JP4621371B2 - Hydrotreating catalyst bed and method for hydrotreating heavy hydrocarbon oil using the catalyst bed - Google Patents
Hydrotreating catalyst bed and method for hydrotreating heavy hydrocarbon oil using the catalyst bed Download PDFInfo
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- JP4621371B2 JP4621371B2 JP2001070403A JP2001070403A JP4621371B2 JP 4621371 B2 JP4621371 B2 JP 4621371B2 JP 2001070403 A JP2001070403 A JP 2001070403A JP 2001070403 A JP2001070403 A JP 2001070403A JP 4621371 B2 JP4621371 B2 JP 4621371B2
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- 239000003054 catalyst Substances 0.000 title claims description 142
- 238000000034 method Methods 0.000 title claims description 25
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- 229930195733 hydrocarbon Natural products 0.000 title claims description 17
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は水素化処理触媒床及びこれを用いた重質炭化水素油の水素化処理方法に関し、より詳しくは、特定の物性を有する二段からなる水素化処理触媒床、及びこれを用いた重質炭化水素油の水素化処理方法に関する。
【０００２】
【従来の技術】
現在、酸性雨等からの環境保護のため、燃料油中の硫黄分は水素化精製処理により低減されており、そこで脱硫触媒が一般に使用されている。しかし、特に常圧残油、減圧残油等の重質油を原料として低硫黄重油を生産する場合において、触媒の脱硫性能の限界から触媒寿命は短く、１年未満となっている。したがって、１年以内で精製装置を停止し、触媒を交換せざるを得ない。また、一般に、より重質の原料油ほど安価であるため、より重質な原料油を通油した方が経済的に望ましいが、製品として硫黄分が同じ低硫黄重油を生産する場合、触媒劣化が著しく大きくなるために触媒寿命が短くなり、経済的に不利になる場合がある。
【０００３】
上記のように、重質油から低硫黄重油を生産する場合、灯軽油の水素化処理に比較して、硫黄分を低減するためには、運転初期から高い温度を必要とする。また、触媒の活性は時間とともに劣化していくため、製品の硫黄分の量を一定に維持するためには、運転温度を徐々に上げていく必要がある。特に、重質油にはバナジウム、ニッケルといった金属分が含まれ、反応中に触媒に堆積して活性を被毒するため、触媒の劣化が著しい。このため、１年以内に装置の上限温度に達し、触媒を交換することとなるわけである。また、より重質な原料油ほど、この金属分が多いため、触媒の劣化が著しく大きくなり、通油量が制限されるという問題がある。
【０００４】
この問題を解決するために、異なる触媒を組み合わせて使用する方法が提案されている。例えば、特開昭６１−２６６４９０号公報には、減圧軽油等のアスファルテンの含有量が２質量％未満である原料油を主に対象とする場合、前段にリンを多く含み、後段にリンを含まない触媒を組み合わせて使用する方法が開示されている。しかしながら、金属分を多く含む常圧残油、減圧残油等の重質油を原料とする場合、効果が不十分である。
【０００５】
【発明が解決しようとする課題】
本発明は、上記観点からなされたもので、原料油中に金属分を多く含む常圧残油、減圧残油等の重質油でも、触媒の運転期間の延長による原料油の増処理や触媒交換頻度の低減が可能な水素化処理触媒床及びそれを用いた重質炭化水素油の水素化処理方法を提供することを目的とするものである。
【０００６】
【課題を解決するための手段】
本発明者らは鋭意研究の結果、上流側に脱金属活性が高く、また金属分の被毒に対する耐性が強い触媒を充填し、下流側に高脱硫活性が高い触媒を充填してなる水素化処理触媒床を使用することにより、上記本発明の目的を効果的に達成しうることを見出し本発明を完成したものである。
【０００７】
すなわち、本発明の要旨は下記のとおりである。
１．上流側が周期律表第６族金属及び周期律表第８〜１０族金属並びに触媒基準で、酸化物基準で０．５〜３．０質量％のリンを担持し、平均細孔直径（ＰＤ）が１４０〜１８０Åの触媒からなり、下流側が周期律表第６族金属及び周期律表第８〜１０族金属並びに触媒基準で、酸化物基準で３．０〜８．０質量％のリンを担持し、平均細孔直径（ＰＤ）が１４０Å未満の触媒からなるものであって、上流側の触媒充填割合が５〜９５容量％、下流側の触媒充填割合が９５〜９容量％である水素化処理触媒床。
２．触媒の平均細孔直径（ＰＤ；Å）と比表面積（ＳＡ；ｍ2 ／ｇ）との関係において、上流側の触媒が下記式（１）を満足し、下流側の触媒が下記式（２）を満足するものである前記１記載の水素化処理触媒床。
【０００８】
ＳＡ＋１．６５ＰＤ ＞ ４１０ ・・・（１）
ＳＡ＋１．６５ＰＤ ≦ ４１０ ・・・（２）
３．周期律表第６族金属がモリブデンであり、周期律表第８〜１０族金属がニッケルである前記１又は２に記載の水素化処理触媒床。
４．担体への金属の担持が、沸点又は分解温度２００℃以上の水溶性有機化合物を含有する含浸液を用いてなされたものである前記１〜３のいずれかに記載の水素化処理触媒床。
５．沸点又は分解温度２００℃以上の水溶性有機化合物がポリエチレングリコールである前記４記載の水素化処理触媒床。
６．前記１〜５のいずれかに記載した水素化処理触媒床を用いた重質炭化水素油の水素化処理方法。
７．前記１〜５のいずれかに記載の水素化処理触媒床のさらに上流側に脱金属触媒を用いたものである請求項６記載の重質炭化水素油の水素化処理方法。
８．重質炭化水素油が減圧軽油、常圧残油又は減圧残油である前記６又は７に記載の重質炭化水素油の水素化処理方法。
【０００９】
【発明の実施の形態】
以下に本発明について詳細に説明する。
本発明の水素化処理触媒床は、上流側触媒と下流側触媒からなり順次説明する。
上流側は周期律表第６族金属及び周期律表第８〜１０族金属並びに触媒基準で、酸化物基準で０．５〜３．０質量％のリンを担持し、平均細孔直径（ＰＤ）が１４０〜１８０Åの触媒からなる。
【００１０】
まず、担体としては、アルミナ、シリカ−アルミナが好ましく、特に、アルミナが好ましい。担体に担持する金属については、周期律表第６族金属として、モリブデン、タングステンなどを挙げることができるが、モリブデンが好ましい。第６族金属の担持量は、触媒基準で、酸化物基準で好ましくは４〜２５質量％、より好ましくは８〜２０質量％である。周期律表第８〜１０族の金属として、コバルト、ニッケルなどを挙げることができるが、ニッケルが好ましい。第８〜１０族金属の担持量は、触媒基準で、酸化物基準で好ましくは１〜８質量％、より好ましくは２〜５質量％である。また、その他の成分としては、リンが必要で、リンを添加すると、触媒の水素化活性が向上し、特に重質炭化水素油を原料とする場合においては、脱硫活性が向上する。その効果は添加量が、触媒基準で、酸化物基準で０．５〜３．０質量％で顕著となる。リンが多すぎると、通常のアルミナ担体上では、モリブデンと凝集酸化物を形成してしまい、モリブデンの分散性が低下してしまい、逆に脱硫活性が低下してしまう。また、触媒上に堆積する油中金属の堆積分布が変化し、触媒の外表面近傍に偏積してしまい、触媒劣化が大きくなるという問題もある。
【００１１】
上記触媒の平均細孔直径（ＰＤ）は１４０〜１８０Åであることが必要である。１４０Å未満であると、原料油中のバナジウム、ニッケルといった金属を除去する脱金属活性が小さくなり、下流側の脱硫触媒を保護することはできない。一方、１８０Åを超えると、担体の表面積が著しく小さくなって、その結果脱硫活性が著しく低下してしまい、下流側の高脱硫活性触媒と組み合わせても全体の脱硫活性が不足して運転温度が高くなりすぎる。
【００１２】
また、上記触媒の平均細孔直径（ＰＤ；Å）と比表面積（ＳＡ；ｍ2 ／ｇ）との関係において、下記式（１）を満足した方が好ましい。
ＳＡ＋１．６５ＰＤ ＞ ４１０ ・・・（１）
上記式（１）を満足しないと、金属分の触媒への堆積による活性被毒に対する耐性が弱くなる場合がある。
【００１３】
次に、上記触媒の製造方法について説明するが、担体としては好ましいアルミナを取り上げる。
アルミナ担体の製造方法は特に限定されないが、水溶性酸性アルミナ塩の水溶液に塩基を添加するか、水溶性塩基性アルミナ塩の水溶液に酸を添加するか、水溶性酸性アルミナ塩の水溶液と水溶性塩基性アルミナ塩の水溶液を混合して得られるゲルを、熟成、乾燥、焼成することによって得られる。
【００１４】
上記の水溶性酸性アルミナ塩として、硫酸アルミニウム，硝酸アルミニウム等を挙げることができ、水溶性塩基アルミナ塩として、アルミン酸ソーダ等を挙げることができる。
上記のアルミナゲルの生成は、一般に５０〜９０℃の温度で行う。
生成したゲルの熟成方法については、一般には、混合時と同じ温度にて酸性及びアルカリ性溶液を交互に加える操作（スイング）を、ｐＨ３．３〜９．３の間で１０回以上、好ましくは１３回以上行うことによって行うことができる。また、ｐＨ１０以上にて温度１２５℃以上、好ましくはｐＨ１１以上にて温度１３０℃以上で、一定の時間攪拌する方法（高温熟成法）を用いることもできる。これをスイング法と組み合わせてもよい。熟成した沈殿を８０〜２００℃（好ましくは１００〜１６０℃）で乾燥させ、４００〜７００℃（好ましくは５００〜６００℃）で焼成する。
【００１５】
なお、上記触媒の平均細孔直径（ＰＤ）を１４０〜１８０Åにする必要があるが、上記のアルミナの熟成において、スイングの回数や熟成時間を調整すればよい。
また、望ましい触媒物性として、前記式（１）を満足するために、アルミナゲルの乾燥条件、押出成型条件等を調整すればよい。例えば、アルミナゲルを乾燥して押出成型する際、加熱しながら捏和して水分を調整する方法などを挙げることができる。
【００１６】
以上のようにして得られたアルミナ担体に、以下の方法で金属を担持することができる。担持法は含浸法が好ましい。周期律表第６族のモリブデン化合物としては、三酸化モリブデン，パラモリブデン酸アンモニウム等が使用され、タングステン化合物としては、三酸化タングステン，タングステン酸アンモニウム等が使用される。また、周期律表第８〜１０族のニッケル化合物としては、硝酸ニッケル，塩基性炭酸ニッケル等が使用され、コバルト化合物としては、硝酸コバルト，塩基性炭酸コバルト等が使用される。さらに、リン化合物としては、五酸化リン，リン酸等が使用される。上記の金属化合物を、周期律表第６族金属は０．７〜４．３モル／リットル、周期律表第８〜１０族の金属は０．３〜２．４モル／リットル、リン化合物は０．１〜１．０モル／リットルの割合で純水に溶解させ、さらに沸点又は分解温度２００℃以上の水溶性有機化合物を５０〜２００ｇ／リットルの割合で溶解させたものを含浸液とし、担体に吸水率と等量になるように調整後含浸させる方が好ましい。その沸点又は分解温度２００℃以上の水溶性有機化合物として、１，３−ブタンジオール，１，４−ブタンジオール，ポリエチレングリコール，ポリオキシエチレンフェニルエーテル，ポリオキシエチレンオクチルフェニルエーテル等のエーテル基含有水溶性高分子、ポリビニルアルコール等のアルコール水溶性高分子、サッカロース，グリコース等の各種糖類、メチルセルロース，水溶性でんぷん等の水溶性多糖類及びこれらの誘導体を使用することができるが、分子量４００以上のポリエチレングリコールが最も好ましい。沸点又は分解温度２００℃以上の水溶性有機化合物を使用することにより、金属の担体での凝集を抑制することができる。
【００１７】
なお、含浸液のｐＨ調整は特に限定されないが、硝酸，塩酸，硫酸等の無機酸、りんご酸，エチレンジアミン４酢酸等の有機酸、アンモニアなどを使用して行うことができる。含浸後乾燥、焼成するが、乾燥温度は通常８０〜２００℃（好ましくは１００〜１５０℃）、焼成温度は通常３００〜６００℃（好ましくは４００〜５５０℃）である。焼成温度が低すぎると、担持成分と担体と十分な結合を持つことができない場合があり、高すぎると、担持成分の凝集が起こり易くなる。
【００１８】
次に、下流側は周期律表第６族金属及び周期律表第８〜１０族金属並びに触媒基準で、酸化物基準で３．０〜８．０質量％のリンを担持し、平均細孔直径（ＰＤ）が１４０Å未満の触媒からなる。
担体としては、上流側の触媒と同じくアルミナが好ましい。担体に担持する金属の種類と量は上流側と同様であるが、リンの量が上流側に比較して高い。リンを添加すると、触媒の水素化活性が向上し、特に重質炭化水素油を原料とする場合においては、脱硫活性が向上する。その効果は添加量が、触媒基準で、酸化物基準で３．０〜８．０質量％で顕著となる。リンが多すぎると、通常のアルミナ担体上では、モリブデンと凝集酸化物を形成してしまい、モリブデンの分散性が低下してしまい、逆に脱硫活性が低下してしまう。
【００１９】
上記触媒の平均細孔直径（ＰＤ）は１４０Å未満であることが必要である。１４０Å以上であると、表面積が小さくなりすぎるために、十分な脱硫活性を得ることができない。
また、上記触媒の平均細孔直径（ＰＤ；Å）と比表面積（ＳＡ；ｍ2 ／ｇ）との関係において、下記式（２）を満足した方が好ましい。
【００２０】
ＳＡ＋１．６５ＰＤ ≦ ４１０ ・・・（２）
上記式（２）を満足すると、上流側の触媒と異なり、金属分の触媒への堆積による活性被毒に対する耐性がさらに強くなる。
次に、上記触媒の製造方法について説明する。担体としては上流側の触媒と同様にアルミナが好ましい。
【００２１】
アルミナの製法については、上流側の場合と比べて、ゲルの熟成の段階で、スイングの回数を少なくしたり、熟成時間を短くする必要がある。そうすることによって、触媒の平均細孔直径を１４０Å未満にすることができる。
また、望ましい触媒物性として、前記式（２）を満足するために、アルミナゲルの乾燥条件、押出成型条件等を調整すればよい。例えば、アルミナゲルを水に懸濁させ、そのスラリーを２００〜３００℃の雰囲気へ噴霧して乾燥する方法（スプレードライ法）等がある。
【００２２】
アルミナ担体に金属を担持する方法については、リンの濃度を０．７〜２．０モル／リットルと増やしたこと以外は上流側触媒の製造方法と同様である。
本発明の水素化処理触媒床は、上流側の触媒充填割合５〜９５容量％に対して、下流側の触媒充填割合９５〜５容量％である。好ましくは、上流側の触媒充填割合１０〜９０容量％に対して、下流側の触媒充填割合９０〜１０容量％である。
【００２３】
次に、本発明の水素化処理触媒床を用いて水素化処理を行う際には、予め安定化処理として予備硫化を行うことが望ましい。この予備硫化処理の条件は特に限定されないが、通常、予備硫化剤として、硫化水素，二硫化炭素，チオフェン，ジメチルジスルフィド等を挙げることができ、軽油等に予備硫化剤を混合した予備硫化油を使用するのが一般的である。処理温度は２００〜４００℃、水素分圧は常圧〜３０ＭＰａの範囲で行われる。
【００２４】
触媒の形状については、特に重質炭化水素油の水素化処理に使用される触媒は、通常押出成形で製造されるものが多く、その形状は実質的に柱状をしている。その断面は円形のものが多いが、三葉型、四葉型など外表面を多くする工夫のあるものもある。また、球状触媒もよく用いられる。球状触媒は圧縮強度や耐磨耗性が特に要求される場合に使用される。
【００２５】
水素化処理条件については、原料油の種類や目的により異なるが、一般的には反応温度２００〜５５０℃（好ましくは２２０〜５００℃）、水素分圧５〜３０ＭＰａ（好ましくは１０〜２５ＭＰａ）の範囲で行われる。
反応形式は特に限定されないが、通常は、固定床，移動床，沸騰床，懸濁床等の種々のプロセスから選択できるが、固定床が好ましい。
【００２６】
固定床の場合の温度、圧力以外の反応条件としては、液空間速度（ＬＨＳＶ）は０．０５〜１０ｈｒ-1（好ましくは０．１〜５ｈｒ-1）、水素／オイル比は５００〜２，５００Ｎｍ3 ／ｋｌ（好ましくは７００〜２，０００Ｎｍ3 ／ｋｌ）である。
本願の第二発明は、前記水素化処理触媒床を用いた重質炭化水素油の水素化処理方法である。
【００２７】
該重質炭化水素として、常圧残油，減圧残油，減圧軽油，脱蝋減圧残油，アスファルテン油，タールサンド油及びこれらを一旦予備的に水素化処理した残油を挙げることができる。原料油の性状として、特に限定されないが、代表的な性状としては下記のとおりである。
比重（１５／４℃）：０．９６４０〜０．９９４０
動粘度（５０℃）：３００〜３，０００ｍｍ2 ／ｓ
硫黄分：２．８〜４．５質量％
窒素分：１，５００〜４，２００ｐｐｍ
金属分（Ｖ＋Ｎｉ）：２０〜１５０ｐｐｍ
残炭分：５〜１８質量％
アスファルテン分：０．５〜１２．０質量％
反応条件としては、上記の原料油を、以上で述べた水素化処理触媒床を充填して水素化処理してもよいが、より高脱硫活性で長寿命な触媒にするために、さらに上流側にアルミナ担体に周期律表第６族の少なくとも一種の金属及び周期律表第８〜１０族から選ばれる少なくとも一種の金属を担持した脱金属触媒を用い、下流側に本発明の水素化処理触媒床を用いた触媒システムにすればよい。
【００２８】
上記の上流側に使用する脱金属触媒の物性等の例を下記に示す。
周期律表第６族の金属として、モリブデン、タングステンなどを挙げることができるが、モリブデンが好ましい。第６族金属の担持量は、触媒基準で、酸化物基準で２〜１５質量％、好ましくは４〜１２質量％である。周期律表第８〜１０族の金属として、コバルト、ニッケルなどを挙げることができるが、ニッケルが好ましい。第８〜１０族金属の担持量は、触媒基準で、酸化物基準で１〜４質量％、好ましくは１．５〜２．５質量％である。担体としては、アルミナが望ましく、触媒の細孔径は１７０〜２５０Å（好ましくは１８０〜２２０Å）、比表面積は、８０〜２００ｍ2 ／ｇ（好ましくは１００〜１８０ｍ2 ／ｇ）、細孔容積は０．４〜１．０ｃｃ／ｇ（好ましくは０．５〜０．９ｃｃ／ｇ）である。
【００２９】
脱金属触媒と本発明の水素化処理触媒床の充填割合は、通常、脱金属触媒が１０〜４０容量％（好ましくは１５〜３０容量％）に対して、本発明の水素化処理触媒床は９０〜６０容量％（好ましくは８５〜７０容量％）である。
【００３０】
【実施例】
次に、本発明を実施例により具体的に説明するが、本発明はこれらの実施例によりなんら制限されるものではない。
〔触媒調製例１〕
純水１リットルに、水酸化ナトリウム３５．４ｇを溶解させ、さらに、アルミン酸ソーダ９９．１ｇを添加して、均一なアルミナ溶液Ｂ１を得た。別に、純水１リットルに硝酸アルミニウム５００ｇを溶解させ、アルミナ溶液Ａ１を得た。そして、純水２．３８リットルを７０℃に加温し、攪拌しながら、アルミナ溶液Ａ１をｐＨ３．６になるまで添加した。次に、アルミナ溶液Ｂ１をｐＨ９．０になるまで添加して、５分間攪拌しながら熟成させた。続いて再びアルミナ溶液Ａ１を添加して、ｐＨを３．６とし、攪拌しながら５分間ゲルを熟成させた。このようにｐＨを３．６から９．０の間で変化させる操作を１０回繰り返した。その後、得られたゲルを濾過、洗浄してアルミナゲルを８５０ｇ得た。このアルミナゲルの水分を８０℃で加熱攪拌して調節し、押出成型を行った。その後、１２０℃、１６時間乾燥させ、さらに５５０℃で２時間焼成してアルミナ担体Ｃ１を得た。
【００３１】
一方、三酸化モリブデン７５ｇ、塩基性炭酸ニッケル３１ｇ（ＮｉＯとして１６．７ｇ）、正リン酸（純度８５％）９．５ｇ、りんご酸１５ｇをイオン交換水に８０℃で加熱溶解させ、冷却後にポリエチレングリコール（分子量４００，分解温度２００℃以上）４０ｇ全量を加え、イオン交換水で２７５ｃｃとした。次にその含浸液５５ｃｃを前記のアルミナ担体Ｃ１の吸水量１００ｇに見合った量に調製し、常圧含浸させた。この担持物を、１２０℃で３時間乾燥させて、空気中５００℃、５時間焼成して触媒Ｄ１を得た。その物性を第１表に示す。
【００３２】
〔触媒調製例２〕
調製例１と同様にして、アルミナ担体Ｃ１を得た。
一方、三酸化モリブデン７８ｇ、塩基性炭酸ニッケル３２ｇ（ＮｉＯとして１７．３ｇ）、正リン酸（純度８５％）３９．４ｇをイオン交換水に８０℃で加熱溶解させ、冷却後にポリエチレングリコール（分子量４００，分解温度２００℃以上）４０ｇ全量を加え、イオン交換水で２７５ｃｃとした。次にその含浸液５５ｃｃを前記のアルミナ担体Ｃ１の吸水量１００ｇに見合った量に調製し、１００ｇに常圧含浸させた。この担持物を、１２０℃で３時間乾燥させて、空気中５００℃、５時間焼成して触媒Ｄ２を得た。その物性を第１表に示す。
【００３３】
〔触媒調製例３〕
調製例３と同様にしてアルミナゲルを８５０ｇ得た。このアルミナゲルをイオン交換水に懸濁させ、２５０℃でスプレードライを行った。その後、水を添加し水分を調整して、押出成型をし、さらに５５０℃で２時間焼成してアルミナ担体Ｃ２を得た。
一方、調製例１と同様の方法でニッケルとモリブデンとリン及びポリエチレングリコールを含む含浸液を調製した。この含浸液５５ｃｃを前記のアルミナ担体Ｃ２の吸水量１００ｇに見合った量に調製し、常圧含浸させた。この担持物を、１２０℃で３時間乾燥させて、空気中５００℃、５時間焼成して触媒Ｄ３を得た。その物性を第１表に示す。
【００３４】
〔触媒調製例４〕
純水１リットルに、水酸化ナトリウム３５．４ｇを溶解させ、さらに、アルミン酸ソーダ９９．１ｇを添加して、均一なアルミナ溶液Ｂ１を得た。別に、純水１リットルに硝酸アルミニウム５００ｇを溶解させ、アルミナ溶液Ａ１を得た。そして、純水２．３８リットルを７０℃に加温し、攪拌しながら、アルミナ溶液Ａ１をｐＨ３．６になるまで添加した。次に、アルミナ溶液Ｂ１をｐＨ９．０になるまで添加して、５分間攪拌しながら熟成させた。続いて再びアルミナ溶液Ａ１を添加して、ｐＨを３．６とし、攪拌しながら５分間ゲルを熟成させた。このようにｐＨを３．６から９．０の間で変化させる操作を６回繰り返した。その後、得られたゲルを濾過、洗浄してアルミナゲルを８５０ｇ得た。このアルミナゲルをイオン交換水に懸濁させ、２５０℃でスプレードライを行った。その後、水を添加し水分を調整し、押出成型を行い、さらに５５０℃で２時間焼成してアルミナ担体Ｃ３を得た。
【００３５】
一方、三酸化モリブデン８９ｇ、塩基性炭酸ニッケル３８ｇ（ＮｉＯとして２０．５ｇ）、正リン酸（純度８５％）４０ｇをイオン交換水に８０℃で加熱溶解させ、冷却後にポリエチレングリコール（分子量４００，分解温度２００℃以上）４０ｇ全量を加え、イオン交換水で２７５ｃｃとした。次にその含浸液５５ｃｃを前記のアルミナ担体Ｃ３の吸水量１００ｇに見合った量に調製し、常圧含浸させた。この担持物を、１２０℃で３時間乾燥させて、空気中５００℃、５時間焼成して触媒Ｓ１を得た。その物性を第１表に示す。
【００３６】
〔触媒調製例５〕
調製例４と同様にしてアルミナ担体Ｃ３を得た。
一方、三酸化モリブデン８６ｇ、塩基性炭酸ニッケル３６ｇ（ＮｉＯとして１９．５ｇ）、正リン酸（純度８５％）９．７ｇ、りんご酸１５ｇをイオン交換水に８０℃で加熱溶解させ、冷却後にポリエチレングリコール（分子量４００，分解温度２００℃以上）４０ｇ全量を加え、イオン交換水で２７５ｃｃとした。次にその含浸液５５ｃｃを前記のアルミナ担体Ｃ３の吸水量１００ｇに見合った量に調製し、常圧含浸させた。この担持物を、１２０℃で３時間乾燥させて、空気中５００℃、５時間焼成して触媒Ｓ２を得た。その物性を第１表に示す。
【００３７】
〔触媒調製例６〕
調製例４と同様にしてアルミナゲルを８５０ｇ得た。このアルミナゲルの水分を８０℃で加熱攪拌して調節し、押出成型を行った。その後、１２０℃、１６時間乾燥させ、さらに５５０℃で２時間焼成してアルミナ担体Ｃ４を得た。
一方、調製例１と同様の方法でニッケルとモリブデンとリン及びポリエチレングリコールを含む含浸液を調製した。この含浸液５５ｃｃを前記のアルミナ担体Ｃ４の吸水量１００ｇに見合った量に調製し、常圧含浸させた。この担持物を、１２０℃で３時間乾燥させて、空気中５００℃、５時間焼成して触媒Ｓ３を得た。その物性を第１表に示す。
【００３８】
【表１】
【表２】
〔脱金属触媒の調製例〕
純水１リットルに、水酸化ナトリウム３５．４ｇを溶解させ、さらに、アルミン酸ソーダ９９．１ｇを添加して、均一なアルミナ溶液Ｂ１を得た。別に、純水１リットルに硝酸アルミニウム５００ｇを溶解させ、アルミナ溶液Ａ１を得た。そして、純水２．３８リットルを７０℃に加温し、攪拌しながら、アルミナ溶液Ａ１をｐＨ３．６になるまで添加した。次に、アルミナ溶液Ｂ１をｐＨ９．０になるまで添加して、５分間攪拌しながら熟成させた。続いて再びアルミナ溶液Ａ１を添加して、ｐＨを３．６とし、攪拌しながら５分間ゲルを熟成させた。このようにｐＨを３．６から９．０の間で変化させる操作を１３回繰り返した。その後、得られたゲルを濾過、洗浄してアルミナゲルを１，０７５ｇ得た。このアルミナゲルの水分を８０℃で加熱攪拌して調節し、押出成型を行った。その後、１２０℃、１６時間乾燥させ、さらに５００℃で２時間焼成してアルミナ担体Ｃ５を得た。
【００４１】
一方、三酸化モリブデン３１ｇ、塩基性炭酸ニッケル１１．１ｇ（ＮｉＯとして６ｇ）、りんご酸５０ｇをイオン交換水に溶解させ、全量を２００ｃｃとした。次にその含浸液５５ｃｃを前記のアルミナ担体Ｃ５の吸水量１００ｇに見合った量に調製し、常圧含浸させた。この担持物を、１２０℃で３時間乾燥させて、空気中５５０℃、５時間焼成して触媒Ｍを得た。その物性を第２表に示す。
【００４２】
【表３】
〔触媒性能評価〕（実施例１〜３及び比較例１〜３）
小型高圧固定床反応装置の反応管に、上記で得られた触媒Ｍ、触媒Ｄ１〜Ｄ３及び触媒Ｓ１〜Ｓ３を第４表に示す割合で上流から充填し、触媒システムとした。次いで、ＬＧＯ（中東系軽質軽油、硫黄分１．１８質量％、窒素分７０ｐｐｍ）にジメチルジスルフィドを添加して硫黄濃度を２．５質量％に調整した予備硫化油を、上記の触媒システムに、水素ガスとともに２５０℃で、水素分圧１３．５ＭＰａで２４時間流通させ、予備硫化を行った。また、原料油としては、金属（バナジウム，ニッケル）含有量が非常に多い中東系原油の常圧残油を用いた。
その性状を第３表に示す。
【００４４】
【表４】
この原料油を、上記の予備硫化後の触媒に、水素ガスとともに流通させて、以下の条件で水素化処理を行った。結果を第４表に示す。
生成油のターゲット硫黄分：０．５質量％
水素分圧：１３．５ＭＰａ
液空間速度（ＬＨＳＶ）：０．６ｈｒ-1
水素／オイル比：８５０Ｎｍ3 ／ｋｌ
【００４６】
【表５】
【発明の効果】
本発明によれば、上流側に脱金属活性が高く、また金属分の被毒に対する耐性が強い触媒を充填し、下流側に高脱硫活性が高い触媒を充填してなる水素化処理触媒床を使用しているので、原料油中に金属分を多く含む常圧残油、減圧残油等の重質油でも、触媒の運転期間の延長による原料油の増処理や触媒交換頻度の低減が可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydrotreating catalyst bed and a method for hydrotreating heavy hydrocarbon oil using the same, and more particularly, to a hydrotreating catalyst bed having two specific stages and a heavy catalyst using the same. The present invention relates to a method for hydrotreating a hydrocarbon oil.
[0002]
[Prior art]
At present, in order to protect the environment from acid rain and the like, the sulfur content in fuel oil is reduced by hydrorefining treatment, and therefore, a desulfurization catalyst is generally used. However, particularly in the case of producing low-sulfur heavy oil using heavy oil such as atmospheric residual oil and reduced-pressure residual oil as a raw material, the catalyst life is short and less than one year due to the limit of the desulfurization performance of the catalyst. Therefore, the refiner must be stopped and the catalyst replaced within one year. In general, heavier feedstocks are less expensive, so it is economically preferable to feed heavier feedstocks. However, when producing low-sulfur heavy oils with the same sulfur content as products, catalyst degradation Is extremely large, which shortens the catalyst life and may be economically disadvantageous.
[0003]
As described above, when low-sulfur heavy oil is produced from heavy oil, a higher temperature is required from the beginning of operation in order to reduce the sulfur content compared to kerosene oil hydrotreatment. Further, since the activity of the catalyst deteriorates with time, it is necessary to gradually increase the operating temperature in order to keep the amount of sulfur in the product constant. In particular, heavy oil contains metal components such as vanadium and nickel, and deposits on the catalyst during the reaction to poison the activity. For this reason, the upper limit temperature of the apparatus is reached within one year, and the catalyst is replaced. In addition, the heavier raw material oil has more metal, so there is a problem that the deterioration of the catalyst is remarkably increased and the amount of oil passing is limited.
[0004]
In order to solve this problem, a method of using a combination of different catalysts has been proposed. For example, in Japanese Patent Application Laid-Open No. 61-266490, when mainly the raw material oil whose content of asphaltenes such as vacuum gas oil is less than 2% by mass, the front stage contains a lot of phosphorus and the rear stage contains phosphorus. Disclosed is a method of using no catalyst in combination. However, when heavy oil such as atmospheric residual oil and reduced pressure residual oil containing a large amount of metal is used as a raw material, the effect is insufficient.
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of the above, and even in heavy oil such as atmospheric residual oil and reduced-pressure residual oil containing a large amount of metal in the raw oil, the raw oil can be increased by extending the operation period of the catalyst or the catalyst. It is an object of the present invention to provide a hydrotreating catalyst bed capable of reducing the exchange frequency and a method of hydrotreating heavy hydrocarbon oil using the catalyst bed.
[0006]
[Means for Solving the Problems]
As a result of diligent research, the present inventors have filled a catalyst with high demetallation activity on the upstream side and a strong resistance against poisoning of metal, and hydrogenation with a catalyst having high desulfurization activity on the downstream side. The inventors have found that the object of the present invention can be effectively achieved by using a treated catalyst bed, and have completed the present invention.
[0007]
That is, the gist of the present invention is as follows.
1. The upstream side carries 0.5 to 3.0% by mass of phosphorus on the basis of oxide, based on periodic table group 6 metal and periodic table group 8 to 10 metal and catalyst, and average pore diameter (PD) Is composed of a catalyst of 140 to 180 mm, and the downstream side carries 3.0 to 8.0 mass% phosphorus on the basis of oxides based on the periodic table group 6 metal and the periodic table group 8 to 10 metal and catalyst. And a hydrogenation catalyst comprising an average pore diameter (PD) of less than 140 mm, wherein the upstream catalyst filling ratio is 5 to 95% by volume and the downstream catalyst filling ratio is 95 to 9% by volume. Treatment catalyst bed.
2. Average pore diameter (PD; Å) and specific surface area (SA; m) of the catalyst2/ G) The hydrotreating catalyst bed as described in 1 above, wherein the upstream catalyst satisfies the following formula (1) and the downstream catalyst satisfies the following formula (2).
[0008]
SA + 1.65PD> 410 (1)
SA + 1.65PD ≦ 410 (2)
3. 3. The hydrotreating catalyst bed according to 1 or 2, wherein the Group 6 metal of the periodic table is molybdenum and the Group 8-10 metal of the periodic table is nickel.
4). 4. The hydrotreating catalyst bed according to any one of 1 to 3, wherein the metal is supported on the support using an impregnating liquid containing a water-soluble organic compound having a boiling point or a decomposition temperature of 200 ° C. or higher.
5. 5. The hydrotreating catalyst bed as described in 4 above, wherein the water-soluble organic compound having a boiling point or a decomposition temperature of 200 ° C. or higher is polyethylene glycol.
6). A method for hydrotreating heavy hydrocarbon oil using the hydrotreating catalyst bed described in any one of 1 to 5 above.
7. The heavy hydrocarbon oil hydrotreating method according to claim 6, wherein a demetallation catalyst is used further upstream of the hydrotreating catalyst bed according to any one of (1) to (5).
8). 8. The method for hydrotreating heavy hydrocarbon oil as described in 6 or 7 above, wherein the heavy hydrocarbon oil is a vacuum gas oil, an atmospheric residue or a vacuum residue.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
The hydrotreating catalyst bed of the present invention is composed of an upstream catalyst and a downstream catalyst, which will be described sequentially.
The upstream side carries 0.5 to 3.0% by mass of phosphorus on the basis of oxide, based on periodic table group 6 metal and periodic table groups 8 to 10 metal and catalyst, and has an average pore diameter (PD ) Consists of 140 to 180 liters of catalyst.
[0010]
First, as the carrier, alumina and silica-alumina are preferable, and alumina is particularly preferable. With respect to the metal supported on the carrier, examples of the Group 6 metal of the periodic table include molybdenum and tungsten. Molybdenum is preferred. The supported amount of the Group 6 metal is preferably 4 to 25% by mass, more preferably 8 to 20% by mass based on the oxide, based on the catalyst. Examples of metals in Groups 8 to 10 of the periodic table include cobalt and nickel, with nickel being preferred. The amount of the Group 8-10 metal supported is preferably 1 to 8% by mass, more preferably 2 to 5% by mass based on the oxide, based on the catalyst. Further, as other components, phosphorus is required. When phosphorus is added, the hydrogenation activity of the catalyst is improved, and particularly when heavy hydrocarbon oil is used as a raw material, the desulfurization activity is improved. The effect becomes significant when the addition amount is 0.5 to 3.0% by mass on the basis of the catalyst and on the basis of the oxide. When there is too much phosphorus, aggregated oxides are formed with molybdenum on a normal alumina support, dispersibility of molybdenum is lowered, and desulfurization activity is lowered. Further, there is a problem that the deposition distribution of the metal in oil deposited on the catalyst changes and accumulates in the vicinity of the outer surface of the catalyst, resulting in a large deterioration of the catalyst.
[0011]
The catalyst must have an average pore diameter (PD) of 140 to 180 mm. If it is less than 140%, the demetallation activity for removing metals such as vanadium and nickel in the feedstock oil becomes small, and the downstream desulfurization catalyst cannot be protected. On the other hand, if it exceeds 180 mm, the surface area of the carrier is remarkably reduced, and as a result, the desulfurization activity is remarkably reduced. Even when combined with the downstream high desulfurization activity catalyst, the overall desulfurization activity is insufficient and the operating temperature is high. Too much.
[0012]
Further, the average pore diameter (PD; Å) and specific surface area (SA; m) of the above catalyst.2/ G), it is preferable to satisfy the following formula (1).
SA + 1.65PD> 410 (1)
If the above formula (1) is not satisfied, the resistance to active poisoning due to deposition of metal on the catalyst may be weakened.
[0013]
Next, although the manufacturing method of the said catalyst is demonstrated, a preferable alumina is taken up as a support | carrier.
The production method of the alumina carrier is not particularly limited, but a base is added to the aqueous solution of the water-soluble acidic alumina salt, an acid is added to the aqueous solution of the water-soluble basic alumina salt, or the aqueous solution of the water-soluble acidic alumina salt and the water-soluble A gel obtained by mixing an aqueous solution of a basic alumina salt is obtained by aging, drying and firing.
[0014]
Examples of the water-soluble acidic alumina salt include aluminum sulfate and aluminum nitrate, and examples of the water-soluble basic alumina salt include sodium aluminate.
The production of the alumina gel is generally performed at a temperature of 50 to 90 ° C.
Regarding the aging method of the generated gel, generally, an operation (swing) in which an acidic solution and an alkaline solution are alternately added at the same temperature as at the time of mixing is performed 10 times or more between pH 3.3 and 9.3, preferably 13 times. It can be done by doing more than once. Further, a method of stirring at a temperature of 125 ° C. or higher at a pH of 10 or higher, preferably 130 ° C. or higher at a pH of 11 or higher (high temperature aging method) can be used. This may be combined with the swing method. The aged precipitate is dried at 80 to 200 ° C. (preferably 100 to 160 ° C.) and calcined at 400 to 700 ° C. (preferably 500 to 600 ° C.).
[0015]
The average pore diameter (PD) of the catalyst needs to be 140 to 180 mm. In the aging of the alumina, the number of swings and the aging time may be adjusted.
Moreover, what is necessary is just to adjust the drying conditions, extrusion molding conditions, etc. of an alumina gel, in order to satisfy said Formula (1) as a desired catalyst physical property. For example, when alumina gel is dried and extruded, a method of kneading while heating to adjust the moisture can be used.
[0016]
A metal can be supported on the alumina support obtained as described above by the following method. The supporting method is preferably an impregnation method. As the molybdenum compound of Group 6 of the periodic table, molybdenum trioxide, ammonium paramolybdate or the like is used, and as the tungsten compound, tungsten trioxide, ammonium tungstate or the like is used. Moreover, nickel nitrate, basic nickel carbonate, etc. are used as a nickel compound of Group 8-10 of a periodic table, and cobalt nitrate, basic cobalt carbonate, etc. are used as a cobalt compound. Furthermore, phosphorus pentoxide, phosphoric acid, etc. are used as a phosphorus compound. In the metal compound, the group 6 metal of the periodic table is 0.7 to 4.3 mol / liter, the metal of the group 8 to 10 of the periodic table is 0.3 to 2.4 mol / liter, and the phosphorus compound is What was dissolved in pure water at a rate of 0.1 to 1.0 mol / liter, and further dissolved a water-soluble organic compound having a boiling point or a decomposition temperature of 200 ° C. or higher at a rate of 50 to 200 g / liter was used as an impregnating solution, It is preferable to impregnate the support after adjustment so as to be equivalent to the water absorption rate. As a water-soluble organic compound having a boiling point or a decomposition temperature of 200 ° C. or higher, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, polyoxyethylene phenyl ether, polyoxyethylene octylphenyl ether, or other ether group-containing water-soluble Water-soluble polymers such as water-soluble polymers such as water-soluble polymers, polyvinyl alcohol and the like, various sugars such as saccharose and glycolose, methylcellulose, water-soluble starch and the like, and polyethylene having a molecular weight of 400 or more. Glycol is most preferred. By using a water-soluble organic compound having a boiling point or decomposition temperature of 200 ° C. or higher, aggregation on a metal carrier can be suppressed.
[0017]
The pH adjustment of the impregnating solution is not particularly limited, but can be performed using an inorganic acid such as nitric acid, hydrochloric acid or sulfuric acid, an organic acid such as malic acid or ethylenediaminetetraacetic acid, ammonia or the like. After impregnation, drying and firing are performed, and the drying temperature is usually 80 to 200 ° C. (preferably 100 to 150 ° C.), and the firing temperature is usually 300 to 600 ° C. (preferably 400 to 550 ° C.). If the calcination temperature is too low, the supported component and the carrier may not be sufficiently bonded. If it is too high, aggregation of the supported component tends to occur.
[0018]
Next, the downstream side carries 3.0 to 8.0% by mass of phosphorus on the basis of oxide based on the periodic table group 6 metal and the periodic table group 8 to 10 metal and catalyst basis, and the average pores It consists of a catalyst with a diameter (PD) of less than 140 mm.
As the support, alumina is preferable as in the upstream catalyst. The type and amount of metal supported on the carrier is the same as that on the upstream side, but the amount of phosphorus is higher than that on the upstream side. When phosphorus is added, the hydrogenation activity of the catalyst is improved, and particularly when heavy hydrocarbon oil is used as a raw material, the desulfurization activity is improved. The effect becomes remarkable when the addition amount is 3.0 to 8.0% by mass on the basis of the catalyst and on the basis of the oxide. When there is too much phosphorus, aggregated oxides are formed with molybdenum on a normal alumina support, dispersibility of molybdenum is lowered, and desulfurization activity is lowered.
[0019]
The catalyst should have an average pore diameter (PD) of less than 140 mm. When it is 140 mm or more, since the surface area becomes too small, sufficient desulfurization activity cannot be obtained.
Further, the average pore diameter (PD; Å) and specific surface area (SA; m) of the above catalyst.2/ G), it is preferable that the following formula (2) is satisfied.
[0020]
SA + 1.65PD ≦ 410 (2)
When the above formula (2) is satisfied, unlike the upstream catalyst, the resistance to active poisoning due to the deposition of metal on the catalyst is further enhanced.
Next, the manufacturing method of the said catalyst is demonstrated. As the support, alumina is preferable as in the upstream catalyst.
[0021]
As for the production method of alumina, it is necessary to reduce the number of swings or shorten the aging time at the stage of aging of the gel as compared with the case of the upstream side. By doing so, the average pore diameter of the catalyst can be less than 140 mm.
Moreover, what is necessary is just to adjust the drying conditions, extrusion molding conditions, etc. of an alumina gel, in order to satisfy said Formula (2) as desired catalyst physical property. For example, there is a method (spray drying method) in which alumina gel is suspended in water and the slurry is sprayed into an atmosphere of 200 to 300 ° C. and dried.
[0022]
The method for supporting the metal on the alumina support is the same as the method for producing the upstream catalyst except that the phosphorus concentration is increased to 0.7 to 2.0 mol / liter.
The hydrotreating catalyst bed of the present invention has a downstream catalyst filling ratio of 95 to 5% by volume with respect to an upstream catalyst filling ratio of 5 to 95% by volume. Preferably, the catalyst filling rate on the downstream side is 90 to 10% by volume with respect to the catalyst filling rate on the upstream side of 10 to 90% by volume.
[0023]
Next, when hydrotreating using the hydrotreating catalyst bed of the present invention, it is desirable to perform preliminary sulfidation in advance as a stabilizing treatment. The conditions for this preliminary sulfidation treatment are not particularly limited, but normally, as the preliminary sulfidizing agent, hydrogen sulfide, carbon disulfide, thiophene, dimethyl disulfide and the like can be mentioned. It is common to use. The treatment temperature is 200 to 400 ° C., and the hydrogen partial pressure is in the range of normal pressure to 30 MPa.
[0024]
As for the shape of the catalyst, in particular, many of the catalysts used for the hydrogenation treatment of heavy hydrocarbon oils are usually produced by extrusion molding, and the shape thereof is substantially columnar. The cross-section is often circular, but there are also devices that devise to increase the outer surface such as a trilobal type and a four-leaf type. Also, spherical catalysts are often used. Spherical catalysts are used when compression strength and wear resistance are particularly required.
[0025]
The hydrotreating conditions vary depending on the type and purpose of the feedstock, but generally the reaction temperature is 200 to 550 ° C. (preferably 220 to 500 ° C.) and the hydrogen partial pressure is 5 to 30 MPa (preferably 10 to 25 MPa). Done in a range.
Although the reaction mode is not particularly limited, it can be usually selected from various processes such as a fixed bed, a moving bed, a boiling bed, and a suspension bed, but a fixed bed is preferable.
[0026]
As reaction conditions other than temperature and pressure in the case of a fixed bed, the liquid space velocity (LHSV) is 0.05 to 10 hr.-1(Preferably 0.1-5 hr-1), Hydrogen / oil ratio is 500-2500 NmThree/ Kl (preferably 700 to 2,000 NmThree/ Kl).
The second invention of the present application is a method for hydrotreating heavy hydrocarbon oil using the hydrotreating catalyst bed.
[0027]
Examples of the heavy hydrocarbon include atmospheric residual oil, vacuum residual oil, vacuum gas oil, dewaxed vacuum residual oil, asphaltene oil, tar sand oil, and residual oil obtained by temporarily hydrotreating these. The properties of the feed oil are not particularly limited, but typical properties are as follows.
Specific gravity (15/4 ° C.): 0.9640 to 0.9940
Kinematic viscosity (50 ° C.): 300 to 3,000 mm2/ S
Sulfur content: 2.8 to 4.5% by mass
Nitrogen content: 1,500-4,200 ppm
Metal content (V + Ni): 20 to 150 ppm
Residual carbon content: 5 to 18% by mass
Asphaltene content: 0.5-12.0% by mass
As the reaction conditions, the above-mentioned feed oil may be hydrotreated by filling the hydrotreating catalyst bed described above, but in order to obtain a catalyst with higher desulfurization activity and longer life, further upstream side In addition, a demetallation catalyst in which at least one metal selected from Group 6 of the periodic table and at least one metal selected from Groups 8 to 10 of the periodic table is supported on an alumina support, and the hydroprocessing catalyst of the present invention is provided downstream. A catalyst system using a bed may be used.
[0028]
Examples of physical properties of the demetallation catalyst used on the upstream side are shown below.
Examples of the metal of Group 6 of the periodic table include molybdenum and tungsten, but molybdenum is preferable. The amount of the Group 6 metal supported is 2 to 15% by mass, preferably 4 to 12% by mass based on the oxide, based on the catalyst. Examples of metals in Groups 8 to 10 of the periodic table include cobalt and nickel, with nickel being preferred. The supported amount of the Group 8-10 metal is 1 to 4% by mass, preferably 1.5 to 2.5% by mass based on the oxide, based on the catalyst. As the support, alumina is desirable, the pore diameter of the catalyst is 170 to 250 mm (preferably 180 to 220 mm), and the specific surface area is 80 to 200 m.2/ G (preferably 100 to 180 m2/ G) and the pore volume is 0.4 to 1.0 cc / g (preferably 0.5 to 0.9 cc / g).
[0029]
The filling ratio of the demetallation catalyst and the hydrotreating catalyst bed of the present invention is usually 10 to 40% by volume (preferably 15 to 30% by volume) of the demetallized catalyst, while the hydrotreating catalyst bed of the present invention is 90 to 60% by volume (preferably 85 to 70% by volume).
[0030]
【Example】
EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not restrict | limited at all by these Examples.
[Catalyst Preparation Example 1]
35.4 g of sodium hydroxide was dissolved in 1 liter of pure water, and 99.1 g of sodium aluminate was further added to obtain a uniform alumina solution B1. Separately, 500 g of aluminum nitrate was dissolved in 1 liter of pure water to obtain an alumina solution A1. Then, 2.38 liters of pure water was heated to 70 ° C., and the alumina solution A1 was added to pH 3.6 while stirring. Next, the alumina solution B1 was added until pH 9.0 and aged with stirring for 5 minutes. Subsequently, the alumina solution A1 was added again to adjust the pH to 3.6, and the gel was aged for 5 minutes while stirring. The operation of changing the pH between 3.6 and 9.0 was repeated 10 times. Thereafter, the obtained gel was filtered and washed to obtain 850 g of alumina gel. The moisture of the alumina gel was adjusted by heating and stirring at 80 ° C., and extrusion molding was performed. Thereafter, it was dried at 120 ° C. for 16 hours and further calcined at 550 ° C. for 2 hours to obtain an alumina carrier C1.
[0031]
On the other hand, 75 g of molybdenum trioxide, 31 g of basic nickel carbonate (16.7 g as NiO), 9.5 g of orthophosphoric acid (purity 85%) and 15 g of malic acid were heated and dissolved in ion-exchanged water at 80 ° C., and after cooling, polyethylene A total amount of 40 g of glycol (molecular weight 400, decomposition temperature 200 ° C. or higher) was added to make 275 cc with ion-exchanged water. Next, 55 cc of the impregnating liquid was prepared in an amount commensurate with the water absorption of 100 g of the alumina carrier C1, and impregnated at normal pressure. This support was dried at 120 ° C. for 3 hours and calcined in air at 500 ° C. for 5 hours to obtain catalyst D1. The physical properties are shown in Table 1.
[0032]
[Catalyst Preparation Example 2]
In the same manner as in Preparation Example 1, an alumina support C1 was obtained.
On the other hand, 78 g of molybdenum trioxide, 32 g of basic nickel carbonate (17.3 g as NiO), and 39.4 g of orthophosphoric acid (purity 85%) were heated and dissolved in ion-exchanged water at 80 ° C. After cooling, polyethylene glycol (molecular weight 400) , Decomposition temperature of 200 ° C. or higher) 40 g total amount was added to make 275 cc with ion-exchanged water. Next, 55 cc of the impregnating solution was prepared to an amount corresponding to the water absorption of 100 g of the alumina carrier C1, and 100 g was impregnated at normal pressure. This support was dried at 120 ° C. for 3 hours and calcined in air at 500 ° C. for 5 hours to obtain catalyst D2. The physical properties are shown in Table 1.
[0033]
[Catalyst Preparation Example 3]
In the same manner as in Preparation Example 3, 850 g of alumina gel was obtained. This alumina gel was suspended in ion-exchanged water and spray-dried at 250 ° C. Thereafter, water was added to adjust the water content, extrusion molding was performed, and the mixture was further fired at 550 ° C. for 2 hours to obtain an alumina carrier C2.
On the other hand, an impregnation liquid containing nickel, molybdenum, phosphorus and polyethylene glycol was prepared in the same manner as in Preparation Example 1. 55 cc of this impregnating solution was prepared in an amount commensurate with the water absorption of 100 g of the alumina carrier C2, and impregnated at normal pressure. This support was dried at 120 ° C. for 3 hours and calcined in air at 500 ° C. for 5 hours to obtain catalyst D3. The physical properties are shown in Table 1.
[0034]
[Catalyst Preparation Example 4]
35.4 g of sodium hydroxide was dissolved in 1 liter of pure water, and 99.1 g of sodium aluminate was further added to obtain a uniform alumina solution B1. Separately, 500 g of aluminum nitrate was dissolved in 1 liter of pure water to obtain an alumina solution A1. Then, 2.38 liters of pure water was heated to 70 ° C., and the alumina solution A1 was added to pH 3.6 while stirring. Next, the alumina solution B1 was added until pH 9.0 and aged with stirring for 5 minutes. Subsequently, the alumina solution A1 was added again to adjust the pH to 3.6, and the gel was aged for 5 minutes while stirring. The operation of changing the pH between 3.6 and 9.0 in this manner was repeated 6 times. Thereafter, the obtained gel was filtered and washed to obtain 850 g of alumina gel. This alumina gel was suspended in ion-exchanged water and spray-dried at 250 ° C. Thereafter, water was added to adjust the moisture content, extrusion molding was performed, and the mixture was further calcined at 550 ° C. for 2 hours to obtain an alumina carrier C3.
[0035]
On the other hand, 89 g of molybdenum trioxide, 38 g of basic nickel carbonate (20.5 g as NiO), and 40 g of normal phosphoric acid (purity 85%) are heated and dissolved in ion-exchanged water at 80 ° C. After cooling, polyethylene glycol (molecular weight 400, decomposition) The total amount of 40 g (temperature of 200 ° C. or higher) was added, and the volume was adjusted to 275 cc with ion-exchanged water. Next, 55 cc of the impregnating liquid was prepared to an amount corresponding to the water absorption of 100 g of the alumina carrier C3 and impregnated at normal pressure. This support was dried at 120 ° C. for 3 hours and calcined in air at 500 ° C. for 5 hours to obtain catalyst S1. The physical properties are shown in Table 1.
[0036]
[Catalyst Preparation Example 5]
In the same manner as in Preparation Example 4, an alumina support C3 was obtained.
On the other hand, 86 g of molybdenum trioxide, 36 g of basic nickel carbonate (19.5 g as NiO), 9.7 g of normal phosphoric acid (purity 85%), and 15 g of malic acid were heated and dissolved in ion-exchanged water at 80 ° C., and after cooling, polyethylene A total amount of 40 g of glycol (molecular weight 400, decomposition temperature 200 ° C. or higher) was added to make 275 cc with ion-exchanged water. Next, 55 cc of the impregnating liquid was prepared to an amount corresponding to the water absorption of 100 g of the alumina carrier C3 and impregnated at normal pressure. This support was dried at 120 ° C. for 3 hours and calcined in air at 500 ° C. for 5 hours to obtain catalyst S2. The physical properties are shown in Table 1.
[0037]
[Catalyst Preparation Example 6]
In the same manner as in Preparation Example 4, 850 g of alumina gel was obtained. The moisture of the alumina gel was adjusted by heating and stirring at 80 ° C., and extrusion molding was performed. Then, it was dried at 120 ° C. for 16 hours and further calcined at 550 ° C. for 2 hours to obtain an alumina carrier C4.
On the other hand, an impregnation liquid containing nickel, molybdenum, phosphorus and polyethylene glycol was prepared in the same manner as in Preparation Example 1. 55 cc of this impregnating liquid was prepared in an amount commensurate with the water absorption of 100 g of the alumina carrier C4 and impregnated at normal pressure. This support was dried at 120 ° C. for 3 hours and calcined in air at 500 ° C. for 5 hours to obtain catalyst S3. The physical properties are shown in Table 1.
[0038]
[Table 1]
[Table 2]
[Preparation Example of Demetallization Catalyst]
35.4 g of sodium hydroxide was dissolved in 1 liter of pure water, and 99.1 g of sodium aluminate was further added to obtain a uniform alumina solution B1. Separately, 500 g of aluminum nitrate was dissolved in 1 liter of pure water to obtain an alumina solution A1. Then, 2.38 liters of pure water was heated to 70 ° C., and the alumina solution A1 was added to pH 3.6 while stirring. Next, the alumina solution B1 was added until pH 9.0 and aged with stirring for 5 minutes. Subsequently, the alumina solution A1 was added again to adjust the pH to 3.6, and the gel was aged for 5 minutes while stirring. Thus, the operation of changing the pH between 3.6 and 9.0 was repeated 13 times. Thereafter, the obtained gel was filtered and washed to obtain 1075 g of alumina gel. The moisture of the alumina gel was adjusted by heating and stirring at 80 ° C., and extrusion molding was performed. Then, it was dried at 120 ° C. for 16 hours and further calcined at 500 ° C. for 2 hours to obtain an alumina carrier C5.
[0041]
On the other hand, 31 g of molybdenum trioxide, 11.1 g of basic nickel carbonate (6 g as NiO), and 50 g of malic acid were dissolved in ion-exchanged water to make a total amount of 200 cc. Next, 55 cc of the impregnating solution was prepared in an amount commensurate with the water absorption of 100 g of the alumina carrier C5 and impregnated at normal pressure. This support was dried at 120 ° C. for 3 hours and calcined in air at 550 ° C. for 5 hours to obtain catalyst M. The physical properties are shown in Table 2.
[0042]
[Table 3]
[Catalyst performance evaluation] (Examples 1-3 and Comparative Examples 1-3)
The catalyst M, the catalysts D1 to D3, and the catalysts S1 to S3 obtained above were charged into the reaction tube of the small high-pressure fixed bed reactor from the upstream in the ratio shown in Table 4 to obtain a catalyst system. Next, a preliminary sulfurized oil in which dimethyl disulfide was added to LGO (Middle Eastern light gas oil, sulfur content 1.18% by mass, nitrogen content 70 ppm) to adjust the sulfur concentration to 2.5% by mass was added to the above catalyst system. Presulfurization was performed by flowing together with hydrogen gas at 250 ° C. and hydrogen partial pressure of 13.5 MPa for 24 hours. Moreover, as the feedstock, a normal-pressure residual oil of Middle Eastern crude oil having a very high metal (vanadium, nickel) content was used.
The properties are shown in Table 3.
[0044]
[Table 4]
This raw material oil was circulated together with hydrogen gas through the catalyst after the preliminary sulfidation, and the hydrogenation treatment was performed under the following conditions. The results are shown in Table 4.
Target sulfur content of the product oil: 0.5% by mass
Hydrogen partial pressure: 13.5 MPa
Liquid space velocity (LHSV): 0.6 hr-1
Hydrogen / oil ratio: 850 NmThree/ Kl
[0046]
[Table 5]
【The invention's effect】
According to the present invention, there is provided a hydrotreating catalyst bed in which a catalyst having high demetallation activity on the upstream side and a strong resistance to poisoning of metal is packed and a catalyst having high desulfurization activity is packed on the downstream side. Because it is used, even with heavy oils such as atmospheric residual oil and vacuum residual oil that contain a large amount of metal in the raw oil, it is possible to increase the raw oil and reduce the frequency of catalyst replacement by extending the operation period of the catalyst. It becomes.
Claims (8)
ＳＡ＋１．６５ＰＤ ＞ ４１０ ・・・（１）
ＳＡ＋１．６５ＰＤ ≦ ４１０ ・・・（２）In the relationship between the average pore diameter (PD; Å) of the catalyst and the specific surface area (SA; m 2 / g), the upstream catalyst satisfies the following formula (1), and the downstream catalyst represents the following formula (2 2) The hydrotreating catalyst bed according to claim 1, wherein:
SA + 1.65PD> 410 (1)
SA + 1.65PD ≦ 410 (2)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0753968A (en) * | 1993-08-09 | 1995-02-28 | Idemitsu Kosan Co Ltd | Hydrotreatment of heavy hydrocarbon oil |
| JP2000313891A (en) * | 1999-01-05 | 2000-11-14 | Idemitsu Kosan Co Ltd | Method and system for desulfurizing fuel oil |
| JP2000351978A (en) * | 1999-06-10 | 2000-12-19 | Idemitsu Kosan Co Ltd | Hydrogenation of heavy oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0753968A (en) * | 1993-08-09 | 1995-02-28 | Idemitsu Kosan Co Ltd | Hydrotreatment of heavy hydrocarbon oil |
| JP2000313891A (en) * | 1999-01-05 | 2000-11-14 | Idemitsu Kosan Co Ltd | Method and system for desulfurizing fuel oil |
| JP2000351978A (en) * | 1999-06-10 | 2000-12-19 | Idemitsu Kosan Co Ltd | Hydrogenation of heavy oil |
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