JP2004195445A - Oxidation method of liquid containing organic sulfur compound, oxidation catalyst, oxidation desulfurization method and oxidation desulfurization apparatus - Google Patents
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【０００１】
【発明の属する技術分野】本発明は有機硫黄化合物を含有する液体の酸化方法、酸化触媒、酸化脱硫方法および酸化脱硫装置に関する。具体的にガソリン、灯油及び水素化脱硫後の軽油等の石油類からの脱硫に適した酸化脱硫方法、酸化触媒、酸化脱硫方法および酸化脱硫装置に関する。
【０００２】
【従来の技術】石油、石炭等の化石燃料の燃焼が原因となる酸性雨に対する対策が急務となったことに伴い、従来以上に、石油製品に対して高い品質が求められるに至り、化石燃料中の硫黄を接触還元して硫化水素とし、これを除去する水素化脱硫方法が対策として広く採用されてきた。しかしながら、この方法の場合には高温高圧の反応条件を余儀なくされる上、（ジ）ベンゾチオフェンを基本骨格とするような、化学的に安定な芳香族アルキル誘導体として硫黄が含有されている場合には、これを還元すること自体が困難な場合があり、十分な脱硫効果を挙げることができないという欠点があった。
【０００３】また、近年、省エネ性が高く、環境負荷が小さいエネルギー技術である燃料電池が、二酸化炭素等の温室効果ガス排出を抑制し、地球温暖化を防止するための重要な開発課題として注目されている。燃料電池を普及させる実用化用途として、小型燃料電池汎用電源や燃料電池自動車が急ピッチで開発されている。燃料電池の水素源としては、様々な候補が挙げられるが、ガソリンや灯油の改質が現実的であり、これがクローズアップされてきた。ところが燃料電池用原料油の硫黄含有量を、従来レベルより遥かに下の数十〜数百ｐｐｂオーダーまで下げなければならない。この解決策として化学吸着による吸着型硫黄除去器が開発中であるが、これは吸着選択性が低く、再生できない高価な吸着剤が使用され、処理能力も低いとされている。
【０００４】以上のように、ガソリン、灯油、軽油等石油系燃料油中の硫黄分については様々な観点から現在の１／１０、ひいては１ｐｐｍ以下に削減することが要求されるに至っているが、その目標を達成することのできる工業的技術は未だ開発されていない。かかる課題を解決する方法として、酸化反応を用いる脱硫方法が提案されている（例えば、特許文献１参照）。この方法は、有機硫黄化合物中の硫黄原子を酸化して有機スルホキシドや有機スルホンの形にすることによる、有機硫黄化合物の著しい物性変化を利用して有機硫黄化合物を除去するものであり、接触還元方法に比して温和な条件下で効率良く脱硫することにおいて優れた方法であり、先に挙げた特許文献１では、低濃度のジベンゾチオフェン（ＤＢＴ）含有液において、極めて穏和な条件下であっても８０％の転化率を達成できることが確認されている。また、非特許文献１では、バッチ式反応器を用い、酸化触媒の存在下、１２０℃で酸化剤を加えた水素化処理した軽油の酸化反応が行われ、酸化後の軽油にＳｉＯ２−Ａｌ２Ｏ３やＳｉＯ２等の吸着剤を入れることによって、軽油中の硫黄分が低減する可能性を報告した（例えば、非特許文献１参照）。
【特許文献１】特開平１１−１４０４６２号（第２−４頁、図１、図２）
【非特許文献１】日本化学会第７９春季年会要旨、１Ｅ６−２５、２００１年３月２８−３１日、神戸
【０００５】
【発明が解決しようとする課題】しかしながら、酸化触媒、酸化剤および酸化方法について、まだ改良の余地がある。また、酸化後硫黄化合物の除去についてもまだ実用化の方法が提案されていない。従って本発明は、有機硫黄化合物を含有する液体の酸化脱硫方法として好適な、有機硫黄化合物を含有する液体の酸化方法、酸化触媒、酸化脱硫方法および酸化脱硫装置を提供することにある。
【０００６】
【課題を解決するための手段】本発明者等は、さらなる高活性に到達するために鋭意研究した結果、酸化剤を添加した有機硫黄化合物含有液体を固体酸化触媒と接触させ、酸化反応を行なうことにより、有機硫黄化合物を含有する液体中の硫黄化合物を硫黄酸化物に転化させ、さらに吸着剤の吸着によって除去することができる手段となることを見出し、本発明に到達した。本発明は、有機硫黄化合物を含有する液体中に酸化剤を添加し、酸化触媒の存在下加熱することにより前記有機硫黄化合物を硫黄酸化物に転化させ、次いで生成した硫黄酸化物を吸着より除去する脱硫方法である。酸化剤として、過酸化水素水、有機過酸化物、有機次亜塩素酸化合物及び有機次亜臭素酸化合物からなる群の中から選択される少なくとも一種の酸化剤を、前記有機硫黄化合物中の硫黄原子の酸化に必要な化学量論量以上添加し、酸化触媒を用いて、触媒酸化反応を行ない、さらにその酸化硫黄化合物を吸着等により除去することを特徴とする、有機硫黄化合物を含有する液体の酸化脱硫方法によって達成された。
【０００７】
【発明の実施の形態】本発明における有機硫黄化合物含有液体は特に限定されるものではないが、特に、その中に含有される有機硫黄化合物が、一般に最も除去することが難しいとされているベンゾチオフェン、ジベンゾチオフェン等のチオフェン類であって、硫黄分の残存量が数百ｐｐｍ以下となったナフサ、ガソリン、灯油、軽油、重油、アスファルテン、オイルサンド油、石炭液化油、石炭系重質油等であることが好ましい。これらのチオフェン類中の硫黄原子が酸化されたスルホキシド及びスルホンは、共に、その物性が元の化合物の物性と大きく異なるので、ろ過や吸着等により、容易に分離することができる。また、微生物を利用して分解することも可能である。
【０００８】本発明で使用する酸化剤は、過酸化水素水、有機過酸化物、有機次亜塩素酸化合物、および有機次亜臭素酸化合物の中から適宜選択することができる。これらの酸化剤は、２種以上を併用しても良い。有機過酸化物の具体例としては、例えば、過蟻酸、過酢酸、ｔｅｒｔ−ブチルヒドロペルオキシド等の過酸化物等がある。反応性、取り扱い性等の観点から本発明においては、特に有機過酸化物を使用することが好ましく、特に、ｔｅｒｔ−ブチルヒドロペルオキシドを使用することが好ましい。
【０００９】酸化剤の使用量は、液体中に含有される酸化されるべき有機硫黄化合物の全てをスルホキシドに酸化するに必要な量以上であれば良いが、通常は、硫黄原子１個あたり、０．５〜３０個の酸素原子、特に１〜１０個の酸素原子を供給する量の酸化剤を添加することが、有機硫黄化合物を速やかにスルホキシド又はスルホンに酸化する上で好ましい。
【００１０】本発明における有機硫黄化合物含有液体と酸化剤を混合し、加熱しても、それだけでは酸化反応が進行しないので、酸化触媒が必要である。ここで、触媒として固体触媒を使用すれば、有機硫黄化合物含有液体中の硫黄化合物を酸化でき、次いで吸着等の処理することによって、従来の水素化脱硫後、引き続き酸化脱硫することが可能である。
【００１１】本発明では固体触媒が、有機硫黄化合物を酸化してスルホキシドやスルホンにすることのできる触媒の中から適宜選択して使用することができる。このような固体触媒は、公知のものの中から適宜選択することができるが、ブレンステッド酸性又はルイス酸性の固体酸触媒、遷移金属酸化物触媒、及び固体塩基触媒が好ましい。担体として、γ−アルミナ、チタニア、シリカ−アルミナ、シリカの中から適宜選択して使用することができ、その中でもγ−アルミナが好ましい。担体の粒径は適宜選択できるが、反応溶液が詰まらない程度の粒径（−３００メッシュ）を有する限りにおいて比較的小さいものが好ましいが、触媒強度と取り扱いの点より２５〜１００メッシュの範囲が好ましい。
【００１２】触媒の担持金属はモリブデン、タングステン、クロム、バナジウム、ニオブ、ジルコニウム、ニッケルの少なくとも１種以上を担持したものが好ましい。担持金属の量は酸化物換算で０〜５０質量％の範囲内であれば良いが、担体に単層程度担持する範囲が好ましく、酸化モリブデンであれば３〜３０質量％、酸化タングステンであれば１０〜５０質量％、酸化クロムであれば５〜３０質量％、酸化バナジウムであれば２〜１５質量％、酸化ニオブであれば１〜１５質量％、酸化ジルコニウムであれば５〜２０質量％の範囲が好ましい。担体としては前述のような担体から少なくとも１種が選択できる。
【００１３】担持方法については、含浸法又はイオン交換法が好ましく、担持する金属化合物を複数回に分けて含浸しても良いが、一度に行うのが効率的である。担持金属化合物は調製する触媒重量の０．５〜１００倍の重量の純水を用いて溶解させてやればよいが、担持金属の分散率を高めるために１〜１０倍の範囲が好ましい。溶解度の低い担持金属化合物を用いる場合には、硝酸やアンモニア水等を加えてもかまわないが、含浸液の安定性を考慮するとｐＨ３〜１１の範囲内が好ましい。含浸後、通常２０〜２００℃（好ましくは１００〜１２０℃）の範囲内で、１〜１２時間（好ましくは２〜６時間）乾燥させる。その後、２００〜５００℃（好ましくは３５０〜４５０℃）で２〜１５時間（好ましくは３〜１２時間）焼成する。
【００１４】酸化した硫黄化合物を有機硫黄化合物含有液体から除去する方法については、蒸留、ろ過、吸着等の分離方法を用いられるが、再生可能な吸着剤を用い、選択的に吸着によって除去することが望ましい。吸着剤として、活性炭、アルミナ、シリカゲル、石油精製プロセスに使われる流動床接触クラッキング（ＦＣＣ）平衡触媒（使用済み）、シリカーアルミナ、モリキュラーシーブ、ゼオライトの中から選択される少なくとも一種の吸着剤を用い、前記有機硫黄酸化物を吸着により除去できる。
【００１５】使用済みの吸着剤の再生に使用する溶媒は公知のもの、たとえば、メタノール、トルエン、スルホラン、ジメチルスルホキシド、アセトニトリル等から適宜選択して、使用することができ、その中でもテトラヒドロフランが好ましい。再生の際の温度は使用する溶媒の沸点以下でよいが、室温が好ましい。
【００１６】つぎに、本発明の有機硫黄化合物を含有する液体の酸化脱硫する方法について説明する。酸化処理条件については、一般的には反応温度０〜４００℃（好ましくは２０〜１２０℃）、常圧〜３気圧（好ましくは常圧）の範囲内で行われる。反応形式は特に限定されないが、通常は、バッチ式装置や流通式装置（固定床、移動床、懸濁床等）の種々のプロセスから選択できるが、流通式固定床が好ましい。流通式固定床の場合の反応条件としては、ＷＨＳＶは０．１〜４００ｈｒ−１（好ましくは０．５〜３００ｈｒ−１）の範囲内が好ましく、有機硫黄化合物を含有する液体中の硫黄分と酸化剤のモル比（Ｏ／Ｓ比）は０．５〜３０（好ましくは１〜１０）が好ましい。吸着脱硫の条件については、一般的には吸着温度−５０〜１００℃（好ましくは０〜５０℃）、常圧〜３気圧（好ましくは常圧）の範囲内で行われる。吸着装置の形式は特に限定されないが、通常は、流通式固定床が好ましい。固定床の場合の反応条件としては、ＷＨＳＶは０．１〜４００ｈｒ−１（好ましくは１〜１００ｈｒ−１）の範囲内が好ましい。
【００１７】本発明の酸化脱硫装置は２段式反応器で構成されている。第１段目の反応器に上記の少なくとも１種の固体触媒を充填し、少なく１種の酸化剤を添加した有機硫黄化合物を含有する液体を連続的に通すことにより有機硫黄化合物を硫黄酸化物に転化し、第２段目の反応器に前述の少なくとも１種の吸着剤を充填し、第１段目の反応器から出てきた酸化反応後の液体から硫黄化合物を選択的に除去することができる。
【００１８】
なお、本発明は上述の実施の形態に限らず本発明の要旨を逸脱することなくその他種々の構成を採り得ることはもちろんである。
【００１９】
【実施例】
以下、実施例によって本発明を更に詳述するが、本発明はこれによって限定されるものではないこともちろんである。
【００２０】
実施例１ 触媒組成としてＭｏＯ３が１６質量％となるように（ただし担体８．４ｇ）モリブデン酸アンモニウム４水和物（（ＮＨ４）６Ｍｏ７Ｏ２４・４Ｈ２Ｏ）をビーカーに入れ、１０ｍｌの純水で完全に溶解させてモリブデン酸アンモニウム水溶液を調製する。そこにγ−アルミナ担体（２５−８０メッシュ）を入れ、振蕩しながらサンドバスで加熱し水分を蒸発させてモリブデン酸アンモニウムを含浸させる。さらに１２０℃で２時間乾燥させた後、４５０℃で１２時間焼成して１６質量％モリブデン酸γ−アルミナ触媒（ＭｏＯ３／γ−Ａｌ２Ｏ３）１０ｇを得た。これを触媒Ａとする。つぎに、触媒Ａを０．１ｇ、２００ｍｌのナス型フラスコに加え、さらに１５００ｐｐｍのジベンゾチオフェン（ＤＢＴ）を含有する水素化処理後軽油（全硫黄含有量：７３０ｐｐｍ）を６５ｍｌ入れ、ｔｅｒｔ−ブチルヒドロペロオキシドと軽油中の全硫黄のモル比（Ｏ／Ｓ）が９になるように、ｔｅｒｔ−ブチルヒドロペロオキシドを０．６３ｇ加えた後、オイルバスを用いて１２０℃に加温し、酸化反応を２時間行なった。これをフレームホトメトリック検出器（ＦＰＤ）付きガスクロマトグラフー（島津製作所：ＧＣ−１４Ａ−ＦＰＤ）で分析したところ、第１表に示すようなＤＢＴの酸化活性が得られた。
【００２１】
実施例２〜４ 実施例１と同様にバナジン酸アンモニウム４水和物（ＮＨ４ＶＯ３）を用い、４質量％Ｖ２Ｏ５／γ−Ａｌ２Ｏ３触媒（触媒Ｂ）、硝酸クロム（Ｃｒ（ＮＯ３）３）を用い、２２質量％ＣｒＯ３／γ−Ａｌ２Ｏ３（触媒Ｃ）、タングステン酸アンモニウム５水和物（（ＮＨ４）１０Ｏ４１Ｗ１２・５Ｈ２Ｏ）を用い、１９．３質量％ＷＯ３／γ−Ａｌ２Ｏ３（触媒Ｄ）をそれぞれ調製した。また、これらの触媒をそれぞれ用い、実施例１と同様の酸化反応を行なったところ、第１表に示すようなＤＢＴの酸化活性が得られた。
【００２２】
実施例５ １２０℃で２時間乾燥させたγ−アルミナ担体を４５０℃で１２時間焼成して、触媒Ｅとする。つぎに触媒Ｅを用い、実施例１と同様の酸化反応を行なったところ、第１表に示すようなＤＢＴの酸化活性が得られた。
【００２３】
実施例６、７ 実施例１と同様の酸化脱硫反応を行なった。ただし、ｔｅｒｔ−ブチルヒドロペロオキシドと軽油中の全硫黄のモル比（Ｏ／Ｓ）がそれぞれ４．５と１になった。その結果を第１表に示した。
【００２４】
比較例１ 特許文献１のＰｔ／Ａｌ２Ｏ３触媒および次亜塩素酸−ｔｅｒｔ−ブチルを用い、実施例１と同様の酸化反応を行なったところ、第１表に示すようなＤＢＴの酸化活性が得られた。
【００２５】
実施例８ 吸着剤としてシリカーアルミナ（表面積５６０ｍ２／ｇ）１ｇを実施例１で酸化反応を行なった軽油に加え、７０℃で３ｈｒ、さらに２０℃で３ｈｒ吸着による硫黄化合物の除去を行った。吸着脱硫後の軽油中の硫黄含有量を蛍光Ｘ線分析装置（島津製作所：ＥＤＸ−８００型）で分析したところ、第２表に示すように酸化−吸着操作によって１０ｐｐｍ以下という低濃度まで硫黄分を削減することができた。
【００２６】
実施例９〜１５ 吸着剤としてモリキューラシーブ４Ａ、モリキューラシーブ１３Ｘ、γ−アルミナ（表面積２５６ｍ２／ｇ）、活性炭（表面積８００−１０００ｍ２／ｇ）、シリカゲル（表面積３４７ｍ２／ｇ）、ＺＳＭ−５ゼオライト、ＮａＹゼオライト（表面積６６３ｍ２／ｇ）をそれぞれ使用し、実施例８と同様の吸着実験を行い、硫黄化合物の除去を行った。その結果を第２表に示した。
【００２７】
比較例２ 実施例８と同様の吸着実験を行い、硫黄化合物の除去を行なった。ただし、１５００ｐｐｍのジベンゾチオフェン（ＤＢＴ）を含有する水素化処理後軽油（全硫黄含有量：７３０ｐｐｍ）の酸化反応を行なわず、そのまま吸着を行った。第２表に示したように酸化反応を行なわず吸着のみでは脱硫率が低かった。
【００２８】
実施例１６ 触媒Ａを０．１ｇ、２００ｍｌのナス型フラスコに加え、さらに１００ｍｌのメスシリンダーに市販の灯油（硫黄濃度５５ｐｐｍ）を１００ｍｌ入れ、ｔｅｒｔ−ブチルヒドロペロオキシドと灯油中の全硫黄のモル比（Ｏ／Ｓ）が２になるように、ｔｅｒｔ−ブチルヒドロペロオキシドを０．０２０ｇ加えた後、オイルバスを用いて１００℃に加温し、酸化反応を２時間行なった。次いで、吸着剤としてシリカゲル（表面積３４７ｍ２／ｇ）１．２ｍｌを充填したカラム中に、常圧、２５℃、ＷＨＳＶ：４ｈｒ−１の条件で前述の酸化した灯油を流下させ、硫黄除去を行った。酸化脱硫後の灯油中の硫黄含有量を微量硫黄分析装置（ダイヤインスツルメンツ：ＴＳ−１００型）で分析し、その結果を第３表に示した。
【００２９】
実施例１７〜２０ 実施例１６と同様の酸化脱硫反応を行なった。ただし、吸着剤としてＦＣＣ平衡触媒、活性化アルミナ、活性炭（表面積８００−１０００ｍ２／ｇ）、シリカ−アルミナ（表面積５６０ｍ２／ｇ）をそれぞれ使用した。その結果を第３表に示した。
【００３０】
実施例２１ ５００ｍｌのメスシリンダーに市販の灯油（硫黄濃度５５ｐｐｍ）を５００ｍｌ入れ、ｔｅｒｔ−ブチルヒドロペロオキシドをＯ／Ｓ比が１０になるように加えた。図１に示したような装置において、第１段目の反応器に触媒Ａ１７．５ｍｌを充填し、常圧、８０℃，ＷＨＳＶ：３０ｈｒ−１の条件で、次いで図１に示したように第２段目の反応器に吸着剤としてシリカゲル３５ｍｌを充填し、常圧、室温、ＷＨＳＶ：４．９ｈｒ−１の条件で前述のような酸化剤を添加した灯油を通した。第１段目の反応器の出口で酸化後の灯油を採取し、これを化学発光硫黄検出装置付きガスクロマトグラフー（アジレント：ＧＣ−ＳＣＤ）でＤＢＴ、４−メチルジベンゾチオフェン（４ＭＤＢＴ）、４，６−ジメチルジベンゾチオフェン（４，６−ＤＭＤＢＴ）及び、これらの化合物の酸化生成物であるジベンゾチオフェンスルホン（ＤＢＴＳ）、４−メチルジベンゾチオフェンスルホン（４ＭＤＢＴＳ）、４，６−ジメチルジベンゾチオフェンスルホン（４，６−ＤＭＤＢＴＳ）を分析したそれぞれの化合物の濃度及び、微量硫黄分析装置（ダイヤインスツルメンツ：ＴＳ−１００型）で分析した灯油中の全硫黄分を第４表に示した。また、第２段目の反応器の出口で酸化脱硫後の灯油を採取し、同様に灯油中の各硫黄化合物および全硫黄分を測定し、第４表に示した。第４表に示すように灯油中の硫黄化合物がほとんど酸化され、スルホン類化合物になり、吸着によって、ほとんど除去できる。一方、酸化反応後ごく少ない未酸化の硫黄化合物が吸着後も残される。また、酸化−吸着操作によって０．４５ｐｐｍという極めて低濃度まで灯油中の硫黄分を削減することができた。
【００３１】
実施例２２ １００ｍｌのメスシリンダーに市販の灯油（硫黄濃度５５ｐｐｍ）を１００ｍｌ入れ、ｔｅｒｔ−ブチルヒドロペロオキシドと灯油中の全硫黄のモル比（Ｏ／Ｓ）が１．５になるように、ｔｅｒｔ−ブチルヒドロペロオキシドを０．０２０ｇ加えた。これを触媒Ａ１ｇを充填した図１に示したように第１段目の反応器に、常圧、１１０℃，ＷＨＳＶ：６０ｈｒ−１の条件で通し、酸化反応のみを行なった。これを化学発光硫黄検出装置付きガスクロマトグラフー（アジレント：ＧＣ−ＳＣＤ）で分析したところ、第５表に示すような各硫黄化合物の酸化活性が得られた。
【００３２】
実施例２３〜２７ 実施例１と同様にタングステン酸アンモニウム５水和物（（ＮＨ４）１０Ｏ４１Ｗ１２・５Ｈ２Ｏ）を用い、３５質量％ＷＯ３／γ−Ａｌ２Ｏ３（触媒Ｆ）、硝酸クロム（Ｃｒ（ＮＯ３）３）を用い、１１質量％ＣｒＯ３／γ−Ａｌ２Ｏ３（触媒Ｇ）、バナジン酸アンモニウム４水和物（ＮＨ４ＶＯ３）を用い、１０質量％Ｖ２Ｏ５／γ−Ａｌ２Ｏ３触媒（触媒Ｈ）、ニオブ酸ナトリウム（Ｎａ２Ｎｂ２Ｏ５）を用い、１０質量％Ｎｂ２Ｏ５／γ−Ａｌ２Ｏ３（触媒Ｉ）、塩化ジルコニウム（ＺｒＣｌ２）を用い、１５質量％ＺｒＯ２／γ−Ａｌ２Ｏ３（触媒Ｊ）をそれぞれ調製した。また、これらの触媒をそれぞれ用い、実施例２２と同様の酸化反応を行なったところ、第５表に示すような各硫黄化合物の酸化活性が得られた。
【００３３】
実施例２８、２９ γ−アルミナ担体の代わりにチタンニア担体およびシリカ担体を使用し、実施例１と同様に１６質量％ＭｏＯ３／ＴｉＯ２（触媒Ｋ）および１６質量％ＭｏＯ３／ＳｉＯ２（触媒Ｌ）を調製した。また、触媒ＫおよびＬを用い、実施例２２と同様の酸化反応を行なったところ、第５表に示すような各硫黄化合物の酸化活性が得られた。
【００３４】
実施例３０ 実施例１と同様にモリブデン酸アンモニウム４水和物（（ＮＨ４）６Ｍｏ７Ｏ２４・４Ｈ２Ｏ）と硝酸ニッケル６水和物（Ｎｉ（ＮＯ３）２・６Ｈ２Ｏ）を用い、触媒組成としてＭｏＯ３が１６質量％と、ＮｉとＭｏのモル比を０．４になるように０．４ＮｉＭｏＯ３／Ａｌ２Ｏ３（触媒Ｍ）を調製した。つぎに触媒Ｍを用い、実施例２２と同様の酸化反応を行なったところ、第５表に示すような各硫黄化合物の酸化活性が得られた。
【００３５】
実施例３１〜３７ 触媒上の酸化モリブデンの担持量を３質量％から２５質量％までになるように、実施例１と同様に３質量％ＭｏＯ３／γ−Ａｌ２Ｏ３（触媒Ｎ）、６質量％ＭｏＯ３／γ−Ａｌ２Ｏ３（触媒Ｏ）、１２質量％ＭｏＯ３／γ−Ａｌ２Ｏ３（触媒Ｐ）、１４質量％ＭｏＯ３／γ−Ａｌ２Ｏ３（触媒Ｑ）、１８質量％ＭｏＯ３／γ−Ａｌ２Ｏ３（触媒Ｒ）、２０質量％ＭｏＯ３／γ−Ａｌ２Ｏ３（触媒Ｓ）および２５質量％ＭｏＯ３／γ−Ａｌ２Ｏ３（触媒Ｔ）を調製した。また、これらの触媒をそれぞれ用い、実施例２２と同様の酸化反応を行なったところ、第５表に示すような各硫黄化合物の酸化活性が得られた。
【００３６】
比較例３ 特許文献１のＰｔ／Ａｌ２Ｏ３触媒および次亜塩素酸−ｔｅｒｔ−ブチルを用い、実施例２２と同様の酸化反応を行なったところ、第５表に示すような各硫黄化合物の酸化活性が得られた。
【００３７】
実施例３８、３９ 実施例２２と同様の酸化反応を行なった。ただし、Ｏ／Ｓ比をそれぞれ１．０、１０および２０になるようにｔｅｒｔ−ブチルヒドロペロオキシドを加えた。その結果を第６表に示した。
【００３８】
実施例４０〜４３ 実施例２２と同様の酸化反応を行なった。ただし、反応温度をそれぞれ３０℃、７０℃、９０℃および１２０℃にした。その結果を第７表に示した。
【００３９】
実施例４４〜４８ 実施例２２と同様の酸化反応を行なった。ただし、ＷＨＳＶを６ｈｒ−１、２０ｈｒ−１、１２０ｈｒ−１、１８０ｈｒ−１、３００ｈｒ−１にした。その結果を第８表に示した。
【００４０】
実施例４９ 実施例２２と同様の酸化反応を行なった。ただし、酸化剤として、ｔｅｒｔ−ブチルヒドロペロオキシドの代わりに、過酸化水素水を０．０１５ｇ使用した。その結果を第９表に示した。
【００４１】
実施例５０ 市販の灯油（硫黄分５５ｐｐｍ）にｔｅｒｔ−ブチルヒドロペロオキシドをＯ／Ｓ比が２になるように加えた。図１に示したような装置において、第１段の反応器での反応条件は第１段目の反応器に触媒Ｐ（１２％Ｍｏ）１０．０ｍｌを充填し、常圧、８０℃，ＷＨＳＶ：６７．３ｈｒ−１の条件で、次いで図１に示したように第２段の反応器に吸着剤としてシリカゲル４０ｍｌを充填し、常圧、２０℃、ＷＨＳＶ：１６．８ｈｒ−１の条件で前述のような酸化剤を添加した灯油を通した。得られた酸化脱硫後の灯油の平均硫黄分を表１０に示した。
【００４２】
実施例５１ 実施例５０と同様の灯油の酸化脱硫を行なった。ただし、第１段目の反応器での酸化反応のＷＨＳＶを２４．８ｈｒ−１に、第２段目の反応器での吸着のＷＨＳＶを７．１ｈｒ−１にした。その結果は表１０に示した。
【００４３】
実施例５２ 実施例５０と同様の灯油の酸化脱硫を行なった。ただし、第１段目の反応器での酸化反応のＷＨＳＶを２２．９ｈｒ−１にし、第２段目の反応器での吸着のＷＨＳＶを１．８ｈｒ−１にした。その結果は表１０に示した。
【００４４】
実施例５３ 市販ガソリン（硫黄分３９．２ｐｐｍ）を用い、実施例２１と同様の酸化脱硫反応を行なった。得られた酸化脱硫後のガソリンの平均硫黄分を表１０に示した。
【００４５】
実施例５４ 水素化処理後の中東系直留軽油（硫黄分３８．８ｐｐｍ）を用い、実施例２１と同様の酸化脱硫反応を行なった。得られた酸化脱硫後の軽油の平均硫黄分を表１０に示した。
【００４６】
比較例４ 市販の灯油（硫黄分５５ｐｐｍ）に次亜塩素酸−ｔｅｒｔ−ブチルをＯ／Ｓ比が２になるように加えた。図１に示したような装置において、第１段の反応器に特許文献１のＰｔ／Ａｌ２Ｏ３触媒１０．０ｍｌを充填し、実施例２１と同様の反応条件下で酸化脱硫反応を行なった。得られた酸化脱硫後の灯油の平均硫黄分を表１０に示した。
【００４７】
比較例５ 市販ガソリン（硫黄分３９．２ｐｐｍ）を用い、比較例４と同様の酸化脱硫反応を行なった。得られた酸化脱硫後のガソリンの平均硫黄分を表１０に示した。
【００４８】
比較例６ 水素化処理後の中東系直留軽油（硫黄分３８．８ｐｐｍ）を用い、比較例４と同様の酸化脱硫反応を行なった。得られた酸化脱硫後の軽油の平均硫黄分を表１０に示した。
【００４９】
実施例５５ 市販の灯油（硫黄濃度５５ｐｐｍ）にｔｅｒｔ−ブチルヒドロペロオキシドをＯ／Ｓ比が１．５になるように加えた。図１に示したような装置において、第１段目の反応器での反応条件は第１段目の反応器に触媒Ａ（１６％Ｍｏ）３．０ｍｌを充填し、常圧、８０℃，ＷＨＳＶ：３０ｈｒ−１の条件で、次いで図１に示したように第２段目の反応器に吸着剤としてシリカゲル２０ｍｌを充填し、常圧、２０℃、ＷＨＳＶ：４．５ｈｒ−１の条件で前述のような酸化剤を添加した灯油を吸着剤の吸着飽和まで通し続けた。吸着剤の吸着能力を示す吸着破過曲線を図２に、求めた吸着破過点（吸着剤の体積ごとに吸着剤の飽和吸着まで処理できる灯油の体積）および得られた酸化脱硫後の灯油の平均硫黄分を第１１表に示した。
【００５０】
実施例５６ 実施例５５で吸着破過をむかえた第２段目の反応器に２０℃で、３０ｍｌのテトラヒドロフラン（ＴＨＦ）を流し、吸着剤を再生した。次いで、実施例５５と同様の酸化脱硫を行なった。その結果を図２及び第１１表に示した。吸着剤が再生することによって、ほとんど実施例５５と同様の酸化脱硫結果を得ることができた。
【００５１】
実施例５７ 実施例５６で吸着破過をむかえた第２段目の反応器に２０℃で、５０ｍｌのテトラヒドロフラン（ＴＨＦ）を流し、吸着剤を再生した。次いで、実施例５５と同様の酸化脱硫を行なった。その結果を図２及び第１１表に示した。吸着剤が再生することによって、ほとんど実施例５５と同様の酸化脱硫結果を得ることができた。
【００５２】
実施例５８ 実施例５７で吸着破過をむかえた第２段目の反応器に２０℃で、１００ｍｌのテトラヒドロフラン（ＴＨＦ）を流し、吸着剤を再生した。次いで、実施例５５と同様の酸化脱硫を行なった。その結果を図２及び第１１表に示した。吸着剤が再生することによって、ほとんど実施例５５と同様の酸化脱硫することができた。
【表１】
【発明の効果】本発明は、酸化剤を添加した有機硫黄化合物を含有する液体を、酸化触媒の存在下、常圧、低温の温和な条件で反応させることにより、酸化脱硫方法の前工程として硫黄化合物をほぼ完全に酸化できる。また、後工程として、シリカゲルやアルミナ等の吸着剤を用い、高選択的に酸化した硫黄化合物を除去できる。さらに酸化触媒を充填し、有機硫黄化合物を硫黄酸化物に転化する第１段の反応器、吸着剤を充填し、第１段目の反応器で生成した硫黄酸化物を選択的に除去する第２段の反応器を有することを特徴とする酸化脱硫装置に、酸化剤を添加した有機硫黄化合物を含有する液体を連続的に通すことにより、工業的価値が極めて大きく、安価に硫黄分が数百ｐｐｂオーダーである石油製品を供給することができる。
【図面の簡単な説明】
【図１】有機硫黄化合物を含有する液体の酸化脱硫装置を示す図である。
【図２】シリカゲルと吸着破過したシリカゲルをＴＨＦによる再生したシリカゲルの酸化後の灯油に対する吸着能力を比較する図である。[0001]
The present invention relates to a method for oxidizing a liquid containing an organic sulfur compound, an oxidation catalyst, an oxidative desulfurization method, and an oxidative desulfurization apparatus. More specifically, the present invention relates to an oxidative desulfurization method, an oxidation catalyst, an oxidative desulfurization method, and an oxidative desulfurization apparatus suitable for desulfurization from petroleum such as gasoline, kerosene, and gas oil after hydrodesulfurization.
[0002]
2. Description of the Related Art With the urgent need to take measures against acid rain caused by the burning of fossil fuels such as petroleum and coal, petroleum products are required to have higher quality than ever before, and Hydrodesulfurization methods for catalytically reducing sulfur in hydrogen to hydrogen sulfide and removing it have been widely adopted as a countermeasure. However, in this method, reaction conditions of high temperature and high pressure are inevitable, and when sulfur is contained as a chemically stable aromatic alkyl derivative having a basic skeleton of (di) benzothiophene, However, in some cases, it is difficult to reduce this itself, and there is a drawback that a sufficient desulfurization effect cannot be obtained.
[0003] In recent years, fuel cells, which are energy technologies with high energy saving and low environmental impact, have been attracting attention as important development issues for suppressing greenhouse gas emissions such as carbon dioxide and preventing global warming. Have been. As a practical application to spread fuel cells, general-purpose power sources for small fuel cells and fuel cell vehicles are being developed at a rapid pace. There are various candidates for the hydrogen source of the fuel cell, but reforming of gasoline and kerosene is realistic and has been highlighted. However, the sulfur content of the fuel oil for fuel cells must be reduced to the order of tens to hundreds of ppb, which is far below the conventional level. As a solution to this, an adsorptive sulfur remover by chemical adsorption is under development, but it is said that this method has a low adsorption selectivity, uses an expensive non-reproducible adsorbent, and has a low treatment capacity.
[0004] As described above, the sulfur content in petroleum fuel oils such as gasoline, kerosene, and gas oil has been required to be reduced to 1/10 of the current level, and further to 1 ppm or less from various viewpoints. No industrial technology has yet been developed to achieve that goal. As a method for solving such a problem, a desulfurization method using an oxidation reaction has been proposed (for example, see Patent Document 1). This method removes an organic sulfur compound by utilizing a remarkable change in physical properties of the organic sulfur compound by oxidizing a sulfur atom in the organic sulfur compound to form an organic sulfoxide or an organic sulfone. This is an excellent method for efficient desulfurization under mild conditions compared to the method. In the above-mentioned Patent Document 1, a low-concentration solution containing dibenzothiophene (DBT) is used under extremely mild conditions. However, it has been confirmed that a conversion of 80% can be achieved. Further, in Non-Patent Document 1, an oxidation reaction of hydrogenated gas oil with an oxidizing agent added at 120 ° C. is performed in the presence of an oxidation catalyst using a batch reactor, and the oxidized gas oil is subjected to SiO 2 oxidation. 2 -Al 2 O 3 And SiO 2 The possibility of reducing the sulfur content in light oil by adding an adsorbent such as described above was reported (for example, see Non-Patent Document 1).
[Patent Document 1] JP-A-11-140462 (pages 2-4, FIGS. 1 and 2)
[Non-Patent Document 1] Abstracts of the 79th Annual Meeting of the Chemical Society of Japan, 1E6-25, March 28-31, 2001, Kobe
[0005]
However, there is still room for improvement in the oxidation catalyst, oxidizing agent and oxidation method. As for the removal of sulfur compounds after oxidation, no practical method has been proposed yet. Accordingly, an object of the present invention is to provide a method for oxidizing a liquid containing an organic sulfur compound, an oxidation catalyst, an oxidative desulfurization method, and an oxidative desulfurization apparatus suitable as a method for oxidative desulfurization of a liquid containing an organic sulfur compound.
[0006]
Means for Solving the Problems The inventors of the present invention have conducted intensive studies to attain even higher activity, and as a result, an organic sulfur compound-containing liquid to which an oxidizing agent has been added is brought into contact with a solid oxidation catalyst to carry out an oxidation reaction. Thus, the present inventors have found that the present invention provides a means for converting a sulfur compound in a liquid containing an organic sulfur compound into a sulfur oxide and removing the sulfur compound by adsorption of an adsorbent, thereby achieving the present invention. In the present invention, an oxidizing agent is added to a liquid containing an organic sulfur compound, and the organic sulfur compound is converted into a sulfur oxide by heating in the presence of an oxidation catalyst, and then the generated sulfur oxide is removed by adsorption. Is a desulfurization method. As the oxidizing agent, hydrogen peroxide solution, organic peroxide, at least one oxidizing agent selected from the group consisting of organic hypochlorous compound and organic hypobromite compound, sulfur in the organic sulfur compound A liquid containing an organic sulfur compound, characterized by adding a stoichiometric amount or more necessary for the oxidation of atoms, performing a catalytic oxidation reaction using an oxidation catalyst, and removing the sulfur oxide compound by adsorption or the like. Was achieved by the oxidative desulfurization method of
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION The organic sulfur compound-containing liquid in the present invention is not particularly limited, but in particular, the organic sulfur compound contained therein is generally considered to be most difficult to remove. Thiophenes, such as thiophene and dibenzothiophene, whose naphtha, gasoline, kerosene, light oil, heavy oil, asphaltenes, oil sand oil, coal liquefied oil, coal heavy oil whose residual amount of sulfur is several hundred ppm or less And the like. Sulfoxide and sulfone in which thiophenes have a sulfur atom oxidized have greatly different physical properties from those of the original compound, and thus can be easily separated by filtration or adsorption. It is also possible to decompose using a microorganism.
The oxidizing agent used in the present invention can be appropriately selected from aqueous hydrogen peroxide, an organic peroxide, an organic hypochlorite compound, and an organic hypobromite compound. These oxidizing agents may be used in combination of two or more. Specific examples of the organic peroxide include, for example, peroxides such as formic acid, peracetic acid, and tert-butyl hydroperoxide. From the viewpoints of reactivity, handleability, and the like, in the present invention, it is particularly preferable to use an organic peroxide, and particularly preferable to use tert-butyl hydroperoxide.
The amount of the oxidizing agent used may be at least the amount necessary to oxidize all of the organic sulfur compounds to be oxidized contained in the liquid to the sulfoxide. It is preferable to add an oxidizing agent in an amount to supply 0.5 to 30 oxygen atoms, particularly 1 to 10 oxygen atoms, in order to quickly oxidize the organic sulfur compound to sulfoxide or sulfone.
[0010] Even if the liquid containing the organic sulfur compound and the oxidizing agent according to the present invention are mixed and heated, the oxidation reaction does not proceed by itself, so that an oxidation catalyst is required. Here, if a solid catalyst is used as a catalyst, it is possible to oxidize a sulfur compound in an organic sulfur compound-containing liquid, and then, by performing treatment such as adsorption, it is possible to continuously perform oxidative desulfurization after conventional hydrodesulfurization. .
In the present invention, the solid catalyst can be appropriately selected and used from catalysts capable of oxidizing an organic sulfur compound to sulfoxide or sulfone. Such a solid catalyst can be appropriately selected from known ones, but a Bronsted or Lewis acidic solid acid catalyst, a transition metal oxide catalyst, and a solid base catalyst are preferred. As the carrier, γ-alumina, titania, silica-alumina, and silica can be appropriately selected and used, and among them, γ-alumina is preferable. The particle size of the carrier can be appropriately selected, but is preferably relatively small as long as it has a particle size (-300 mesh) that does not clog the reaction solution, but the range of 25 to 100 mesh is preferred from the viewpoint of catalyst strength and handling. preferable.
The metal supported on the catalyst preferably supports at least one of molybdenum, tungsten, chromium, vanadium, niobium, zirconium and nickel. The amount of the supported metal may be in the range of 0 to 50% by mass in terms of oxide, but is preferably in the range of about a single layer supported on a carrier, 3 to 30% by mass for molybdenum oxide, and 3 to 30% by mass for tungsten oxide. 10 to 50% by mass, 5 to 30% by mass for chromium oxide, 2 to 15% by mass for vanadium oxide, 1 to 15% by mass for niobium oxide, 5 to 20% by mass for zirconium oxide A range is preferred. As the carrier, at least one kind can be selected from the carriers described above.
The loading method is preferably an impregnation method or an ion-exchange method. The metal compound to be loaded may be impregnated in a plurality of times, but it is efficient to carry it out at once. The supported metal compound may be dissolved using pure water having a weight of 0.5 to 100 times the weight of the catalyst to be prepared, but is preferably in a range of 1 to 10 times in order to increase the dispersion ratio of the supported metal. When using a supported metal compound having low solubility, nitric acid or aqueous ammonia may be added, but the pH is preferably in the range of 3 to 11 in consideration of the stability of the impregnating liquid. After the impregnation, it is dried usually in the range of 20 to 200 ° C (preferably 100 to 120 ° C) for 1 to 12 hours (preferably 2 to 6 hours). Thereafter, baking is performed at 200 to 500 ° C (preferably 350 to 450 ° C) for 2 to 15 hours (preferably 3 to 12 hours).
As a method for removing the oxidized sulfur compound from the liquid containing the organic sulfur compound, a separation method such as distillation, filtration, or adsorption may be used. Is desirable. At least one adsorbent selected from activated carbon, alumina, silica gel, fluidized bed catalytic cracking (FCC) equilibrium catalyst used in petroleum refining processes (used), silica-alumina, molecular sieve, and zeolite And the organic sulfur oxide can be removed by adsorption.
The solvent used for regenerating the used adsorbent can be appropriately selected from known solvents, for example, methanol, toluene, sulfolane, dimethyl sulfoxide, acetonitrile and the like, and among them, tetrahydrofuran is preferred. The temperature at the time of regeneration may be lower than the boiling point of the solvent used, but is preferably room temperature.
Next, a method for oxidatively desulfurizing a liquid containing an organic sulfur compound according to the present invention will be described. The oxidation treatment is generally performed at a reaction temperature of 0 to 400 ° C. (preferably 20 to 120 ° C.) and a normal pressure to 3 atm (preferably normal pressure). Although the reaction type is not particularly limited, it can be generally selected from various processes of a batch type apparatus or a flow type apparatus (fixed bed, moving bed, suspension bed, etc.), but a flow type fixed bed is preferable. As the reaction conditions in the case of a flow-type fixed bed, WHSV is 0.1 to 400 hours. -1 (Preferably 0.5 to 300 hours -1 ) Is preferable, and the molar ratio (O / S ratio) between the sulfur content and the oxidizing agent in the liquid containing the organic sulfur compound is preferably 0.5 to 30 (preferably 1 to 10). The conditions for the adsorption desulfurization are generally in the range of an adsorption temperature of −50 to 100 ° C. (preferably 0 to 50 ° C.) and normal pressure to 3 atm (preferably normal pressure). The type of the adsorption device is not particularly limited, but usually a flow-type fixed bed is preferred. As the reaction conditions in the case of a fixed bed, WHSV is 0.1 to 400 hours. -1 (Preferably 1 to 100 hours -1 ) Is preferable.
The oxidative desulfurization apparatus of the present invention is constituted by a two-stage reactor. The first-stage reactor is charged with at least one solid catalyst as described above, and a liquid containing an organic sulfur compound to which at least one oxidizing agent is added is continuously passed through to convert the organic sulfur compound into a sulfur oxide. And filling the second stage reactor with at least one adsorbent as described above, and selectively removing sulfur compounds from the liquid after the oxidation reaction coming out of the first stage reactor. Can be.
[0018]
Note that the present invention is not limited to the above-described embodiment, but can adopt various other configurations without departing from the gist of the present invention.
[0019]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but it is needless to say that the present invention is not limited thereto.
[0020]
Example 1 MoO as a catalyst composition 3 Is adjusted to 16% by mass (provided that 8.4 g of the carrier is used) and ammonium molybdate tetrahydrate ((NH 4 ) 6 Mo 7 O 24 ・ 4H 2 O) is placed in a beaker and completely dissolved with 10 ml of pure water to prepare an aqueous solution of ammonium molybdate. A γ-alumina carrier (25-80 mesh) is put therein, and heated in a sand bath while shaking to evaporate water and impregnate with ammonium molybdate. After further drying at 120 ° C. for 2 hours, it was calcined at 450 ° C. for 12 hours and then 16% by mass of γ-alumina molybdate catalyst (MoO 2 3 / Γ-Al 2 O 3 ) 10 g were obtained. This is designated as catalyst A. Next, 0.1 g of Catalyst A was added to a 200 ml eggplant-shaped flask, and 65 ml of hydrogenated gas oil (total sulfur content: 730 ppm) containing 1500 ppm of dibenzothiophene (DBT) was further added. 0.63 g of tert-butyl hydroperoxide was added so that the molar ratio (O / S) of the peroxide to the total sulfur in the gas oil was 9, and the mixture was heated to 120 ° C. using an oil bath and oxidized. The reaction was performed for 2 hours. This was analyzed by a gas chromatograph with a flame photometric detector (FPD) (Shimadzu Corporation: GC-14A-FPD), and the oxidation activity of DBT as shown in Table 1 was obtained.
[0021]
Examples 2 to 4 As in Example 1, ammonium vanadate tetrahydrate (NH 4 VO 3 4% by mass V 2 O 5 / Γ-Al 2 O 3 Catalyst (catalyst B), chromium nitrate (Cr (NO 3 ) 3 ) Using 22% by mass CrO 3 / Γ-Al 2 O 3 (Catalyst C), ammonium tungstate pentahydrate ((NH 4 ) 10 O 41 W 12 ・ 5H 2 O) and 19.3 mass% WO 3 / Γ-Al 2 O 3 (Catalyst D) was prepared respectively. When an oxidation reaction was carried out in the same manner as in Example 1 using each of these catalysts, the oxidation activity of DBT as shown in Table 1 was obtained.
[0022]
Example 5 A γ-alumina support dried at 120 ° C. for 2 hours was calcined at 450 ° C. for 12 hours to obtain a catalyst E. Next, when the same oxidation reaction as in Example 1 was carried out using the catalyst E, the oxidation activity of DBT as shown in Table 1 was obtained.
[0023]
Examples 6 and 7 The same oxidative desulfurization reaction as in Example 1 was performed. However, the molar ratio (O / S) of tert-butyl hydroperoxide to the total sulfur in the gas oil was 4.5 and 1, respectively. The results are shown in Table 1.
[0024]
Comparative Example 1 Pt / Al of Patent Document 1 2 O 3 When an oxidation reaction was carried out in the same manner as in Example 1 using a catalyst and -tert-butyl hypochlorite, the oxidation activity of DBT as shown in Table 1 was obtained.
[0025]
Example 8 Silica-alumina (surface area: 560 m) as an adsorbent 2 / G) 1 g was added to the gas oil that had been subjected to the oxidation reaction in Example 1, and sulfur compounds were removed by adsorption at 70 ° C. for 3 hours and further at 20 ° C. for 3 hours. The sulfur content in the gas oil after the adsorption and desulfurization was analyzed with a fluorescent X-ray analyzer (EDX-800, Shimadzu Corporation). As shown in Table 2, the sulfur content was reduced to a low concentration of 10 ppm or less by the oxidation-adsorption operation as shown in Table 2. Could be reduced.
[0026]
Examples 9 to 15 As a sorbent, molicula sieve 4A, molicula sieve 13X, γ-alumina (surface area: 256 m 2 / G), activated carbon (surface area 800-1000m) 2 / G), silica gel (surface area: 347 m) 2 / G), ZSM-5 zeolite, NaY zeolite (surface area 663 m 2 / G), and the same adsorption experiment as in Example 8 was performed to remove sulfur compounds. The results are shown in Table 2.
[0027]
Comparative Example 2 The same adsorption experiment as in Example 8 was performed to remove sulfur compounds. However, the adsorption reaction was carried out without performing the oxidation reaction of the hydrogenated gas oil (total sulfur content: 730 ppm) containing 1500 ppm of dibenzothiophene (DBT). As shown in Table 2, the desulfurization rate was low only by adsorption without performing the oxidation reaction.
[0028]
Example 16 0.1 g of Catalyst A was added to a 200 ml eggplant-shaped flask, and 100 ml of commercially available kerosene (sulfur concentration: 55 ppm) was further placed in a 100 ml measuring cylinder, and tert-butyl hydroperoxide and a mole of total sulfur in kerosene After adding 0.020 g of tert-butyl hydroperoxide so that the ratio (O / S) became 2, the mixture was heated to 100 ° C. using an oil bath, and the oxidation reaction was performed for 2 hours. Next, silica gel (surface area: 347 m) was used as an adsorbent. 2 / G) In a column packed with 1.2 ml, normal pressure, 25 ° C., WHSV: 4 hr -1 Under the conditions described above, the oxidized kerosene was allowed to flow down to remove sulfur. The sulfur content in the kerosene after the oxidative desulfurization was analyzed by a trace sulfur analyzer (Dia Instruments: TS-100), and the results are shown in Table 3.
[0029]
Examples 17 to 20 The same oxidative desulfurization reaction as in Example 16 was performed. However, FCC equilibrium catalyst, activated alumina, activated carbon (surface area 800-1000 m 2 / G), silica-alumina (surface area: 560 m) 2 / G). The results are shown in Table 3.
[0030]
Example 21 A 500 ml measuring cylinder was charged with 500 ml of commercially available kerosene (sulfur concentration: 55 ppm), and tert-butyl hydroperoxide was added so that the O / S ratio became 10. In the apparatus as shown in FIG. 1, 17.5 ml of the catalyst A was charged into the first-stage reactor, and normal pressure, 80 ° C., WHSV: 30 hr -1 Then, as shown in FIG. 1, 35 ml of silica gel was charged into the second-stage reactor as an adsorbent under normal pressure, room temperature, and WHSV: 4.9 hr. -1 Under the conditions described above, kerosene to which the oxidizing agent was added was passed. At the outlet of the first-stage reactor, the oxidized kerosene was collected, and this was subjected to DBT, 4-methyldibenzothiophene (4MDBT), 4,4 by gas chromatography (Agilent: GC-SCD) equipped with a chemiluminescent sulfur detector. 6-dimethyldibenzothiophene (4,6-DMDBT) and oxidation products of these compounds, dibenzothiophene sulfone (DBTS), 4-methyldibenzothiophene sulfone (4MDBTS), and 4,6-dimethyldibenzothiophene sulfone (4 , 6-DMDBTS) and the total sulfur content in kerosene analyzed with a trace sulfur analyzer (Dia Instruments: TS-100) are shown in Table 4. Further, kerosene after oxidative desulfurization was sampled at the outlet of the second-stage reactor, and the respective sulfur compounds and the total sulfur content in kerosene were measured in the same manner. As shown in Table 4, sulfur compounds in kerosene are almost oxidized to sulfone compounds, which can be almost completely removed by adsorption. On the other hand, very little unoxidized sulfur compound remains after the oxidation reaction even after the adsorption. Further, the sulfur content in kerosene could be reduced to an extremely low concentration of 0.45 ppm by the oxidation-adsorption operation.
[0031]
Example 22 100 ml of commercially available kerosene (sulfur concentration: 55 ppm) was placed in a 100 ml measuring cylinder, and tert-butyl hydroperoxide was added so that the molar ratio (O / S) of total sulfur in the kerosene was 1.5. 0.020 g of -butylhydroperoxide was added. As shown in FIG. 1 filled with 1 g of the catalyst A, this was charged into the first-stage reactor at normal pressure, 110 ° C. and WHSV: 60 hr. -1 And only the oxidation reaction was performed. This was analyzed by gas chromatography with a chemiluminescent sulfur detector (Agilent: GC-SCD), and the oxidation activity of each sulfur compound as shown in Table 5 was obtained.
[0032]
Examples 23 to 27 As in Example 1, ammonium tungstate pentahydrate ((NH 4 ) 10 O 41 W 12 ・ 5H 2 O) and 35 mass% WO 3 / Γ-Al 2 O 3 (Catalyst F), chromium nitrate (Cr (NO 3 ) 3 ) And 11 mass% CrO 3 / Γ-Al 2 O 3 (Catalyst G), ammonium vanadate tetrahydrate (NH 4 VO 3 ) Using 10% by mass V 2 O 5 / Γ-Al 2 O 3 Catalyst (catalyst H), sodium niobate (Na 2 Nb 2 O 5 ) Using 10% by mass Nb 2 O 5 / Γ-Al 2 O 3 (Catalyst I), zirconium chloride (ZrCl 2 ) Using 15% by mass ZrO 2 / Γ-Al 2 O 3 (Catalyst J) was prepared. When an oxidation reaction was carried out in the same manner as in Example 22 using each of these catalysts, the oxidation activity of each sulfur compound as shown in Table 5 was obtained.
[0033]
Examples 28 and 29 A titanium dioxide carrier and a silica carrier were used in place of the γ-alumina carrier, and 16% 3 / TiO 2 (Catalyst K) and 16% by mass MoO 3 / SiO 2 (Catalyst L) was prepared. When the same oxidation reaction as in Example 22 was performed using catalysts K and L, the oxidation activity of each sulfur compound as shown in Table 5 was obtained.
[0034]
Example 30 In the same manner as in Example 1, ammonium molybdate tetrahydrate ((NH 4 ) 6 Mo 7 O 24 ・ 4H 2 O) and nickel nitrate hexahydrate (Ni (NO 3 ) 2 ・ 6H 2 O) and MoO as a catalyst composition. 3 Is 16% by mass and 0.4NiMoO so that the molar ratio of Ni and Mo is 0.4. 3 / Al 2 O 3 (Catalyst M) was prepared. Next, when the same oxidation reaction as in Example 22 was carried out using the catalyst M, the oxidation activity of each sulfur compound as shown in Table 5 was obtained.
[0035]
Examples 31 to 37 3% by mass of MoO as in Example 1 so that the supported amount of molybdenum oxide on the catalyst was 3% by mass to 25% by mass. 3 / Γ-Al 2 O 3 (Catalyst N), 6% by mass MoO 3 / Γ-Al 2 O 3 (Catalyst O), 12% by mass MoO 3 / Γ-Al 2 O 3 (Catalyst P), 14% by mass MoO 3 / Γ-Al 2 O 3 (Catalyst Q), 18% by mass MoO 3 / Γ-Al 2 O 3 (Catalyst R), 20% by mass MoO 3 / Γ-Al 2 O 3 (Catalyst S) and 25% by mass MoO 3 / Γ-Al 2 O 3 (Catalyst T) was prepared. When an oxidation reaction was carried out in the same manner as in Example 22 using each of these catalysts, the oxidation activity of each sulfur compound as shown in Table 5 was obtained.
[0036]
Comparative Example 3 Pt / Al of Patent Document 1 2 O 3 Using a catalyst and -tert-butyl hypochlorite, the same oxidation reaction as in Example 22 was carried out. As a result, the oxidation activity of each sulfur compound as shown in Table 5 was obtained.
[0037]
Examples 38 and 39 The same oxidation reaction as in Example 22 was performed. However, tert-butyl hydroperoxide was added so that the O / S ratio became 1.0, 10 and 20, respectively. The results are shown in Table 6.
[0038]
Examples 40 to 43 The same oxidation reaction as in Example 22 was performed. However, the reaction temperatures were 30 ° C., 70 ° C., 90 ° C. and 120 ° C., respectively. The results are shown in Table 7.
[0039]
Examples 44 to 48 The same oxidation reaction as in Example 22 was performed. However, the WHSV is 6 hours -1 , 20hr -1 , 120hr -1 , 180hr -1 , 300hr -1 I made it. The results are shown in Table 8.
[0040]
Example 49 The same oxidation reaction as in Example 22 was performed. However, instead of tert-butyl hydroperoxide, 0.015 g of hydrogen peroxide was used as the oxidizing agent. The results are shown in Table 9.
[0041]
Example 50 Tert-butyl hydroperoxide was added to commercially available kerosene (sulfur content: 55 ppm) so that the O / S ratio became 2. In the apparatus as shown in FIG. 1, the reaction conditions in the first-stage reactor are as follows. The first-stage reactor is charged with 10.0 ml of the catalyst P (12% Mo), and the pressure is 80.degree. : 67.3 hr -1 Then, as shown in FIG. 1, 40 ml of silica gel was charged into the second-stage reactor as an adsorbent as shown in FIG. 1, and normal pressure, 20 ° C., WHSV: 16.8 hr -1 Under the conditions described above, kerosene to which the oxidizing agent was added was passed. Table 10 shows the average sulfur content of the obtained kerosene after oxidative desulfurization.
[0042]
Example 51 The same oxidative desulfurization of kerosene as in Example 50 was performed. However, the WHSV of the oxidation reaction in the first-stage reactor was 24.8 hr. -1 The WHSV of the adsorption in the second-stage reactor was 7.1 hr. -1 I made it. The results are shown in Table 10.
[0043]
Example 52 The same oxidative desulfurization of kerosene as in Example 50 was performed. However, the WHSV of the oxidation reaction in the first-stage reactor was 22.9 hr. -1 And the WHSV of the adsorption in the second-stage reactor is 1.8 hr. -1 I made it. The results are shown in Table 10.
[0044]
Example 53 The same oxidative desulfurization reaction as in Example 21 was performed using commercially available gasoline (sulfur content: 39.2 ppm). Table 10 shows the average sulfur content of the obtained gasoline after oxidative desulfurization.
[0045]
Example 54 The same oxidative desulfurization reaction as in Example 21 was performed using Middle Eastern straight-run gas oil (having a sulfur content of 38.8 ppm) after the hydrotreating. Table 10 shows the average sulfur content of the obtained gas oil after oxidative desulfurization.
[0046]
Comparative Example 4 -tert-butyl hypochlorite was added to commercially available kerosene (sulfur content: 55 ppm) so that the O / S ratio became 2. In the apparatus as shown in FIG. 1, the Pt / Al of Patent Document 1 is added to the first stage reactor. 2 O 3 10.0 ml of the catalyst was charged, and an oxidative desulfurization reaction was performed under the same reaction conditions as in Example 21. Table 10 shows the average sulfur content of the obtained kerosene after oxidative desulfurization.
[0047]
Comparative Example 5 The same oxidative desulfurization reaction as in Comparative Example 4 was performed using a commercially available gasoline (sulfur content: 39.2 ppm). Table 10 shows the average sulfur content of the obtained gasoline after oxidative desulfurization.
[0048]
Comparative Example 6 The same oxidative desulfurization reaction as in Comparative Example 4 was performed using a Middle Eastern straight-run gas oil (having a sulfur content of 38.8 ppm) after hydrotreating. Table 10 shows the average sulfur content of the obtained gas oil after oxidative desulfurization.
[0049]
Example 55 Tert-butyl hydroperoxide was added to commercially available kerosene (sulfur concentration: 55 ppm) so that the O / S ratio became 1.5. In the apparatus as shown in FIG. 1, the reaction conditions in the first-stage reactor are as follows. The first-stage reactor is charged with 3.0 ml of catalyst A (16% Mo), WHSV: 30 hr -1 Then, as shown in FIG. 1, the second stage reactor was charged with 20 ml of silica gel as an adsorbent at normal pressure, 20 ° C., WHSV: 4.5 hr. -1 Under the conditions described above, kerosene to which the oxidizing agent was added was continued to pass until the adsorption saturation of the adsorbent. The adsorption breakthrough curve showing the adsorption capacity of the adsorbent is shown in FIG. 2, and the obtained adsorption breakthrough point (volume of kerosene that can be processed up to the saturated adsorption of the adsorbent for each volume of the adsorbent) and the obtained kerosene after oxidative desulfurization Are shown in Table 11.
[0050]
Example 56 The adsorbent was regenerated by flowing 30 ml of tetrahydrofuran (THF) at 20 ° C. into the second-stage reactor in the case of adsorption breakthrough in Example 55. Next, the same oxidative desulfurization as in Example 55 was performed. The results are shown in FIG. 2 and Table 11. By regenerating the adsorbent, almost the same oxidative desulfurization results as in Example 55 could be obtained.
[0051]
Example 57 The adsorbent was regenerated by flowing 50 ml of tetrahydrofuran (THF) at 20 ° C. into the second-stage reactor in the case of adsorption breakthrough in Example 56. Next, the same oxidative desulfurization as in Example 55 was performed. The results are shown in FIG. 2 and Table 11. By regenerating the adsorbent, almost the same oxidative desulfurization results as in Example 55 could be obtained.
[0052]
Example 58 At 20 ° C., 100 ml of tetrahydrofuran (THF) was flowed into the second-stage reactor facing adsorption breakthrough in Example 57 to regenerate the adsorbent. Next, the same oxidative desulfurization as in Example 55 was performed. The results are shown in FIG. 2 and Table 11. By regenerating the adsorbent, almost the same oxidative desulfurization as in Example 55 could be performed.
[Table 1]
According to the present invention, a liquid containing an organic sulfur compound to which an oxidizing agent has been added is allowed to react under mild conditions of normal pressure and low temperature in the presence of an oxidation catalyst, so that it can be used as a pre-step of the oxidative desulfurization method. Almost completely oxidize sulfur compounds. Further, as a post-process, a highly selectively oxidized sulfur compound can be removed by using an adsorbent such as silica gel or alumina. Further, a first-stage reactor for charging an oxidation catalyst and converting an organic sulfur compound into a sulfur oxide, and a first-stage reactor for charging an adsorbent and selectively removing the sulfur oxide generated in the first-stage reactor. By continuously passing a liquid containing an organic sulfur compound to which an oxidizing agent has been added through an oxidizing desulfurization apparatus characterized by having a two-stage reactor, the industrial value is extremely large, and the sulfur content can be reduced at a low cost. It can supply petroleum products on the order of 100 ppb.
[Brief description of the drawings]
FIG. 1 is a diagram showing a liquid oxidative desulfurization device containing an organic sulfur compound.
FIG. 2 is a graph comparing the adsorption abilities of kerosene after oxidation of silica gel and silica gel obtained by regenerating silica gel which has been adsorbed and broken through with THF.
Claims (16)
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