JP6133859B2 - 芳香族抽出型炭化水素流の水素化処理 - Google Patents
芳香族抽出型炭化水素流の水素化処理 Download PDFInfo
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Description
a.初期炭化水素供給原料を、易変性有機硫黄化合物を含有する芳香族リーン留分および無反応性芳香族有機硫黄化合物を含有する芳香族リッチ留分に分離すること;
b.水素の存在下で前記芳香族リッチ留分と異性化触媒とを接触させて、特定の化合物の立体障害性を取り除き、異性化物および任意の残留未反応水素を含む異性化流出物を生じさせること;
c.前記芳香族リーン留分および前記異性化流出物に穏やかな水素化処理を施し、それによって硫黄含量を低減すること;および
d.水素化処理された炭化水素生成物を回収するステップ。
a.初期炭化水素供給原料を芳香族抽出ゾーンにさらし、穏やかな水素化処理プロセスを施す際に異なる反応性を有する異なる種類の有機硫黄化合物を含有する、芳香族リーン留分および芳香族リッチ留分を得ること;
b.前記芳香族リーン留分中の有機硫黄化合物は、主に、脂肪族分子、例えばスルフィド、ジスルフィド、メルカプタンを含む易変性有機硫黄化合物であり、穏やかな条件下で作動する水素化処理ゾーンにこの留分を直接通過させて、有機硫黄化合物を除去すること;および
c.主に、芳香族分子、例えば特定のベンゾチオフェン(例えば、長鎖アルキル化ベンゾチオフェン)、ジベンゾチオフェンおよびアルキル誘導体、例えば立体障害4,6-ジメチルジベンゾチオフェンを含む無反応性有機硫黄化合物である有機硫黄化合物を含有する前記芳香族リッチ留分を異性化反応ゾーンに通過させ、立体障害無反応性有機硫黄化合物を穏やかな操作条件での水素化処理に対してより反応性の異性体へと変換し、異性化された流出物を穏やかな水素化処理プロセスに循環させる。
Claims (7)
- 望ましくない有機硫黄化合物の濃度を下げるための炭化水素供給物の処理方法であって、以下:
芳香族抽出操作によって、炭化水素供給物を、易変性有機硫黄化合物を含有する芳香族リーン留分および立体障害無反応性芳香族有機硫黄化合物を含有する芳香族リッチ留分に分離すること、ここで、芳香族リッチ留分は、ベンゾチオフェン、ベンゾチオフェンのアルキル化誘導体、ジベンゾチオフェン、ジベンゾチオフェンのアルキル誘導体、ベンゾナフテノチオフェン、およびベンゾナフテノチオフェンのアルキル誘導体を含むか、または、芳香族リッチ留分は、ピロール、キノリン、アクリジン、カルバゾールおよびそれらの誘導体を含む芳香族窒素化合物を含む;
前記芳香族リッチ留分を吸着材と接触させて窒素含量を低減させ、吸着流出物を生じさせること;
前記吸着流出物と異性化触媒とを150℃〜350℃の範囲の温度で水素の存在下で接触させ、特定の化合物の立体障害性を取り除き、異性化物および残留未反応水素を含む異性化流出物を生じさせること、ここで、異性化触媒は、260℃の温度での非晶質シリカ-アルミナ触媒の酸性度よりも少なくとも15倍の酸性度を有する;
前記芳香族リーン留分および前記異性化流出物に穏やかな水素化処理プロセスを施し、それによって硫黄含量を低減すること、ここで、穏やかな水素化処理プロセスの操作条件は、20バール〜40バールの範囲の水素分圧、320℃〜380℃の範囲の温度、および、オイル1リットルあたり200リットルの水素(標準化)〜オイル1リットルあたり300リットルの水素(標準化)の範囲の穏やかな水素化処理プロセスにおける水素供給量を含む;および
水素化処理炭化水素生成物を回収すること
を含み、ここで、炭化水素供給物は、0.05重量%〜2重量%の範囲の硫黄および10ppmw〜3,000ppmwの範囲の窒素を含有する、180℃〜450℃の範囲で沸騰する直留ガスオイルである、方法。 - 炭化水素供給物を、芳香族リーン留分および芳香族リッチ留分に分離することは、以下:
炭化水素供給物および有効量の抽出溶媒を抽出ゾーンにさらし、
主な割合の炭化水素供給物の芳香族含分および抽出溶媒の一部を含有する抽出物、および
主な割合の炭化水素供給物の非芳香族含量および一部の抽出溶媒を含有するラフィネート
を生じさせること;
前記ラフィネートから少なくとも実質的に一部の抽出溶媒を分離し、芳香族リーン留分を穏やかな水素化処理プロセスへ送ること;および
前記抽出物から少なくとも実質的に一部の抽出溶媒を分離し、芳香族リッチ留分を芳香族リッチ留分と異性化触媒とを接触させるステップへ送ること
を含む、請求項1に記載の方法。 - 芳香族リーン留分は脂肪族有機硫黄化合物を含む、請求項1に記載の方法。
- 脂肪族有機硫黄化合物は、スルフィド、ジスルフィドおよびメルカプタンを含む、請求項3に記載の方法。
- 芳香族リッチ留分と吸着材とを接触させるステップは、以下:
a.2つの充填カラムの第1に芳香族リッチ留分を通過させ;
b.第1カラムを通る流れを止めながら、芳香族リッチ留分を第1カラムから第2カラムへと移動させ;
c.第1カラム中の吸着材から、窒素含有化合物および/または多核芳香族化合物を脱着および除去し、それによって該吸着材を再生し;
d.第2カラムを通る流れを止めながら、芳香族リッチ留分を第2カラムから第1カラムへと移動させ;
e.第2カラム中の吸着材から、窒素含有化合物および/または多核芳香族化合物を脱着および除去し、それによって該吸着材を再生し;
f.ステップ(a)〜(e)を繰り返すこと、それにより、芳香族リッチ留分の処理が連続的であること
を含む、請求項1に記載の方法。 - 望ましくない有機硫黄化合物を含有する炭化水素供給物の処理装置であって、以下:
炭化水素供給物から芳香族有機硫黄化合物を抽出可能な芳香族分離ゾーン、ここで、該芳香族分離ゾーンは、炭化水素供給物を受入用の入口、芳香族リッチ出口および芳香族リーン出口を含む;
260℃の温度での非晶質シリカ-アルミナ触媒の酸性度よりも少なくとも15倍の酸性度を有する異性化触媒を含有し、150℃〜350℃の範囲の温度で操作され、前記芳香族リッチ出口と流体連通する入口、および、異性化物排出用の異性化反応ゾーン出口を有する、異性化反応ゾーン;および
20バール〜40バールの範囲の水素分圧、320℃〜380℃の範囲の温度、および、オイル1リットルあたり200リットルの水素(標準化)〜オイル1リットルあたり300リットルの水素(標準化)の範囲の穏やかな水素化処理プロセスにおける水素供給量で操作される水素化処理ゾーンであって、前記異性化反応ゾーン出口と流体連通し、前記芳香族リーン出口と流体連通する入口を有する水素化処理ゾーン、ここで該水素化処理ゾーンは、水素化処理炭化水素生成物を排出するための水素化処理ゾーン出口を含む
を含む、装置。 - 芳香族リッチ排出口と流体連通する入口、および、低減濃度の窒素含有化合物を有する抽出物を排出用の吸着ゾーン出口を有する、吸着ゾーンをさらに含み、ここで、前記異性化反応ゾーン入口は該吸着ゾーン出口と流体連通する、請求項6に記載の装置。
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US201161513184P | 2011-07-29 | 2011-07-29 | |
US61/513,184 | 2011-07-29 | ||
PCT/US2012/048463 WO2013019586A2 (en) | 2011-07-29 | 2012-07-27 | Hydrotreating of aromatic-extracted hydrocarbon streams |
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JP2014524969A5 JP2014524969A5 (ja) | 2015-09-10 |
JP6133859B2 true JP6133859B2 (ja) | 2017-05-24 |
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JP2014523042A Expired - Fee Related JP6133859B2 (ja) | 2011-07-29 | 2012-07-27 | 芳香族抽出型炭化水素流の水素化処理 |
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EP (1) | EP2737019A2 (ja) |
JP (1) | JP6133859B2 (ja) |
KR (1) | KR101973703B1 (ja) |
CN (1) | CN103827265B (ja) |
WO (1) | WO2013019586A2 (ja) |
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US11613714B2 (en) * | 2021-01-13 | 2023-03-28 | Saudi Arabian Oil Company | Conversion of aromatic complex bottoms to useful products in an integrated refinery process |
US11542442B1 (en) | 2022-04-05 | 2023-01-03 | Saudi Arabian Oil Company | Hydrocracking process and system including separation of heavy poly nuclear aromatics from recycle with heteropoly acids |
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2012
- 2012-07-27 WO PCT/US2012/048463 patent/WO2013019586A2/en active Application Filing
- 2012-07-27 EP EP12819035.2A patent/EP2737019A2/en not_active Withdrawn
- 2012-07-27 KR KR1020147005101A patent/KR101973703B1/ko active IP Right Grant
- 2012-07-27 US US13/559,806 patent/US9546328B2/en active Active
- 2012-07-27 CN CN201280045307.2A patent/CN103827265B/zh active Active
- 2012-07-27 JP JP2014523042A patent/JP6133859B2/ja not_active Expired - Fee Related
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CN103827265B (zh) | 2016-08-17 |
US9546328B2 (en) | 2017-01-17 |
US20170145323A1 (en) | 2017-05-25 |
WO2013019586A2 (en) | 2013-02-07 |
KR20140064798A (ko) | 2014-05-28 |
KR101973703B1 (ko) | 2019-04-29 |
CN103827265A (zh) | 2014-05-28 |
WO2013019586A3 (en) | 2013-07-11 |
JP2014524969A (ja) | 2014-09-25 |
US9714392B2 (en) | 2017-07-25 |
US20130062255A1 (en) | 2013-03-14 |
EP2737019A2 (en) | 2014-06-04 |
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