二烷基甲硫醚之形式之0.5%硫化物未處理之腐蝕率：軟鋼＝39.9 MPY
實例3
216C，不添加硫化物未處理之腐蝕率：軟鋼＝45.5 MPY，5Cr＝36.3 MPY
實例4
316C，不添加硫化物未處理之腐蝕率：1010軟鋼＝143 MPY
實例5
316C，添加二丁硫醚之形式之0.5%硫化物未處理之腐蝕率：1010 MS＝76 MPY
實例6
使用高溫高壓釜來評估自委內瑞拉原油(Venezuelan crude oil)衍生之脫氣HVG0中多個比較性及有前景之腐蝕抑制劑。在蒸氣空間中懸掛一個靜態碳鋼試樣。兩個碳鋼試樣以約2 fps在液相中旋轉。將液相溫度控制在600℉維持約20小時。使用重量損失、表面積及曝露時間來計算未處理及處理之試樣之總體腐蝕率，以mpy為單位。結果如下所示。
＊ ＊ ＊ ＊ ＊ ＊ ＊
以上具有C字母字首之測試化合物標識表示比較實例。如上述實例中所示，四酸性芳族化合物(I)及苯偏三酸酯及酐II對於降低與高溫原油(特定言之為含有環烷酸之原油)接觸之金屬表面之腐蝕有效。本發明之處理物亦不含有已經證明在可能之觸媒中毒及熱不穩定性方面各自存在問題的磷或硫化物部分。
亦注意到，本發明之處理物為彼等含有原油及石油餾出物之系統(其中皆有環烷酸及含硫化合物存在)中之有效腐蝕抑制劑。如此項技術所已知，在含硫化合物、特別為硫化氫存在時，環烷酸腐蝕表現得異常嚴重。

Claims (10)

  1. 一種抑制在加熱至約350℉與約790℉之間之溫度的原油或高溫餾出物的加工中所使用之裝置之內金屬表面腐蝕的方法，其包含向該原油或高溫石油餾出物中添加腐蝕抑制量之腐蝕抑制劑，該腐蝕抑制劑係選自種類(I)與(II)及其混合物，其中該腐蝕抑制劑(I)具有下式： 其中W、X、Y及Z皆存在且相同或不同，且係獨立選自由OH、COOH及COOR1 組成之群，其限制條件為W、X、Y及Z之相鄰對可選自；R1 為具有約1至16個碳原子之烷基部分且Ar為芳族化合物；該腐蝕抑制劑(II)具有下式： 其中R2 及R3 為COOR5 、或，其限制條件為當R2 或R3 之一為或時，則另一個為或，從而足以形成連接R2 及R3 官能基之酐基，每一R5 係獨立選自具有約1至約16個碳原子之烷基；R4 為COOR6 ，其中R6 為具有約1至約16個碳原子之烷基。
  2. 如請求項1之方法，其中Ar為經取代之苯。
  3. 如請求項2之方法，其中該腐蝕抑制劑(I)係選自由沒食子酸、苯均四酸、沒食子酸丙酯、沒食子酸辛酯、苯均四酸四辛酯及1,2,4,5－苯四甲酸二酐組成之群。
  4. 如請求項3之方法，其中該腐蝕抑制劑(I)為苯均四酸。
  5. 如請求項2之方法，其中該腐蝕抑制劑(II)係選自1,2,4－苯三甲酸酐及苯偏三酸三辛酯。
  6. 如請求項3之方法，其中該原油或石油餾出物包含環烷酸且該腐蝕抑制劑為誘發腐蝕之環烷酸。
  7. 如請求項6之方法，其中該原油或石油餾出物進一步包含含硫化合物。
  8. 如請求項1之方法，其中向該原油或餾出物中添加之腐蝕抑制劑(I)及/或(II)之量為足以產生以體積計約1至5,000 ppm之濃度之量。
  9. 如請求項8之方法，其中該濃度為約100至約1500 ppm。
  10. 如請求項3之方法，其中該腐蝕抑制劑為1,2,4,5－苯四甲酸二酐。
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