JP4001412B2

JP4001412B2 - Method and apparatus for producing equilibrium catalyst

Info

Publication number: JP4001412B2
Application number: JP35294097A
Authority: JP
Inventors: 伸樹関根; 克哉渡辺; 孝夫木村; 満大井
Original assignee: Cosmo Oil Co Ltd
Current assignee: Cosmo Oil Co Ltd
Priority date: 1997-12-22
Filing date: 1997-12-22
Publication date: 2007-10-31
Anticipated expiration: 2017-12-22
Also published as: JPH11179192A

Description

【０００１】
【発明の属する技術分野】
本発明は、新触媒と、新触媒が触媒反応に寄与し、その触媒活性が低下した状態の失活触媒とが混在している触媒流動層内の触媒、即ち平衡触媒の形状及び性状に近似した模擬触媒の製造方法及びその装置に関し、更に詳細には、実装置の平衡触媒に極めて良く近似した模擬触媒を製造する方法及びその装置に関するものである。
【０００２】
【従来の技術】
流動接触分解法（ＦＣＣ法）により原料油を軽質油に分解するＦＣＣ装置の流動層触媒として使用されるＦＣＣ触媒は、装置内で、新しいフレッシュな触媒、即ち新触媒と、新触媒が触媒反応に寄与してその触媒活性が低下した状態の失活触媒とが混在した状態で触媒流動層を構成している。ここで、新触媒と失活触媒とが混在した混合触媒を平衡触媒と言う。本明細書で、新触媒とは、触媒製造工場から製品として出荷された状態の新しい触媒を言い、失活触媒とは、新触媒が触媒反応に寄与して触媒活性が低下した触媒を言い、触媒活性が低下した状態の触媒を再生した再生触媒をも含む、新触媒以外の触媒という概念である。
ＦＣＣ装置の軽質油の収率及び性状等は、実装置内でＦＣＣ反応に寄与しているＦＣＣ触媒、即ち平衡触媒の性能に大きく依存しているので、平衡触媒の性能評価は極めて重要である。
実装置の触媒の性能評価に当たり、実装置に投入する新触媒を評価しても、新触媒は触媒活性が高すぎて、平衡触媒とは全く異なった値になり、平衡触媒の性能とは相関関係がないために、評価の実質的な意義がない。そこで、通常は、平衡触媒に類似した模擬触媒を調製し、模擬触媒の性能を実験室試験により評価し、実装置の使用触媒、即ち平衡触媒の性能としている。
【０００３】
そして、平衡触媒の性能評価用の模擬触媒として、通常、新触媒を予め強制的に劣化させて失活触媒を調製し、その触媒活性を評価している。
新触媒を強制的に劣化させて触媒性能評価用の模擬触媒を調製する方法（以下、簡単に模擬平衡化法と言う）には、従来、ミッチェル（Michel) 法、或いは触媒メーカーが開発した、ＣＰＳ法、ＥＴＭ法、ＣＭＤ法、ＣＤ法等がある。
【０００４】
ミッチェル法は、触媒の乾燥工程、Ｎｉ、Ｖの含浸工程、Ｎｉ、Ｖの焼成工程、及び水蒸気処理工程から構成されている。
乾燥工程では、新触媒を温度５００℃で５時間加熱して乾燥する。Ｎｉ、Ｖの含浸工程では、触媒をビーカに入れ、続いて、触媒の細孔容積と同じ体積のナフテン酸ニッケル及びナフテン酸バナジウムのベンゼン溶液を触媒の入ったビーカに入れて溶液を触媒に含浸させる。溶液を触媒に含浸させた後、触媒を攪拌しながら乾燥する。Ｎｉ、Ｖの焼成工程では、触媒を温度５００℃で５時間焼成して、Ｎｉ、Ｖを触媒に担持させる。水蒸気工程では、Ｎｉ、Ｖを担持させた触媒を８００℃の温度で６時間水蒸気と接触させ、スチーミング処理を施す。
ＣＰＳ法、ＥＴＭ法、ＣＭＤ法、ＣＤ法等も、基本的には、ミッチェル法と同様な工程を備え、回分法で必要量の模擬触媒を調製している。
【０００５】
【発明が解決しようとする課題】
しかし、従来の模擬平衡化法で調製した触媒試料は、触媒全部を強制劣化させているために、触媒が失活触媒の性状に近似し、実装置の平衡触媒とは性状が全く異なるという問題があった。
【０００６】
例えば、実装置の平衡触媒とミッチェル法による模擬平衡化触媒との間には、触媒粒子中のＶの分布を除いて、次の表１に示すように性状の相違が生じている。

これでは、実装置の平衡触媒とは異なる性状の触媒の性能を評価することになり、実装置での触媒の性能を正しく評価することは出来ない。
【０００７】
そこで、本発明の目的は、実装置の平衡触媒に近似した平衡触媒を調製する方法及びその方法の実施に必要な装置を提供することである。
【０００８】
【課題を解決するための手段】
上記目的を達成するために、本発明に係る平衡触媒の製造方法は、新触媒と、新触媒が触媒反応に寄与し、その触媒活性が低下した状態の失活触媒とが混在している触媒流動層内の触媒、即ち平衡触媒の形状及び性状に近似した模擬触媒を製造する方法であって、
触媒槽から新触媒を連続的に供給する工程と、
供給された新触媒と、金属を付着させた金属付着触媒とを空気と高温水蒸気との混合雰囲気に導入して、新触媒及び金属付着触媒を所定温度に昇温する共に新触媒及び金属付着触媒を焼成かつスチーミング処理し、処理した新触媒及び金属付着触媒からなる混合触媒を連続的に送出する昇温・焼成・スチーミング工程と、
混合触媒を高温状態に維持しつつ移送する移送工程と、
移送された混合触媒を所定の冷却温度に冷却する冷却工程と、
金属又は金属化合物を溶媒に溶解した金属溶液を不活性ガスでアトマイジングして生成した噴霧状の溶液を混合触媒に付着させ昇温し、溶媒を蒸発させて金属付着触媒を連続的に生成する金属付着工程と、
不活性ガスを導入して混合触媒をストリッピングし、混合触媒に付着した溶媒の蒸気を分離させて得た金属付着触媒を連続的に送出するストリッピング工程と
を備え、
ストリッピング工程を経た金属付着触媒を連続的に昇温・焼成・スチーミング工程に送出し、新触媒を昇温・焼成・スチーミング工程に導入しつつ、新触媒及び金属付着触媒を昇温・焼成・スチーミング工程とストリッピング工程との間で循環させることを特徴としている。
【０００９】
触媒槽から新触媒を連続的に供給する工程では、例えば窒素ガス、空気等の気体による気体搬送により触媒槽から新触媒を連続的に昇温・焼成・スチーミング工程に移行させる。
昇温・焼成・スチーミング工程では、昇温・焼成・スチーミングできる限りその方法には制約はないが、例えば、新触媒及び金属付着触媒の触媒層の下部に空気と高温水蒸気を導入して触媒層を流動化しつつ空気と高温水蒸気との混合雰囲気に触媒を曝して新触媒及び金属付着触媒を所定温度に昇温する共に新触媒及び金属付着触媒を焼成しかつスチーミングする。
【００１０】
触媒等の粉体を移送管により高速で移送すると、粉体粒子同士が接触して静電気を発生し、静電気の吸引力により粉体が管壁に付着したり、粉体同士が集合したりして移送管を閉塞するという問題がある。
そこで、本発明方法では、ディアクティベータから金属付着触媒形成塔に混合触媒を移送する際に、ディアクティベータから出た混合触媒を所定温度、例えば５００℃程度に維持し、それにより静電気の発生を防止して、金属付着触媒形成塔に移送している。
【００１１】
一方、噴霧状の溶液を混合触媒に付着させる際には、混合触媒が高温であると、噴霧状の溶液が混合触媒に付着する前に乾燥し、金属が混合触媒に付着することができない。
そこで、本発明方法では、混合触媒を金属付着触媒形成塔に導入する際に、冷却工程により、混合触媒を室温程度に一旦冷却している。冷却工程では、空冷又は水冷により、或いはその双方により冷却する。例えば昇温・焼成・スチーミング工程を経た高温の混合触媒を、先ず、空冷して４００℃程度に冷却して移送し、次いで、水冷により常温、例えは１５℃程度に冷却する。水冷するには、例えば混合触媒を移送する移送管を二重管で構成し、外管に冷却水を流す。
【００１２】
昇温・焼成・スチーミング工程では５００〜１２００℃の範囲の温度に新触媒及び金属付着触媒を昇温し、移送工程では、３００℃〜４００℃の範囲の温度に維持して触媒を移送する。
冷却工程では、金属付着工程で噴霧状の溶液を混合触媒に付着し易くするために、１０〜５０℃の範囲の温度に混合触媒を冷却し、金属付着工程では、三流体ノズル先端で混合触媒に金属溶液を付着させ、更に付着した金属溶液から溶媒を蒸発させるために、１００〜２５０℃の範囲の温度に混合触媒を昇温し、ストリッピング工程では、ストリッピング効果を高め、かつ静電気の発生を防止するために、２００〜５００℃の範囲の温度に金属付着触媒を維持する。
ストリッピング工程では、ストリッピングできる限りその方法には制約はないが、例えば、金属付着触媒の触媒層の下部に不活性ガスを導入して金属付着触媒を流動化しつつストリッピングし、金属付着触媒に付着した溶媒の蒸気を分離させる。
【００１３】
上述の本発明方法を実施する平衡触媒の製造装置は、新触媒と、新触媒が触媒反応に寄与し、その触媒活性が低下した状態の失活触媒とが混在している触媒流動層内の触媒、即ち平衡触媒の形状及び性状に近似した模擬触媒を製造する装置であって、
空気と高温水蒸気との混合雰囲気内で、供給された新触媒及び金属付着触媒を所定温度に昇温すると共に新触媒及び金属付着触媒を焼成かつスチーミングして触媒活性を低下させ、混合触媒として送出するディアクティベータと、
金属又は金属化合物を溶媒に溶解した金属溶液を不活性ガスでアトマイジングして生成して噴霧状の溶液を混合触媒に付着させて金属付着触媒を形成する金属付着部を上部に、金属付着触媒に付着した溶媒の蒸気を分離するストリッピング部を下部に備え、金属付着触媒を連続してディアクティベータに送出する金属付着触媒形成塔と、
新触媒を連続的にディアクティベータに供給する触媒連続供給装置と、
ディアクティベータから流出した混合触媒を冷却しつつ金属付着触媒形成塔に気体輸送により移送する移送手段と
を備えていることを特徴としている。
【００１４】
好適には、金属付着触媒形成塔の金属付着部及びストリッピング部に触媒を加熱する加熱手段を備えて、金属付着効率及びストリッピング効率が高くなるように触媒を加熱する。
更に好適には、ディアクティベータは、新触媒と金属付着触媒との混合体からなる触媒層の下部に空気と高温水蒸気を導入して触媒層を流動化しつつ空気と高温水蒸気との混合雰囲気に触媒を曝し、新触媒及び金属付着触媒を所定温度に昇温する共に新触媒及び金属付着触媒を焼成・スチーミングする。
また、好適には、金属付着触媒形成塔は、金属付着触媒の触媒層の下部に不活性ガスを導入して金属付着触媒を流動化しつつ金属付着触媒に付着した溶媒の蒸気を窒素ガスでストリッピングする。
更に好適には、ディアクティベータと移送手段との間及び金属付着触媒形成塔のストリッピング部とディアクティベータとの間に、それぞれ、スライドバルブを設け、スライドバルブの弁開度により触媒の循環量を調整する。
【００１５】
【発明の実施の形態】
以下に、添付図面を参照し、実施例を挙げて本発明の実施の形態を具体的かつ詳細に説明する。
平衡触媒の製造装置の実施形態例
本実施形態例は、本発明に係る平衡触媒の製造装置の実施形態の一つの例であって、図１は本実施形態例の平衡触媒の製造装置の構成を示すフローシート、図２は触媒連続供給装置の構成を示す模式的断面図、及び図３はアトマイザーの断面図である。
本実施形態例の平衡触媒の製造装置１０（以下、簡単に製造装置１０と言う）は、新触媒と、新触媒が触媒反応に寄与して触媒活性が低下した状態の失活触媒とが混在している触媒流動層内の触媒、即ち平衡触媒の形状及び性状に近似した模擬触媒を製造する装置である。
製造装置１０は、触媒連続供給装置１２と、ディアクティベータ１４と、金属付着部１６を上部に、ストリッピング部１８を下部に有する金属付着触媒形成塔２０と、ディアクティベータ１４から金属付着触媒形成塔２０に混合触媒を移送しつつ金属付着触媒形成塔２０に入る前で冷却するようにした触媒移送管２１を備えている。
【００１６】
触媒連続供給装置
触媒連続供給装置１２は、新触媒をディアクティベータ１４に連続的に供給する装置であって、図２に示すように、新触媒を収容し、流動化させる触媒槽２２と、触媒槽２２を上昇させる上昇装置２４とを備えている。
上昇装置２４は、下部支持板２６と、下部支持板２６に設けられたネジ孔２８を貫通して上方に延びるネジ棒３０と、ネジ棒３０の上端に設けられ、触媒槽２２を支持しつつネジ棒３０の回転により上方に上昇する上昇板３２と、上昇板３２の上昇運動を案内する２本の案内棒３４Ａ、Ｂと、一方の案内棒３４Ａの上部に設けられた上部支持板３８と、ネジ棒３０のネジ回転装置（図示せず）とを備えている。
【００１７】
触媒槽２２は、脱着自在な蓋４０を有する筒状の容器であって、内部に触媒層を収容する。触媒槽２２は、下部に気体、例えば窒素ガスを導入する下部導入口４２、下部導入口４２に連通した気体分配室４３、及び気体分配室４３上に設けられ、多孔板により形成された分散板４４を備え、下部導入口４２より導入した気体を分散板４４により分散させて、分散板４４上に触媒流動層を形成する。
更に、触媒槽２２は、蓋４０に設けられた貫通孔４６を経て上方から触媒槽２２内に下降している触媒移送管４８と、蓋４０に下端が固定され、上端が上昇装置２４の上部支持板３８に固定され、触媒移送管４８を包囲しつつ伸縮自在な外管、例えば蛇腹管５０とを備えている。
また、上部支持板３８に支持された上部導入口５１から、気体、例えば窒素ガスを、蛇腹管５０の内側及び貫通孔４６を経由して、触媒槽２２内に導入するようになっている。
【００１８】
触媒槽２２では、下部導入口４２、気体分配室４３及び分散板４４を経て分散、導入された気体、例えば窒素ガスにより流動化した触媒流動層の上面に、触媒移送管４８の下端開口が、常時、接触するようになっている。
後述するように、触媒槽２２を所定速度で上昇させると、触媒移送管４８の下端開口と触媒流動層の上面とが同じ相対的位置関係、即ち相互に接触状態になる位置関係を常に維持するように、触媒が触媒槽２２から触媒移送管４８を経て送出される。
以上の構成により、触媒流動層の上面が、上部導入口５１、蛇腹管５０の内側及び蓋４０の貫通孔４６を経て導入された窒素ガス及び触媒流動層より抜け出した窒素ガスにより押圧されるので、触媒流動層の上層部が触媒移送管４８の内側に押し入るようにして入り、気体、例えば窒素ガスによる気体搬送によりディアクティベータ１４に移送される。
上昇装置２４は、ネジ棒３０をネジ回転装置により回転させて上昇させ、これにより、上昇板３２及び触媒槽２２を上昇させる。ネジ回転装置を調整してネジ棒３０の上昇速度を制御することにより、触媒移送管４８の下端開口が、触媒槽２２内の触媒流動層の上面に常に接触するようになっている。
触媒槽２２の径が、５mmの時には、導入口５１から０．０１Ｌ〜４Ｌ／分、導入口４２から０．０１〜１０Ｌ／分の窒素ガスを導入する。
【００１９】
ディアクティベータ
ディアクティベータ１４は、空気と高温水蒸気との混合雰囲気内で、供給された新触媒を昇温すると共に新触媒及び金属付着触媒を焼成かつスチーミングして触媒活性を低下させ、混合触媒として送出する機器であって、図１に示すように、上部の円筒部５２と、下部の逆円錐状部５４とから構成される。
円筒部５２には、新触媒及び金属付着触媒を導入する触媒導入管５８と、空気と高温水蒸気との混合気体を導入する空気／水蒸気導入管６０と、サイクロン６２とが設けてある。触媒導入管５８は、金属付着触媒形成塔２０の下部から延びる金属付着触媒移送管５６及び触媒移送管４８に接続している。
また、逆円錐状部５４は、触媒層のデッドスペースが生じないように角度、例えば１５°の角度が付いていて、逆円錐状部５４の下端には、スライドバルブ６４を介して触媒移送管２１に接続している。
触媒導入管５８は、円筒部５２の頂部から下降して、円筒部５２のほぼ中間に下端開口を備え、そこから金属付着触媒と窒素ガスに同伴された新触媒とを円筒部５２内に導入する。
【００２０】
空気／水蒸気導入管６０は、円筒部５２の頂部から下降し、逆円錐状部５４のほぼ最下部に下端開口を備え、そこから空気と高温水蒸気を流出させ、逆円錐状部５４に滞留する、金属付着触媒と新触媒との混合体からなる触媒層を流動化する。
サイクロン６２は、触媒流動層から上昇する空気、水蒸気及び新触媒を同伴搬送してきた窒素ガスから同伴触媒粒子を分離して気体のみ外部に放出する。
スライドバルブ６４は、弁の開度を調整できるスライド式弁体を備えて逆円錐状部５４の下端の触媒出口に設けられ、ディアクティベータ１４から金属付着触媒形成塔２０に移送する触媒の流量を制御している。
ディアクティベータ１４は、後述するように、触媒を加熱する加熱手段を備え、４００〜１２００℃の温度範囲の高温状態、例えば８００℃に保たれており、触媒の焼成及びスチーミングが行われる。目的に応じて、温度を変更することもできる。
ディアクティベータ１４の底部に窒素ガスを導入する導入口６５を備え、導入口６５から窒素ガスを導入し、ディアクティベータ１４から送出される混合触媒に付着した空気及び水蒸気をストリッピングする。
【００２１】
触媒移送管
触媒移送管２１は、内管と外管との二重管として構成されて、内管は、新触媒と金属付着触媒との混合触媒をディアクティベータ１４から金属付着触媒形成塔２０の金属付着部１６に窒素ガスにより気体搬送し、外管は、冷却水を流して内管を流れる混合触媒を冷却する。
触媒移送管２１は、図１に示すように、ディアクティベータ１４の触媒出口近傍の管体の一方の端部に窒素ガスの導入口６６を備え、導入口６６から導入された窒素ガスによりディアクティベータ１４から出て来た混合触媒を気体搬送する。
以上の構成により、触媒移送管２１は、混合触媒を高温に維持して静電気の発生を防ぎつつ搬送し、金属付着触媒形成塔２０の入口で所定の冷却温度になるように高温の混合触媒を冷却水により冷却する。
触媒移動管２１の径が、５mmの時、窒素ガスの導入量は、１〜５リットル／分である。
【００２２】
金属付着触媒形成塔
金属付着触媒形成塔２０は、上部の金属付着部１６で、金属又は金属化合物を溶媒に溶解した金属溶液（以下、金属溶液と言う）を窒素ガスでアトマイジングして生成した噴霧状の溶液を混合触媒に付着させ、次いで金属付着触媒に付着した溶液から溶媒を蒸発させて、下部のストリッピング部１８で、金属付着触媒に付着した溶媒の蒸気をストリッピングし、金属付着触媒を形成する。
【００２３】
金属付着部１６は、図１に示すように、円筒体として形成され、アトマイザー６８と、サイクロン７０とを備えている。
アトマイザー６８は、図３に示すように、金属溶液を供給する内管７２と、内管７２の外側にアトマイジング用の窒素ガスを注入する窒素ガスノズル７４と、窒素ガスノズル７４の外側に設けられ、混合触媒を同伴搬送する窒素ガスを導入する外管７６とからなる３流体ノズルと、３流体ノズル下方に設けられた加熱手段、例えば電気ヒータ（図示せず）とを備えた円筒管として構成されている。
アトマイザー６８の円筒管に設けた加熱手段は、３流体ノズル先端で混合触媒に付着した金属溶液から溶媒を蒸発させるために１００〜４００℃の範囲の温度に加熱、昇温する。
内管７２を流れる金属溶液は、窒素ガスノズル７４から注入された窒素ガスにより３流体ノズル先端でアトマイジングされて、噴霧状の液滴となって噴射され、外管７６から流出した混合触媒に３流体ノズル先端近傍で付着する。
更に言えば、３流体ノズルとして構成されたアトマイザー６８は、触媒移送管２１から移送された混合触媒に、窒素ガスによりアトマイジングされて生成した噴霧状の金属溶液、例えばナフテン酸ニッケル及びナフテン酸バナジウムのトルエン溶液を付着させる装置である。
サイクロン７０は、ストリッピング部１８に形成された触媒流動層から上昇する窒素ガス及び混合触媒を同伴搬送してきた窒素ガス及び金属溶液の溶媒蒸気から同伴触媒粒子を分離して気体のみ外部に放出する。
【００２４】
ストリッピング部１８は、金属付着部１６より径の小さい円筒体として構成され、ストリッピング部１８の最下部に設けられた窒素ガスの導入口７８と、円筒体の外側にストリッピング１８内の触媒を加熱昇温する発熱体（図示せず）と、ストリッピング部１８の最下部の触媒出口に設けられたスライドバルブ８０とを備えている。ストリッピング部１８は、通常、２００〜５００℃の温度範囲に維持されている。
ストリッピング部１８は、導入口７８から窒素ガスを導入し、金属付着部１６から落下して来た金属付着触媒の滞留する触媒層を流動化しつつ加熱された触媒に付着した溶媒蒸気をストリッピングして分離し、金属付着触媒を生成する。
スライドバルブ８０は、弁の開度を調整できるスライド式弁体を備えてストリッピング部１８の下端の触媒出口に設けられ、金属付着触媒形成塔２０からディアクティベータ１４に循環する金属付着触媒の流量を制御している。
【００２５】
平衡触媒の製造方法の実施形態例
本実施形態例は、本発明に係る平衡触媒の製造方法の実施形態の一例であって、上述した製造装置１０を用いて、平衡触媒を製造する例である。
以下に、図１及び図２を参照して、本実施形態例の平衡触媒の製造方法を説明する。
製造装置１０の各機器の寸法は、以下の通りである。
ディアクティベータ１４：呼び径４Ｂ配管×高さ９００mm
触媒移送管２１：呼び径１／４インチチューブ×長さ３６００mm
金属付着触媒形成塔２０
アトマイザー６８：呼び径２Ｂ配管×高さ２５０mm
金属付着部１６：呼び径４Ｂ配管×高さ２３０mm
ストリッピング部１８：呼び径１インチチューブ×高さ６００mm
（１）装置のスタートアップ
製造装置１０の運転条件の設定
先ず、ディアクティベータ１４、触媒移送管２１及び金属付着触媒形成塔２０の運転条件を以下のように設定し、定常状態に移行させる。

【００２７】
３．２）ストリッピング部１８
温度：３５０℃
サイクロン用窒素の導入量：１．０リットル／分
サイクロン温度：２７５℃
ストリッピング用窒素：微小量
【００２８】
製造装置１０の系内を上記の運転状態に維持し、次いで触媒連続供給装置１２から新触媒を系内に投入して、ディアクティベータ１４の下部のスライドバルブ６４を開放し、循環させる。
【００２９】
触媒連続供給装置１２からの触媒の供給
触媒連続供給装置１２の触媒槽２２内に新触媒を２リットルを投入し、次いで導入口５１から０．２Ｌ／分、導入口４２から１．０Ｌ／分の窒素ガスを流して触媒を流動状態にすると共に、２．５ｇ／分の流量で新触媒を移送するように、上昇装置２４を制御する。
【００３０】
新触媒の強制劣化
ディアクティベータ１４に供給された新触媒は、８００℃の高温水蒸気と接触し、加熱及びスチーミングされて、強制劣化する。
【００３１】
新触媒の移送
新触媒は、ディアクティベータ１４からスライドバルブ６４により循環量制御されて触媒移送管２１に入る。
触媒移送管２１により、強制劣化した新触媒は、静電気の発生を防止するために高温に維持されながら金属付着触媒形成塔２０に移送され、触媒移送管２１の外管を流れる冷却水により金属付着触媒形成塔２０に入る前に室温に冷却される。触媒を冷却するのは、触媒の温度が高温であると、金属溶液を触媒に付着させる際、溶媒が過乾燥し、ニッケル及びバナジウムが付着しないためである。
触媒移送管２１の窒素ガスの導入量は、１．４リットル／分である。
【００３２】
金属溶液の付着
金属付着触媒形成塔２０の金属付着部１６に移送された新触媒は、金属付着部１６で、ニッケル及びバナジウムを担持する。
金属付着部１６に移送された新触媒は、アトマイザー６８内の３流体ノズルから噴霧されたナフテン酸ニッケル及びナフテン酸バナジウムのトルエン溶液と接触する。これにより、溶液が新触媒に付着する。アトマイザー６８は、新触媒を２５０℃に昇温し、金属溶液が付着し瞬間に金属溶液から溶剤を蒸発させ、触媒を瞬間的に乾燥する。尚、トルエン溶媒中のニッケルとバナジウムとは、直ぐに反応して沈殿物を形成するので、アトマイザー６８の内管７２に導入する直前で、ナフテン酸ニッケルとナフテン酸バナジウムの２つのトルエン溶液を混合する。
アトマイザー６８の温度は、ニッケル、バナジウムを付着・乾燥させ、かつ静電気を防ぐために２５０℃に設定されている。
溶液が付着した触媒は、下方のストリッピング部１８に落下し、気体は、サイクロン７０によって同伴触媒が分離され、排ガスとして系外に排出される。サイクロンの温度は、通常、１５０〜４５０℃の温度範囲であって、本実施形態例では、２７５℃である。
【００３３】
ストリッピング及び金属付着触媒の形成
ナフテン酸ニッケル及びバナジウムの付着した触媒は、ストリッピング部１８で窒素ガスによりストリッピングされて、金属付着触媒となる。窒素ガスの供給量は微小量、例えば０．３リットル／分である。
ストリッピング部１８の下端のスライドバルブ８０は、ストリッピング部１８内の触媒流動層のレベルを一定に維持し、かつディアクティベータ１４からの逆流を防止しつつ金属付着触媒をディアクティベータ１４に移送する。ストリッピング部１８の温度は３５０℃に維持されている。
【００３４】
ディアクティベータ１４に再供給された金属付着触媒は、触媒連続供給装置１２から連続して導入された新触媒と共に空気と高温水蒸気雰囲気に接触し、８００℃の高温空気で焼成され、ニッケル及びバナジウムが触媒に完全に担持されると同時に高温水蒸気によりスチーミングされ、強制劣化する。
【００３５】
触媒循環量の制御
本製造装置１０では、触媒循環量が、スライドバルブ６６、８０の弁開度によって制御され、１０〜１００ｇ／分の範囲で制御できるようになっている。
製造装置１０のスタートアップ状態では、系内に存在する触媒量が少なく、そのため、循環量を低く設定し、２０ｇ／分で運転する。製造装置１０の運転を継続するにつれて、系内に存在する触媒量は増加して行く。そこで、触媒量の増加に伴い、触媒循環量も上昇させることが必要となり、運転末期では７０ｇ／分まで循環量を増加させる。これら循環量は、すべてスライドバルブ６６、８０の弁開度によって制御し、搬送用の気体導入量などは変化させない。
また、一般的に触媒循環量は多いほど好ましく、また、ディアクティベータ１４の滞留時間は短い方が好ましい。
【００３６】
運転初期では、ディアクティベータ１４のレベルが低いため、触媒循環量を上げると、触媒移送管２１に送入した窒素ガスがスライドバルブ６４を通ってディアクティベータ１４に逆流するので、好ましくない。しかし、初期には触媒循環量を低くしても、触媒量自体が少ないため、滞留時間は長くならない。
運転末期では、触媒量及び触媒循環量共に多いため、結果として、ディアクティベータ１４の滞留時間は、短く初期とほぼ同じとなる。製造装置１０を運転する上で、新触媒と金属付着触媒との良好な分布をもつ平衡触媒を得るためには、滞留時間及び循環量の制御が重要である。
【００３７】
（２）装置の定常運転
以上の工程を経て、ディアクティベータ１４では、新触媒と金属付着触媒とが混在する定常状態に到る。
【００３８】
（３）装置の運転終了
触媒連続供給装置１２からの新触媒の供給が終われば、即ち触媒槽２２に投入した触媒を全量移送し終わった時点で、本実施形態例の平衡触媒の製造は、終了する。ただし、触媒を更に劣化させたい場合は触媒を新たに供給することなく、循環させ、高温水蒸気による劣化のみを行うことも可能である。
【００３９】
以下の手順では、ディアクティベータ１４内に供給された新触媒と金属付着触媒とが混合した混合触媒として、系内を循環し、製造装置１０内には、新触媒と金属付着触媒とが分布を持って存在している。
このことが、本装置の最大の特徴であって、従来の模擬平衡化法及びその実施装置では、新触媒と金属付着触媒との分布がなく、一様に強制劣化させられた触媒である。
【００４０】
本実施形態例により得た平衡触媒は、次の表２に示すように実装置の平衡触媒の性状に極めて近似している。

本実施形態例の平衡触媒中のＮｉが粒子表面に多く分布している状態、またＶが粒子内に均一に分布している状態は、ＥＰＭＡ測定により実装置の平衡触媒のＮｉ及びＶの分布をそれぞれ示す図５（ａ）及び（ｂ）と、本実施形態例の平衡触媒のＮｉ及びＶの分布をそれぞれ示す図４（ａ）及び（ｂ）との比較から明らかなように、実装置の平衡触媒に極めて近似している。
【００４１】
また、本実施形態例により得た平衡触媒を評価するために、試験装置に本実施形態例の平衡触媒、実装置から得た平衡触媒、及びミッチェル法により調整した模擬平衡化触媒をそれぞれ使用して原料油を接触分解反応させ、表３に示す結果を得た。
本試験では、いずれの触媒にも２５００ppm のＮｉ及び５０００ppm のＶを付着させ、原料油として減圧軽油と脱硫重油との等量の混合油を使用した。
【表３】

表３から判る通り、本実施形態例の平衡触媒は、実装置から得た平衡触媒の分解性能と極めて良く近似している。一方、従来のミッチェル法により調整した模擬平衡化触媒は、種々の点で、特に、触媒上のコーク、水素ガス及び軽質炭化水素ガスの発生率の点で、実装置から得た平衡触媒の分解性能からかなり遊離している。
従って、触媒の原料油分解性能を評価する際、本発明に係る平衡触媒の製造方法により得た平衡触媒を使って試験装置で試験することにより、実装置での触媒の原料油分解性能を極めて高い近似性で推定することができる。
【００４２】
【発明の効果】
本発明方法によれば、新触媒及び金属付着触媒を所定温度に昇温する共に新触媒及び金属付着触媒を焼成かつスチーミングし、新触媒及び金属付着触媒からなる混合触媒を連続的に送出する昇温・焼成・スチーミング工程と、混合触媒を所定の冷却温度に冷却する冷却工程と、金属溶液を不活性ガスでアトマイジングして生成した噴霧状の溶液を混合触媒に付着させ、溶液付着触媒を所定温度に昇温し、乾燥させて、金属付着触媒を連続的に生成する金属付着工程と、不活性ガスを導入して混合触媒をストリッピングし、混合触媒に付着した溶媒蒸気を分離させて得た金属付着触媒を連続的に送出するストリッピング工程とを備え、新触媒を昇温・焼成・スチーミング工程に導入しつつ、金属付着触媒を昇温・焼成・スチーミング工程とストリッピング工程との間で循環させることにより、実装置の平衡触媒に極めて近似した模擬触媒を調製することができる。
本発明装置は、本発明方法を実施するのに最適な装置を実現している。
【図面の簡単な説明】
【図１】実施形態例の平衡触媒の製造装置の構成を示すフローシートである。
【図２】触媒連続供給装置の構成を示す模式的断面図である。
【図３】アトマイザーの断面図である。
【図４】図４（ａ）及び（ｂ）は、それぞれ、実施形態例の平衡触媒の製造方法により得た平衡触媒のＶ及びＮｉの担持状況を示す写真の写しである。
【図５】図５（ａ）及び（ｂ）は、それぞれ、実装置から得た平衡触媒のＶ及びＮｉの担持状況を示す写真の写しである。
【符号の説明】
１０実施形態例の平衡触媒の製造装置
１２触媒連続供給装置
１４ディアクティベータ
１６金属付着部
１８ストリッピング部
２０金属付着触媒形成塔
２１触媒移送管
２２触媒槽
２４上昇装置
２６下部支持板
２８ネジ孔
３０ネジ棒
３２上昇板
３４Ａ、Ｂ案内棒
３８上部支持板
４０蓋
４２下部導入口
４３気体分配室
４４分散板
４６貫通孔
４８触媒移送管
５０蛇腹管
５１上部導入口
５２円筒部
５４逆円錐状部
５６金属付着触媒移送管
５８触媒導入管
６０空気／水蒸気導入管
６２サイクロン
６４スライドバルブ
６５、６６導入口
６８アトマイザー
７０サイクロン
７２内管
７４窒素ガスノズル
７６外管
７８導入口
８０スライドバルブ[0001]
BACKGROUND OF THE INVENTION
The present invention approximates the shape and properties of a catalyst in a catalyst fluidized bed in which a new catalyst and a deactivated catalyst in which the new catalyst contributes to the catalytic reaction and its catalytic activity is reduced, that is, an equilibrium catalyst. More particularly, the present invention relates to a method and an apparatus for manufacturing a simulated catalyst that is very close to an equilibrium catalyst of an actual apparatus.
[0002]
[Prior art]
The FCC catalyst used as the fluidized bed catalyst of the FCC unit that breaks down the raw material oil into light oil by the fluid catalytic cracking method (FCC method) is a new fresh catalyst, that is, a new catalyst and a new catalyst in the device. The catalyst fluidized bed is configured in a state in which a deactivated catalyst in a state where the catalytic activity is reduced due to contribution to the catalyst is mixed. Here, a mixed catalyst in which a new catalyst and a deactivated catalyst are mixed is referred to as an equilibrium catalyst. In this specification, a new catalyst means a new catalyst in a state shipped as a product from a catalyst manufacturing factory, and a deactivated catalyst means a catalyst in which the new catalyst contributes to the catalytic reaction and the catalytic activity is reduced, It is a concept of a catalyst other than a new catalyst, including a regenerated catalyst obtained by regenerating a catalyst in a state in which the catalytic activity is lowered.
Since the yield and properties of light oil in the FCC unit greatly depend on the performance of the FCC catalyst that contributes to the FCC reaction in the actual unit, that is, the performance of the equilibrium catalyst, the performance evaluation of the equilibrium catalyst is extremely important. .
In evaluating the performance of the actual catalyst, even if the new catalyst to be introduced into the actual device is evaluated, the new catalyst has too high catalytic activity and is completely different from the equilibrium catalyst. Since there is no relationship, there is no substantial significance of evaluation. Therefore, usually, a simulated catalyst similar to the equilibrium catalyst is prepared, and the performance of the simulated catalyst is evaluated by a laboratory test to obtain the performance of the actual catalyst used, that is, the performance of the equilibrium catalyst.
[0003]
As a simulation catalyst for evaluating the performance of an equilibrium catalyst, a new catalyst is usually forcibly deteriorated in advance to prepare a deactivated catalyst, and its catalytic activity is evaluated.
A method for forcibly degrading a new catalyst to prepare a simulated catalyst for evaluating catalyst performance (hereinafter simply referred to as a simulated equilibration method) has been developed by the Michel method or a catalyst manufacturer. There are CPS method, ETM method, CMD method, CD method and the like.
[0004]
The Mitchell method is composed of a catalyst drying step, a Ni and V impregnation step, a Ni and V firing step, and a water vapor treatment step.
In the drying step, the new catalyst is dried by heating at a temperature of 500 ° C. for 5 hours. In the Ni and V impregnation step, the catalyst is placed in a beaker, and then a benzene solution of nickel naphthenate and vanadium naphthenate having the same volume as the pore volume of the catalyst is placed in the beaker containing the catalyst and the catalyst is impregnated with the solution. Let After impregnating the catalyst with the solution, the catalyst is dried with stirring. In the firing step of Ni and V, the catalyst is fired at a temperature of 500 ° C. for 5 hours to carry Ni and V on the catalyst. In the water vapor process, the catalyst carrying Ni and V is brought into contact with water vapor at a temperature of 800 ° C. for 6 hours to perform a steaming treatment.
The CPS method, ETM method, CMD method, CD method, and the like basically include the same steps as the Mitchell method, and a necessary amount of a simulated catalyst is prepared by a batch method.
[0005]
[Problems to be solved by the invention]
However, since the catalyst sample prepared by the conventional simulated equilibration method has forcibly deteriorated the entire catalyst, the catalyst approximates the property of the deactivated catalyst, and the property is completely different from the equilibrium catalyst of the actual device. was there.
[0006]
For example, there is a difference in properties between the equilibrium catalyst of the actual apparatus and the simulated equilibrium catalyst by the Mitchell method, as shown in Table 1 below, except for the distribution of V in the catalyst particles.

Thus, the performance of the catalyst having a property different from that of the equilibrium catalyst of the actual apparatus is evaluated, and the performance of the catalyst in the actual apparatus cannot be correctly evaluated.
[0007]
Accordingly, an object of the present invention is to provide a method for preparing an equilibrium catalyst approximate to the equilibrium catalyst of an actual device and an apparatus necessary for carrying out the method.
[0008]
[Means for Solving the Problems]
In order to achieve the above object, the method for producing an equilibrium catalyst according to the present invention is a catalyst in which a new catalyst and a deactivated catalyst in which the new catalyst contributes to the catalytic reaction and its catalytic activity is reduced are mixed. A method for producing a simulated catalyst that approximates the shape and properties of a catalyst in a fluidized bed, ie, an equilibrium catalyst,
Continuously supplying new catalyst from the catalyst tank;
The supplied new catalyst and the metal-attached catalyst with metal attached are introduced into a mixed atmosphere of air and high-temperature steam, and the temperature of the new catalyst and the metal-attached catalyst is increased to a predetermined temperature. Firing and steaming process, and continuously raising the mixed catalyst consisting of the treated new catalyst and metal adhesion catalyst, firing, steaming process,
A transfer step of transferring the mixed catalyst while maintaining a high temperature state;
A cooling step for cooling the transferred mixed catalyst to a predetermined cooling temperature;
A spray solution prepared by atomizing a metal solution in which a metal or metal compound is dissolved in an inert gas with an inert gas is attached to the mixed catalyst, the temperature is increased, and the solvent is evaporated to continuously produce a metal-attached catalyst. A metal adhesion process;
A stripping step of continuously feeding the metal-attached catalyst obtained by introducing an inert gas to strip the mixed catalyst and separating the vapor of the solvent attached to the mixed catalyst;
With
The metal-attached catalyst that has undergone the stripping process is continuously sent to the temperature raising, firing, and steaming process, and the new catalyst and the metal-attached catalyst are heated and introduced while the new catalyst is introduced into the temperature raising, firing, and steaming process. It is characterized by being circulated between the firing / steaming process and the stripping process.
[0009]
In the process of continuously supplying the new catalyst from the catalyst tank, the new catalyst is continuously transferred from the catalyst tank to the temperature raising / firing / steaming process by gas transfer using a gas such as nitrogen gas or air.
In the temperature raising / firing / steaming process, the method is not limited as long as the temperature raising / firing / steaming can be performed. For example, air and high-temperature steam are introduced into the lower layer of the catalyst layer of the new catalyst and the metal adhesion catalyst. The catalyst is exposed to a mixed atmosphere of air and high-temperature steam while fluidizing the catalyst layer to raise the temperature of the new catalyst and the metal-attached catalyst to a predetermined temperature, and the new catalyst and the metal-attached catalyst are calcined and steamed.
[0010]
When powder such as a catalyst is transferred at high speed by a transfer tube, the powder particles come into contact with each other to generate static electricity, and the powder attracts to the tube wall due to electrostatic attraction, or the powder collects. Therefore, there is a problem that the transfer pipe is blocked.
Therefore, in the method of the present invention, when the mixed catalyst is transferred from the deactivator to the metal-attached catalyst forming tower, the mixed catalyst output from the deactivator is maintained at a predetermined temperature, for example, about 500 ° C., thereby generating static electricity. Is transferred to the metal-attached catalyst-forming tower.
[0011]
On the other hand, when adhering the spray-like solution to the mixed catalyst, if the mixed catalyst is at a high temperature, the spray-like solution is dried before adhering to the mixed catalyst, and the metal cannot adhere to the mixed catalyst.
Therefore, in the method of the present invention, when the mixed catalyst is introduced into the metal-attached catalyst forming tower, the mixed catalyst is once cooled to about room temperature by a cooling step. In the cooling step, cooling is performed by air cooling, water cooling, or both. For example, a high-temperature mixed catalyst that has undergone a temperature raising / firing / steaming process is first cooled with air and cooled to about 400 ° C., and then cooled to room temperature, for example, about 15 ° C. by water cooling. For water cooling, for example, a transfer pipe for transferring the mixed catalyst is constituted by a double pipe, and cooling water is supplied to the outer pipe.
[0012]
In the temperature raising / firing / steaming process, the temperature of the new catalyst and the metal adhesion catalyst is raised to a temperature in the range of 500 to 1200 ° C., and in the transfer process, the catalyst is transferred while maintaining the temperature in the range of 300 to 400 ° C. .
In the cooling process, the mixed catalyst is cooled to a temperature in the range of 10 to 50 ° C. in order to facilitate the adhesion of the spray solution to the mixed catalyst in the metal adhesion process. In order to evaporate the solvent from the adhered metal solution, the temperature of the mixed catalyst is raised to a temperature in the range of 100 to 250 ° C. In the stripping step, the stripping effect is increased and In order to prevent generation, the metal deposition catalyst is maintained at a temperature in the range of 200-500 ° C.
In the stripping step, the method is not limited as long as it can be stripped. For example, an inert gas is introduced into the lower part of the catalyst layer of the metal adhesion catalyst, and the metal adhesion catalyst is fluidized to perform stripping. The vapor of the solvent adhering to is separated.
[0013]
The apparatus for producing an equilibrium catalyst for carrying out the above-described method of the present invention is a catalyst fluidized bed in which a new catalyst and a deactivated catalyst in which the new catalyst contributes to the catalytic reaction and its catalytic activity is reduced are mixed. An apparatus for producing a catalyst, that is, a simulated catalyst approximating the shape and properties of an equilibrium catalyst,
In a mixed atmosphere of air and high-temperature steam, the supplied new catalyst and metal-deposited catalyst are heated to a predetermined temperature, and the new catalyst and metal-deposited catalyst are calcined and steamed to reduce the catalytic activity, and as a mixed catalyst A deactivator to send,
Metal adhering catalyst is formed by atomizing a metal solution in which a metal or metal compound is dissolved in an inert gas with an inert gas and attaching a spray-like solution to the mixed catalyst to form a metal adhering catalyst. A metal-attached catalyst-forming tower that is provided with a stripping section for separating the vapor of the solvent attached to the bottom, and continuously sends the metal-attached catalyst to the deactivator;
A continuous catalyst supply device for continuously supplying a new catalyst to the deactivator;
A transport means for transporting the mixed catalyst flowing out from the deactivator to the metal-attached catalyst forming tower by gas transport while cooling;
It is characterized by having.
[0014]
Preferably, a heating means for heating the catalyst is provided in the metal adhering part and the stripping part of the metal adhering catalyst forming tower, and the catalyst is heated so that the metal adhering efficiency and the stripping efficiency are increased.
More preferably, the deactivator introduces air and high-temperature steam into the lower part of the catalyst layer made of a mixture of the new catalyst and the metal-deposited catalyst, and fluidizes the catalyst layer to create a mixed atmosphere of air and high-temperature steam. The catalyst is exposed, the new catalyst and the metal adhesion catalyst are heated to a predetermined temperature, and the new catalyst and the metal adhesion catalyst are calcined and steamed.
Preferably, the metal-adhered catalyst forming tower introduces an inert gas into the lower part of the catalyst layer of the metal-adhered catalyst to fluidize the metal-adhered catalyst and stir the vapor of the solvent adhering to the metal-adhered catalyst with nitrogen gas. Ripping.
More preferably, a slide valve is provided between the deactivator and the transfer means and between the stripping part of the metal-attached catalyst forming tower and the deactivator, respectively, and the catalyst is circulated according to the opening degree of the slide valve. Adjust the amount.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below specifically and in detail with reference to the accompanying drawings.
Embodiment of an apparatus for producing an equilibrium catalyst
This embodiment is an example of an embodiment of an apparatus for producing an equilibrium catalyst according to the present invention. FIG. 1 is a flow sheet showing the configuration of the apparatus for producing an equilibrium catalyst according to this embodiment, and FIG. FIG. 3 is a schematic cross-sectional view showing the configuration of the continuous supply apparatus, and FIG. 3 is a cross-sectional view of the atomizer.
The equilibrium catalyst manufacturing apparatus 10 (hereinafter simply referred to as the manufacturing apparatus 10) of the present embodiment includes a mixture of a new catalyst and a deactivated catalyst in which the new catalyst contributes to the catalytic reaction and the catalytic activity is reduced. It is an apparatus for producing a simulated catalyst that approximates the shape and properties of the catalyst in the catalyst fluidized bed, that is, the equilibrium catalyst.
The production apparatus 10 includes a continuous catalyst supply device 12, a deactivator 14, a metal adhering catalyst forming tower 20 having a metal adhering portion 16 at an upper portion and a stripping portion 18 at a lower portion, and a metal adhering catalyst from the deactivator 14. A catalyst transfer pipe 21 is provided which is cooled before entering the metal-attached catalyst forming tower 20 while transferring the mixed catalyst to the forming tower 20.
[0016]
Catalyst continuous supply device
The continuous catalyst supply device 12 is a device for continuously supplying a new catalyst to the deactivator 14. As shown in FIG. 2, the catalyst continuous supply device 12 contains a catalyst tank 22 for accommodating and fluidizing the new catalyst, and a catalyst tank 22. And a lifting device 24 for lifting.
The ascending device 24 is provided at the upper end of the lower support plate 26, the screw rod 30 extending through the screw hole 28 provided in the lower support plate 26, and the screw rod 30, while supporting the catalyst tank 22. Ascending plate 32 that rises upward by the rotation of screw rod 30, two guide rods 34A and B for guiding the ascending motion of ascending plate 32, and an upper support plate 38 provided on the upper portion of one guide rod 34A And a screw rotating device (not shown) of the screw rod 30.
[0017]
The catalyst tank 22 is a cylindrical container having a detachable lid 40 and accommodates a catalyst layer therein. The catalyst tank 22 is provided in the lower part inlet 42 which introduce | transduces gas, for example, nitrogen gas into the lower part, the gas distribution chamber 43 connected to the lower inlet 42, and the gas distribution room 43, and the dispersion | distribution board formed by the perforated plate 44, the gas introduced from the lower inlet 42 is dispersed by the dispersion plate 44 to form a catalyst fluidized bed on the dispersion plate 44.
Further, the catalyst tank 22 has a lower end fixed to the catalyst transfer pipe 48 that descends into the catalyst tank 22 from above through a through hole 46 provided in the lid 40, and an upper end that is an upper part of the lifting device 24. An outer tube, for example, a bellows tube 50, which is fixed to the support plate 38 and can be expanded and contracted while surrounding the catalyst transfer tube 48 is provided.
A gas, for example, nitrogen gas is introduced into the catalyst tank 22 from the upper inlet 51 supported by the upper support plate 38 via the inside of the bellows tube 50 and the through hole 46.
[0018]
In the catalyst tank 22, the lower end opening of the catalyst transfer pipe 48 is formed on the upper surface of the catalyst fluidized bed fluidized by the gas introduced, for example, nitrogen gas, dispersed and introduced through the lower inlet 42, the gas distribution chamber 43 and the dispersion plate 44. It is always in contact.
As will be described later, when the catalyst tank 22 is raised at a predetermined speed, the lower end opening of the catalyst transfer pipe 48 and the upper surface of the catalyst fluidized bed always maintain the same relative positional relationship, that is, the positional relationship in which they are in contact with each other. As described above, the catalyst is sent out from the catalyst tank 22 through the catalyst transfer pipe 48.
With the above configuration, the upper surface of the catalyst fluidized bed is pressed by the nitrogen gas introduced from the upper inlet 51, the inside of the bellows tube 50 and the through hole 46 of the lid 40, and the nitrogen gas escaped from the catalyst fluidized bed. The upper layer portion of the catalyst fluidized bed enters the inside of the catalyst transfer pipe 48 and is transferred to the deactivator 14 by gas conveyance with gas, for example, nitrogen gas.
The raising device 24 rotates the screw rod 30 by the screw rotating device to raise it, thereby raising the raising plate 32 and the catalyst tank 22. The lower end opening of the catalyst transfer pipe 48 is always in contact with the upper surface of the catalyst fluidized bed in the catalyst tank 22 by adjusting the screw rotating device to control the rising speed of the screw rod 30.
When the diameter of the catalyst tank 22 is 5 mm, nitrogen gas is introduced from the inlet 51 to 0.01 L to 4 L / min and from the inlet 42 to 0.01 to 10 L / min.
[0019]
Deactivator
The deactivator 14 raises the temperature of the supplied new catalyst in a mixed atmosphere of air and high-temperature steam, and calcinates and steams the new catalyst and the metal-deposited catalyst to reduce the catalytic activity, and sends it as a mixed catalyst. As shown in FIG. 1, the device includes an upper cylindrical portion 52 and a lower inverted conical portion 54.
The cylindrical portion 52 is provided with a catalyst introduction pipe 58 for introducing a new catalyst and a metal adhesion catalyst, an air / water vapor introduction pipe 60 for introducing a mixed gas of air and high-temperature steam, and a cyclone 62. The catalyst introduction pipe 58 is connected to a metal adhesion catalyst transfer pipe 56 and a catalyst transfer pipe 48 extending from the lower part of the metal adhesion catalyst forming tower 20.
Further, the reverse conical portion 54 has an angle, for example, an angle of 15 ° so that a dead space of the catalyst layer does not occur, and a catalyst transfer pipe is connected to the lower end of the reverse conical portion 54 via a slide valve 64. 21 is connected.
The catalyst introduction pipe 58 descends from the top of the cylindrical portion 52 and has a lower end opening substantially in the middle of the cylindrical portion 52, from which a metal adhering catalyst and a new catalyst accompanied by nitrogen gas are introduced into the cylindrical portion 52. To do.
[0020]
The air / steam introduction pipe 60 descends from the top of the cylindrical part 52 and has a lower end opening at substantially the lowest part of the inverted conical part 54, from which air and high temperature steam flow out and stays in the inverted conical part 54. Then, the catalyst layer made of a mixture of the metal adhesion catalyst and the new catalyst is fluidized.
The cyclone 62 separates the entrained catalyst particles from the nitrogen gas that has been carried along with the air, water vapor, and new catalyst rising from the catalyst fluidized bed, and releases only the gas to the outside.
The slide valve 64 includes a slide type valve element that can adjust the opening of the valve, and is provided at the catalyst outlet at the lower end of the inverted conical portion 54. Is controlling.
As will be described later, the deactivator 14 includes a heating means for heating the catalyst, and is maintained at a high temperature in a temperature range of 400 to 1200 ° C., for example, 800 ° C., and the catalyst is fired and steamed. The temperature can be changed according to the purpose.
An introduction port 65 for introducing nitrogen gas is provided at the bottom of the deactivator 14, nitrogen gas is introduced from the introduction port 65, and air and water vapor attached to the mixed catalyst delivered from the deactivator 14 are stripped.
[0021]
Catalyst transfer pipe
The catalyst transfer pipe 21 is configured as a double pipe consisting of an inner pipe and an outer pipe, and the inner pipe is a mixed catalyst of a new catalyst and a metal adhering catalyst from the deactivator 14 to the metal adhering to the metal adhering catalyst forming tower 20. The gas is conveyed to the part 16 by nitrogen gas, and the outer pipe cools the mixed catalyst flowing in the inner pipe by flowing cooling water.
As shown in FIG. 1, the catalyst transfer pipe 21 is provided with a nitrogen gas inlet 66 at one end of the tube near the catalyst outlet of the deactivator 14, and the nitrogen gas introduced from the inlet 66 is deactivated. The mixed catalyst coming out of the activator 14 is conveyed by gas.
With the above configuration, the catalyst transfer pipe 21 conveys the mixed catalyst while maintaining the mixed catalyst at a high temperature while preventing the generation of static electricity, and the high temperature mixed catalyst is set so as to reach a predetermined cooling temperature at the inlet of the metal-attached catalyst forming tower 20. Cool with cooling water.
When the diameter of the catalyst moving tube 21 is 5 mm, the amount of nitrogen gas introduced is 1 to 5 liters / minute.
[0022]
Metal adhesion catalyst formation tower
The metal adhesion catalyst formation tower 20 is a spray-like solution produced by atomizing a metal solution obtained by dissolving a metal or a metal compound in a solvent (hereinafter referred to as a metal solution) with nitrogen gas at the upper metal adhesion portion 16. The solvent is evaporated from the solution adhering to the mixed catalyst and then adhering to the metal adhering catalyst, and the vapor of the solvent adhering to the metal adhering catalyst is stripped by the lower stripping unit 18 to form the metal adhering catalyst.
[0023]
As shown in FIG. 1, the metal adhering portion 16 is formed as a cylindrical body and includes an atomizer 68 and a cyclone 70.
As shown in FIG. 3, the atomizer 68 is provided on the outer side of the inner tube 72 for supplying the metal solution, the nitrogen gas nozzle 74 for injecting nitrogen gas for atomizing to the outside of the inner tube 72, and the nitrogen gas nozzle 74, It is configured as a cylindrical tube provided with a three-fluid nozzle composed of an outer tube 76 for introducing nitrogen gas that carries the mixed catalyst and a heating means provided below the three-fluid nozzle, for example, an electric heater (not shown). ing.
The heating means provided in the cylindrical tube of the atomizer 68 heats and raises the temperature to a temperature in the range of 100 to 400 ° C. in order to evaporate the solvent from the metal solution attached to the mixed catalyst at the tip of the three-fluid nozzle.
The metal solution flowing through the inner pipe 72 is atomized at the tip of the three-fluid nozzle by the nitrogen gas injected from the nitrogen gas nozzle 74, sprayed as spray-like droplets, and is added to the mixed catalyst flowing out from the outer pipe 76. It adheres near the tip of the fluid nozzle.
Further, the atomizer 68 configured as a three-fluid nozzle is a sprayed metal solution generated by atomizing the mixed catalyst transferred from the catalyst transfer pipe 21 with nitrogen gas, for example, nickel naphthenate and vanadium naphthenate. This is a device for adhering a toluene solution.
The cyclone 70 separates the entrained catalyst particles from the nitrogen gas rising from the catalyst fluidized bed formed in the stripping section 18 and the nitrogen gas that has been carried along with the mixed catalyst and the solvent vapor of the metal solution, and releases only the gas to the outside. .
[0024]
The stripping section 18 is configured as a cylindrical body having a diameter smaller than that of the metal adhering section 16, a nitrogen gas inlet 78 provided at the lowermost portion of the stripping section 18, and a catalyst in the stripping 18 outside the cylindrical body. A heating element (not shown) that heats and heats and a slide valve 80 provided at the lowermost catalyst outlet of the stripping unit 18 is provided. The stripping part 18 is normally maintained in a temperature range of 200 to 500 ° C.
The stripping unit 18 introduces nitrogen gas from the introduction port 78 and strips the solvent vapor adhering to the heated catalyst while fluidizing the catalyst layer in which the metal adhering catalyst falling from the metal adhering unit 16 stays. To produce a metal deposition catalyst.
The slide valve 80 is provided with a slide type valve element that can adjust the opening degree of the valve, and is provided at the catalyst outlet at the lower end of the stripping unit 18. The slide valve 80 circulates from the metal adhesion catalyst formation tower 20 to the deactivator 14. The flow rate is controlled.
[0025]
Embodiment of production method of equilibrium catalyst
This embodiment is an example of an embodiment of a method for producing an equilibrium catalyst according to the present invention, and is an example in which an equilibrium catalyst is produced using the production apparatus 10 described above.
Below, with reference to FIG.1 and FIG.2, the manufacturing method of the equilibrium catalyst of this embodiment is demonstrated.
The dimensions of each device of the manufacturing apparatus 10 are as follows.
Deactivator 14: Nominal diameter 4B piping x height 900mm
Catalyst transfer pipe 21: Nominal diameter 1/4 inch tube x length 3600 mm
Metal adhesion catalyst formation tower 20
Atomizer 68: Nominal diameter 2B piping x height 250mm
Metal adhesion part 16: Nominal diameter 4B piping x height 230mm
Stripping part 18: nominal diameter 1 inch tube x height 600mm
(1) Device startup
Setting the operating conditions of the manufacturing apparatus 10
First, the operating conditions of the deactivator 14, the catalyst transfer pipe 21 and the metal-attached catalyst forming tower 20 are set as follows, and a steady state is entered.

[0027]
3.2) Stripping unit 18
Temperature: 350 ° C
Introduction amount of nitrogen for cyclone: 1.0 liter / min
Cyclone temperature: 275 ° C
Nitrogen for stripping: Minute amount
[0028]
The inside of the system of the manufacturing apparatus 10 is maintained in the above operating state, and then a new catalyst is introduced into the system from the continuous catalyst supply apparatus 12, and the slide valve 64 below the deactivator 14 is opened and circulated.
[0029]
Supply of catalyst from catalyst continuous supply device 12
2 liters of a new catalyst is charged into the catalyst tank 22 of the continuous catalyst supply device 12, then 0.2 L / min from the inlet 51 and 1.0 L / min from the inlet 42 are flowed to flow the catalyst. And the ascending device 24 is controlled to transfer the new catalyst at a flow rate of 2.5 g / min.
[0030]
Forced deterioration of new catalyst
The new catalyst supplied to the deactivator 14 comes into contact with high-temperature steam at 800 ° C., is heated and steamed, and is forcibly deteriorated.
[0031]
Transfer of new catalyst
The new catalyst enters the catalyst transfer pipe 21 from the deactivator 14 with the circulation amount controlled by the slide valve 64.
The new catalyst that has been forcibly deteriorated by the catalyst transfer pipe 21 is transferred to the metal-adhered catalyst formation tower 20 while being maintained at a high temperature in order to prevent generation of static electricity, and the metal adheres to it by the cooling water flowing through the outer pipe of the catalyst transfer pipe 21. Before entering the catalyst forming tower 20, it is cooled to room temperature. The reason for cooling the catalyst is that if the temperature of the catalyst is high, when the metal solution is deposited on the catalyst, the solvent is overdried and nickel and vanadium are not deposited.
The amount of nitrogen gas introduced into the catalyst transfer pipe 21 is 1.4 liters / minute.
[0032]
Metal solution adhesion
The new catalyst transferred to the metal adhering portion 16 of the metal adhering catalyst forming tower 20 carries nickel and vanadium in the metal adhering portion 16.
The new catalyst transferred to the metal adhering portion 16 comes into contact with a toluene solution of nickel naphthenate and vanadium naphthenate sprayed from a three-fluid nozzle in the atomizer 68. As a result, the solution adheres to the new catalyst. The atomizer 68 raises the temperature of the new catalyst to 250 ° C., the metal solution adheres, the solvent is evaporated from the metal solution instantly, and the catalyst is dried instantaneously. Since nickel and vanadium in the toluene solvent react immediately to form a precipitate, the two toluene solutions of nickel naphthenate and vanadium naphthenate are mixed immediately before being introduced into the inner tube 72 of the atomizer 68. .
The temperature of the atomizer 68 is set to 250 ° C. in order to adhere and dry nickel and vanadium and prevent static electricity.
The catalyst to which the solution adheres falls to the lower stripping section 18, and the gas is discharged from the system as exhaust gas after the entrained catalyst is separated by the cyclone 70. The temperature of the cyclone is usually in a temperature range of 150 to 450 ° C., and is 275 ° C. in the present embodiment example.
[0033]
Stripping and metal deposition catalyst formation
The catalyst to which nickel naphthenate and vanadium are adhered is stripped by nitrogen gas at the stripping section 18 to become a metal adhesion catalyst. The supply amount of nitrogen gas is a minute amount, for example, 0.3 liter / min.
The slide valve 80 at the lower end of the stripping unit 18 keeps the level of the catalyst fluidized bed in the stripping unit 18 constant, and prevents the metal adhering catalyst to the deactivator 14 while preventing the backflow from the deactivator 14. Transport. The temperature of the stripping section 18 is maintained at 350 ° C.
[0034]
The metal adhesion catalyst re-supplied to the deactivator 14 is brought into contact with air and a high-temperature steam atmosphere together with a new catalyst continuously introduced from the continuous catalyst supply device 12, and is baked in high-temperature air at 800 ° C. Is fully supported by the catalyst and at the same time is steamed by high-temperature steam and forcedly deteriorates.
[0035]
Control of catalyst circulation rate
In this manufacturing apparatus 10, the catalyst circulation amount is controlled by the valve opening degree of the slide valves 66 and 80, and can be controlled in the range of 10 to 100 g / min.
In the start-up state of the production apparatus 10, the amount of catalyst present in the system is small, and therefore the circulation rate is set low and the operation is performed at 20 g / min. As the operation of the production apparatus 10 continues, the amount of catalyst present in the system increases. Therefore, it is necessary to increase the catalyst circulation rate as the catalyst amount increases, and the circulation rate is increased to 70 g / min at the end of the operation. These circulation amounts are all controlled by the valve openings of the slide valves 66 and 80, and the amount of gas introduced for conveyance is not changed.
In general, the larger the catalyst circulation amount, the better. Also, the deactivator 14 has a shorter residence time.
[0036]
Since the level of the deactivator 14 is low at the initial stage of operation, if the catalyst circulation amount is increased, the nitrogen gas fed into the catalyst transfer pipe 21 flows back to the deactivator 14 through the slide valve 64, which is not preferable. However, even if the catalyst circulation rate is initially reduced, the residence time does not increase because the catalyst amount itself is small.
At the end of operation, both the amount of catalyst and the amount of catalyst circulation are large, and as a result, the residence time of the deactivator 14 is short and substantially the same as the initial time. In operating the production apparatus 10, in order to obtain an equilibrium catalyst having a good distribution of the new catalyst and the metal adhesion catalyst, it is important to control the residence time and the circulation rate.
[0037]
(2) Steady operation of the device
Through the above steps, the deactivator 14 reaches a steady state in which the new catalyst and the metal adhesion catalyst are mixed.
[0038]
(3) End of equipment operation
When the supply of the new catalyst from the continuous catalyst supply device 12 is finished, that is, when the entire amount of the catalyst charged into the catalyst tank 22 has been transferred, the production of the equilibrium catalyst of this embodiment is finished. However, when it is desired to further deteriorate the catalyst, it is possible to circulate the catalyst without newly supplying the catalyst and to perform only the deterioration due to high-temperature steam.
[0039]
In the following procedure, the new catalyst supplied into the deactivator 14 and the metal adhering catalyst are circulated in the system as a mixed catalyst, and the new catalyst and the metal adhering catalyst are distributed in the manufacturing apparatus 10. Is present.
This is the greatest feature of the present apparatus. In the conventional simulation equilibration method and the apparatus for carrying out the same, there is no distribution of the new catalyst and the metal adhesion catalyst, and the catalyst is uniformly forcibly deteriorated.
[0040]
The equilibrium catalyst obtained by the present embodiment is very close to the properties of the equilibrium catalyst of the actual apparatus as shown in Table 2 below.

The state in which a large amount of Ni in the equilibrium catalyst of the present embodiment is distributed on the particle surface and the state in which V is uniformly distributed in the particle indicate the distribution of Ni and V in the equilibrium catalyst of the actual apparatus by EPMA measurement. 5 (a) and 5 (b), respectively, and FIGS. 4 (a) and 4 (b) showing the distribution of Ni and V in the equilibrium catalyst of the present embodiment, respectively, the actual apparatus It is very close to the equilibrium catalyst.
[0041]
Further, in order to evaluate the equilibrium catalyst obtained by this embodiment, the equilibrium catalyst of this embodiment, the equilibrium catalyst obtained from the actual apparatus, and the simulated equilibrium catalyst adjusted by the Mitchell method are used for the test apparatus. The raw oil was subjected to catalytic cracking reaction, and the results shown in Table 3 were obtained.
In this test, 2500 ppm of Ni and 5000 ppm of V were attached to any of the catalysts, and an equal amount of mixed oil of vacuum gas oil and desulfurized heavy oil was used as a raw material oil.
[Table 3]

As can be seen from Table 3, the equilibrium catalyst of the present embodiment is very close to the decomposition performance of the equilibrium catalyst obtained from the actual apparatus. On the other hand, the simulated equilibration catalyst prepared by the conventional Mitchell method decomposes the equilibrium catalyst obtained from the actual equipment in various points, particularly in terms of the generation rate of coke, hydrogen gas and light hydrocarbon gas on the catalyst. It is quite free from performance.
Therefore, when evaluating the raw material oil cracking performance of the catalyst, the raw material oil cracking performance of the catalyst in the actual device is extremely improved by testing with the test equipment using the equilibrium catalyst obtained by the method for producing the balanced catalyst according to the present invention. It can be estimated with high closeness.
[0042]
【The invention's effect】
According to the method of the present invention, the new catalyst and the metal adhesion catalyst are heated to a predetermined temperature, the new catalyst and the metal adhesion catalyst are calcined and steamed, and the mixed catalyst comprising the new catalyst and the metal adhesion catalyst is continuously sent out. Temperature rise / firing / steaming process, cooling process for cooling the mixed catalyst to a predetermined cooling temperature, and atomized solution generated by atomizing a metal solution with an inert gas is attached to the mixed catalyst to adhere the solution. The catalyst is heated to a predetermined temperature and dried to continuously produce a metal-attached catalyst, and the mixed catalyst is stripped by introducing an inert gas, and the solvent vapor attached to the mixed catalyst is separated. A stripping process for continuously feeding the metal-adhered catalyst obtained in this manner, and introducing the new catalyst into the temperature raising / firing / steaming process, By circulating between the mappings step, the simulated catalyst very close to the equilibrium catalyst in the actual device can be prepared.
The device of the present invention realizes an optimum device for carrying out the method of the present invention.
[Brief description of the drawings]
FIG. 1 is a flow sheet showing the configuration of an equilibrium catalyst production apparatus according to an embodiment.
FIG. 2 is a schematic cross-sectional view showing a configuration of a continuous catalyst supply apparatus.
FIG. 3 is a cross-sectional view of an atomizer.
FIGS. 4 (a) and 4 (b) are photocopies showing the loading status of V and Ni of the equilibrium catalyst obtained by the method of manufacturing the equilibrium catalyst of the embodiment, respectively.
FIGS. 5 (a) and 5 (b) are photocopies showing the state of loading of V and Ni on the equilibrium catalyst obtained from the actual apparatus, respectively.
[Explanation of symbols]
10. Apparatus for producing equilibrium catalyst according to embodiment
12 Catalyst continuous supply device
14 Deactivator
16 Metal adhesion part
18 Stripping section
20 Metal adhesion catalyst formation tower
21 Catalyst transfer pipe
22 Catalyst tank
24 Lifting device
26 Lower support plate
28 Screw holes
30 Screw rod
32 Climbing plate
34A, B Guide rod
38 Upper support plate
40 lids
42 Lower inlet
43 Gas distribution chamber
44 Dispersion plate
46 Through hole
48 Catalyst transfer pipe
50 bellows tube
51 Upper inlet
52 Cylindrical part
54 Reverse cone
56 Metal adhesion catalyst transfer pipe
58 Catalyst introduction pipe
60 Air / steam inlet pipe
62 Cyclone
64 Slide valve
65, 66 inlet
68 atomizer
70 Cyclone
72 Inner pipe
74 Nitrogen gas nozzle
76 Outer pipe
78 Introduction
80 Slide valve

Claims

A catalyst in a catalyst fluidized bed in which a new catalyst and a deactivated catalyst in which the new catalyst contributes to the catalytic reaction and its catalytic activity is reduced, that is, a simulated catalyst that approximates the shape and properties of the equilibrium catalyst A method of manufacturing comprising:
Continuously supplying new catalyst from the catalyst tank;
The supplied new catalyst and the metal-attached catalyst with metal attached are introduced into a mixed atmosphere of air and high-temperature steam, and the temperature of the new catalyst and the metal-attached catalyst is increased to a predetermined temperature. Firing and steaming process, and continuously raising the mixed catalyst consisting of the treated new catalyst and metal adhesion catalyst, firing, steaming process,
A transfer step of transferring the mixed catalyst while maintaining a high temperature state;
A cooling step for cooling the transferred mixed catalyst to a predetermined cooling temperature;
A spray solution prepared by atomizing a metal solution in which a metal or metal compound is dissolved in an inert gas with an inert gas is attached to the mixed catalyst, the temperature is increased, and the solvent is evaporated to continuously produce a metal-attached catalyst. A metal adhesion process;
A stripping step of continuously feeding the metal adhering catalyst obtained by introducing an inert gas to strip the mixed catalyst and separating the vapor of the solvent adhering to the mixed catalyst;
The metal-attached catalyst that has undergone the stripping process is continuously sent to the temperature raising, firing, and steaming process, and the new catalyst and the metal-attached catalyst are heated and introduced while the new catalyst is introduced into the temperature raising, firing, and steaming process. A method for producing an equilibrium catalyst comprising circulating between a calcination / steaming step and a stripping step.

2. The method for producing an equilibrium catalyst according to claim 1, wherein in the metal attaching step, after the metal solution is attached to the cooled mixed catalyst, the temperature of the mixed catalyst is raised to a predetermined temperature.

In the temperature raising, firing, and steaming process, air and high-temperature steam are introduced into the lower part of the catalyst layer composed of a mixture of a new catalyst and a metal-attached catalyst, and the catalyst layer is fluidized to create a mixed atmosphere of air and high-temperature steam. The catalyst is exposed to raise the temperature of the new catalyst and the metal-attached catalyst to a predetermined temperature, and the new catalyst and the metal-attached catalyst are calcined and steamed,
In the stripping step, an inert gas is introduced into the lower part of the catalyst layer of the metal adhesion catalyst, and the metal adhesion catalyst is stripped while fluidizing to separate the vapor of the solvent adhering to the metal adhesion catalyst. Item 3. The method for producing an equilibrium catalyst according to Item 1 or 2.

In the temperature raising / firing / steaming process, the temperature of the new catalyst and the metal adhesion catalyst is raised to a temperature in the range of 500 to 1200 ° C., and in the transfer process, the catalyst is transferred while maintaining the temperature in the range of 300 ° C. to 400 ° C. The mixed catalyst is cooled to a temperature in the range of 10 to 50 ° C. in the cooling step, the mixed catalyst is heated to a temperature in the range of 100 to 250 ° C. in the metal adhesion step, and the temperature in the range of 200 to 500 ° C. in the stripping step. The method for producing an equilibrium catalyst according to claim 2 or 3, wherein the metal-deposited catalyst is maintained at a temperature of 5%.

A catalyst in a catalyst fluidized bed in which a new catalyst and a deactivated catalyst in which the new catalyst contributes to the catalytic reaction and its catalytic activity is reduced, that is, a simulated catalyst that approximates the shape and properties of the equilibrium catalyst An apparatus for manufacturing,
In a mixed atmosphere of air and high-temperature steam, the supplied new catalyst and metal-deposited catalyst are heated to a predetermined temperature, and the new catalyst and metal-deposited catalyst are calcined and steamed to reduce the catalytic activity, and as a mixed catalyst A deactivator to send,
Metal adhering catalyst is formed by atomizing a metal solution in which a metal or metal compound is dissolved in an inert gas with an inert gas and attaching a spray-like solution to the mixed catalyst to form a metal adhering catalyst. A metal-attached catalyst-forming tower that is provided with a stripping section for separating the vapor of the solvent attached to the lower part, and continuously sends the metal-attached catalyst to the deactivator;
A continuous catalyst supply device for continuously supplying a new catalyst to the deactivator;
An apparatus for producing an equilibrium catalyst, comprising: a transport unit that transports the mixed catalyst flowing out from the deactivator to the metal-attached catalyst forming tower by gas transport while cooling.

The apparatus for producing an equilibrium catalyst according to claim 5, further comprising heating means for heating the catalyst in the metal adhering portion and the stripping portion of the metal adhering catalyst forming tower.

The deactivator introduces air and high-temperature steam into the lower part of the catalyst layer consisting of a mixture of a new catalyst and metal-attached catalyst, fluidizes the catalyst layer, and attaches the new catalyst and metal to the mixed atmosphere of air and high-temperature steam. The apparatus for producing an equilibrium catalyst according to claim 5 or 6, wherein the catalyst is exposed to the mixture, the temperature is raised to a predetermined temperature, and the new catalyst and the metal adhesion catalyst are calcined and steamed.

The metal adhering catalyst formation tower is characterized by stripping the vapor of the solvent adhering to the metal adhering catalyst with the inert gas while introducing the inert gas into the lower part of the catalyst layer of the metal adhering catalyst and fluidizing the metal adhering catalyst. The apparatus for producing an equilibrium catalyst according to any one of claims 5 to 7.

9. A slide valve is provided between the deactivator and the transfer means and between the stripping part of the metal-deposited catalyst forming tower and the deactivator, respectively. The apparatus for producing an equilibrium catalyst according to any one of the above items.