JP5322307B2 - 改善された触媒組成物 - Google Patents
改善された触媒組成物 Download PDFInfo
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- JP5322307B2 JP5322307B2 JP2009509518A JP2009509518A JP5322307B2 JP 5322307 B2 JP5322307 B2 JP 5322307B2 JP 2009509518 A JP2009509518 A JP 2009509518A JP 2009509518 A JP2009509518 A JP 2009509518A JP 5322307 B2 JP5322307 B2 JP 5322307B2
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- catalyst
- proton density
- proton
- catalyst sample
- sample
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- DEQLTFPCJRGSHW-UHFFFAOYSA-N hexadecylbenzene Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1 DEQLTFPCJRGSHW-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LIXVMPBOGDCSRM-UHFFFAOYSA-N nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1 LIXVMPBOGDCSRM-UHFFFAOYSA-N 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- BEZDDPMMPIDMGJ-UHFFFAOYSA-N pentamethylbenzene Chemical compound CC1=CC(C)=C(C)C(C)=C1C BEZDDPMMPIDMGJ-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000000264 spin echo pulse sequence Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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Description
本発明の非限定的な実施例に用いた装置及び原料の予備処理方法を以下で説明する。
撹拌棒及び固定された触媒バスケットを備えた300mlのパー(Parr)バッチ反応管を活性及び選択性の測定のために用いた。反応管は、ベンゼン及びプロピレンをそれぞれ導入するための2つのリムーバブル管が取り付けられていた。
市販グレードのベンゼンをモレキュラーシーブ13X、モレキュラーシーブ4A、Engelhard F−24クレイ、及びSelexsorb CDを用いて調製した。市販の特定の気相源から得られたポリマーグレードのプロピレンをモレキュラーシーブ5A及びSelexsorb CDを用いて調製した。市販の特定の気相源から得られた超高純度の窒素をモレキュラーシーブ5A及びSelexsorb CDを用いて調製した。全ての原料処理物質は使用する前に260℃で12時間乾燥させた。以下でいうベンゼン、プロピレン、及び窒素は、それぞれ、市販グレードのベンゼンポリマーグレードのプロピレン、及び超高純度の窒素を意味し、本明細書に記載のように前処理されたものを意味する。
本発明において、触媒サンプルのプロトン密度を決定するためのNMR法を以下のように行った。触媒サンプルのプロトン密度は、図1に示すようなシャローベッド(shallow bed)CAVERNデバイスを用いて決定した。図1のように、CAVERNデバイスは、上部ハウジング5及び下部ハウジング6からなり、ジョイント12で結合されており、触媒床14の上にガラスのトラップドア16を持ち上げるための機構11、バキュームライン20に用いる装置、及びサーモカップル13を介した加熱手段を有する。外径5mmのガラスチューブ17を3mmのステンレススチロールロッド15上にスライドして、該ロッドを覆うようにし、エンドキャップ18とガラストトラップドア16の間に位置させる。ステンレススチールロッド15は機構11を回転させることにより後退し、それによりガラスチューブ17が触媒床14の上に、ガラストラッパー16を持ち上げる。CAVERNデバイスを緩やかに回転又は振ることにより、触媒サンプル(示さず)がMASローター19の中に落ちる。この方法はゼオライト及び酸化金属の粉末に有効である。CAVERNデバイスの操作に関しての詳細は、Xu,T.、Haw,J.F.Top.Catal.1997,4,109−118に記載されている。該文献を参照により本明細書に援用する。
特定の触媒組成物のPDIは、元の未処理の触媒組成物のプロトン密度に対する新たに処理された触媒組成物のプロトン密度の比で決定される。そのような新たに処理された触媒組成物は本明細書で説明するプロトン調節技術又はプロトン密度を変更することができる他の技術を用いて処理される。オリジナルの未処理の触媒組成物は、本明細書で説明するプロトン調節技術又はプロトン密度を変更することができる他の技術を用いて処理されていてもよく、処理されていなくてもよい。前述のように、「プロトン密度」の語は触媒組成物1グラム当たりの酸性プロトン及び/又は非酸性プロトンのミリモル(mmol)数を意味する。新たに処理された触媒組成物のプロトン密度及びオリジナルの未処理の触媒組成物のプロトン密度は同じ温度、例えば、約20℃乃至約25℃の室温で測定される。それゆえ、特定の触媒組成物のPDIは、所与の温度で測定された新たに処理された触媒組成物を、同じ所与の温度で測定されたオリジナルの未処理の触媒組成物のプロトン密度で割って決定される。
反応性試験のための触媒組成物を調製するために、特定量の触媒サンプルを、空気の存在下、ex−situ乾燥温度(以下、「特定のEx−suit乾燥温度」という)のオーブン内で2時間乾燥させた。この触媒サンプルをオーブンから出し、重量を測定した。水晶チップをバスケットの下に敷き、触媒サンプルを水晶の第一層の上のバスケットに入れた。次いで、水晶チップを触媒サンプルの上においた。触媒サンプル及び水晶を含む前記バスケットを空気存在下、特定のEx−situ乾燥温度のオーブン内で16時間乾燥させた。
A.プロトン含量調節技術#1
本発明の1つの態様において、酸性細孔性結晶性物質を含み、触媒1グラム当たりのプロトンのミリモル数で測定される第一水和状態を有する触媒サンプルを適したコンテナ内に置く。液体の水、特に脱イオン水をコンテナ内に下からゆっくりと入れ、触媒サンプルから空気を抜いた。サンプルが水に完全に浸るまで水を入れ、水のレベルが触媒サンプルの上方約1/4”(0.635cm)に達した。前記触媒サンプル及び水を、少なくとも約1秒、好ましくは約1分乃至約60分、又は以上の特定の接触時間(以下、「接触時間」という)静置して、第二水和状態を有する触媒サンプルを生成した。前記第二水和状態は(触媒1グラム当たりのプロトンのミリモル数で測定して)前記第一水和状態よりも高い値を有する。前記接触時間の後、前記水を別の容器に注ぎ、前記触媒サンプルを少なくとも8時間室温で風乾し、(触媒サンプル1グラム当たりのミリモル数で測定される)第三水和状態を有する触媒サンプルを得た。
触媒のサンプルは気相(窒素等の適切な担体を含んでいてもいなくてもよい)中で、特定の接触温度(以下、「接触温度」という)及び特定の接触圧力(以下、「接触圧力」という)において、水に接触させられる。
実施例1の触媒サンプルは80重量%のMCM−49及び20重量%のアルミナ(Al2O3)から成る。このプロトン密度は250℃の特定のNMR前処理温度で、前述のプロトン密度測定のためのNMR手順で決定した。前記プロトン密度は触媒1グラム当たり1.71mmol(第一水和状態)であった。
実施例1の触媒サンプルの別の一部分を約1時間の特定の接触時間でプロトン含量調節技術#1を用いて処理をして、第三水和状態を有する実施例2の処理された触媒サンプルを得た。この処理された触媒サンプルの第三水和状態のプロトン密度は、250℃の特定のNMR前処理温度において、前述の方法でプロトン密度を決定するためのNMR方法を用いて測定して、触媒1グラム当たり1.85mmol(第三水和状態)であった。
実施例3の触媒サンプルは80重量%のゼオライトベータ及び20重量%のアルミナからなる。このプロトン密度は250℃の特定のNMR処理温度で、前述のプロトン密度測定のためのNMR手順で決定した。前記プロトン密度は触媒1グラム当たり2.48mmol(第一水和状態)であった。
実施例3の触媒サンプルの別の一部分について、約1時間の特定の接触時間でプロトン含量調節技術#1を用いて試験を行い、第三水和状態を有する実施例4の処理された触媒サンプルを得た。この処理された触媒サンプルのプロトン密度は、250℃の特定のNMR前処理温度において、前述の方法でプロトン密度を決定するためのNMR方法を用いて測定して、触媒1グラム当たり2.77mmol(第三水和状態)であった。
実施例1の触媒サンプルを、200℃の接触温度及び445kPa−a(50psig)の接触圧力で、プロトン含量調節技術#2に従って、水蒸気で飽和された窒素で処理した。得られた触媒をプロトン含量調節技術#1で処理し、第三水和状態を有する実施例5の処理された触媒サンプルを得た。この処理された触媒サンプルのプロトン密度は、250℃の特定のNMR前処理温度において、前述の方法でプロトン密度を決定するためのNMR方法を用いて測定して、触媒1グラム当たり1.76mmol(第三水和状態)であった。
実施例6の触媒サンプルは80重量%のMCM−49及び20重量%のアルミナから成る。このプロトン密度は150℃の特定のNMR前処理温度で、前述のプロトン密度測定のためのNMR手順で決定した。前記プロトン密度は触媒1グラム当たり2.59mmol(第一水和状態)であった。
実施例6の触媒サンプルの別の一部分について、約1時間の特定の接触時間でプロトン含量調節技術#1を用いて試験を行い、第三水和状態を有する実施例7の処理された触媒サンプルを得た。この処理された触媒サンプルの第三水和状態のプロトン密度は、150℃の特定のNMR前処理温度において、前述の方法でプロトン密度を決定するためのNMR方法を用いて測定して、触媒1グラム当たり3.16mmol(第三水和状態)であった。
この実施例の触媒サンプルは65重量%のMCM−22及び35重量%のアルミナからなる。このプロトン密度は250℃の特定のNMR処理温度で、前述のプロトン密度測定のためのNMR手順で決定した。前記プロトン密度は触媒1グラム当たり1.46mmol(第一水和状態)であった。
少なくとも1部分を失活させた実施例8のサンプルの一部分を以下の2工程で再生した。第一に、前記触媒サンプルを2.0容量%の水素及び炭化水素を有する雰囲気下で385℃の温度で加熱した。酸素濃度を最初に0.4容量%に増やし、その後、触媒温度が最高で467℃に達する間に、再度0.7容量%に増やした。次に、0.7容量%の酸素濃度を有する101kPa−a(1気圧)中で触媒を450℃に加熱し、最大触媒温度を510℃に維持する間に酸素濃度を7.0容量%に増やした。
実施例6の触媒サンプルを水蒸気で飽和した窒素中で、220℃の接触時間及び445kPa−a(50psig)の接触圧力で、プロトン含量調節技術#2に従って処理した。得られた触媒サンプルをプロトン含量調節技術#1で処理し、第三水和状態を有する実施例10の処理された触媒サンプルを得た。前記処理された触媒サンプルのプロトン密度は150℃の特定のNMR前処理温度で、前述のプロトン密度を調節するためのNMR手順を用いて決定した。前記プロトン密度は触媒1グラム当たり2.67mmolであった(第三水和状態)。
実施例11の触媒サンプルは非結晶性のタングステンジルコニア(WZrO2)からなる。250℃の特定のNMR前処理温度で、前述のように、プロトン密度を決定するためのNMR方法に従ってこのプロトン密度を決定した。前記プロトン密度は触媒1グラム当たり0.37mmolであった(第一水和状態)。
実施例11の触媒サンプルを約1時間の接触時間で、プロトン含量調節技術#1に従って、処理して、第三の水和状態を有する実施例12の処理された触媒サンプルを生成した。処理されたサンプルのプロトン密度は250℃の特定のNMR前処理温度で、前述のように、プロトン密度を決定子するためのNMR方法に従って決定して、触媒1グラム当たり0.41mmolであった(第三水和状態)。
Claims (7)
- 触媒組成物を生成する方法であって、前記方法は、
(a)第一水和状態を有し、MWW構造タイプの物質である酸性細孔性結晶性物質を含み、第一プロトン密度を有する第一触媒を提供する工程、
(b)500℃までの接触温度で液体又は気体状態の水と前記第一触媒を接触させて、プロトンを付加し第二プロトン密度を有する第二触媒を生成する工程であって、前記第二プロトン密度の値は、同じ条件下で測定した第一プロトン密度の値よりも大きいようにする工程、及び
(c)工程(b)の第二触媒を約550℃までの乾燥温度で乾燥して、前記第二触媒から少なくとも1つのプロトンを除去して第三プロトン密度を有する触媒組成物を生成する工程であって、前記触媒組成物の触媒活性が前記第二触媒の触媒活性よりも大きく、前記第三プロトン密度の値は、同じ条件下で測定した、第一プロトン密度の値及び第二プロトン密度の値の間にあるようにする工程、を含む方法。 - 前記MWW構造タイプの物質が、MCM−22、PSH−3、SSZ−25、ERB−1、ITQ−1、ITQ−2、ITQ−30、MCM−36、MCM−49、MCM−56、及びこれらの混合物からなる群より選択される、請求項1の方法。
- 前記工程(b)が約1℃乃至約99℃の接触温度で約1分乃至約60分行われる、請求項1の方法。
- 前記工程(c)が約100℃乃至約200℃の乾燥温度で約0.01乃至約24時間行われる、請求項1の方法。
- 工程(c)で得られた触媒組成物が1.0より大きく2.0未満のプロトン密度指数を有する、請求項1の方法。
- 工程(c)で得られた前記触媒組成物が約1.01乃至約1.85のプロトン密度指数を有する、請求項5の方法。
- 前記第三プロトン密度が触媒1グラム当たり2.24mmolより大きい、請求項6の方法。
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