JP6018198B2 - 芳香族分離を伴う統合型水素化および異性化処理プロセス - Google Patents
芳香族分離を伴う統合型水素化および異性化処理プロセス 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、例えばスルフィド、ジスルフィド、メルカプタンを含む脂肪族分子へ効果的に変換する条件下で作動する水素化処理ゾーンにさらし、変換化合物および非変換無反応性芳香族有機硫黄化合物を含有する水素化処理流出物を生じさせること;
b.水素化処理流出物を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;
c.前記芳香族リッチ留分と異性化触媒とを水素の存在下で接触させて、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;および
d.異性化流出物を水素化処理ゾーンへ循環させること。
a.穏やかな条件下で作動する水素化処理ゾーン中で初期炭化水素供給原料を水素化処理し、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の少なくとも一部を除去し、異性化有機硫黄化合物を除去すること;
b.水素化処理流出物を芳香族抽出ゾーン中で分離し、芳香族リーン留分および芳香族リッチ留分を得ること;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より反応性の異性体へと変換し、異性化流出物を穏やかな水素化処理プロセスに再利用すること
を含むプロセス。
Claims (19)
- 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:
炭化水素供給物に、
易変性有機硫黄化合物を変換し、
変換化合物および非変換立体障害無反応性芳香族有機硫黄化合物を含有する水素化処理流出物を生じさせる
に有効な、穏やかな水素化処理プロセスを施すこと;
芳香族抽出操作によって、水素化処理流出物を、水素化処理炭化水素生成物として回収され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;
前記芳香族リッチ留分と異性化触媒とを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;および
前記異性化流出物の少なくとも一部を水素化処理ゾーンに循環させること
を含み、
前記芳香族リッチ留分と前記異性化触媒とを接触させる前に、該芳香族リッチ留分と吸着材とを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をさらに含む、
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。 - 炭化水素供給原料は、180℃〜450℃の範囲で沸騰し、2重量%以下の硫黄および3,000ppmw以下の窒素を含有する直留ガスオイルであり;
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100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、
請求項1または2に記載の方法。 - 前記芳香族リッチ留分と前記異性化触媒とを接触させた後で、異性化流出物をフラッシングし、軽質異性化流出物および重質異性化流出物を生じさせ;
前記重質異性化流出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;および
前記軽質異性化流出物を回収すること
をさらに含む、請求項1〜3のいずれかに記載の方法。 - 少なくとも一部の重質異性化流出物を穏やかな水素化処理のステップへ戻し、再循環させることをさらに含む、請求項4に記載の方法。
- 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:
炭化水素供給物に、
易変性有機硫黄化合物を変換し、
変換化合物および非変換立体障害無反応性芳香族有機硫黄化合物を含有する水素化処理流出物を生じさせる
に有効な、穏やかな水素化処理プロセスを施すこと;
芳香族抽出操作によって、水素化処理流出物を、水素化処理炭化水素生成物として回収され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;
前記芳香族リッチ留分と異性化触媒とを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;および
前記異性化流出物の少なくとも一部を水素化処理ゾーンに循環させること
を含み、
前記芳香族リッチ留分と前記異性化触媒とを接触させた後で、異性化流出物をフラッシングし、軽質異性化流出物および重質異性化流出物を生じさせ;
前記重質異性化流出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;および
前記軽質異性化流出物を回収すること
をさらに含む、
方法。 - 少なくとも一部の重質異性化流出物を穏やかな水素化処理のステップへ戻し、再循環させることをさらに含む、請求項6に記載の方法。
- 水素化処理流出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前に、該水素化処理流出物をフラッシングし、軽質水素化処理流出物および重質水素化処理流出物を生じさせること;
前記重質水素化処理流出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;および
前記軽質水素化処理流出物を回収すること
をさらに含む、請求項1〜7のいずれかに記載の方法。 - 少なくとも一部の重質水素化処理流出物を穏やかな水素化処理のステップへと再循環させることをさらに含む、請求項8に記載の方法。
- 水素化処理流出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:
水素化処理流出物および有効量の抽出溶媒を抽出ゾーンにさらし、
主な割合の水素化処理流出物の芳香族含分および一部の抽出溶媒を含有する抽出物、および
主な割合の水素化処理流出物の非芳香族含分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、水素化処理炭化水素生成物として芳香族リーン留分を回収すること;
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1〜9のいずれかに記載の方法。 - 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1〜10のいずれかに記載の方法。
- 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11に記載の方法。
- 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、請求項1〜12のいずれかに記載の方法。
- 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、請求項1〜12のいずれかに記載の方法。
- 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、請求項1〜14のいずれかに記載の方法。
- 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を150℃〜350℃の範囲の温度で実施する、請求項1〜15のいずれかに記載の方法。
- 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:
易変性有機硫黄化合物を変換する操作が可能な穏やかな水素化処理ゾーン、ここで、該穏やかな水素化処理ゾーンは、炭化水素供給物を受入用の入口、および、水素化処理流出物を排出用の出口を含む;
水素化処理流出物から芳香族有機硫黄化合物を抽出する操作が可能な芳香族分離ゾーン、ここで、該芳香族分離ゾーンは、水素化処理流出物を受入用の入口、芳香族リッチ出口および芳香族リーン出口を含む;および
芳香族リッチ出口と流体連通する入口、および、異性化物を再循環させるための穏やかな水素化処理ゾーン入口と流体連通する異性化反応ゾーン出口を有する、異性化反応ゾーン
を含み、
異性化流出物排出出口と流体連通する入口、軽質異性化流出物の排出出口、および、芳香族分離ゾーンと流体連通する重質異性化流出物の排出用の出口を有するフラッシングゾーンをさらに含む、装置。 - 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:
易変性有機硫黄化合物を変換する操作が可能な穏やかな水素化処理ゾーン、ここで、該穏やかな水素化処理ゾーンは、炭化水素供給物を受入用の入口、および、水素化処理流出物を排出用の出口を含む;
水素化処理流出物から芳香族有機硫黄化合物を抽出する操作が可能な芳香族分離ゾーン、ここで、該芳香族分離ゾーンは、水素化処理流出物を受入用の入口、芳香族リッチ出口および芳香族リーン出口を含む;および
芳香族リッチ出口と流体連通する入口、および、異性化物を再循環させるための穏やかな水素化処理ゾーン入口と流体連通する異性化反応ゾーン出口を有する、異性化反応ゾーン
を含み、
芳香族リッチ排出出口と流体連通する入口、および、低減された窒素含有化合物の濃度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む装置であって、該異性化反応ゾーン入口は吸着ゾーン出口と流体連通する、
装置。 - 水素化処理流出物排出出口と流体連通する入口、軽質水素化処理流出物を排出用の出口、および、芳香族分離ゾーンと流体連通する重質水素化処理流出物を排出用の出口を有するフラッシングゾーンをさらに含む、請求項17または18に記載の装置。
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