JP2017504480A - エチレン反応における触媒活性化のための改変された予備形成方法 - Google Patents
エチレン反応における触媒活性化のための改変された予備形成方法 Download PDFInfo
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- JP2017504480A JP2017504480A JP2016561091A JP2016561091A JP2017504480A JP 2017504480 A JP2017504480 A JP 2017504480A JP 2016561091 A JP2016561091 A JP 2016561091A JP 2016561091 A JP2016561091 A JP 2016561091A JP 2017504480 A JP2017504480 A JP 2017504480A
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- chromium
- ethylene
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- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
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- 239000011651 chromium Substances 0.000 claims abstract description 37
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 31
- 239000003446 ligand Substances 0.000 claims abstract description 30
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- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 7
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Classifications
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- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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- B01J2531/62—Chromium
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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Abstract
Description
[エチレンの三量化]
300ml圧力反応器は、ディップチューブと、サーモウェルと、ガス同伴性撹拌器(gas entrainment stirrer)と、冷却コイルと、温度、圧力および撹拌速度の制御ユニットとを備えていた。圧力反応器の構成部品はそれぞれ、データ収集システムに接続した。圧力反応器を乾燥窒素で不活性化し、それに無水トルエン100mlを充填した。トルエン1.5ml中のリガンド((フェニル)2PN(イソプロピル)P(フェニル)NH(イソプロピル))68mgを、窒素雰囲気下でCrCl3(thf)3(thf=テトラヒドロフラン)37mgと混ぜ合わせた。この触媒溶液を、反応器に移す前に、トルエン中のトリエチルアルミニウム(TEA)の1.9mol/l溶液1.7mlと共に、一定量の窒素を流しながら、様々な時間にわたり撹拌した。
[改変されたエチレン三量化]
図4には、クロム化合物およびリガンドについての標準生産時(生成物60kg)の曲線と、最適化されていない、より長い予備活性化時間を持つ曲線(下段部の曲線)、および最適化された、より短い予備活性化時間を持つ曲線(中段部の曲線)という2つの曲線とが示されている。これらの曲線は、クロムおよびその他の触媒成分の濃度が同じであるとき、最適化されていない、より長い活性化時間が、低い活性につながることを示している。上段部および下段部の線は、同じ活性化時間を有するものだったが、高いクロム濃度を有していた(上段部の線で0.1mmol、中段部の線で0.025)。これは、生成量増加が、濃度の効果ではなく、主に予備活性化の効果であることを示している。
Claims (20)
- 触媒性能を向上させるための方法、好ましくはエチレンのオリゴマ化における触媒性能を向上させるための方法、より好ましくはエチレンの1−ヘキセンへの三量化における触媒性能を向上させるための方法であって、
少なくとも1種のリガンドと少なくとも1種のクロム源とを少なくとも1種の溶媒中で予備混合して、予備混合組成物を形成する工程と、
前記予備混合組成物を活性化剤により活性化して、活性化組成物を形成する工程と、および
予備の前記活性化組成物を反応器に供給する工程と、
を含むことを特徴とする方法。 - 請求項1に記載の方法であって、前記リガンドが、((フェニル)2PN(イソプロピル)P(フェニル)NH(イソプロピル))であることを特徴とする方法。
- 請求項1から2のいずれか1項に記載の方法であって、前記クロム源が、塩化クロム、クロムアセチルアセトナート、またはこれらの少なくとも1つを含む組合せであることを特徴とする方法。
- 請求項1から3のいずれか1項に記載の方法であって、前記溶媒が、トルエンを含むことを特徴とする方法。
- 請求項1から4のいずれか1項に記載の方法であって、前記溶媒が、約0.1%〜約95%の間の濃度で供給されることを特徴とする方法。
- 請求項1から5のいずれか1項に記載の方法であって、前記活性化剤が、トリエチルアルミニウムであることを特徴とする方法。
- 請求項1から6のいずれか1項に記載の方法であって、前記活性化する工程が、前記予備混合組成物を前記活性化剤と前記反応器の外で混合し、撹拌する工程を含むことを特徴とする方法。
- 請求項7に記載の方法であって、前記混合の時間が、約1分〜約18時間の間であることを特徴とする方法。
- エチレンのオリゴマ化における触媒性能を向上させるための方法、より好ましくはエチレンの1−ヘキセンへの三量化における触媒性能を向上させるための方法であって、
((フェニル)2PN(イソプロピル)P(フェニル)NH(イソプロピル))と少なくとも1種のクロム源とをトルエン中で予備混合して、予備混合組成物を形成する工程と、
前記予備混合組成物を活性化剤により活性化して、活性化組成物を形成する工程と、および
予備の前記活性化組成物を反応器に供給する工程と、
を含むことを特徴とする方法。 - 請求項9に記載の方法であって、前記クロム源が、塩化クロム、クロムアセチルアセトナート、またはこれらの少なくとも1つを含む組合せであることを特徴とする方法。
- 請求項9または10に記載の方法であって、前記トルエンが、約0.1%〜約95%の間の濃度で供給されることを特徴とする方法。
- 請求項9から11のいずれか1項に記載の方法であって、前記活性化剤が、トリエチルアルミニウムであることを特徴とする方法。
- 請求項9から12のいずれか1項に記載の方法であって、前記活性化する工程が、前記反応器の外で混合し、撹拌する工程を含むことを特徴とする方法。
- 請求項13に記載の方法であって、前記混合の時間が約1分〜約18時間の間であることを特徴とする方法。
- 触媒性能を向上させるためのシステム、好ましくはエチレンのオリゴマ化における触媒性能を向上させるためのシステム、より好ましくはエチレンの1−ヘキセンへの三量化における触媒性能を向上させるためのシステムであって、
1種または複数種のリガンドと、1種または複数種のクロム源と、1種または複数種の溶媒と、1種または複数種の活性化剤との投入物を受け入れるための予備混合チャンバと、
1つまたは複数の撹拌器と、および
予備活性化した予備形成組成物を受け取るために、前記予備混合チャンバと流体連通した反応槽と、
を備えることを特徴とするシステム。 - 請求項15に記載のシステムであって、前記1種または複数種のリガンドおよび1種または複数種のクロム源が同時に供給されることを特徴とするシステム。
- 請求項15または16に記載のシステムであって、前記リガンドが、((フェニル)2PN(イソプロピル)P(フェニル)NH(イソプロピル))であることを特徴とするシステム。
- 請求項15から17のいずれか1項に記載のシステムであって、前記クロム源が、塩化クロム、クロムアセチルアセトナート、およびこれらの組合せであることを特徴とするシステム。
- 請求項15から18のいずれか1項に記載のシステムであって、前記溶媒が、トルエンであることを特徴とするシステム。
- 請求項15から18のいずれか1項に記載のシステムであって、前記活性化剤が、トリエチルアルミニウムであることを特徴とするシステム。
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US20120041241A1 (en) * | 2009-02-16 | 2012-02-16 | Sean William Ewart | Oligomerisation of olefinic compounds in the presence of an activated oligomerisation catalyst |
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