JP4253581B2 - ナフサの脱硫方法 - Google Patents
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Description
(a)触媒有効量の水素化処理触媒の存在下、硫黄含有ナフサを接触水素化処理条件下で水素と接触させて、水素化脱硫ナフサを形成する工程;
(b)前記水素化脱硫ナフサを、水、水酸化アルカリ金属、フタロシアニンスルホン酸コバルトおよびアルキルフェノール類を含有し、少なくとも、
(i)溶解アルカリ金属アルキルフェニラート、溶解水酸化アルカリ金属、水および溶解スルホン化コバルトフタロシアニンを含有する第1相;および
(ii)水および溶解水酸化アルカリ金属を含有する第2相
の2相を有する処理組成物の第1相と接触させる工程;
(c)メルカプタン硫黄を前記水素化脱硫ナフサから前記第1相に抽出する工程;および
(d)前記水素化脱硫ナフサよりメルカプタン硫黄が少ない、品質向上されたナフサを分離する工程
を含むことを特徴とするナフサの脱硫方法に関する。
酸化量の酸素、およびメルカプタン硫黄を含む前記第1相を酸化領域に導き、前記第1相内のメルカプタン硫黄をジスルフィドに酸化する工程;
前記ジスルフィドを前記第1相から分離する工程;および
再利用のために前記第1相を工程(b)に導く工程
を更に含む連続的な方法である。好ましくは、前記工程(b)の接触は、添加酸素なしで、即ち実質的に嫌気性の条件下で行なわれる。
(a)触媒有効量の水素化処理触媒の存在下、硫黄含有ナフサを接触水素化処理条件下で水素と接触させて、水素化脱硫ナフサを形成する工程;
(b)前記水素化脱硫ナフサを抽出剤組成物と接触させる工程であって、
(i)前記抽出剤は、それと類似の水性水酸化アルカリ金属と実質的に混和せず、
(ii)前記抽出剤は、水、溶解アルカリ金属アルキルフェニラート、溶解水酸化アルカリ金属および溶解スルホン化コバルトフタロシアニンを含有する
ことを特徴とする工程;
(c)メルカプタン硫黄を前記水素化脱硫ナフサから前記抽出剤に抽出する工程;および
(d)前記水素化脱硫ナフサよりメルカプタン硫黄が少ない、品質向上されたナフサを分離する工程
を含むことを特徴とするナフサの脱硫方法に関する。
酸化量の酸素または他の何らかの酸素含有ガス、およびメルカプタン硫黄を含む前記抽出剤を酸化領域に導き、前記メルカプタン硫黄をジスルフィドに酸化する工程;
前記ジスルフィドを前記抽出剤から分離する工程;および
再利用のために前記抽出剤を工程(b)に導く工程
を更に含む連続的な方法である。好ましくは、前記工程(b)の接触は、添加酸素なしで、即ち実質的に嫌気性の条件下で行なわれる。
(i)メルカプチド類を、処理溶液から例えば蒸気ストリッピングによりストリッピングする工程;および
(ii)再利用前に処理溶液をポリッシングする工程
のうち1つ以上を前記方法に組み込むこともできる。メルカプチド類の触媒酸化が前記方法に含まれる場合、触媒的有効量のスルホン化コバルトフタロシアニンを触媒として使用できる。
(i)組成が、水−水酸化アルカリ金属−アルカリ金属アルキルフェニラート相図のうちの2相域中に位置し、従って組成が1相域および2相域と底相との相境界域に位置する上相を形成するか;
(ii)底相はなく、組成が1相域と2相域との相境界域に位置する
ような成分濃度を有する。
収束レーザー光反射測定装置(Focused Laser Beam Reflecatance Measuring Device(FBRM(登録商標)))であるレーゼンテック(LASENTECH)(登録商標)(レーザーセンサー・テクノロジー社(Laser Sensor Technology,Inc.)、米国ワシントン州レドモンド)を用いて、連続ナフサ相における分散水性カリウムクレジラートの液滴径をモニターした。前記装置は、迅速スピニングレーザービームから後方反射率を測定して、ビームの焦点を通過する粒子の「コード長」の分布を測定する。球形粒子の場合、コード長は粒子直径に直接比例する。このデータは、1千個の線形場におけるコード長によって分類される1秒当たりのカウント数として採取される。典型的には、1秒当たり数十万のコード長を測定してコード長サイズ分布の統計的に有意な測定値が提供される。この方法論は、変化する工程変数の関数としてこの分布の変化を検出するために特に適している。
メルカプタン抽出係数Keqの測定は、以下のとおり実施された。約50mlの選択的水素化処理ナフサを、テフロン(登録商標)被覆スターラーバーを入れた250mlシュレンクフラスコ中に注いだ。このフラスコをゴム管で不活性ガス/真空マニホールドに取り付けた。前記ナフサを、反復排出/窒素再充填サイクル(20回)により脱気した。これらの実験中は酸素を除去して、抽出メルカプチドアニオン類が酸素と反応してナフサ溶解性ジスルフィド類を生成することを防止した。ナフサは室温で比較的高揮発性のため、脱気ナフサのサンプル10mlを2つ、この時点でシリンジにより取り出し、脱気後原料中の総硫黄量を得た。蒸発ロスのため、硫黄含量は典型的には2〜7wppm(硫黄)増加した。脱気後、ナフサを温度制御油浴に入れ、攪拌しながら120°Fで平衡にした。所望成分の三相図決定後、組成が2相領域に配置されるように操作用抽出剤を調製した。過剰の抽出剤も調製し、脱気し、所望の容量を測定してから、標準的な不活性雰囲気での操作法を用いてシリンジにより攪拌ナフサに移した。ナフサと抽出剤は、120°Fで5分間激しく攪拌してから攪拌を止めて、2相を分離させた。約5分後、窒素雰囲気下のまま20mlの抽出ナフサを取り出して、2本のサンプル用バイアルに充填した。典型的には、元の原料のサンプル2つについても、X線蛍光法により分析して総硫黄を決定した。前記サンプルは、データの完全性を保証するために全て2回分析する。原料から除かれた硫黄は全て、水性抽出剤へのメルカプタン抽出によるという妥当な仮説がなされた。この仮説は、メルカプタン含量を測定した数回の操作で証明された。説明したように、抽出係数Keqは、抽出後、メルカプタン類の形態で存在する抽出剤中の硫黄(「メルカプタン硫黄」)の濃度を、後で抽出を行った選択的水素化処理ナフサ中のメルカプチド類の形態の硫黄(同じく「メルカプタン硫黄」と呼ばれる)の濃度で割った割合として、下記式:
図2に示されるように、相図中の2相領域の面積は、アルキルフェノールの分子量と共に増加する。これらの相図は、標準的な従来法により実験的に決定された。相間線は、分子量の関数としてシフトし、また2相領域内の抽出剤相の組成を決定する。種々の分子量のアルキルフェノール類から調製された2相抽出剤の抽出率を比較するために、抽出剤は、上層に約30重量%の一定のアルキルフェノール含量を有するよう調製した。従って、分子量の異なる3種のアルキルフェノール類に関して、抽出剤相中の濃度がこの濃度に達するように各々出発組成物を選択した。この基準で、3−メチルフェノール、2,4−ジメチルフェノールおよび2,3,5−トリメチルフェノールを比較した。この結果を図2に示す。
代表的な処理溶液を、458グラムのKOH、246グラムの水および198グラムのアルキルフェノール類を室温で組み合わせることにより調製した。30分間攪拌後、混合物を放置して2相に分離させ、それらを分離した。抽出剤(低比重)相は、抽出剤の全重量に対し約21重量%のKOHイオン、約48重量%のカリウムメチルフェニラートイオンおよび約31重量%の水という組成を有し、底相(高比重)は、底相重量に対し約53重量%のKOHイオンと残余水を含んでいた。
代表的2相処理溶液を実施例4と同様に調製した。抽出剤相は、抽出剤の全重量に対し約21重量%のKOHイオン、約48重量%のカリウムジメチルフェニラートイオンおよび約31重量%の水を有し、底相は、底相重量に対し約52重量%のKOHイオンと残余水を含んでいた。
3種の処理組成物(操作番号2、4および6)を、組成が2相領域内に配置されるよう調製した。上相(抽出剤)を処理組成物から分離後、実施例2に記載されたようにしてナフサと接触させ、各抽出剤に関するKeqを測定した。前記ナフサは、約C5以上の分子量を有する戻りメルカプタン類などの戻りメルカプタン類を含んでいた。結果を表2に記載する。
Claims (8)
- (a)触媒有効量の水素化処理触媒の存在下、硫黄含有ナフサを接触水素化処理条件下で水素と接触させて、水素化脱硫ナフサを形成する工程;
(b)前記水素化脱硫ナフサを、水、水酸化アルカリ金属、スルホン化コバルトフタロシアニンおよびアルキルフェノール類を含有し、
(i)アルカリ金属アルキルフェノラート、水酸化アルカリ金属、水およびスルホン化コバルトフタロシアニンを含有する第1相;および
(ii)水および水酸化アルカリ金属を含有する第2相
の少なくとも2相を有する処理組成物の第1相と接触させる工程;
(c)メルカプタン硫黄を前記水素化脱硫ナフサから前記第1相に抽出する工程;および
(d)前記水素化脱硫ナフサよりメルカプタン硫黄が少ない、品質向上されたナフサを分離する工程
を含み、
その際、前記組成物は、前記組成物の重量に対し、15〜55重量%のアルキルフェノール類、10〜500wppmのスルホン化コバルトフタロシアニン、25〜60重量%の水酸化アルカリ金属および10〜50重量%の水を含有する、ことを特徴とするナフサの脱硫方法。 - (a)実質的に嫌気性の条件下で、選択的水素化処理ナフサを抽出剤組成物と接触させる工程であって、
(i)前記組成物は、前記組成物の重量に対し、10〜50重量%の水、25〜60重量%の水酸化アルカリ金属、10〜500wppmのスルホン化コバルトフタロシアニンおよび10〜50重量%のアルキルフェノール類を組み合わせることにより形成され、
(ii)前記形成された組成物は、前記組成物の重量に対し、10〜95重量%のアルカリ金属アルキルフェノラート、1〜40重量%の水酸化アルカリ金属、10〜500wppmのスルホン化コバルトフタロシアニンおよび残余水を含有する単一液相である、
ことを特徴とする工程;
(b)メルカプタン硫黄を前記ナフサから前記組成物に抽出する工程;および
(c)(i)メルカプタン硫黄を含む前記組成物、および(ii)前記選択的水素化処理ナフサよりメルカプタン硫黄が少ない、品質向上されたナフサを分離する工程
を含むことを特徴とする、選択的水素化処理ナフサの連続的な処理・品質向上方法。 - 前記第1相は、工程(b)の接触工程において、親水性金属繊維上に添加されてそれに沿って流れ、前記炭化水素は、前記第1相の流れと並流して前記第1相上を流れることを特徴とする請求項1に記載のナフサの脱硫方法。
- 前記メルカプタンは、戻りメルカプタンであることを特徴とする請求項1または2に記載の方法。
- 酸化量の酸素、および前記工程(c)からの前記第1相を酸化領域に導き、前記第1相内のメルカプタン硫黄をジスルフィドに酸化する工程;
前記ジスルフィドを前記第1相から分離する工程;および
前記第1相をポリッシング領域に導き、そこで前記第1相から、水非混和性の溶剤でジスルフィドを更に分離する工程
を更に含み、
前記工程(b)の接触は、実質的に嫌気性の条件下で行なわれる
ことを特徴とする請求項1に記載のナフサの脱硫方法。 - 前記組成物は、工程(a)の接触工程において、親水性金属繊維上に添加されてそれに沿って流れ、前記選択的水素化処理ナフサは、前記組成物の流れと並流して前記組成物上を流れることを特徴とする請求項2に記載の連続的な処理・品質向上方法。
- 前記アルキルフェノール類の少なくとも一部は、前記選択的水素化処理ナフサから得られるクレゾール類であることを特徴とする請求項2に記載の連続的な処理・品質向上方法。
- (d)酸化量の酸素、およびメルカプタン硫黄を含む前記組成物を酸化領域に導き、前記メルカプタン硫黄をジスルフィドに酸化する工程;
(e)前記ジスルフィドを前記組成物から分離する工程;および
(f)前記工程(e)の前記組成物の少なくとも一部をポリッシング領域に導き、そこで前記組成物から、前記組成物を再使用する前に、水非混和性の溶剤でジスルフィドを更に分離する工程
を更に含むことを特徴とする請求項2に記載の連続的な処理・品質向上方法。
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US29932901P | 2001-06-19 | 2001-06-19 | |
US29934601P | 2001-06-19 | 2001-06-19 | |
PCT/US2002/018901 WO2002102940A1 (en) | 2001-06-19 | 2002-06-14 | Naphtha desulfurization method |
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JP2003506392A Expired - Fee Related JP4253580B2 (ja) | 2001-06-19 | 2002-06-14 | 液体炭化水素の処理方法 |
JP2003506390A Expired - Fee Related JP4253578B2 (ja) | 2001-06-19 | 2002-06-14 | 炭化水素処理用組成物および炭化水素処理の制御方法 |
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