JP4242055B2 - Hydrotreating catalyst and hydrocarbon oil hydrotreating method using the same - Google Patents

Description

式中ｎはマトリックス最大含有量成分粒子の個数の測定値であり、ａｉは面内に存在するｉ番目の粒子の面積の測定値である。
【００２７】
Ｐパラメータも同様に、ＥＰＭＡ面分析の結果画像をイメージアナリシスフリーソフトウェアＮＩＨ Imageにより解析し、次式により算出される。
【式２】

式中ｍは面を等面積の区画に分けたときの区画数の測定値であり、ｂｉはｉ番目の区画内の分散粒子の面積の測定値である。
前記式▲１▼または▲２▼を満足するマトリックス成分を含有する触媒は、該成分の濃度分布が均等であり、また、粒子径が均一であり、かつ粒子相互の間隔が均等であることを示したものである。
【００２８】
本発明の水素化処理用触媒は、前記構成から高比表面積を有する点が特徴の一つであり、窒素吸着等温線を求め、ＢＥＴの多分子層吸着理論を用いて算出した比表面積が１００m²/g以上、好ましくは１５０m²/g以上のものである。全細孔容積は０．１ml/g〜２ml/g、好ましくは０．２ml/g〜１．５ml/gであり、側面破壊強度は０．１ kg/mm以上、特に０．２ kg/mm以上であり、また、マトリックス相の最大含有量成分は前記式▲１▼または▲２▼を満足し均質性に優れたものである。
【００２９】
なお、触媒の形状は、円柱状、タブレット状、球状その他断面四ツ葉状等の異形状のいずれでもよく、反応塔内の充填密度を制御できる形状およびサイズを選定すればよい。特に本発明の水素化処理用触媒は多孔性であることから充填密度を大きくするためには触媒成形体のサイズを調整することが好ましい。通常、直径として平均０．５mm〜２０mmのものが充填密度の増加と圧力損失の抑制の観点から好適である。
【００３０】
本発明の水素化処理用触媒は、以上の特性を有することから炭化水素油の水素化処理用触媒として良好な触媒である。特に、難脱硫性硫黄化合物を含む軽油留分の高度水素化脱硫には極めて有用である。
【００３１】
次に、本発明の水素化処理用触媒の好ましい製造方法について説明する。
本発明の水素化処理用触媒は、前記物性が得られるように製造条件を制御すればいずれの方法で製造してもよいが、次の工程（Ｉ）および（II）：
（Ｉ）下記の（ａ）、（ｂ₁ ）、（ｂ₁₁）および（ｂ₂ ）の触媒成分：
（ａ） (i) アルミニウム化合物 および／または
(ii)ケイ素、マグネシウム、カルシウム、ホウ素、ジルコニウム、チタニウム、トリウム、セリウム、ハフニウムおよびリンの化合物からなる群より選択される少なくとも一種の化合物との混合物
（ｂ₁) モリブデン硫化物形成化合物
（ｂ₁₁）モリブデン以外の周期表第６Ａ族元素の化合物からなる群より選択される少なくとも一種の化合物
（ｂ₂) 周期表第８族元素の化合物からなる群より選択される少なくとも一種の化合物
を有機溶媒の存在下において沈殿剤溶液と接触させることによりゲルスラリーを調製し、得られたゲルスラリーを熟成後乾燥し触媒前駆体を調製する工程 および
（II）前記工程（Ｉ）にて得られた触媒前駆体に炭化水素溶媒および水を添加し熱分解する工程
により製造することができる。
【００３２】
工程（Ｉ）の具体的な実施の形態としては、例えば次の工程（Ｉａ）〜（Ｉｄ）を経由することが好ましい。
工程（Ｉａ）：Ｍｏ硫化物形成化合物の溶液を含有する沈殿剤水溶液を調製する工程
工程（Ｉｂ）：耐火性無機酸化物マトリックス成分の出発原料としての含酸素有機金属化合物およびプロモータ成分の化合物を有機溶媒に添加して均一溶液を調製する工程
工程（Ｉｃ）：工程（Ｉｂ）にて得られた均一溶液に工程（Ｉａ）にて得られた沈殿剤水溶液を添加しゲルスラリーを調製する工程
工程（Ｉｄ）：工程（Ｉｃ）にて得られたゲルスラリーを熟成した後乾燥する工程
【００３３】
前記工程（Ｉ）の触媒前駆体の調製工程においてＭｏ硫化物形成化合物は、ポーラスなＭｏＳ₂ を生成するものであれば限定されるものではないが、モリブデン酸アンモニウム塩等の無機金属塩のほか酢酸塩、シュウ酸塩等の有機金属塩を挙げることができる。具体的には７−モリブデン酸アンモニウム、テトラチオモリブデン酸アンモニウム、ポリチオモリブデン酸アンモニウム、１２−モリブド１−リン酸、ヘテロポリオキソモリブデン酸等を用いることができる。特に好ましいＭｏ硫化物形成化合物はテトラチオモリブデン酸アンモニウムおよびポリチオモリブデン酸アンモニウムであるが、例えば、７−モリブデン酸アンモニウムに硫化水素または硫化アンモニウムを添加してテトラチオモリブデン酸アンモニウムを調製してもよい。
【００３４】
プロモータ成分の出発原料としては、タングステン、クロム、鉄、コバルト、ニッケル、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金、銅、亜鉛、マンガン、レニウム等の硝酸塩、硫酸塩、塩化物、オキシ塩化物、硫化物またはこれらの金属の酸のアンモニウム塩等を挙げることができる。また、これらの無機塩のほかに酢酸塩、シュウ酸塩およびアルコキシド等の有機塩を用いることもできる。具体的には、リンタグステン酸、テトラチオタングステン酸アンモニウム、硝酸コバルト、硫酸コバルト、塩化コバルト、硝酸ニッケル、硫酸ニッケル、塩化ニッケル等を例示することができる。
【００３５】
前記耐火性無機酸化物マトリックス成分の出発原料としてアルミニウム、ケイ素、マグネシウム、カルシウム、ホウ素、ジルコニウム、チタン、トリウム、セリウム、ハフニウム、ガリウム等のアルコキシド、アセチルアセトネート、カルボキシレート等を挙げることができるが、操作上の容易さからアルコキシル基の炭素数が１〜５のアルコキシドが好ましい。例えばアルミニウムメトキシド、アルミニウムエトキシド、アルミニウムイソプロポキシド、アルミニウムブトキシド、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、テトラｔ−ブトキシシラン、マグネシウムメトキシド、マグネシウムエトキシド、マグネシウムイソプロポキシド、カルシウムメトキシド、ホウ素メトキシド、ホウ素エトキシド、ジルコニウムエトキシド、ジルコニウムプロポキシド、ジルコニウムｓｅｃ−ブトキシド、チタンエトキシド、チタンイソプロポキシド、ハフニウムエトキシド等を使用することができる。
また、出発原料としてはアルコキシド等の有機化合物のほか、有機溶媒に可溶で均一溶液を調製することができるものであれば無機化合物も用いることができる。例えば、硝酸塩、硫酸塩、塩化物、オキシ塩化物等の無機塩を使用することができる。
【００３６】
有機溶媒としては、前記触媒成分（ａ）、（ｂ₁)、（ｂ₁₁）および（ｂ₂)の均一溶液が得られるように溶解させるものであれば特に限定されるものではないが、１価アルコール、２価アルコール、ケトアルコール、アミノアルコール、カルボン酸等を用いることができる。特に、２価アルコールが好ましい。２価アルコールとしては、例えば、ヘキシレングリコール、３−メチル−１，３−ブタンジオール、２，５−ジメル−２，５−ヘキサンジオール、２，３−ブタンジオール、２，４−ペンタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、２，５−ヘキサンジオール、１，２−シクロヘキサンジオール、１，３−シクロヘキサンジオール等を用いることができる。
【００３７】
前記有機溶媒は、前記触媒成分（ａ）の金属化合物に対し、モル比で０．１〜５０、好ましくは１〜２０の割合で用いることができる。有機溶媒が５０モルを超えると溶媒が過剰となり次工程で均一なゲルスラリーを生成させることが困難となる。一方、０．１モルに達しないと流動的なゲルが得られず、均質性の高い触媒を製造することができないという問題が生じる。
【００３８】
本発明の工程（Ｉ）においては、触媒成分（ａ）の前記含酸素有機金属化合物および触媒成分（ｂ₁)、（ｂ₁₁）および（ｂ₂)の無機金属化合物に前記非水溶媒を添加し任意の手段で攪拌して均一溶液を調製する。均一溶液の調製の温度は限定されるものではなく、溶媒等の種類により任意に選択すればよいが反応試剤の変質を抑制し、かつ調製時間の短縮を図るには１０℃〜１００℃の範囲が好ましい。
触媒成分の同時沈殿およびそれに伴う共沈を行なわせる際に使用される沈殿剤溶液としては、水、アンモニア水溶液、アミン水溶液、硫化水素水溶液、硫化アンモニウム水溶液、チオシアン酸アンモニウム水溶液、シュウ酸水溶液、リン酸水溶液、尿素水溶液、チオ尿素水溶液を挙げることができる。また、沈殿剤溶液は、単独で、または互いに混合して使用することができる。使用に際しては触媒成分の種類および添加方式により適宜選択すればよい。特に、アンモニア水溶液、硫化水素水溶液、硫化アンモニウム水溶液またはチオ尿素水溶液およびそれらの混合物を用いることにより高脱硫活性触媒を提供することができる。
【００３９】
工程（II）の熱分解工程においては、前記工程（Ｉ）にて得られた触媒前駆体に有機溶媒および水を添加し、得られる混合物を水素ガスの存在下において加圧下にて熱分解に供する。
熱分解工程における有機溶媒としては液状炭化水素、硫化炭素等を挙げることができるが、液状炭化水素が好ましく、特に炭素数８〜１５の脂肪族炭化水素が好適である。有機溶媒および水の添加量は、触媒前駆体中のＭｏ含有量に対して重量比でそれぞれ２０〜４００および０〜６０を用いることができ、特に水の添加量は０〜２０の範囲が好ましい。また、水素ガス量は限定されるものでないが、例えば、有機溶媒１ｍｏｌに対して、０．０５ｍｏｌ〜１０ｍｏｌを使用することができる。
熱分解条件としては、温度２５０℃〜５００℃、好ましくは３００℃〜４５０℃、圧力０．１ＭＰａ〜１００ＭＰａ、好ましくは０．１ＭＰａ〜３０ＭＰａを採用することができ、Ｍｏ成分がポーラスなＭｏＳ₂ 結晶に転化するまで同条件下に維持すればよい。また、反応形式としては、流通式またはバッチ式のいずれをも採用することができる。
工程（II）で得られた触媒前駆体は、次の工程（III)に供し、その含水溶媒量を濾過、沈降分離、遠心分離またはエバポレーションにより調整した後、工程（IV）にて、風乾、熱風乾燥、加熱乾燥、凍結乾燥等の方法で乾燥する。乾燥は還元、不活性、硫化雰囲気下等で行われる。
【００４０】
以上の如くして本発明の水素化処理用触媒を製造することができる。また、触媒成形体は、前記いずれかの工程、例えば工程（II）の前での成形処理により調製することができる。成形方法としては、打状成形、押出成形、転動造粒等の方法を採用してもよい。
【００４１】
次に、本発明の炭化水素油の水素化処理方法について説明する。
本発明の水素化処理方法は、炭化水素油と水素との接触によるあらゆる反応を包含するものであり、水素化精製、水素化脱硫、水素化脱窒素、水素化脱芳香族、水添異性化、水素化分解、水素化脱蝋および水素化脱金属等の反応を挙げることができ、所望の目的により適宜反応条件を選定することにより実施することができる。本発明の水素化処理用触媒は、特に炭化水素油の水素化脱硫方法において好適である。
【００４２】
炭化水素油としては、特に限定されるものではなく、例えば石油原油の常圧蒸留留出油、常圧蒸留残渣油、減圧蒸留留出油、減圧蒸留残渣油、分解軽油、ラフィネート、水素化精製油、脱アスファルト油、スラックワックス、フィッシャートロプシュワックスまたはこれらの混合物等のほか、タールサンド油、シェールオイル、石炭液化油等を挙げることができる。特に難脱硫硫黄化合物および窒素化合物の除去の必要な減圧軽油、分解軽油および直留軽油等を用いることができる。
【００４３】
減圧軽油は、常圧蒸留残渣油をさらに減圧蒸留して得られ、約３７０℃〜約６１０℃の範囲の沸点を有する留出油であり、硫黄分、窒素分および金属分を相当量（例えば、硫黄分２．０重量％、窒素分８００重量ppm ）含有するものもある。硫黄分としては、例えば、４−メチルジベンゾチオフェン、４，６−ジメチルジベンゾチオフェンなどの硫黄化合物が含有され、窒素分としてはピリジン類、アミン類、アミド類などの塩基性窒素化合物や、ピロール類などの弱塩基性窒素化合物が含有され、金属分としてはニッケル、バナジウム、鉄などが含有される。本発明の水素化処理用触媒を用いることにより、このような減圧軽油の脱硫および脱窒素を最も効率よく行うことができる。
分解軽油としては、残渣油をコーカーおよびビスブレーカーなどで熱分解して得られる約２００℃以上の沸点を有する軽油留分、接触分解装置から得られるライトサイクルガスオイル（ＬＣＧＯ）およびヘビーサイクルガスオイル（ＨＣＧＯ）などを挙げることができる。
【００４４】
また、前記の常圧蒸留留出油として直留ライトナフサ、直留ヘビーナフサ、灯油留分等も処理することができ、さらに本発明の水素化処理方法において処理可能な原料油として接触分解ナフサ、熱分解ナフサ、水蒸気分解ナフサ等の各種分解装置から得られるガソリン成分その他燃料油成分として用いられる約２５０℃以下の沸点を有する軽質留分等を挙げることができる。
【００４５】
水素化処理方法の反応条件は、特に限定されるものではなく、例えば炭化水素油の種類、目的反応の種類、目標とする脱硫率および脱窒素率などにより適宜選択することができる。すなわち、水素化脱硫においては反応温度；１５０℃〜５００℃、好ましくは２００℃〜４５０℃、反応圧力；０．１ＭＰａ〜３５ＭＰａ（１kg/cm²〜３５０kg/cm²）、好ましくは０．５ＭＰａ〜３０ＭＰａ（５kg/cm²〜３００kg/cm²）、水素含有ガスレイト；３０リットル/リットル 〜２０００リットル/リットル 、好ましくは３５リットル/リットル 〜１８００リットル/リットル および液空間速度；０．０１V/H/V 〜２０．０V/H/V 、好ましくは０．０５V/H/V 〜１０．０V/H/V を採用することができる。さらに反応温度２５０℃〜４００℃、反応圧力４ＭＰａ〜１０ＭＰａ（４０kg/cm²〜１００kg/cm²）、水素含有ガスレイト１８０リットル/リットル 〜２３０リットル/リットル および液空間速度０．８V/H/V 〜１．５V/H/V の条件を包含するものが好ましい。水素含有ガスとしては、水素濃度が６０％〜１００％の範囲のものを用いることができる。
【００４６】
本発明の水素化処理用触媒は、脱硫活性、脱窒素活性、脱芳香族活性等およびそれらの活性維持能が高いために、通常では活性劣化が比較的早く過酷度の高い反応条件下、特に低反応圧においても、長期にわたり高い脱硫率等を達成することができる。
また、炭化水素油の水素化処理を行うにあたり、触媒は、固定床、流動床、沸騰床または移動床のいずれの形式でも使用することができるが、装置面または操作上から、通常、固定床を採用することが好ましい。また、二基以上の複数基の反応塔を結合して水素化処理を行なうことにより、高度の脱硫率等を達成することができる。このような観点から、特に炭化水素油が重質油である場合には、多段反応塔を使用することが好ましい。さらには、反応方式として、高度反応率を達成するために水素含有ガスと原料油が反応器内で同一方向に流れるコカレント方式、水素含有ガスと原料油が対向流で流れるカウンターカレント方式等のいずれの方式をも採用することができる。
【００４７】
【実施例】
次に、本発明について実施例および比較例により具体的に説明する。もっとも本発明は、実施例等により何ら限定されるものではない。
なお、実施例等において触媒原材料として次の如き反応試剤を使用し、各触媒の物性（多孔性、強度、表面積等）および触媒活性等の特性は後記の方法で評価した。
反応試剤
７−モリブデン酸アンモニウム (NH₄)₆MoO₇O₂₄・4H₂O
１２−モリブド１−リン酸 H₃(PMo₁₂O₄₀)・6H₂O
テトラチオタングステン酸アンモニウム (NH₄)₂WS₄
硝酸コバルト Co(NO₃)₂・6H₂O
硝酸ニッケル Ni(NO₃)₂・6H₂O
アルミニウムイソプロポキシド Al(i-OC₃H₇)₃
テトラエトキシシラン Si(OC₂H₅)₄
【００４８】
実施例１（ＳＮＣＭＳＡＭ１５）
７−モリブデン酸アンモニウム１６．５ｇを純水３６３．３ｇに溶解させ、さらに溶液にｐＨ＝９．７になるようにアンモニア水を加えた。そして、この溶液に、５％H₂S/H₂ガスを５００ml/minの割合で８．５時間攪拌しながら流通させ、さらにＮ₂ ガスを２００ml/minの割合で１２時間攪拌しながら流通させ、加水分解水溶液とした。この時溶液ｐＨ＝９．２であった。
次に、アルミニウムイソプロポキシド１４．０ｇ、硝酸コバルト２０．８ｇおよびヘキシレングリコール２５４．２ｇを混合し、８０℃で４．５時間攪拌し均一溶液とした。
その後、前記方法で調製した加水分解水溶液を１０ml/minの速度で、前記均一溶液に滴下し加水分解させ沈殿物を含有するスラリーを調製した。スラリーを９０℃で１０時間保持し熟成させた後、ロータリーエバポレータにより乾燥し、触媒前駆体を得た。触媒前駆体中の触媒成分は４４．５ wt.％であった。
【００４９】
触媒前駆体２．０ｇをｎ−トリデカン２４．０ｇおよび純水５．５ｇと共にバッチ式反応器に充填し、さらに水素ガスを導入し、反応器内圧力を１．０ＭＰａとした。この反応器を３７５℃に保持したサンドバスに投入、急速に昇温し、振盪させながら同温で３０分間保持した。反応器を室温まで冷却後、濾過し、ＭｏＳ−ＳＭＵＳ触媒ＳＮＣＭＳＡＭ１５を得た。ＳＮＣＭＳＡＭ１５は物性評価の結果、ポーラスＭｏＳ₂ 結晶（直径２０Å以上の細孔を有する。）が存在し、このＭｏＳ₂ 結晶とプロモータ成分が複合化していることが確認され、Al成分の均質性も優れたものであった。活性評価では難脱硫性硫黄化合物（ＤＢＴ、４，６ＤＭＤＢＴ）の脱硫に対して高活性を示し、かつ高活性維持能を有することが判明した。触媒の化学組成、触媒物性および活性評価結果を表４に示す。
【００５０】
実施例２（ＳＮＣＭＳＡＭ０８）
７−モリブデン酸アンモニウム１６．５ｇを純水３６３．３ｇに溶解させ、さらに溶液にｐＨ＝９．７になるようにアンモニア水を加えた。そして、この溶液に、５％H₂S/H₂ガスを５００ml/minの割合で１１時間攪拌しながら流通させ、さらにＮ₂ ガスを２００ml/minの割合で１２時間攪拌しながら流通させ、加水分解水溶液とした。この時溶液ｐＨ＝９．１であった。
次に、アルミニウムイソプロポキシド１４．０ｇ、硝酸コバルト２０．８ｇおよびヘキシレングリコール２５４．２ｇを混合し、８０℃で４．５時間攪拌し均一溶液とした。
その後、前記方法で調製した加水分解水溶液を１０ml/minの速度で、前記均一溶液に滴下し加水分解させ沈殿物を含有するスラリーを調製した。スラリーを９０℃で１０時間保持し熟成させた後、ロータリーエバポレータにより乾燥し、触媒前駆体を得た。触媒前駆体中の触媒成分は４８．０ wt.％であった。
【００５１】
触媒前駆体１．９ｇをｎ−トリデカン２４．０ｇおよび純水５．５ｇと共にバッチ式反応器に充填し、さらに水素ガスを導入し、反応器内圧力を７．０ＭＰａとした。この反応器を３７５℃に保持したサンドバスに投入、急速に昇温し、振盪させながら同温で３０分間保持した。
次いで、反応器を室温まで冷却し、冷却後、濾過し、ＭｏＳ−ＳＭＵＳ触媒ＳＮＣＭＳＡＭ０８を得た。ポーラスＭｏＳ₂ 結晶とプロモータ成分の複合化が確認された。触媒活性評価においては難脱硫性硫黄化合物の脱硫に対し、高活性を示し、かつ、活性維持能にも優れたものであった。また、ＬＧＯ−Ｄを原料油とし表１の反応条件下において行なった水素化脱硫についても高活性を示し、高脱硫率を得た。触媒の化学組成、触媒物性および活性評価結果を表４に示す。
【００５２】
実施例３（ＳＮＣＭＳＡＭ１１）
７−モリブデン酸アンモニウム１６．５ｇを純水３６３．３ｇに溶解させ、さらに溶液にｐＨ＝９．７になるようにアンモニア水を加えた。そして、この溶液に、５％H₂S/H₂ガスを５００ml/minの割合で９時間攪拌しながら流通させ、さらにＮ₂ ガスを２００ml/minの割合で１２時間攪拌しながら流通させ、加水分解水溶液とした。この時溶液ｐＨ＝９．３であった。
次に、アルミニウムイソプロポキシド３０．１ｇ、硝酸コバルト８．０ｇおよびヘキシレングリコール２９１．７ｇを混合し、８０℃で４．５時間攪拌し均一溶液とした。
その後、前記方法で調製した加水分解水溶液を１０ｍｌ／ｍｉｎの速度で、前記均一溶液に滴下し加水分解させ沈殿物を含有するスラリーを調製した。スラリーを９０℃で１０時間保持し熟成させた後、ロータリーエバポレータにより乾燥し、触媒前駆体を得た。触媒前駆体中の触媒成分は４６．２ wt.％であった。
【００５３】
触媒前駆体１．９ｇをｎ−トリデカン２４．０ｇおよび純水５．５ｇと共にバッチ式反応器に充填し、さらに水素ガスを導入し、反応器内圧力を１．０ＭＰａとした。この反応器を３７５℃に保持したサンドバスに投入、急速に昇温し、振盪させながら同温で３０分間保持した。
次いで、反応器を室温まで冷却し、冷却後、濾過し、ＭｏＳ−ＳＭＵＳ触媒ＳＮＣＭＳＡＭ１１を得た。ポーラスＭｏＳ₂ 結晶（直径２０Å以上の細孔を有する。）が存在し、該結晶とプロモータ成分が複合化していることが確認された。また、Al成分の均質性にも優れ、脱硫活性（ＤＢＴ活性、４，６ＤＭＤＢＴ活性）および活性維持能に優れたものであることが判明した。触媒の化学組成、触媒物性および活性評価結果を表４に示す。
【００５４】
実施例４（ＳＮＣＭＳＡＭ０９）
７−モリブデン酸アンモニウム１４．１ｇを純水３０８．８ｇに溶解させ、さらに溶液にｐＨ＝９．７になるようにアンモニア水を加えた。そして、この溶液に、５％H₂S/H₂ガスを４００ml/minの割合で１２時間攪拌しながら流通させ、さらにＮ₂ ガスを２００ml/minの割合で１２時間攪拌しながら流通させ、加水分解水溶液とした。この時溶液ｐＨ＝９．１であった。
次に、アルミニウムイソプロポキシド２４．５ｇ、テトラエトキシシラン２．６ｇ、硝酸コバルト１７．２ｇおよびヘキシレングリコール２９５．０ｇを混合し、８０℃で４．５時間攪拌し均一溶液とした。
その後、前記方法で調製した加水分解水溶液を１０ml/minの速度で、前記均一溶液に滴下し加水分解させ沈殿物を含有するスラリーを調製した。スラリーを９０℃で１０時間保持し熟成させた後、ロータリーエバポレータにより乾燥し、触媒前駆体を得た。触媒前駆体中の触媒成分は５１．３ wt.％であった。
【００５５】
触媒前駆体２．１ｇをｎ−トリデカン２４．０ｇおよび純水５．５ｇと共にバッチ式反応器に充填し、さらに水素ガスを導入し、反応器内圧力を１．０ＭＰａとした。この反応器を３７５℃に保持したサンドバスに投入、急速に昇温し、振盪させながら同温で３０分間保持した。
次いで、反応器を室温まで冷却し、冷却後、濾過し、ＭｏＳ−ＳＭＵＳ触媒ＳＮＣＭＳＡＭ０９を得た。ポーラスＭｏＳ₂ 結晶（直径２０Å以上の細孔を有する。）が存在し、該結晶とプロモータ成分が複合化していることが確認された。また、Al成分の均質性にも優れ、脱硫活性（ＤＢＴ活性、４，６ＤＭＤＢＴ活性）および活性維持能に優れたものであることが判明した。触媒の化学組成、触媒物性および活性評価結果を表４に示す。
【００５６】
実施例５（ＳＮＣＭＳＡＭ２１）
７−モリブデン酸アンモニウム９．４ｇを純水２０５．９ｇに溶解させ、さらに溶液にｐＨ＝９．７になるようにアンモニア水を加えた。そして、この溶液に、５％H₂S/H₂ガスを５００ml/minの割合で５時間攪拌しながら流通させ、さらにＮ₂ ガスを２００ml/minの割合で１２時間攪拌しながら流通させた。この時溶液はｐＨ＝９．３であった。
次に、テトラチオタングステン酸アンモニウム（Aldrich Chem.Co.製、No.33673-4）２．８ｇを純水７１．０ｇに溶解させ、さらにその溶液にｐＨ＝９．３となるようにアンモニア水を加えた。この溶液を前記の溶液に加え加水分解水溶液とした。
また、アルミニウムイソプロポキシド４１．１ｇ、硝酸コバルト１３．６ｇおよびヘキシレングリコール３３５．９ｇを混合し、８０℃で４．５時間攪拌し均一溶液を調製した。
その後、前記方法で調製した加水分解水溶液を１０ml/minの速度で、前記均一溶液に滴下し加水分解させ沈殿物を含有するスラリーを調製した。スラリーを９０℃で１０時間保持し熟成させた後、ロータリーエバポレータにより乾燥し、触媒前駆体を得た。触媒前駆体中の触媒成分は４５．５ wt.％であった。
【００５７】
触媒前駆体３．５ｇをｎ−トリデカン２４．０ｇおよび純水５．５ｇと共にバッチ式反応器に充填し、さらに水素ガスを導入し、反応器内圧力を１．０ＭＰａとした。この反応器を３７５℃に保持したサンドバスに投入、急速に昇温し、振盪させながら同温で３０分間保持した。
次いで、反応器を室温まで冷却し、冷却後、濾過し、ＭｏＳ−ＳＭＵＳ触媒ＳＮＣＭＳＡＭ２１を得た。ポーラスＭｏＳ₂ 結晶（直径２０Å以上の細孔を有する。）が存在し、該結晶とプロモータ成分が複合化していることが確認された。また、Al成分の均質性にも優れ、脱硫活性（ＤＢＴ活性、４，６ＤＭＤＢＴ活性）および活性維持能に優れたものであることが判明した。触媒の化学組成、触媒物性および活性評価結果を表５に示す。
【００５８】
実施例６（ＳＮＣＭＳＡＭ１２）
７−モリブデン酸アンモニウム６．０ｇを純水１３０．８ｇに溶解させ、さらに溶液にｐＨ＝９．７になるようにアンモニア水を加えた。そして、この溶液に、５％H₂S/H₂ガスを５００ml/minの割合で３時間攪拌しながら流通させ、さらにＮ₂ ガスを２００ml/minの割合で１２時間攪拌しながら流通させ、加水分解水溶液とした。この時溶液ｐＨ＝９．１であった。
次に、アルミニウムイソプロポキシド６７．９ｇ、テトラエトキシシラン４．１ｇ、硝酸コバルト４．７ｇおよびヘキシレングリコール４３７．０ｇを混合し、８０℃で４．５時間攪拌し均一溶液とした。
その後、前記方法で調製した加水分解水溶液を１０ml/minの速度で、前記均一溶液に滴下し加水分解させ沈殿物を含有するスラリーを調製した。スラリーを９０℃で１０時間保持し熟成させた後、ロータリーエバポレータにより乾燥し、触媒前駆体を得た。触媒前駆体中の触媒成分は４８．７ wt.％であった。
【００５９】
触媒前駆体５．１ｇをｎ−トリデカン２４．０ｇおよび純水５．５ｇと共にバッチ式反応器に充填し、さらに水素ガスを導入し、反応器内圧力を１．０ＭＰａとした。この反応器を３７５℃に保持したサンドバスに投入、急速に昇温し、振盪させながら同温で３０分間保持した。
次いで、反応器を室温まで冷却し、冷却後、濾過し、ＭｏＳ−ＳＭＵＳ触媒ＳＮＣＭＳＡＭ１２を得た。触媒の化学組成、触媒物性および活性評価結果を表５に示す。
【００６０】
実施例７（ＮＣＭＳＡＭ１３）
７−モリブデン酸アンモニウム１６．５ｇを純水３６３．３ｇに溶解させ、さらに溶液にｐＨ＝９．８になるようにアンモニア水を加えた。そして、この溶液に、５％H₂S/H₂ガスを５００ml/minの割合で８．５時間攪拌しながら流通させ、さらにＮ₂ ガスを２００ml/minの割合で１２時間攪拌しながら流通させ、加水分解水溶液とした。この時溶液ｐＨ＝９．３であった。
次に、アルミニウムイソプロポキシド１１．２ｇ、テトラエトキシシラン２．４ｇ、硝酸コバルト２０．８ｇおよびヘキシレングリコール２５１．９ｇを混合し、８０℃で４．５時間攪拌し均一溶液とした。
その後、前記方法で調製した加水分解水溶液を１０ml/minの速度で、前記均一溶液に滴下し加水分解させ沈殿物を含有するスラリーを調製した。スラリーを９０℃で１０時間保持し熟成させた後、ロータリーエバポレータにより乾燥し、触媒前駆体を得た。触媒前駆体中の触媒成分は４５．３ wt.％であった。
【００６１】
触媒前駆体２．０ｇをｎ−トリデカン２４．０ｇおよび純水５．５ｇと共にバッチ式反応器に充填し、さらに水素ガスを導入し、反応器内圧力を１．０ＭＰａとした。この反応器を３７５℃に保持したサンドバスに投入、急速に昇温し、振盪させながら同温で３０分間保持した。反応器を室温まで冷却後、濾過し、ＭｏＳ−ＳＭＵＳ触媒ＳＮＣＭＳＡＭ１３を得た。物性評価の結果、ポーラスＭｏＳ₂ 結晶（直径２０Å以上の細孔を有する。）が存在し、該結晶とプロモータ成分が複合化していることが確認された。また、Al成分の均質性にも優れ、脱硫活性（ＤＢＴ活性、４，６ＤＭＤＢＴ活性）および活性維持能に優れたものであることが判明した。触媒の化学組成、触媒物性、均質性、比表面積の測定結果および活性評価結果を表５に示す。
【００６２】
実施例８（ＮＣＭＳＡＭ２０）
７−モリブデン酸アンモニウム１１．０ｇを純水２４２．２ｇに溶解させ、さらに溶液にｐＨ＝９．９になるようにアンモニア水を加えた。そして、この溶液に、５％H₂S/H₂ガスを５００ml/minの割合で６時間攪拌しながら流通させ、さらにＮ₂ ガスを２００ml/minの割合で１２時間攪拌しながら流通させ、加水分解水溶液とした。この時溶液ｐＨ＝９．５であった。
次に、アルミニウムイソプロポキシド４３．１ｇ、硝酸コバルト１３．６ｇおよびヘキシレングリコール３４８．０ｇを混合し、８０℃で４．５時間攪拌し均一溶液とした。
その後、前記方法で調製した加水分解水溶液を１０ml/minの速度で、前記均一溶液に滴下し加水分解させ沈殿物を含有するスラリーを調製した。スラリーを９０℃で１０時間保持し熟成させた後、ロータリーエバポレータにより乾燥し、触媒前駆体を得た。触媒前駆体中の触媒成分は４４．８ wt.％であった。
【００６３】
触媒前駆体３．０ｇをｎ−トリデカン２４．０ｇおよび純水５．５ｇと共にバッチ式反応器に充填し、さらに水素ガスを導入し、反応器内圧力を１．０ＭＰａとした。この反応器を３７５℃に保持したサンドバスに投入、急速に昇温し、振盪させながら同温で３０分間保持した。反応器を室温まで冷却後、濾過し、ＭｏＳ−ＳＭＵＳ触媒ＳＮＣＭＳＡＭ２０を得た。ポーラスＭｏＳ₂ 結晶（直径２０Å以上の細孔を有する。）が存在し、該結晶とプロモータ成分が複合化していることが確認された。また、Al成分の均質性にも優れ、脱硫活性（ＤＢＴ活性、４，６ＤＭＤＢＴ活性）および活性維持能に優れたものであることが判明した。触媒の化学組成、触媒物性および活性評価結果を表５に示す。
【００６４】
実施例９（ＳＮＣＭＳＡＭ２２）
アルミニウムイソプロポキシド１４．０ｇ、硝酸コバルト２０．８ｇおよびヘキシレングリコール２５４．２ｇを混合し、８０℃で４．５時間攪拌し、均一溶液とした。
その後、この均一溶液にポリモリブデン酸アンモニウム((NH₄)₂Mo₃S₁₃)２３．２ｇを添加し、さらに、純水３６３．３ｇに溶液ｐＨ＝９．１になるようにアンモニア水を加えた加水分解水溶液を１０ml/minの速度で、滴下、加水分解し、沈殿物を含有するスラリーを調製した。スラリーを９０℃で１０時間保持し熟成させた後、ロータリーエバポレータにより乾燥し、触媒前駆体を得た。このとき、触媒前駆体は触媒成分を４８．３ wt.％含有していた。
１．８５ｇの触媒前駆体をｎ−トリデカン２４．０ｇ、純水５．５ｇと共にバッチ式反応器に充填し、さらに水素ガスを導入し、反応器内圧力を１．０ＭＰａとする。この反応器を、３７５℃に保持したサンドバスに投入し急速昇温し、振とうさせながら３０分間保持した。
反応器を室温まで冷却後、濾過し、ＭｏＳ−ＳＭＵＳ触媒（ＳＮＣＭＳＡＭ２２）を得た。触媒組成、触媒物性および活性評価結果を表５に示す。
【００６５】
比較例１（比較触媒ａ）
アルミニウムイソプロポキシド１３０．１ｇとヘキシレングリコール８２０．７ｇを混合し、完全に溶解するまで８０℃で４時間攪拌した後、テトラエトキシシラン１３．９ｇを添加し、さらに８０℃で３時間攪拌した。
その後、１２−モリブド１−リン酸１１．２ｇ、硝酸コバルト9．７ｇおよび硝酸ニッケル２．３ｇを添加し、さらに８０℃で１７時間攪拌し均一溶液を調製した。
得られた均一溶液に、８０℃で純水９８mlを１ml／分の速度で滴下し、加水分解により生成した沈澱物を含有するスラリーを調製した。
攪拌終了後、スラリーを９０℃に加熱保持しながら８８時間静置し熟成した。熟成終了後、スラリーをロータリーエバポレータで蒸発乾固し、さらに６５０℃、空気気流中で焼成し、表６に示す化学組成の比較触媒ａを得た。
比較触媒ａの物性評価の結果、活性成分は酸化物であり、硫化後もポーラスＭｏＳ₂ 結晶の存在は認められなかった。なお、Al成分については均質性を有するものであった。また、表６に示すように脱硫活性および活性維持能は低いものであった。
【００６６】
比較例２（比較触媒ｂ）
純水２．０リットルを約７０℃に加熱し、これに水酸化ナトリウム水溶液を添加し、ｐＨ約１２のアルカリ水を調製した。次にこのアルカリ水に硫酸アルミニウム水溶液（硫酸アルミニウム５１８．０ｇ、純水７１０．０ｇ）を加えた後、水酸化ナトリウムまたは硝酸溶液でｐＨを８．４〜８．８に調整し、約７０℃で約０．５時間熟成した。これによりアルミナ水和物の沈澱（ゲル）を含む水溶液が得られた。この水溶液にケイ酸ナトリウム水溶液（３号水ガラス、純水２１０ｇ）を加え、硝酸溶液により、ｐＨを８．８〜９．２に調整し、約７０℃で０．５時間熟成した。これによりアルミナ水和物の表面にシリカ水和物が沈着した沈澱粒子を含むスラリー液が得られた。このスラリー液を濾過し、濾別したケーキは濾過した後の濾液のナトリウム濃度が５ppm 以下になるまで炭酸アンモニウム水溶液で洗浄した。このケーキを８０℃の混練機中で成型可能な水分量になるまで乾燥しながら混練し、押出成形機により１．５mmφの円柱状ペレットに成形した。成形されたペレットは１２０℃で１６時間乾燥し、さらに７００℃で３時間焼成して担体とした。
次いでこの担体に７−モリブデン酸アンモニウムの水溶液を含浸させ、１２０℃で乾燥し４５０℃で焼成した。次に硝酸コバルトと硝酸ニッケルを含有する水溶液を含浸させ、１２０℃乾燥し、５００℃で焼成し、表６に示す比較触媒ｂとした。
比較触媒ｂの物性評価の結果、活性成分は酸化物であり、硫化後もポーラスＭｏＳ₂ 結晶の存在は認められなかった。なお、Al成分については均質性を有するものであった。表６に示すように脱硫活性および活性維持能ともに低いものであった。
【００６７】
比較例３（比較触媒ｃ）
アルミニウムイソプロポキシド１３０．１ｇとヘキシレングリコール８２０．７ｇを混合し、完全に溶解するまで８０℃で４時間攪拌した後、テトラエトキシシラン１３．９ｇを添加し、さらに８０℃で３時間攪拌した。
その後、１２−モリブド１−リン酸１１．２ｇ、硝酸コバルト9．７ｇおよび硝酸ニッケル２．３ｇを添加し、さらに８０℃で１７時間攪拌し均一溶液を調製した。
得られた均一溶液に、８０℃で純水９８ｍｌを１ｍｌ／分の速度で滴下し、加水分解により生成した沈澱物を含有するスラリーを調製した。
攪拌終了後、スラリーを９０℃に加熱保持しながら８８時間静置し熟成した。熟成終了後、スラリーをロータリーエバポレータで蒸発乾固し、さらに６５０℃、空気気流中で焼成し、表６に示す化学組成の比較触媒ｃを得た。
比較触媒ｃの物性評価の結果、活性成分は酸化物であり、硫化後もポーラスＭｏＳ₂ 結晶の存在は認められなかった。なお、Al成分については均質性を有することが認められた。表６に示すように脱硫活性および活性維持能はともに低いものであった。
【００６８】
［１］触媒物性評価
多孔性
透過型電子顕微鏡（ＴＥＭ）観察像の画像解析により評価した。
(i) ＴＥＭ観察方法
▲１▼試料準備
試料をノルマルヘキサン中に入れ、混合して懸濁させた後、液中浮遊粒子をスポイトで吸い取り、試料グリッドに滴下した。これらの作業は、窒素雰囲気中で実施した。
▲２▼ＴＥＭ観察条件
加速電圧：３００ｋＶ
観察視野：明視野
観察倍率：１００万倍
写真倍率：１８０万倍
使用装置：ＪＥＭ−３０１０（日本電子（株）製）
【００６９】
(ii)画像解析方法
ＴＥＭ像をイメージスキャナーでコンピュータに取り込み、デジタル化する。そのデジタル画像を二値化処理した後、フリーソフトウエアのNIH- image にて、ＭｏＳ₂ 層状結晶部分の２次元高速フーリエ変換（ＦＦＴ）を行なうことにより、細孔構造を示すパワースペクトル像を求めた。
次に、このパワースペクトル像をその中心について動径方向に積分して、横軸に細孔径（中心からの距離の逆数）、縦軸にスペクトル強度を取ることにより、ＭｏＳ₂ 結晶相自体の持つ細孔分布を求めた。
【００７０】
破壊強度
触媒前駆体をφ２０mm錠剤成型器を用いて２ton/cm² で圧粉成型した後に、アルミナ乳鉢で粉砕し、３５０μｍ〜５００μm の粒子を分級し、それをバッチ式反応器で熱処理した後に、木屋式側面破壊強度測定器により触媒側面破壊強度を測定した。
【００７１】
比表面積
定容量法Ｎ₂ ガス吸着方式によりＢＥＴ比表面積を求めた。
測定装置として、ＢＥＬＳＯＲＰ２８ＳＡ（日本ベル株式会社製）を用いた。測定試料をサンプル管に導入し、２×１０^-1Torr以下まで脱気した後、２００℃で１．５時間真空中で前処理を行なった後、窒素の吸着等温線を測定した。そして、その吸着側の吸着等温線からＢＥＴの多分子層吸着理論を用いて試料の表面積を求めた。
【００７２】
均質性
ＥＰＭＡ（電子線プローブマイクロアナライザー(Electron Probe Microa nalyzer)（島津製作所製ＥＰＭ−８１０Ｑ））を用い、次の要領で測定した。
・試料作製
触媒試料をポリエステル樹脂に包埋し、切削法により平滑な触媒断面を得た後、表面にカーボンコーティングを施した。
・測定条件
加速電圧：１５ＫＶ
試料電流：０．０５μＡ
ビームサイズ：１μｍφ
測定線：Ａｌ−Ｋα
・ＥＰＭＡ線分析：１μｍステップで触媒直径方向について分析。
【００７３】
［２］触媒活性評価
固定床流通式反応評価装置による脱硫（ＨＤＳ）活性評価および流通式オートクレーブ反応評価装置による脱硫（ＨＤＳ）活性評価を行なった。反応条件および操作の詳細は次の通り。
１）固定床流通式反応評価装置による脱硫（ＨＤＳ）活性評価
試験油（ＬＧＯ−Ｄ）の性状、反応評価装置および反応条件は表１に示す。
操作は次の手順で行なった。
４．６ｇの触媒を反応器のなかに充填した後、硫化溶液（ヘキサデカンにジメチルダイサルファイドを加え、硫黄含有量を４ wt.％Ｓにしたもの）を１．５cc/min、Ｈ₂ ガスを６０cc/minの流量で反応器に流し、以下のプログラムで硫化した。
室温から４０分かけて３１０℃まで昇温し、同温度で５時間保持した。その後、ＬＧＯ−Ｄを導入した。導入完了後反応圧力に昇圧し、その後３０分かけて３２０℃まで昇温し、ＨＤＳ反応を行なった。試験油を導入して所定時間、反応を継続した後にプロダクト中の硫黄濃度を測定し、ＨＤＳ活性を求めた。
ＨＤＳ活性は、以下の式により算出した。
（ＨＤＳ活性）＝（触媒重量当たりの液空間速度）×［1/S^0.5−1/S₀ ^0.5 ］
式中のＳはプロダクト中の硫黄濃度、Ｓ₀ はフィード中の硫黄濃度を示す。
【００７４】
２）流通式オートクレーブ反応評価装置による脱硫（ＨＤＳ）活性評価
評価試験条件を表２に示す。
０．３ｇの触媒を反応器に充填した後、硫化溶液（ヘキサデカンにジメチルダイサルファイドを加え、硫黄含有量を４ wt.％Ｓにしたもの）を０．１５cc/min、Ｈ₂ ガスを６０cc/minの流量で反応器に流し、以下のプログラムで硫化した。室温から４０分かけて３１０℃まで昇温し、同温度で１．５時間保持した。その後、各評価条件に合わせた試験油を導入した。導入完了後９kg/cm²-Gに昇圧し、その後３０分かけて各評価条件の温度まで昇温し、ＨＤＳ反応を行なった。試験油を導入して所定時間、反応を継続した後、試験条件１の場合には、プロダクト中のＤＢＴおよび４，６ＤＭＤＢＴの濃度を、試験条件２および３の場合にはプロダクト中の硫黄濃度を測定し、それぞれＨＤＳ活性を求めた。
【００７５】
ＨＤＳ活性は、以下の式により算出した。
・試験条件１の場合
ＨＤＳ活性(DBT)=（触媒重量当たりの液空間速度）×(N_DBT,O-N_DBT)/(N_DBT)
式中のＮ_DBT,0 はフィード中のＤＢＴ濃度、Ｎ_DBT はプロダクト中のＤＢＴ濃度であり、ＤＢＴはジベンゾチオフェンを示す。
【００７６】
ＨＤＳ活性(4,6DMDBT)
＝( 触媒重量当たりの液空間速度) ×(N_4,6DMDBT,0-N_4,6DMDBT)/(N_4,6DMDBT)
式中のＮ_4,6DMDBT,0はフィード中の４，６ＤＭＤＢＴ濃度、Ｎ_4,6DMDBTはプロダクト中の４，６ＤＭＤＢＴ濃度であり、４，６ＤＭＤＢＴは、４，６−ジメチルジベンゾチオフェンを示す。
【００７７】
・試験条件２および３の場合
（ＨＤＳ活性）＝（触媒重量当たりの液空間速度）×［1/S^0.5−1/S₀ ^0.5 ］
式中のＳはプロダクト中の硫黄濃度、Ｓ₀ はフィード中の硫黄濃度を示す。
【００７８】
【表１】

【００７９】
【表２】

【００８０】
【表３】

【００８１】
【表４】

【００８２】
【表５】

【００８３】
【表６】

【００８４】
【発明の効果】
ポーラスな層状ＭｏＳ₂ 結晶中にプロモータ成分を複合化した活性相と無機酸化物マトリックス相とからなる水素化処理用触媒を実現したことからＭｏ硫化物の含有量を増加させ高活性化を図ることができ、難脱硫硫黄化合物を含有する炭化水素供給原料の脱硫・脱窒素反応において高度の反応活性および活性維持能を達成することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydrotreating catalyst, a process for producing the same, and a hydrotreating process for hydrocarbon oil using the same, and more particularly, an active component phase containing porous molybdenum sulfide and a refractory inorganic oxidation. A catalyst for hydroprocessing formed by compounding a product matrix phase (hereinafter referred to as “MoS-SMU catalyst” as necessary in the description of the present invention), and a sulfur-containing / nitrogen-containing hydrocarbon oil using the catalyst, in particular, The present invention relates to a method for hydrotreating a light oil fraction.
According to the present invention, hydrocarbon oil hydrorefining, hydrodesulfurization, hydrodenitrogenation, hydrodearomatization, hydroisomerization, hydrocracking, hydrodewaxing, hydrodemetallation, etc. It is possible to provide a hydrotreating catalyst useful for all reactions by contact between hydrogen oil and hydrogen, and a hydrotreating method using the hydrotreating catalyst.
[0002]
[Prior art]
Catalysts for hydrotreating hydrocarbon oils include refractory inorganic oxides such as alumina, silica, magnesia, zirconia, titania, etc., Group 6A elements molybdenum, tungsten, chromium, etc. and Group 8 elements of the same table Various compounds obtained by supporting a hydrogenation active component selected from the group consisting of cobalt, nickel and the like have been developed.
Such a hydrotreating catalyst generally impregnates a refractory inorganic oxide carrier with a solution of a compound such as molybdenum, tungsten, chromium, cobalt, or nickel, which is a hydrogenation active component, and then undergoes drying and calcination steps. Has been prepared by a manufacturing method.
[0003]
On the other hand, in recent years, a high degree of desulfurization / denitrogenation of gas oil fractions has been required from the viewpoint of environmental conservation measures, and therefore, realizing a highly active catalyst has become an inevitable problem for the catalyst development field. In order to obtain a highly active catalyst, it is necessary to increase the active site of the catalyst. Therefore, various methods for supporting a large amount of active components have been studied.
However, in the conventional hydrorefining catalyst, if the Mo content is increased in order to increase the active sites, if the Mo content exceeds a certain amount, for example, 20% by weight or more, the MoS in the calcination step and the sulfurization step of the catalyst production process₂ There is a problem that the particles are aggregated, and the active point is decreased and the activity is decreased.
[0004]
For example, the hydrorefining catalyst disclosed in JP-A-61-157350 has a Mo of MoS.₂ MoS containing 20% or more₂ And a cocatalyst component are combined, but the specific surface area is still extremely small, the number of active sites is small, and there are still points to be improved in order to obtain high activity.
[0005]
As a coal liquefaction catalyst, porous MoS₂ Crystal-only bulk catalysts have been proposed (American Chemical Society (Fuel Chemistry) (J. Amer, Chem. Soc., Div. Fuel Chem.42, (3), 550 (1997). )), There is no disclosure about the point of use as a hydrotreating catalyst for hydrocarbon oils, and it is necessary to solve the following problems (1) and (2) in order to be usable as a hydrotreating catalyst. It was.
[0006]
That is, the bulk catalyst is
(1) It lacks the activity required as a catalyst for hydroprocessing hydrocarbon oils.
(2) The lack of strength required as a hydrotreating catalyst
It had the problem of.
In view of the above-described conventional technical development situation, development of a highly active hydrotreating catalyst containing a large amount of Mo sulfide and having a porous active phase has been desired.
[0007]
[Problems to be solved by the invention]
Therefore, in view of the above development situation, the first object of the present invention is to provide a hydrotreating catalyst containing a porous Mo sulfide and a promoter component and having sufficient strength, high reaction activity and activity maintenance ability. The second object is to provide a method for advanced hydrotreating of a sulfur-containing / nitrogen-containing hydrocarbon oil using the hydrotreating catalyst.
[0008]
[Means for Solving the Problems]
Accordingly, the present inventors have made extensive studies in order to solve the above-mentioned problems of the present invention. As a result, the present invention goes through a conventional sulfidation process comprising firing the Mo component supported on the support and bringing it into contact with the sulfur compound. Without porous Mo sulfide, in particular porous MoS₂ As a result, it was conceived that a highly active catalyst having an increased active site can be realized by increasing the Mo content, and the present invention has been completed based on these findings.
[0009]
Therefore, the first of the present invention is
A hydrotreating catalyst comprising a composite of an active phase composed of a hydrogenation active component and a refractory inorganic oxide matrix phase, wherein the active phase is porous layered MoS₂ A catalyst for hydroprocessing having a high specific surface area, characterized in that the following promoter component is compounded in the crystal:
Promoter component: Compound of at least one element selected from the group consisting of Group 6A elements and Group 8 elements of the Periodic Table excluding molybdenum
It is about.
[0010]
The second of the present invention is
Hydrocarbon oil hydrotreating method comprising contacting hydrocarbon oil with hydrotreating catalyst of the first invention under hydrotreating conditions in the presence of hydrogen
It is about.
[0011]
The present invention relates to the hydrotreating catalyst and the hydrotreating method of hydrocarbon oil using the catalyst, and more preferred embodiments are as follows.
(1) The porous layered MoS₂ A catalyst for hydroprocessing, wherein the crystal is an active component having pores having a pore diameter of 20 mm or more.
(2) The promoter component in the active phase is the layered MoS₂ A catalyst for hydrotreatment which is a metal component which is not so large as to be confirmed by TEM observation in the crystal and whose presence can be confirmed by EDS observation.
[0012]
(3) The component of the refractory inorganic oxide matrix phase is alumina, silica, magnesia, calcium oxide, boria, zirconia, titania, tria, ceria, hafnia, phosphorus oxide, alumina-silica, alumina-magnesia, alumina-oxidation Calcium, alumina-boria, alumina-titania, alumina-phosphorus oxide, alumina-zirconia, alumina-tria, alumina-titania-zirconia, silica-magnesia, silica-zirconia, silica-boria, silica-tria, silica-titania, alumina At least one selected from the group consisting of silica-zirconia, alumina-silica-boria, alumina-silica-magnesia, alumina-silica-hafnia, alumina-silica-phosphorus oxide and alumina-silica-boria-phosphorus oxide Hydrotreating catalyst is an inorganic oxide.
(4) The component of the refractory inorganic oxide matrix phase is alumina, silica, magnesia, alumina-silica, alumina-magnesia, alumina-boria, alumina-titania, alumina-phosphorus oxide, alumina-silica-boria, alumina- A hydrotreating catalyst which is at least one oxide selected from the group consisting of silica-magnesia, alumina-silica-phosphorus oxide, and alumina-silica-boria-phosphorus oxide.
[0013]
(5) The specific surface area is 100 m.²/ g or more hydrotreating catalyst.
(6) The maximum content component in the refractory inorganic oxide matrix phase is the following formula (1) by EPMA line analysis:
N_max -N_min ≦ 2 × [3 × (N₀)^0.5 + 0.2 × N₀ ] ………… ▲ 1 ▼
(However, in formula (1), N_max , N_min And N_o Are respectively the maximum value, the minimum value, and the average value of the concentration measurement values of the matrix maximum content component by EPMA line analysis. )
Or the following formula (2) by EPMA surface analysis
0.8 ≦ S parameter <1 and 0.8 ≦ P parameter <1 ………… (2)
(However, in the formula (2), the S parameter and the P parameter are indices indicating the uniformity of the particle and the distribution of the particles of the maximum matrix content component by EPMA surface analysis, respectively.)
A catalyst for hydroprocessing, which is an inorganic oxide component that satisfies the requirements.
[0014]
(7) Carbonization wherein the hydrocarbon oil is at least one selected from the group consisting of straight-run naphtha, catalytic cracking naphtha, steam cracking naphtha, pyrolysis naphtha, light gas oil, vacuum gas oil, catalytic cracking gas oil and pyrolysis gas oil. A method for hydrotreating hydrogen oil.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The hydrotreating catalyst of the present invention comprises the following active phase of component (a) and matrix phase of component (b);
(A) Porous layered MoS₂ Active phase composed of hydrogenation active component obtained by complexing crystal and promoter component
(B) Refractory inorganic oxide matrix phase
Is a composite.
[0016]
The active phase composed of the hydrogenation active component of the component (a) is a porous layered MoS.₂ Promoter component is compounded in the crystal, porous layered MoS₂ Crystal is layered MoS₂ It is composed of crystals and pores surrounded by the crystals. MoS₂ The pores of the crystals have a pore distribution ranging from 6.2 to 300 mm in diameter, and the presence of pores having a diameter of 20 mm or more is highly active for the hydroprocessing catalyst of the present invention. From the viewpoint of pursuing.
[0017]
Such layered MoS₂ The presence of crystals can be identified by image analysis of a transmission electron microscope (Transmission Electron Microscopy (hereinafter abbreviated as “TEM” where necessary)) observation image.
The method for image analysis of the TEM image is not particularly limited, but is preferably performed by the following method.
That is, a TEM image is captured by a computer with an image scanner to create a digital image. After the digital image is binarized, frequency analysis is performed by performing two-dimensional Fourier transform (FFT) to create a power spectrum image indicating the pore structure.
Next, the power spectrum image is integrated in the radial direction about the center, the distance (reciprocal of pore diameter) is taken on the horizontal axis, the spectral intensity is taken on the vertical axis, and the intensity distribution is obtained to obtain the frequency component (pore diameter). Component) and the corresponding spectral intensity height can be quantitatively analyzed.
Thus, from observation of a TEM image, porous layered MoS₂ The presence of crystals can be identified.
[0018]
The active phase is a porous layered MoS₂ The crystal and the promoter component are combined, but the combination of the promoter component particles is layered MoS.₂ Dispersed in the crystal and the presence of the component is not so large as to be confirmed by TEM observation, and is measured by an energy dispersive X-ray spectroscope (hereinafter referred to as “EDS” if necessary). Then, it is shown in a state where its existence can be confirmed. TEM observation and EDS observation are based on the following measurement conditions. That is, using a measurement apparatus: JEM-3010 (manufactured by JEOL Ltd.), TEM observation was performed under the conditions of acceleration voltage: 300 kV, observation field: bright field, observation magnification: 1,000,000 times, photo magnification: 1.8 million times. To do. Observed layered MoS₂ The inside of the crystal is measured by EDS to confirm the presence of the promoter component.
[0019]
The promoter component is a compound of Group 6A elements and Group 8 elements of the periodic table excluding molybdenum, and is a compound of at least one element selected from the group consisting of these elements and a third promoter component. Compounds can be used. Specific examples include tungsten and chromium of Group 6A elements of the periodic table, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum and the like of Group 8 elements of the same table. Further, as the third promoter component, the Group 1B element copper, the Group 2B element zinc, the Group 4 element manganese, the Group 7 element rhenium, etc. are also included in the Group 6A element and / or the Group 8 element. It can be used in combination with elements or independently.
[0020]
These promoter components use nitrates, sulfates, chlorides, oxychlorides, sulfides, ammonium salts of these metal acids, and organic salts such as acetates, oxalates, and alkoxides. be able to. Particularly preferred are nitrates, alkoxides and the like.
[0021]
Next, the component (b) of the hydrotreating catalyst of the present invention will be described.
The component (b) contains a refractory inorganic oxide that constitutes the hydrotreating catalyst. The refractory inorganic oxide matrix includes alumina, silica, magnesia, calcium oxide, boria, zirconia, titania, tria, ceria, hafnia, phosphorus oxide, etc., but other various metal oxides are also used. be able to. Particularly composed of two or more component oxides, such as alumina-silica, alumina-magnesia, alumina-calcium oxide, alumina-boria, alumina-titania, alumina-phosphorus oxide, alumina-zirconia, alumina-tria, alumina- Titania-zirconia, silica-magnesia, silica-zirconia, silica-boria, silica-tria, silica-titania and the like can be selected.
[0022]
A preferred refractory inorganic oxide matrix is composed of alumina, or alumina and silica, and preferably contains 2 to 40% by weight, particularly 5 to 25% by weight of silica, depending on the desired reaction. Further, magnesia, boria, titania, zirconia, ceria, hafnia, tria, phosphorus oxide and the like are combined as a third component with alumina and silica. Specifically, alumina-silica-boria, alumina-silica-titania, alumina-silica-zirconia, alumina-silica-ceria, alumina-silica-magnesia, alumina-silica-hafnia, alumina-silica-phosphorus oxide, alumina- Examples thereof include silica-boria-phosphorus oxide and the like.
Also, zeolites and clay minerals such as montmorillonite, kaolinite, halloysite, bentonite, attapulgite and the like can be used as a refractory inorganic oxide matrix component in combination with alumina, silica or alumina-silica.
[0023]
According to the present invention, a particularly preferred hydrotreating catalyst is one in which the active phase and the matrix phase are complexed and the matrix components are uniformly dispersed in the catalyst. Specifically, the homogeneity is such that the component having the highest content among the matrix components is an electron probe probe analyzer (hereinafter referred to as “EPMA” in this specification)) line analysis or surface analysis. Thus, the following expression (1) or (2) is satisfied.
[0024]
An EPMA analyzer is a device that performs composition analysis of a spot region irradiated with an electron beam by measuring characteristic X-rays obtained by irradiating a substance with an accelerated electron beam. The catalyst particle cross section is scanned with an electron beam to perform line analysis, and the concentration analysis of a specific element in the particle cross section in the depth direction can be performed. The present inventors measured the concentration distribution of the highest content component of the matrix in the cross section of the catalyst molded body such as catalyst particles by EPMA line analysis, and obtained EPMA line analysis measurement data obtained by quantifying the fluctuation range, As a result of accumulation and analysis from repeated experiments, it has been found that a catalyst satisfying the relationship of the formula (1) contributes to a high degree of homogeneity and a reaction activity such as a desulfurization activity.
Formula (1) is expressed as follows.
N_max -N_min ≦ 2 × [3 × (N_o)^0.5 + 0.2 × N_o ] ………… ▲ 1 ▼
However, in formula (1), N_max , N_min And N_o Are respectively the maximum value, the minimum value, and the average value of the concentration measurement values of the matrix maximum content component by EPMA line analysis.
[0025]
On the other hand, the EPMA surface analysis measures the particle size and distribution form of the matrix maximum content component, and quantifies the uniformity of particle size and the uniformity of particle distribution by image analysis.
From the EPMA surface analysis, it was found that a catalyst satisfying the following formula (2) has a high degree of homogeneity and has a remarkable effect in desulfurization activity and the like.
Equation (2) is expressed as follows.
0.8 ≦ S parameter <1 and 0.8 ≦ P parameter <1 ………… (2)
However, in the formula (2), the S parameter and the P parameter are indices indicating the uniformity of the particle size and the uniformity of the particle distribution of the matrix maximum content component by EPMA surface analysis, respectively.
[0026]
The S parameter is calculated using the following equation after analyzing the image of the EPMA surface analysis by the image analysis free software NIH Image.
[Formula 1]

In the formula, n is a measured value of the number of matrix maximum content component particles, and ai is a measured value of the area of the i-th particle existing in the plane.
[0027]
Similarly, the P parameter is obtained by analyzing an image obtained as a result of the EPMA surface analysis using the image analysis free software NIH Image, and is calculated by the following equation.
[Formula 2]

In the formula, m is a measured value of the number of sections when the surface is divided into equal-area sections, and bi is a measured value of the area of dispersed particles in the i-th section.
A catalyst containing a matrix component satisfying the above formula (1) or (2) has a uniform concentration distribution of the component, a uniform particle diameter, and a uniform spacing between particles. It is shown.
[0028]
The hydrotreating catalyst of the present invention is characterized in that it has a high specific surface area from the above-mentioned configuration. A nitrogen adsorption isotherm was obtained and the specific surface area calculated using the BET multi-layer adsorption theory was 100 m.²/ g or more, preferably 150 m²More than / g. The total pore volume is 0.1 ml / g to 2 ml / g, preferably 0.2 ml / g to 1.5 ml / g, and the lateral fracture strength is 0.1 kg / mm or more, especially 0.2 kg / mm. In addition, the maximum content component of the matrix phase satisfies the above formula (1) or (2) and is excellent in homogeneity.
[0029]
The shape of the catalyst may be any of an irregular shape such as a columnar shape, a tablet shape, a spherical shape, or a four-leaf cross section, and a shape and size that can control the packing density in the reaction tower may be selected. In particular, since the hydrotreating catalyst of the present invention is porous, it is preferable to adjust the size of the catalyst molded body in order to increase the packing density. Usually, a diameter of 0.5 mm to 20 mm on average is suitable from the viewpoint of increasing the packing density and suppressing pressure loss.
[0030]
The hydrotreating catalyst of the present invention is a good catalyst as a hydrotreating catalyst for hydrocarbon oils because of the above characteristics. In particular, it is extremely useful for the advanced hydrodesulfurization of light oil fractions containing hardly desulfurizable sulfur compounds.
[0031]
Next, a preferred method for producing the hydrotreating catalyst of the present invention will be described.
The hydrotreating catalyst of the present invention may be produced by any method as long as the production conditions are controlled so that the above physical properties can be obtained, but the following steps (I) and (II):
(I) The following (a), (b₁ ), (B₁₁) And (b₂ ) Catalyst component:
(A) (i) an aluminum compound and / or
(ii) a mixture with at least one compound selected from the group consisting of compounds of silicon, magnesium, calcium, boron, zirconium, titanium, thorium, cerium, hafnium and phosphorus
(B₁) Molybdenum sulfide forming compound
(B₁₁) At least one compound selected from the group consisting of compounds of Group 6A elements of the periodic table other than molybdenum
(B₂) At least one compound selected from the group consisting of compounds of Group 8 elements of the periodic table
Preparing a catalyst slurry by bringing the gel slurry into contact with a precipitant solution in the presence of an organic solvent, aging the resulting gel slurry and drying the catalyst slurry; and
(II) A step of adding a hydrocarbon solvent and water to the catalyst precursor obtained in the step (I) and thermally decomposing it.
Can be manufactured.
[0032]
As a specific embodiment of the step (I), it is preferable to go through the following steps (Ia) to (Id), for example.
Step (Ia): Step of preparing an aqueous precipitant solution containing a solution of Mo sulfide-forming compound
Step (Ib): A step of preparing a homogeneous solution by adding an oxygen-containing organometallic compound as a starting material of a refractory inorganic oxide matrix component and a promoter component compound to an organic solvent.
Step (Ic): A step of preparing a gel slurry by adding the precipitant aqueous solution obtained in Step (Ia) to the uniform solution obtained in Step (Ib).
Step (Id): Step of aging the gel slurry obtained in Step (Ic) and then drying it
[0033]
In the step of preparing the catalyst precursor in the step (I), the Mo sulfide-forming compound is a porous MoS.₂ Although it will not be limited if it produces | generates, Organic metal salts, such as acetate and an oxalate other than inorganic metal salts, such as ammonium molybdate, can be mentioned. Specifically, ammonium 7-molybdate, ammonium tetrathiomolybdate, ammonium polythiomolybdate, 12-molybdo 1-phosphate, heteropolyoxomolybdic acid, or the like can be used. Particularly preferred Mo sulfide-forming compounds are ammonium tetrathiomolybdate and ammonium polythiomolybdate. For example, ammonium tetrathiomolybdate can be prepared by adding hydrogen sulfide or ammonium sulfide to ammonium 7-molybdate. Good.
[0034]
Starting materials for promoter components include tungsten, chromium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, zinc, manganese, rhenium, nitrates, sulfates, chlorides, oxychlorides , Sulfides or ammonium salts of these metal acids. In addition to these inorganic salts, organic salts such as acetates, oxalates and alkoxides can also be used. Specific examples include phosphorus tagsteinic acid, ammonium tetrathiotungstate, cobalt nitrate, cobalt sulfate, cobalt chloride, nickel nitrate, nickel sulfate, nickel chloride and the like.
[0035]
Examples of the starting material for the refractory inorganic oxide matrix component include aluminum, silicon, magnesium, calcium, boron, zirconium, titanium, thorium, cerium, hafnium, gallium and other alkoxides, acetylacetonate, and carboxylate. From the viewpoint of ease of operation, an alkoxide having 1 to 5 carbon atoms in the alkoxyl group is preferable. For example, aluminum methoxide, aluminum ethoxide, aluminum isopropoxide, aluminum butoxide, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrat-butoxysilane, magnesium methoxide, magnesium ethoxide, magnesium isopropoxide, calcium Methoxide, boron methoxide, boron ethoxide, zirconium ethoxide, zirconium propoxide, zirconium sec-butoxide, titanium ethoxide, titanium isopropoxide, hafnium ethoxide and the like can be used.
In addition to organic compounds such as alkoxides, inorganic compounds can be used as starting materials as long as they are soluble in an organic solvent and can prepare a uniform solution. For example, inorganic salts such as nitrates, sulfates, chlorides and oxychlorides can be used.
[0036]
Examples of the organic solvent include the catalyst components (a) and (b₁), (B₁₁) And (b₂Although it will not specifically limit if it is made to melt | dissolve so that the uniform solution of) may be obtained, Monohydric alcohol, dihydric alcohol, keto alcohol, amino alcohol, carboxylic acid, etc. can be used. In particular, dihydric alcohols are preferred. Examples of the dihydric alcohol include hexylene glycol, 3-methyl-1,3-butanediol, 2,5-dimer-2,5-hexanediol, 2,3-butanediol, 2,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol and the like can be used.
[0037]
The organic solvent can be used in a molar ratio of 0.1 to 50, preferably 1 to 20 with respect to the metal compound of the catalyst component (a). If the organic solvent exceeds 50 moles, the solvent becomes excessive and it becomes difficult to produce a uniform gel slurry in the next step. On the other hand, if it does not reach 0.1 mol, a fluid gel cannot be obtained, and there is a problem that a highly homogeneous catalyst cannot be produced.
[0038]
In step (I) of the present invention, the oxygen-containing organometallic compound and the catalyst component (b) of the catalyst component (a)₁), (B₁₁) And (b₂The non-aqueous solvent is added to the inorganic metal compound and the mixture is stirred by any means to prepare a uniform solution. The temperature for preparing the homogeneous solution is not limited, and may be arbitrarily selected depending on the type of solvent and the like. However, in order to suppress alteration of the reaction reagent and to shorten the preparation time, the temperature range is from 10 ° C to 100 ° C. Is preferred.
Examples of the precipitant solution used for simultaneous precipitation of catalyst components and accompanying coprecipitation include water, aqueous ammonia, aqueous amine, aqueous hydrogen sulfide, aqueous ammonium sulfide, aqueous ammonium thiocyanate, aqueous oxalic acid, phosphorous Examples thereof include an aqueous acid solution, an aqueous urea solution, and an aqueous thiourea solution. In addition, the precipitant solutions can be used alone or mixed with each other. In use, it may be appropriately selected depending on the type of catalyst component and the method of addition. In particular, a highly desulfurization active catalyst can be provided by using an aqueous ammonia solution, an aqueous hydrogen sulfide solution, an aqueous ammonium sulfide solution, an aqueous thiourea solution, or a mixture thereof.
[0039]
In the thermal decomposition step of step (II), an organic solvent and water are added to the catalyst precursor obtained in the step (I), and the resulting mixture is subjected to thermal decomposition under pressure in the presence of hydrogen gas. Provide.
Examples of the organic solvent in the thermal decomposition step include liquid hydrocarbons and carbon sulfide, but liquid hydrocarbons are preferable, and aliphatic hydrocarbons having 8 to 15 carbon atoms are particularly preferable. The addition amount of the organic solvent and water can be 20 to 400 and 0 to 60, respectively, in weight ratio with respect to the Mo content in the catalyst precursor, and the addition amount of water is particularly preferably in the range of 0 to 20. . Moreover, although the amount of hydrogen gas is not limited, 0.05 mol-10 mol can be used with respect to 1 mol of organic solvents, for example.
As thermal decomposition conditions, a temperature of 250 ° C. to 500 ° C., preferably 300 ° C. to 450 ° C., a pressure of 0.1 MPa to 100 MPa, preferably 0.1 MPa to 30 MPa can be adopted, and MoS is a porous MoS.₂ What is necessary is just to maintain the same conditions until it converts into a crystal | crystallization. Moreover, as a reaction format, either a flow type or a batch type can be adopted.
The catalyst precursor obtained in step (II) is subjected to the next step (III), and its water content is adjusted by filtration, sedimentation separation, centrifugation or evaporation, and then air-dried in step (IV). , Drying by hot air drying, heat drying, freeze drying and the like. Drying is performed in a reducing, inert, sulfurized atmosphere or the like.
[0040]
As described above, the hydrotreating catalyst of the present invention can be produced. Moreover, a catalyst molded object can be prepared by the shaping | molding process before one of the said processes, for example, process (II). As the molding method, methods such as punching molding, extrusion molding, rolling granulation and the like may be employed.
[0041]
Next, the hydrotreating method for hydrocarbon oil of the present invention will be described.
The hydrotreating method of the present invention includes all reactions by contacting hydrocarbon oil with hydrogen, and includes hydrorefining, hydrodesulfurization, hydrodenitrogenation, hydrodearomatic, hydroisomerization. , Hydrocracking, hydrodewaxing, hydrodemetallation, and the like, and can be carried out by appropriately selecting reaction conditions according to the desired purpose. The hydrotreating catalyst of the present invention is particularly suitable for a hydrodesulfurization method for hydrocarbon oil.
[0042]
The hydrocarbon oil is not particularly limited. For example, atmospheric crude oil distillation distillation oil, atmospheric distillation residue oil, vacuum distillation oil residue, vacuum distillation residue oil, cracked gas oil, raffinate, hydrorefining In addition to oil, deasphalted oil, slack wax, Fischer-Tropsch wax, or a mixture thereof, tar sand oil, shale oil, coal liquefied oil, and the like can be given. In particular, a vacuum gas oil, a cracked gas oil, a straight-run gas oil, etc. that require removal of the hard desulfurized sulfur compound and nitrogen compound can be used.
[0043]
Vacuum gas oil is obtained by further distilling atmospheric distillation residue oil under reduced pressure, and is a distillate having a boiling point in the range of about 370 ° C. to about 610 ° C., and contains a considerable amount of sulfur, nitrogen and metal (for example, And 2.0% by weight of sulfur and 800% by weight of nitrogen). Examples of the sulfur content include sulfur compounds such as 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene. Examples of the nitrogen content include basic nitrogen compounds such as pyridines, amines and amides, and pyrroles. A weak basic nitrogen compound such as nickel, vanadium, iron, etc. is contained as a metal component. By using the hydrotreating catalyst of the present invention, such desulfurization and denitrogenation of vacuum gas oil can be most efficiently performed.
As the cracked light oil, a light oil fraction having a boiling point of about 200 ° C. or higher obtained by pyrolyzing the residual oil with a coker, a bisbreaker or the like, a light cycle gas oil (LCGO) and a heavy cycle gas oil obtained from a catalytic cracker (HCGO).
[0044]
Further, straight-run light naphtha, straight-run heavy naphtha, kerosene fraction and the like can be treated as the above atmospheric distillation distillate, and catalytic cracking naphtha as a feedstock that can be treated in the hydrotreating method of the present invention, Examples thereof include a light fraction having a boiling point of about 250 ° C. or less, which is used as a gasoline component and other fuel oil components obtained from various cracking apparatuses such as pyrolysis naphtha and steam cracking naphtha.
[0045]
The reaction conditions of the hydrotreating method are not particularly limited, and can be appropriately selected depending on, for example, the type of hydrocarbon oil, the type of target reaction, the target desulfurization rate and denitrogenation rate. That is, in hydrodesulfurization, reaction temperature: 150 ° C. to 500 ° C., preferably 200 ° C. to 450 ° C., reaction pressure; 0.1 MPa to 35 MPa (1 kg / cm²~ 350kg / cm²), Preferably 0.5 MPa to 30 MPa (5 kg / cm²~ 300kg / cm²), Hydrogen-containing gas rate; 30 liter / liter to 2000 liter / liter, preferably 35 liter / liter to 1800 liter / liter and liquid space velocity; 0.01 V / H / V to 20.0 V / H / V, preferably 0.05V / H / V to 10.0V / H / V can be employed. Furthermore, the reaction temperature is 250 ° C. to 400 ° C., the reaction pressure is 4 MPa to 10 MPa (40 kg / cm²~ 100kg / cm²), A hydrogen-containing gas rate of 180 liters / liter to 230 liters / liter and a liquid space velocity of 0.8 V / H / V to 1.5 V / H / V are preferable. As the hydrogen-containing gas, one having a hydrogen concentration in the range of 60% to 100% can be used.
[0046]
The hydrotreating catalyst of the present invention has high desulfurization activity, denitrogenation activity, dearomatic activity, etc. and their ability to maintain their activity, and therefore the reaction deterioration is usually relatively fast and severe under severe reaction conditions. Even at a low reaction pressure, a high desulfurization rate or the like can be achieved over a long period of time.
In the hydrotreating of hydrocarbon oil, the catalyst can be used in any form of a fixed bed, a fluidized bed, a boiling bed or a moving bed. Is preferably adopted. Moreover, a high degree of desulfurization rate or the like can be achieved by performing a hydrogenation treatment by combining two or more reaction towers. From such a viewpoint, when the hydrocarbon oil is a heavy oil, it is preferable to use a multistage reaction tower. Furthermore, as a reaction method, either a cocurrent method in which the hydrogen-containing gas and the feedstock oil flow in the same direction in the reactor in order to achieve a high reaction rate, a countercurrent method in which the hydrogen-containing gas and the feedstock oil flow in an opposite flow, etc. This method can also be adopted.
[0047]
【Example】
Next, the present invention will be specifically described with reference to examples and comparative examples. However, the present invention is not limited to the examples.
In Examples and the like, the following reaction reagents were used as catalyst raw materials, and properties such as physical properties (porosity, strength, surface area, etc.) and catalytic activity of each catalyst were evaluated by the methods described later.
Reaction reagent
7-Ammonium molybdate (NH_Four)₆MoO₇O_{twenty four}・ 4H₂O
12-molybdo 1-phosphate H_Three(PMo₁₂O₄₀) ・ 6H₂O
Ammonium tetrathiotungstate (NH_Four)₂WS_Four
Cobalt nitrate Co (NO_Three)₂・ 6H₂O
Nickel nitrate Ni (NO_Three)₂・ 6H₂O
Aluminum isopropoxide Al (i-OC_ThreeH₇)_Three
Tetraethoxysilane Si (OC₂H_Five)_Four
[0048]
Example 1 (SNCMSAM15)
16.5 g of 7-ammonium molybdate was dissolved in 363.3 g of pure water, and ammonia water was further added to the solution so that pH = 9.7. And to this solution 5% H₂S / H₂Gas was circulated at a rate of 500 ml / min for 8.5 hours with stirring, and N₂ The gas was circulated with stirring at a rate of 200 ml / min for 12 hours to obtain a hydrolyzed aqueous solution. At this time, the solution pH was 9.2.
Next, 14.0 g of aluminum isopropoxide, 20.8 g of cobalt nitrate, and 254.2 g of hexylene glycol were mixed and stirred at 80 ° C. for 4.5 hours to obtain a uniform solution.
Thereafter, the hydrolyzed aqueous solution prepared by the above method was dropped into the homogeneous solution at a rate of 10 ml / min and hydrolyzed to prepare a slurry containing a precipitate. The slurry was held at 90 ° C. for 10 hours for aging, and then dried by a rotary evaporator to obtain a catalyst precursor. The catalyst component in the catalyst precursor was 44.5 wt.%.
[0049]
A batch reactor was charged with 2.0 g of the catalyst precursor together with 24.0 g of n-tridecane and 5.5 g of pure water, hydrogen gas was further introduced, and the internal pressure of the reactor was 1.0 MPa. This reactor was put into a sand bath maintained at 375 ° C., rapidly heated, and held at the same temperature for 30 minutes while shaking. The reactor was cooled to room temperature and then filtered to obtain a MoS-SMU catalyst SNCMSAM15. SNCSAMSAM15 is the result of physical properties evaluation, porous MoS₂ There are crystals (having pores with a diameter of 20 mm or more), and this MoS₂ It was confirmed that the crystal and the promoter component were combined, and the homogeneity of the Al component was also excellent. In the activity evaluation, it was found that the highly active sulfur compound (DBT, 4,6DMDBT) exhibits high activity against desulfurization and has high activity maintaining ability. Table 4 shows the chemical composition, catalyst physical properties, and activity evaluation results of the catalyst.
[0050]
Example 2 (SNCMSAM08)
16.5 g of 7-ammonium molybdate was dissolved in 363.3 g of pure water, and ammonia water was further added to the solution so that pH = 9.7. And to this solution 5% H₂S / H₂Gas was circulated at a rate of 500 ml / min for 11 hours with stirring, and N₂ The gas was circulated with stirring at a rate of 200 ml / min for 12 hours to obtain a hydrolyzed aqueous solution. At this time, the solution pH was 9.1.
Next, 14.0 g of aluminum isopropoxide, 20.8 g of cobalt nitrate, and 254.2 g of hexylene glycol were mixed and stirred at 80 ° C. for 4.5 hours to obtain a uniform solution.
Thereafter, the hydrolyzed aqueous solution prepared by the above method was dropped into the homogeneous solution at a rate of 10 ml / min and hydrolyzed to prepare a slurry containing a precipitate. The slurry was held at 90 ° C. for 10 hours for aging, and then dried by a rotary evaporator to obtain a catalyst precursor. The catalyst component in the catalyst precursor was 48.0 wt.%.
[0051]
A batch reactor was charged with 1.9 g of the catalyst precursor together with 24.0 g of n-tridecane and 5.5 g of pure water, and hydrogen gas was further introduced to adjust the pressure in the reactor to 7.0 MPa. This reactor was put into a sand bath maintained at 375 ° C., rapidly heated, and held at the same temperature for 30 minutes while shaking.
Next, the reactor was cooled to room temperature, filtered after cooling, and MoS-SMUS catalyst SNCMSAM08 was obtained. Porous MoS₂ Compounding of crystal and promoter components was confirmed. In the evaluation of the catalyst activity, it showed high activity against desulfurization of hardly desulfurizable sulfur compounds and was excellent in activity maintenance ability. Further, hydrodesulfurization performed under the reaction conditions shown in Table 1 using LGO-D as a raw material oil showed high activity, and a high desulfurization rate was obtained. Table 4 shows the chemical composition, catalyst physical properties, and activity evaluation results of the catalyst.
[0052]
Example 3 (SNCMSAM11)
16.5 g of 7-ammonium molybdate was dissolved in 363.3 g of pure water, and ammonia water was further added to the solution so that pH = 9.7. And to this solution 5% H₂S / H₂Gas was circulated at a rate of 500 ml / min for 9 hours while stirring, and N₂ The gas was circulated with stirring at a rate of 200 ml / min for 12 hours to obtain a hydrolyzed aqueous solution. At this time, the solution pH was 9.3.
Next, 30.1 g of aluminum isopropoxide, 8.0 g of cobalt nitrate and 291.7 g of hexylene glycol were mixed and stirred at 80 ° C. for 4.5 hours to obtain a uniform solution.
Thereafter, the aqueous hydrolyzed solution prepared by the above method was dropped into the homogeneous solution at a rate of 10 ml / min and hydrolyzed to prepare a slurry containing a precipitate. The slurry was held at 90 ° C. for 10 hours for aging, and then dried by a rotary evaporator to obtain a catalyst precursor. The catalyst component in the catalyst precursor was 46.2 wt.%.
[0053]
A batch reactor was charged with 1.9 g of the catalyst precursor together with 24.0 g of n-tridecane and 5.5 g of pure water, and hydrogen gas was further introduced to adjust the pressure in the reactor to 1.0 MPa. This reactor was put into a sand bath maintained at 375 ° C., rapidly heated, and held at the same temperature for 30 minutes while shaking.
Then, the reactor was cooled to room temperature, filtered after cooling, and MoS-SMU catalyst SNCMSAM11 was obtained. Porous MoS₂ It was confirmed that crystals (having pores with a diameter of 20 mm or more) existed, and the crystals and promoter components were complexed. It was also found that the Al component was excellent in homogeneity and excellent in desulfurization activity (DBT activity, 4,6DMDBT activity) and activity maintenance ability. Table 4 shows the chemical composition, catalyst physical properties, and activity evaluation results of the catalyst.
[0054]
Example 4 (SNCMSAM09)
14.1 g of ammonium 7-molybdate was dissolved in 308.8 g of pure water, and ammonia water was further added to the solution so that pH = 9.7. And to this solution 5% H₂S / H₂Gas was circulated at a rate of 400 ml / min for 12 hours with stirring, and N₂ The gas was circulated with stirring at a rate of 200 ml / min for 12 hours to obtain a hydrolyzed aqueous solution. At this time, the solution pH was 9.1.
Next, 24.5 g of aluminum isopropoxide, 2.6 g of tetraethoxysilane, 17.2 g of cobalt nitrate and 295.0 g of hexylene glycol were mixed and stirred at 80 ° C. for 4.5 hours to obtain a uniform solution.
Thereafter, the hydrolyzed aqueous solution prepared by the above method was dropped into the homogeneous solution at a rate of 10 ml / min and hydrolyzed to prepare a slurry containing a precipitate. The slurry was held at 90 ° C. for 10 hours for aging, and then dried by a rotary evaporator to obtain a catalyst precursor. The catalyst component in the catalyst precursor was 51.3 wt.%.
[0055]
A batch type reactor was charged with 2.1 g of the catalyst precursor together with 24.0 g of n-tridecane and 5.5 g of pure water, hydrogen gas was further introduced, and the internal pressure of the reactor was 1.0 MPa. This reactor was put into a sand bath maintained at 375 ° C., rapidly heated, and held at the same temperature for 30 minutes while shaking.
Subsequently, the reactor was cooled to room temperature, filtered after cooling, and MoS-SMUS catalyst SNCMSAM09 was obtained. Porous MoS₂ It was confirmed that crystals (having pores with a diameter of 20 mm or more) existed, and the crystals and promoter components were complexed. It was also found that the Al component was excellent in homogeneity and excellent in desulfurization activity (DBT activity, 4,6DMDBT activity) and activity maintenance ability. Table 4 shows the chemical composition, catalyst physical properties, and activity evaluation results of the catalyst.
[0056]
Example 5 (SNCMSAM21)
9.4 g of ammonium 7-molybdate was dissolved in 205.9 g of pure water, and ammonia water was further added to the solution so that pH = 9.7. And to this solution 5% H₂S / H₂Gas was circulated at a rate of 500 ml / min for 5 hours with stirring, and N₂ The gas was circulated at a rate of 200 ml / min with stirring for 12 hours. At this time, the solution had pH = 9.3.
Next, 2.8 g of ammonium tetrathiotungstate (manufactured by Aldrich Chem. Co., No. 33673-4) is dissolved in 71.0 g of pure water, and ammonia water is added so that the solution has a pH of 9.3. Was added. This solution was added to the above solution to obtain a hydrolyzed aqueous solution.
Further, 41.1 g of aluminum isopropoxide, 13.6 g of cobalt nitrate and 335.9 g of hexylene glycol were mixed and stirred at 80 ° C. for 4.5 hours to prepare a uniform solution.
Thereafter, the hydrolyzed aqueous solution prepared by the above method was dropped into the homogeneous solution at a rate of 10 ml / min and hydrolyzed to prepare a slurry containing a precipitate. The slurry was held at 90 ° C. for 10 hours for aging, and then dried by a rotary evaporator to obtain a catalyst precursor. The catalyst component in the catalyst precursor was 45.5 wt.%.
[0057]
A batch type reactor was charged with 3.5 g of the catalyst precursor together with 24.0 g of n-tridecane and 5.5 g of pure water, hydrogen gas was further introduced, and the internal pressure of the reactor was 1.0 MPa. This reactor was put into a sand bath maintained at 375 ° C., rapidly heated, and held at the same temperature for 30 minutes while shaking.
Next, the reactor was cooled to room temperature, filtered after cooling, and MoS-SMU catalyst SNCMSAM21 was obtained. Porous MoS₂ It was confirmed that crystals (having pores with a diameter of 20 mm or more) existed, and the crystals and promoter components were complexed. It was also found that the Al component was excellent in homogeneity and excellent in desulfurization activity (DBT activity, 4,6DMDBT activity) and activity maintenance ability. Table 5 shows the chemical composition, catalyst physical properties, and activity evaluation results of the catalyst.
[0058]
Example 6 (SNCMSAM12)
6.0 g of ammonium 7-molybdate was dissolved in 130.8 g of pure water, and ammonia water was added to the solution so that the pH was 9.7. And to this solution 5% H₂S / H₂Gas was circulated at a rate of 500 ml / min for 3 hours with stirring, and N₂ The gas was circulated with stirring at a rate of 200 ml / min for 12 hours to obtain a hydrolyzed aqueous solution. At this time, the solution pH was 9.1.
Next, 67.9 g of aluminum isopropoxide, 4.1 g of tetraethoxysilane, 4.7 g of cobalt nitrate, and 437.0 g of hexylene glycol were mixed and stirred at 80 ° C. for 4.5 hours to obtain a uniform solution.
Thereafter, the hydrolyzed aqueous solution prepared by the above method was dropped into the homogeneous solution at a rate of 10 ml / min and hydrolyzed to prepare a slurry containing a precipitate. The slurry was held at 90 ° C. for 10 hours for aging, and then dried by a rotary evaporator to obtain a catalyst precursor. The catalyst component in the catalyst precursor was 48.7 wt.%.
[0059]
A batch type reactor was charged with 5.1 g of the catalyst precursor together with 24.0 g of n-tridecane and 5.5 g of pure water, hydrogen gas was further introduced, and the internal pressure of the reactor was 1.0 MPa. This reactor was put into a sand bath maintained at 375 ° C., rapidly heated, and held at the same temperature for 30 minutes while shaking.
Subsequently, the reactor was cooled to room temperature, filtered after cooling, and MoS-SMU catalyst SNCMSAM12 was obtained. Table 5 shows the chemical composition, catalyst physical properties, and activity evaluation results of the catalyst.
[0060]
Example 7 (NCMSAM13)
16.5 g of ammonium 7-molybdate was dissolved in 363.3 g of pure water, and ammonia water was further added to the solution so that the pH was 9.8. And to this solution 5% H₂S / H₂Gas was circulated at a rate of 500 ml / min for 8.5 hours with stirring, and N₂ The gas was circulated with stirring at a rate of 200 ml / min for 12 hours to obtain a hydrolyzed aqueous solution. At this time, the solution pH was 9.3.
Next, 11.2 g of aluminum isopropoxide, 2.4 g of tetraethoxysilane, 20.8 g of cobalt nitrate and 251.9 g of hexylene glycol were mixed and stirred at 80 ° C. for 4.5 hours to obtain a uniform solution.
Thereafter, the hydrolyzed aqueous solution prepared by the above method was dropped into the homogeneous solution at a rate of 10 ml / min and hydrolyzed to prepare a slurry containing a precipitate. The slurry was held at 90 ° C. for 10 hours for aging, and then dried by a rotary evaporator to obtain a catalyst precursor. The catalyst component in the catalyst precursor was 45.3 wt.%.
[0061]
A batch reactor was charged with 2.0 g of the catalyst precursor together with 24.0 g of n-tridecane and 5.5 g of pure water, hydrogen gas was further introduced, and the internal pressure of the reactor was 1.0 MPa. This reactor was put into a sand bath maintained at 375 ° C., rapidly heated, and held at the same temperature for 30 minutes while shaking. The reactor was cooled to room temperature and then filtered to obtain a MoS-SMU catalyst SNCMSAM13. As a result of physical property evaluation, porous MoS₂ It was confirmed that crystals (having pores with a diameter of 20 mm or more) existed, and the crystals and promoter components were complexed. It was also found that the Al component was excellent in homogeneity and excellent in desulfurization activity (DBT activity, 4,6DMDBT activity) and activity maintenance ability. Table 5 shows the chemical composition, catalyst physical properties, homogeneity, specific surface area measurement results and activity evaluation results of the catalyst.
[0062]
Example 8 (NCMSAM20)
11.0 g of ammonium 7-molybdate was dissolved in 242.2 g of pure water, and ammonia water was further added to the solution so that pH = 9.9. And to this solution 5% H₂S / H₂Gas was circulated at a rate of 500 ml / min for 6 hours with stirring, and N₂ The gas was circulated with stirring at a rate of 200 ml / min for 12 hours to obtain a hydrolyzed aqueous solution. At this time, the solution pH was 9.5.
Next, 43.1 g of aluminum isopropoxide, 13.6 g of cobalt nitrate, and 348.0 g of hexylene glycol were mixed and stirred at 80 ° C. for 4.5 hours to obtain a uniform solution.
Thereafter, the hydrolyzed aqueous solution prepared by the above method was dropped into the homogeneous solution at a rate of 10 ml / min and hydrolyzed to prepare a slurry containing a precipitate. The slurry was held at 90 ° C. for 10 hours for aging, and then dried by a rotary evaporator to obtain a catalyst precursor. The catalyst component in the catalyst precursor was 44.8 wt.%.
[0063]
A batch reactor was charged with 3.0 g of the catalyst precursor together with 24.0 g of n-tridecane and 5.5 g of pure water, and hydrogen gas was further introduced to adjust the pressure in the reactor to 1.0 MPa. This reactor was put into a sand bath maintained at 375 ° C., rapidly heated, and held at the same temperature for 30 minutes while shaking. The reactor was cooled to room temperature and then filtered to obtain a MoS-SMU catalyst SNCMSAM20. Porous MoS₂ It was confirmed that crystals (having pores with a diameter of 20 mm or more) existed, and the crystals and promoter components were complexed. It was also found that the Al component was excellent in homogeneity and excellent in desulfurization activity (DBT activity, 4,6DMDBT activity) and activity maintenance ability. Table 5 shows the chemical composition, catalyst physical properties, and activity evaluation results of the catalyst.
[0064]
Example 9 (SNCMSAM22)
14.0 g of aluminum isopropoxide, 20.8 g of cobalt nitrate and 254.2 g of hexylene glycol were mixed and stirred at 80 ° C. for 4.5 hours to obtain a uniform solution.
After that, the polymolybdate ((NH_Four)₂Mo_ThreeS₁₃) 23.2 g was added, and a hydrolyzed aqueous solution in which ammonia water was added to 363.3 g of pure water so that the solution pH = 9.1 was added dropwise at a rate of 10 ml / min. A slurry containing was prepared. The slurry was held at 90 ° C. for 10 hours for aging, and then dried by a rotary evaporator to obtain a catalyst precursor. At this time, the catalyst precursor contained 48.3 wt.% Of a catalyst component.
1.85 g of the catalyst precursor is charged into a batch reactor together with 24.0 g of n-tridecane and 5.5 g of pure water, and further hydrogen gas is introduced to adjust the internal pressure of the reactor to 1.0 MPa. This reactor was put into a sand bath maintained at 375 ° C., rapidly heated, and held for 30 minutes while shaking.
The reactor was cooled to room temperature and then filtered to obtain a MoS-SMUS catalyst (SNCMSAM22). Table 5 shows the catalyst composition, catalyst physical properties, and activity evaluation results.
[0065]
Comparative Example 1 (Comparative Catalyst a)
130.1 g of aluminum isopropoxide and 820.7 g of hexylene glycol were mixed and stirred at 80 ° C. for 4 hours until completely dissolved, then 13.9 g of tetraethoxysilane was added, and further stirred at 80 ° C. for 3 hours. .
Thereafter, 11.2 g of 12-molybdo 1-phosphoric acid, 9.7 g of cobalt nitrate and 2.3 g of nickel nitrate were added, and the mixture was further stirred at 80 ° C. for 17 hours to prepare a uniform solution.
To the obtained uniform solution, 98 ml of pure water was added dropwise at 80 ° C. at a rate of 1 ml / min to prepare a slurry containing a precipitate formed by hydrolysis.
After completion of the stirring, the slurry was allowed to stand for 88 hours while being heated and maintained at 90 ° C. for aging. After completion of aging, the slurry was evaporated to dryness with a rotary evaporator, and further fired in an air stream at 650 ° C. to obtain a comparative catalyst a having the chemical composition shown in Table 6.
As a result of evaluating the physical properties of the comparative catalyst a, the active component is an oxide, and the porous MoS after sulfiding.₂ The presence of crystals was not observed. The Al component was homogeneous. Further, as shown in Table 6, the desulfurization activity and activity maintenance ability were low.
[0066]
Comparative Example 2 (Comparative catalyst b)
2.0 liters of pure water was heated to about 70 ° C., and an aqueous sodium hydroxide solution was added thereto to prepare alkaline water having a pH of about 12. Next, after adding an aqueous aluminum sulfate solution (518.0 g of aluminum sulfate, 710.0 g of pure water) to this alkaline water, the pH was adjusted to 8.4 to 8.8 with a sodium hydroxide or nitric acid solution, For about 0.5 hours. As a result, an aqueous solution containing a precipitate (gel) of alumina hydrate was obtained. A sodium silicate aqueous solution (No. 3 water glass, 210 g of pure water) was added to this aqueous solution, and the pH was adjusted to 8.8 to 9.2 with a nitric acid solution, followed by aging at about 70 ° C. for 0.5 hour. As a result, a slurry liquid containing precipitated particles in which silica hydrate was deposited on the surface of alumina hydrate was obtained. The slurry was filtered, and the cake separated by filtration was washed with an aqueous ammonium carbonate solution until the sodium concentration of the filtrate after filtration was 5 ppm or less. The cake was kneaded while being dried in a kneading machine at 80 ° C. until the water content was moldable, and formed into a 1.5 mmφ cylindrical pellet by an extruder. The formed pellets were dried at 120 ° C. for 16 hours and further calcined at 700 ° C. for 3 hours to obtain a carrier.
Next, this support was impregnated with an aqueous solution of ammonium 7-molybdate, dried at 120 ° C., and fired at 450 ° C. Next, it was impregnated with an aqueous solution containing cobalt nitrate and nickel nitrate, dried at 120 ° C., and fired at 500 ° C. to obtain a comparative catalyst b shown in Table 6.
As a result of evaluating the physical properties of the comparative catalyst b, the active component is an oxide, and the porous MoS after sulfiding.₂ The presence of crystals was not observed. The Al component was homogeneous. As shown in Table 6, both desulfurization activity and activity maintenance ability were low.
[0067]
Comparative Example 3 (Comparative Catalyst c)
130.1 g of aluminum isopropoxide and 820.7 g of hexylene glycol were mixed and stirred at 80 ° C. for 4 hours until completely dissolved, then 13.9 g of tetraethoxysilane was added, and further stirred at 80 ° C. for 3 hours. .
Thereafter, 11.2 g of 12-molybdo 1-phosphoric acid, 9.7 g of cobalt nitrate and 2.3 g of nickel nitrate were added, and the mixture was further stirred at 80 ° C. for 17 hours to prepare a uniform solution.
To the obtained uniform solution, 98 ml of pure water was added dropwise at a rate of 1 ml / min at 80 ° C. to prepare a slurry containing a precipitate formed by hydrolysis.
After completion of the stirring, the slurry was allowed to stand for 88 hours while being heated and maintained at 90 ° C. for aging. After completion of aging, the slurry was evaporated to dryness with a rotary evaporator, and further fired in an air stream at 650 ° C. to obtain a comparative catalyst c having the chemical composition shown in Table 6.
As a result of evaluating the physical properties of the comparative catalyst c, the active component was an oxide, and the porous MoS after sulfidation.₂ The presence of crystals was not observed. The Al component was found to have homogeneity. As shown in Table 6, the desulfurization activity and activity maintenance ability were both low.
[0068]
[1] Evaluation of catalyst properties
Porous
Evaluation was performed by image analysis of a transmission electron microscope (TEM) observation image.
(i) TEM observation method
(1) Sample preparation
The sample was placed in normal hexane, mixed and suspended, and suspended particles in the liquid were sucked with a dropper and dropped onto the sample grid. These operations were performed in a nitrogen atmosphere.
(2) TEM observation conditions
Acceleration voltage: 300kV
Observation field: Bright field
Observation magnification: 1 million times
Photo magnification: 1.8 million times
Device used: JEM-3010 (manufactured by JEOL Ltd.)
[0069]
(ii) Image analysis method
The TEM image is captured by a computer with an image scanner and digitized. After binarizing the digital image, the free software NIH-image uses MoS₂ By performing two-dimensional fast Fourier transform (FFT) of the layered crystal portion, a power spectrum image showing a pore structure was obtained.
Next, this power spectrum image is integrated in the radial direction with respect to the center, and the pore diameter (reciprocal of the distance from the center) is taken on the horizontal axis, and the spectral intensity is taken on the vertical axis.₂ The pore distribution of the crystal phase itself was determined.
[0070]
destruction strength
The catalyst precursor is 2 ton / cm using a φ20mm tablet press.² After compacting with an alumina mortar, the particles of 350 μm to 500 μm were classified, heat-treated with a batch reactor, and then measured for catalyst side fracture strength with a Kiya side fracture strength meter.
[0071]
Specific surface area
Constant volume method N₂ The BET specific surface area was determined by a gas adsorption method.
BELSORP28SA (made by Nippon Bell Co., Ltd.) was used as a measuring device. The measurement sample is introduced into the sample tube and 2 × 10^-1After deaeration to below Torr, pretreatment was carried out in vacuum at 200 ° C. for 1.5 hours, and then an nitrogen adsorption isotherm was measured. Then, the surface area of the sample was determined from the adsorption isotherm on the adsorption side using the BET multi-layer adsorption theory.
[0072]
Homogeneity
EPMA (Electron Probe Microanalyzer (EPM-810Q, manufactured by Shimadzu Corporation)) was used for measurement in the following manner.
・ Sample preparation
A catalyst sample was embedded in a polyester resin, a smooth catalyst cross section was obtained by a cutting method, and then a carbon coating was applied to the surface.
·Measurement condition
Accelerating voltage: 15KV
Sample current: 0.05 μA
Beam size: 1μmφ
Measuring line: Al-Kα
EPMA line analysis: Analysis in the catalyst diameter direction in 1 μm step.
[0073]
[2] Evaluation of catalyst activity
Desulfurization (HDS) activity evaluation by a fixed bed flow type reaction evaluation apparatus and desulfurization (HDS) activity evaluation by a flow type autoclave reaction evaluation apparatus were performed. Details of the reaction conditions and operation are as follows.
1) Desulfurization (HDS) activity evaluation using a fixed bed flow reaction evaluation system
Table 1 shows properties of the test oil (LGO-D), reaction evaluation apparatus, and reaction conditions.
The operation was performed according to the following procedure.
After charging 4.6 g of catalyst into the reactor, a sulfurized solution (hexadecane with dimethyl disulfide added to a sulfur content of 4 wt.% S) was added to 1.5 cc / min, H₂ The gas was flowed through the reactor at a flow rate of 60 cc / min and sulfided with the following program.
The temperature was raised from room temperature to 310 ° C. over 40 minutes, and kept at the same temperature for 5 hours. Thereafter, LGO-D was introduced. After completion of the introduction, the reaction pressure was increased to 320 ° C. over 30 minutes, and HDS reaction was performed. After introducing the test oil and continuing the reaction for a predetermined time, the sulfur concentration in the product was measured to determine the HDS activity.
The HDS activity was calculated by the following formula.
(HDS activity) = (Liquid space velocity per catalyst weight) × [1 / S^0.5−1 / S₀ ^0.5 ]
S in the formula is the sulfur concentration in the product, S₀ Indicates the sulfur concentration in the feed.
[0074]
2) Desulfurization (HDS) activity evaluation using a flow-type autoclave reaction evaluation device
Table 2 shows the evaluation test conditions.
After charging the reactor with 0.3 g of catalyst, a sulfurized solution (hexadecane with dimethyl disulfide added to a sulfur content of 4 wt.% S) was added at 0.15 cc / min, H₂ The gas was flowed through the reactor at a flow rate of 60 cc / min and sulfided with the following program. The temperature was raised from room temperature to 310 ° C. over 40 minutes and kept at the same temperature for 1.5 hours. Then, the test oil according to each evaluation condition was introduced. 9kg / cm after completion of introduction²The pressure was increased to -G, and then the temperature was raised to the temperature of each evaluation condition over 30 minutes to carry out the HDS reaction. After introducing the test oil and continuing the reaction for a predetermined time, in the case of the test condition 1, the concentrations of DBT and 4,6DMDBT in the product, and in the case of the test conditions 2 and 3, the sulfur concentration in the product are set. Each was measured and HDS activity was determined.
[0075]
The HDS activity was calculated by the following formula.
・ In the case of test condition 1
HDS activity (DBT) = (Liquid space velocity per catalyst weight) x (N_{DBT, O}-N_DBT) / (N_DBT)
N in the formula_{DBT, 0} Is the DBT concentration in the feed, N_DBT Is the DBT concentration in the product, and DBT represents dibenzothiophene.
[0076]
HDS activity (4,6DMDBT)
= (Liquid space velocity per catalyst weight) x (N_{4,6DMDBT, 0}-N_4,6DMDBT) / (N_4,6DMDBT)
N in the formula_{4,6DMDBT, 0}Is the 4,6DMDBT concentration in the feed, N_4,6DMDBTIs the concentration of 4,6DMDBT in the product, and 4,6DMDBT represents 4,6-dimethyldibenzothiophene.
[0077]
・ In the case of test conditions 2 and 3
(HDS activity) = (Liquid space velocity per catalyst weight) × [1 / S^0.5−1 / S₀ ^0.5 ]
S in the formula is the sulfur concentration in the product, S₀ Indicates the sulfur concentration in the feed.
[0078]
[Table 1]

[0079]
[Table 2]

[0080]
[Table 3]

[0081]
[Table 4]

[0082]
[Table 5]

[0083]
[Table 6]

[0084]
【The invention's effect】
Porous layered MoS₂ Since a catalyst for hydroprocessing consisting of an active phase composed of a promoter component in the crystal and an inorganic oxide matrix phase has been realized, it is possible to increase the Mo sulfide content and achieve high activation, making it difficult to desulfurize. High reaction activity and activity maintenance ability can be achieved in the desulfurization / denitrogenation reaction of hydrocarbon feedstocks containing sulfur compounds.

Claims (2)

A catalyst for hydrotreating a hydrocarbon oil comprising an active phase composed of a hydrogenation active component and a refractory inorganic oxide matrix phase, wherein the active phase has a layered MoS having pores having a pore diameter of 20 mm or more _A catalyst for hydrotreating a hydrocarbon oil having a high specific surface area, wherein particles of the following promoter component are dispersed in _two crystals.
Promoter component: Compound of at least one element selected from the group consisting of Group 6A elements and Group 8 elements of the Periodic Table excluding molybdenum     A method for hydrotreating a hydrocarbon oil, comprising contacting the hydrocarbon oil with a hydrotreating medium according to claim 1 in the presence of hydrogen under hydrotreating conditions.