TW201833076A - 具有低的鹽腐蝕性之油可溶性硫化物清除劑與製造及使用彼等清除劑之方法 - Google Patents

具有低的鹽腐蝕性之油可溶性硫化物清除劑與製造及使用彼等清除劑之方法 Download PDF

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TW201833076A
TW201833076A TW106142642A TW106142642A TW201833076A TW 201833076 A TW201833076 A TW 201833076A TW 106142642 A TW106142642 A TW 106142642A TW 106142642 A TW106142642 A TW 106142642A TW 201833076 A TW201833076 A TW 201833076A
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formaldehyde
reaction product
substituted hydroxylamine
alkyl
fluid
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席泰許 葛漢許洋 巴葛里亞
高葛瑞 卡帕林
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美商奇異電器公司
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Abstract

本發明提供可用於減小流體流中之硫化物濃度之硫化物清除劑及使用彼等清除劑之方法。該等清除劑包含甲醛/N-經取代之羥基胺之油可溶性反應產物且可用於減小例如黏性烴油流中之H2 S含量。

Description

具有低的鹽腐蝕性之油可溶性硫化物清除劑與製造及使用彼等清除劑之方法
本發明係關於油可溶性N-經取代之羥基胺/甲醛反應產物(下文中有時稱為AHAF)、製造其之方法及使用其以減少流體(即，氣體或液體)流中之硫化物含量之方法。
硫化氫或H2 S係具有惡臭氣味之透明有毒氣體。其亦高度易燃。全世界的環境保護署(Environmental Protection Agency)及其他管製機構嚴格控制H2 S至環境中之釋放。H2 S可存在於井水、廢水及其他水性系統中。H2 S通常存在於原油及天然氣儲量中，且在商業使用此等儲量之前必須使其減少。在處理之前該等儲量中之H2 S濃度通常隨位置而變化且在天然氣中之濃度通常高於原油儲量。舉例而言，在天然氣儲量中，H2 S可自小於100 ppm至3000 ppm變化。允許的H2 S含量亦將隨位置變化。美國將天然氣管道中之H2 S限制為4 ppm/100標準立方呎(0.3 gr/100 scf)。 通常，藉由使用會與硫化物反應之化學品處理烴流以減少硫化物，包括有機硫化物、硫醇(mercaptan、thiol)、COS及H2 S。該等化學品稱為清除劑或甜味劑。 單乙醇胺(MEA)三嗪係廣泛使用之H2 S清除劑；然而，高胺鹽腐蝕電位係精煉廠操作之主要問題。由於MEA三嗪係基於水之產品，故其具有限制其在高黏性流中應用之質量傳遞限制。 大多數烴儲量係在井口附近連續處理，但在別處以分批或類似應用處理烴並不少見。井口附近之連續處理裝置將硫化物清除劑直接注入烴管道中。注入系統通常包括化學品注入幫浦及三通或霧化噴嘴，以將清除劑引入管道中。所需清除劑之量將端視多種因素變化，包括所用清除劑之類型、井中H2 S之量、可允許之H2 S限值及井流速。因此，所添加以處理烴管道之清除劑之量通常在以烴流之體積計約1 ppm至約100,000 ppm之範圍內。提供一定管道長度以容許清除劑與硫化物之間之接觸。
在某些實施例中，本發明係關於減少流體流中之硫化物之方法，其包含使流體流與具有下式之N-經取代之羥基胺/甲醛反應產物接觸：其中n係約0至10之整數且R1 及R2 各自獨立地選自H、C1 -C10 直鏈、具支鏈及環狀烷基、烯基或芳基；限制條件係R1 及R2 二者不均為H。硫化物可(例如)包含一或多個選自由以下組成之群之成員：有機硫化物、硫醇(mercaptan、thiol)、COS及H2 S。流體流可包含烴流或水性流。 基於1,000,000份流體流，使以體積計約1至100,000 ppm之反應產物與流體流接觸。在其他實施例中，使約500至3,000 ppm之反應產物與流體流接觸。 在其他實例性實施例中，上式之R1 及R2 皆係C1 -C10 烷基。在一些實施例中，R1 及R2 二者係乙基。 本發明之其他實施例係關於製造N-經取代之羥基胺/甲醛反應產物之方法，其包含使具有式RR'NOH之N-經取代之羥基胺與甲醛反應，其中R及R'各自獨立地選自H、直鏈、具支鏈及環狀C1 -C10 烷基、烯基或芳基；限制條件係R及R'二者不均為H。該方法在約高於60℃之溫度下進行約0.5至2.0小時。在一些實施例中，反應係在有機溶劑之存在下進行，且在其他實施例中，反應係在約80至90℃之溫度下進行。 在一些實施例中，N-經取代之羥基胺係選自一或多個選自由以下組成之群之成員：N,N-二甲基羥基胺、N,N-二乙基羥基胺、N,N-二苄基羥基胺、N-乙基羥基胺、N-丙基羥基胺、N-異丙基羥基胺、N-丁基羥基胺、N-苯基羥基胺、N-環己基羥基胺、N-第三丁基羥基胺、N-苄基羥基胺。 在某些實施例中，甲醛:N-經取代之羥基胺之莫耳比率係約0.5至5莫耳甲醛:N-經取代之羥基胺。在其他實施例中，甲醛:N-經取代之羥基胺之莫耳比率係約1至3莫耳甲醛:1莫耳N-經取代之羥基胺。在一些實施例中，甲醛係呈多聚甲醛之形式。 在其他實施例中，N-經取代之羥基胺/甲醛反應產物(AHAF)具有以下結構：其中n係0至10之整數；R1 及R2 各自獨立地選自H、C1 -C10 直鏈、具支鏈及環狀烷基、烯基或芳基；限制條件係R1 及R2 二者不均為H。在某些實施例中，反應產物係油可溶性的。在一些實施例中，R1 及R2 二者係C1 -C10 烷基，例如乙基。
本發明之一個態樣係關於製造N-經取代之羥基胺/甲醛反應產物(AHAF)之方法，其中使具有式RR'NOH之N-經取代之羥基胺與甲醛(例如，多聚甲醛)純淨的或在有機溶劑之存在下反應。反應可在高於約60℃之溫度下進行約0.5至2.0小時。在某些實施例中，反應可在約80至90℃之溫度下實施約1小時。在上文N-經取代之羥基胺式中，R及R'獨立地選自H、直鏈、具支鏈及環狀C1 -C10 烷基、烯基或芳基；限制條件係R及R'二者不均為H。R及R'之實例包括甲基、乙基、丙基、丁基、戊基、己基、辛基及癸基。尤其值得注意的是二乙基羥基胺(DEHA)。 在一些實施例中，羥基胺係選自由以下組成之群：N,N-二甲基羥基胺、N,N-二乙基羥基胺、N,N-二苄基羥基胺、N-乙基羥基胺、N-丙基羥基胺、N-異丙基羥基胺、N-丁基羥基胺、N-苯基羥基胺、N-環己基羥基胺、N-第三丁基羥基胺、N-苄基羥基胺。 在採用有機溶劑之彼等實施例中，可以實例性方式提及重芳香族石腦油溶劑。加成反應產物可保留在溶劑中，且其可如此使用以減少烴流體流之硫化物含量，或加成物可經由習用分離技術自反應介質分離並然後用作硫化物清除劑。可提及之其他有機溶劑包括戊烷、己烷、環己烷、苯、甲苯、氯仿、二乙醚、二氯甲烷、四氫呋喃(THF)、乙酸乙酯等。反應物甲醛:N-經取代之羥基胺之莫耳比率可在約0.5至5:1之範圍內且亦可以實例性形式提及約1至3:1之比率。 AHAF反應產物具有以下結構：其中n係約0至10之整數；R1 及R2 各自獨立地選自H、C1 -C10 直鏈、具支鏈及環狀烷基、烯基或芳基；限制條件係R1 及R2 二者不均為H。在其中DEHA與甲醛(例如，多聚甲醛)反應之情形下，R1 及R2 二者係乙基。 在本發明之其他態樣中，揭示自流體流減少硫化物之方法，其中使AHAF反應產物與含有一或多種有機硫化物、硫醇(mercaptan、thiol)、COS及H2 S之此等流體流接觸。流體流可包括液體及氣體介質且該等流可係烴流或水性流。反應產物可以以流體流之體積計約1 ppm至100, 000 ppm之量採用。可提及之其他實例性劑量範圍包括500至3,000 ppm、尤其約1,000 ppm。 AHAF反應產物具有優點，此乃因與流體流接觸之冶金存在低胺鹽腐蝕風險，且與諸如二丙胺及二丁胺等胺相比，具有較高閃點；由此減少安全性及處置問題。加成物具有低PPI (鹽沈澱指數)，由此降低鹽腐蝕風險。加成物係油可溶性的且因此可用於重質黏性烴流中。 在其他實例性實施例中，所處理之流體流可包含流體烴流或水性流體流。該等流體流可(例如)包含來自油田製程、管道、罐、油輪、精煉廠及化學工廠之氣體/液體混合物。此外，流體流可包含農場排放物、城市用水等。其他額外流體流包括含有H2 S之水、廢水及製程用水。 將結合以下說明性實例進一步闡述本發明，該等實例不應理解為限制本發明。 實例 實例1 甲醛: DEHA加成物(2:1莫耳比率)，純淨的。 將45 gm固體多聚甲醛置於燒瓶中。添加無水DEHA (65 gm)。將混合物攪拌並加熱至90℃保持1小時，直至多聚甲醛完全溶解為止。冷卻至室溫，收集110 gm加成物(100%)。 實例2 甲醛: DEHA加成物(2:1莫耳比率)，在溶劑中。 將65 gm固體多聚甲醛置於燒瓶中。添加無水DEHA (89 gm)及51 gm芳香族A-150溶劑。將混合物攪拌並加熱至90℃保持1小時，直至多聚甲醛完全溶解為止。芳香族A-150係重芳香族溶劑石腦油。冷卻至室溫，收集205 gm加成物(100%)。 實例3 甲醛: DEHA加成物(1:1莫耳比率)，純淨的。 將23 gm固體多聚甲醛置於燒瓶中。添加無水DEHA (65 gm)。將混合物攪拌並加熱至90℃保持1小時，直至多聚甲醛完全溶解為止。冷卻至室溫，收集88 gm加成物(100%)。 實例4 甲醛: DEHA加成物(1:1莫耳比率)，在溶劑中。 將33 gm之量之固體多聚甲醛置於燒瓶中。添加無水DEHA (89 gm)及51 gm芳香族A-150溶劑。將混合物攪拌並加熱至90℃保持1小時，直至多聚甲醛完全溶解為止。冷卻至室溫，收集173 gm加成物(100%)。 實例5 為證實N-經取代之羥基胺-甲醛加成物減少烴介質中之H2 S之效能，將500 ml中之150 ml釜底燃料與硫化物清除劑候選化學品混合或不與其混合並加熱至75℃。在2小時後使用染色/德爾格(dragger)管量測頂部空間H2 S蒸氣濃度。下表顯示所得數據。 表 DMAPA =二甲基胺基丙胺 * * * * * 儘管已闡述本發明之說明性實施例，但應理解本發明並非如此受限，且可在不偏離本發明之情形下做出修改。本發明之範圍係藉由在文義侵害或均等論分析下考慮之隨附專利申請範圍來界定。

Claims (25)

  1. 一種減少流體中之硫化物之方法，其包含使該流體與N-經取代之羥基胺與甲醛之反應產物(AHAF)接觸。
  2. 如請求項1之方法，其中該N-經取代之羥基胺包含一或多個選自由以下組成之群之成員：N,N-二甲基羥基胺、N,N-二乙基羥基胺、N,N-二苄基羥基胺、N-乙基羥基胺、N-丙基羥基胺、N-異丙基羥基胺、N-丁基羥基胺、N-苯基羥基胺、N-環己基羥基胺、N-第三丁基羥基胺、N-苄基羥基胺。
  3. 如請求項1之方法，其中該反應產物(AHAF)具有下式：其中n係約0至10且R1 及R2 各自獨立地選自H、C1 -C10 直鏈、具支鏈及環狀烷基、烯基或芳基；限制條件係R1 及R2 二者不均為H。
  4. 如請求項1之方法，其中該等硫化物包含一或多個選自由以下組成之群之成員：有機硫化物、硫醇(mercaptan、thiol)、COS及H2 S。
  5. 如請求項1之方法，其中該流體係烴。
  6. 如請求項1之方法，其中該流體係天然氣。
  7. 如請求項1之方法，其中該流體係水。
  8. 如請求項1之方法，其中該流體係烴、水及氣體之多相混合物。
  9. 如請求項5之方法，其中該烴係選自由以下組成之群之烴油：原油、石腦油、柴油、釜底燃料、船用柴油、柏油及瀝青。
  10. 如請求項1之方法，其中基於1百萬份該流體，使以體積計約1 ppm至100,000 ppm之該反應產物與該流體接觸。
  11. 如請求項10之方法，其中使約500至3,000 ppm之該反應產物與該流體接觸。
  12. 如請求項3之方法，其中R1 及R2 二者係C1 -C10 烷基。
  13. 如請求項12之方法，其中R1 及R2 二者係乙基。
  14. 一種製造二烷基羥基胺/甲醛反應產物之方法，其包含使式RR'NOH之羥基胺與甲醛反應，其中R及R'各自獨立地選自H、直鏈、具支鏈及環狀C1 -C10 烷基、烯基或芳基；限制條件係R1 及R2 二者不均為H；該方法在約高於60℃之溫度下進行約0.5至2.0小時。
  15. 如請求項14之方法，其中該反應係在有機溶劑之存在下進行。
  16. 如請求項14之方法，其中該反應係在約80℃至90℃之溫度下進行。
  17. 如請求項14之方法，其中R及R'二者係C1 -C10 烷基。
  18. 如請求項17之方法，其中R及R'二者係乙基。
  19. 如請求項14之方法，其中甲醛:N-經取代之羥基胺之莫耳比率係約0.5至5莫耳甲醛對約1莫耳N-經取代之羥基胺。
  20. 如請求項19之方法，其中甲醛:N-經取代之羥基胺之莫耳比率係約1至3莫耳甲醛對約1莫耳N-經取代之羥基胺。
  21. 如請求項19之方法，其中該甲醛係多聚甲醛。
  22. 一種N-經取代之羥基胺/甲醛反應產物，其具有以下結構：其中n係0至10之整數；R1 及R2 各自獨立地選自H、C1 -C10 直鏈、具支鏈烷基、烯基或芳基，限制條件係R1 及R2 二者不均為H。
  23. 如請求項22之反應產物，其中該反應產物係油可溶性的。
  24. 如請求項23之反應產物，其中R1 及R2 二者係C1 -C10 烷基。
  25. 如請求項24之反應產物，其中R1 及R2 二者係乙基。
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