TW201716360A - 使用含有矽及鉬之催化劑進行烯烴歧化之方法 - Google Patents
使用含有矽及鉬之催化劑進行烯烴歧化之方法 Download PDFInfo
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- TW201716360A TW201716360A TW105124191A TW105124191A TW201716360A TW 201716360 A TW201716360 A TW 201716360A TW 105124191 A TW105124191 A TW 105124191A TW 105124191 A TW105124191 A TW 105124191A TW 201716360 A TW201716360 A TW 201716360A
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- molybdenum
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Abstract
本發明係關於利用催化劑實施烯烴歧化之方法,該催化劑包含中孔性基質及至少元素鉬及矽,該等元素係藉由至少一種包含鉬及矽且具有至少一個Si-O-Mo鍵序列之前驅物併入至該基質中。
Description
烯烴歧化在各種化學領域中係重要反應。在有機合成中,使用藉由有機金屬錯合物催化之此反應來獲得各種高附加值分子。在石油化學中,烯烴歧化具有重大實際利益,尤其對於再平衡來源於蒸汽裂解之輕烯烴(例如乙烯、丙烯及丁烯)而言。具體而言,鑒於市場上丙烯使用增加,使乙烯與2-丁烯交叉歧化以產生丙烯係所關注之反應。
不同類型之催化劑均能夠用於歧化反應中。可使用其組成元素均可溶於反應介質中之均相催化劑或不溶於反應介質中之異相催化劑。
輕烯烴之歧化利用異相催化劑。已知之解決方案係闡述於專利US 8,586,813,2013中之技術,其使用基於沈積於二氧化矽載體上之氧化鎢WO3/SiO2之催化劑。然而,基於鎢之異相催化劑係在相對較高之溫度下(通常在大於300℃之溫度下)操作且僅具中等活性。
此外,已知基於氧化錸Re2O7之歧化催化劑(例如闡述於Chauvin等人之出版物Journal of Molecular Catalysis 1991,65,39中之彼等)在接近於環境溫度之溫度下具有良好活性。亦已開發其他基於氧化鉬之
催化劑,例如闡述於出版物D.P.Debecker等人,J.Catal.,2011,277,2,154中及Shell公司所擁有之專利GB 1,164,687及GB 1,117,968中之彼等。Shell之方法使用(例如)基於沈積於鋁載體上之鉬及鈷氧化物CoMoO4/Al2O3且摻雜有磷之催化劑,如專利US 4,754,099中所述。
鉬(Mo)之一個益處在於其較錸(Re)便宜。另外,其穩定性及其活性係介於錸(Re)與鎢(W)中間。特別地,鉬可自環境溫度起始具有活性。
製備基於氧化鉬(MoO3)之催化劑係以標準方式藉由在諸如二氧化矽、氧化鋁或多孔鋁矽酸鹽之載體上用鉬鹽或含有鉬之雜多陰離子(例如同多陰離子七鉬酸銨)之水溶液浸漬來實施。然而,自七鉬酸銨類型之前驅物製備之催化劑缺少活性及穩定性。已製備出基於其他雜多陰離子(例如H3PMo12O40)之催化劑,且其可顯著地增加活性,但需要進一步改良。
因此,業內仍需要開發針對烯烴之歧化反應且更具體而言針對用於產生丙烯之乙烯與2-丁烯之間之歧化就活性及選擇性而言具有改良性能之新穎催化劑。
本申請人在其改良用於烯烴歧化之異相催化劑之性能之研究中已開發出用於烯烴之歧化反應之新穎催化劑。該等催化劑係自中孔性基質及至少一種前驅物製備,前驅物包含鉬及矽且具有至少一個Si-O-Mo鍵序列。出人意料地,已發現,與使用不具有Si-O-Mo鍵序列之先前技術之其他前驅物製備之催化劑相比,使用該等類型之前驅物製備本發明之催化劑使所獲得之用於烯烴之歧化反應之異相催化劑之活性及穩定性得以改良。因此,烯烴之轉化得以改良。催化劑之穩定性亦得以改良。
本發明之目標係提供使用催化劑進行烯烴歧化之方法,該催化劑就活性及選擇性而言與使用先前技術之異相催化劑相比具有改良性
能。
根據本發明之催化劑具有能夠在再生前操作更長時間週期之優點,此對於本發明之方法之操作成本具有顯著經濟影響。
本發明係關於藉由使烯烴與催化劑接觸來實施烯烴之歧化之方法,該催化劑包含中孔性基質及至少元素鉬及矽,該等元素係藉由至少一種包含鋁及矽且具有至少一個Si-O-Mo鍵序列之前驅物併人至該基質中。
有利地,根據本發明之前驅物係含有矽氧基配體且包含至少一個Si-O-Mo鍵序列之鉬配位錯合物及/或包含至少一個Si-O-Mo鍵序列之基於鉬之雜多陰離子類型之前驅物。
當根據本發明之前驅物係含有矽氧基配體之鉬配位錯合物時,其有利地對應於式(I)Mom(=Y)n(≡N)n’(X)z(=CR2)r(OSiR3)p (I)其中-彼此相同或不同之Y基團可選自O、S及NR’,-彼此相同或不同之X基團可選自鹵化物,例如F、Cl、Br、I;經取代或未經取代之烷基、環烷基或芳基;經取代或未經取代之環戊二烯基;烷氧基;芳氧基;矽氧基;醯胺;氫基;硝基;羧酸鹽;乙醯基丙酮酸鹽;磺酸鹽;β-雙烯酮亞胺基;吡咯亞胺;脒基;硫氰酸鹽或NR2-CS2 -基,-彼此相同或不同之R基團可選自較佳包含於1與10個碳原子之間之經取代或未經取代之烷基、環烷基及芳基,或選自經取代或未經取代之烷氧基及芳氧基,-彼此相同或不同之R’基團可選自經取代或未經取代之烷基、環
烷基及芳基,-m等於1或2,-n係包含於0與4之間,-n’係包含於0與2之間,-z係包含於0與9之間,-r係包含於0與2之間,-p係包含於1與10之間。
有利地,當根據本發明之前驅物係含有矽氧基配體之鉬配位錯合物類型之前驅物時,其對應於式(Ia):Mom(≡N)n’(OSiR3)p (Ia)其中-彼此相同或不同之R基團可選自較佳包含於1與10個碳原子之間之經取代或未經取代之烷基、環烷基及芳基,或選自經取代或未經取代之環烷基及芳基,-m等於1或2,-n’係包含於0與2之間,-p係包含於1與10之間。
有利地,當根據本發明之前驅物係含有矽氧基配體之鉬配位錯合物類型之前驅物時,其對應於式(Ib)Mom(=O)n(OSiR3)p (Ib)其中-彼此相同或不同之R基團可選自較佳包含於1與10個碳原子之間之經取代或未經取代之烷基、環烷基及芳基,或選自經取代或未經取代之烷氧基及芳氧基,-m等於1或2,
-n係包含於0與4之間,-p係包含於1與10之間。
根據本發明,含有矽氧基配體之鉬配位錯合物類型之前驅物亦可在其配位層中含有一或多個L型配體、視情況多齒配體。L型配體可選自含磷化合物,例如膦、次膦酸鹽、亞膦酸鹽、亞磷酸鹽;含氧化合物,例如醚;含氮化合物,例如胺;含氮芳香族化合物,例如吡啶及/或啡啉;及/或含硫化合物,例如硫醚。
含有矽氧基配體之鉬配位錯合物類型之前驅物可(例如)選自以下化合物:MoO(OSiMe3)CN(CS2-NEt2)2、Mo(=N-(2,6-二-iPrC6H3))(tBu)(=CHtBu)(OSi(OtBu)3)、Mo(=S)(=NiPr)(OSitBu3)2、Mo(=O)(OSitBu3)4、Mo(≡N)(OSiPh3)3(C6H5N)或Mo2(OSiMe3)6。
當根據本發明之前驅物係基於鉬之雜多陰離子類型之前驅物時,其有利地對應於式(II)(SixMomMbOyHh)q-.nH2O (II)其中,●x至少等於1,●m大於或等於1,●b大於或等於0,●m+b大於或等於5,●y大於或等於20,●h係包含於0與12之間,●q係包含於1與20之間,●n係包含於0與200之間,●x、m、b、y、h、n及q係整數,M係除矽及鉬之外之金屬元素。
有利地,當根據本發明之前驅物係雜多陰離子類型之前驅物
時,其對應於式(II):(SixMomMbOyHh)q-.nH2O (II)其中,●x等於1或2,●m大於或等於1,●b大於或等於0,●m+b大於或等於5,●y係包含於20與50之間,●h係包含於0與12之間,●q係包含於3與12之間,●n係包含於0與200之間;●x、m、b、y、h、n及q係整數,M係選自鋁、鋅、鎳、鈷、鎢、釩、鈮、鉭、鐵及銅之金屬元素,較佳地M係選自鋁、鈷及鎢之金屬元素,更佳地選自鋁及鈷,且更佳地金屬元素M係鈷。
對應於式(II)之基於鉬之雜多陰離子類型之前驅物可以鹽之形式或以酸之形式併入中孔性基質中。在其中雜多陰離子類型之前驅物係以酸之形式併入之情形下,電荷q-由質子H+補償。當雜多陰離子係以鹽之形式引入時,雜多陰離子之鹽之反離子係選自熟習此項技術者已知之所有陽離子。舉例而言,可提及質子、銨、鏻、鹼金屬、鹼土金屬、過渡元素等。鹽可包含相同陽離子或不同陽離子之混合物。對應於式(I)、(Ia)或(Ib)之含有矽氧基配體之鉬配位錯合物類型之前驅物藉由其化學性質係以中性形式併入。
可使用一或多種對應於式(II)之基於鉬之雜多陰離子類型之前驅物。可使用一或多種對應於式(I)、(Ia)或(Ib)之含有矽氧基配體之鉬配位錯合物類型之前驅物。
基於鉬之雜多陰離子類型之前驅物可含有一或多種選自以下各
項之金屬元素M:鋁、鋅、鎳、鈷、鎢、釩、鈮、鉭、鐵及銅,取代上述式之該雜多陰離子前驅物中所含之一或多個鉬原子。較佳地,金屬元素M係選自鋁、鈷及鎢,更佳地選自鋁及鈷,且更佳地金屬元素M係鈷。
當用於製備本發明之歧化方法中所利用之催化劑之基於鉬之雜多陰離子類型之前驅物不含金屬元素M時,其有利地選自由以下各項形成之群:式Si2Mo5O23 8-. nH2O之Strandberg雜多陰離子、式SiMo6O24 8-之Anderson雜多陰離子、式SiMo12O40 4-. nH2O之Keggin雜多陰離子、式SiMo11O39 8-. nH2O之缺位Keggin雜多陰離子、式SiMo9O34 10-. nH2O之缺位Keggin雜多陰離子、式Si2Mo18O62 8-. nH2O之Dawson雜多陰離子、式Si5Mo30O110 20-. nH2O之Preyssler雜多陰離子。
當用於製備根據本發明之歧化方法中所利用之催化劑之基於鉬之雜多陰離子類型之前驅物含有除鉬及矽之外之金屬元素M(M較佳係鈷)時,其有利地選自由以下各項形成之群:式Si2Mo4CoO23 12-. nH2O之Strandberg雜多陰離子、式SiMo5CoO24 12-. nH2O之Anderson雜多陰離子、式SiMo11CoO40 8-. nH2O之Keggin雜多陰離子、式SiMo10CoO39 12-. nH2O之缺位Keggin雜多陰離子、式SiMo8CoO34 14-. nH2O之缺位Keggin雜多陰離子、式Si2Mo17CoO62 12-. nH2O之Dawson雜多陰離子、式Si5Mo29CoO110 24-. nH2O之Preyssler雜多陰離子,(其製備精確地闡述於申請案FR 2,764,211中)。
根據本發明之中孔性基質有利地係基於至少一種選自以下各項之元素X之氧化物之基質:矽、鋁、鈦、鋯、鎂、鑭、鈰及其混合物。較佳地,元素X係鋁或鋁與矽之混合物。更佳地,元素X係鋁。
經描述為中孔性之該基於氧化物之基質根據本發明應理解為意指包含根據IUPAC分類孔徑在2nm與50nm之間變化之孔之基質(K.S.W.Sing、D.H.Everett、W.R.A.Haul、L.Moscou、J.Pierotti、J.
Rouquerol、T.Siemieniewska,Pure Appl.Chem.1985,57,603)及/或中孔結構化之中孔性基質(即具有均勻孔徑且在整個該基質中週期性分佈之中孔)及/或具有多級孔隙度之基質(即除中孔之外亦包含微孔及/或大孔)。
優先地,使用基於氧化鋁之中孔性基質,其根據BET方法具有10m2/g至500m2/g且較佳至少50m2/g之比表面積及至少0.1ml/g之孔體積且較佳包含於0.3ml/g與1.2ml/g之間之孔體積。
本發明所用之催化劑包含藉由根據本發明之式(I)、(Ia)或(Ib)及/或式(II)之前驅物提供之包含於1%與40%之間、較佳2%與30%之間、較佳2%與20%之間之鉬元素之重量含量,其表示為鉬之重量相對於中孔性基質之重量之百分比。
本發明所用之催化劑包含藉由根據本發明之式(I)、(Ia)或(Ib)及/或式(II)之前驅物提供之包含於0.01%與50%之間、較佳0.02%與35%之間、較佳0.02%與25%之間之矽元素之重量含量,其表示為矽元素之重量相對於中孔性基質之重量之百分比。
較佳地,當前驅物係本發明之含有矽氧基配體之鉬配位錯合物時,藉由根據本發明之前驅物提供之矽元素之重量含量係包含於1%與25%之間,其表示為矽元素之重量相對於中孔性基質之重量之百分比。
較佳地,當前驅物係本發明之基於鉬之雜多陰離子時,藉由根據本發明之前驅物提供之矽元素之重量含量係包含於0.02%與10%之間,其表示為矽元素之重量相對於中孔性基質之重量之百分比。
較佳地,當前驅物係前驅物之混合物時,藉由根據本發明之前驅物提供之矽元素之重量含量對應於藉由前驅物之每一者提供之矽元素之重量含量之總和。
本發明之催化劑可根據熟習此項技術者已知之方法製備。
在本發明所用之催化劑之製備方法之變化形式中,包含鉬及矽且具有至少一個Si-O-Mo鍵序列之前驅物係沈積於基於氧化物之預成型之中孔性基質之表面上。
預成型之中孔性基質可商業購得或根據熟習此項技術者已知之方法合成,尤其藉由使用「傳統」無機合成方法:在溫和溫度及壓力條件下自鹽沈澱/凝膠化;或「現代」金屬有機方法:在溫和溫度及壓力條件下自醇鹽沈澱/凝膠化。在本文之剩餘部分中且為清晰起見,將該等方法簡單稱為「溶膠-凝膠(sol-gel)」。
預成型之中孔性基質可呈粉末之形式或(例如)以以下形式成型:粒化、壓碎或篩分之粉末、顆粒、錠劑、珠粒、輪狀物、球狀物或擠出物(可係中空或非中空之圓柱體、例如具有2、3、4或5個葉片之多葉片圓柱體、扭曲圓柱體)或環等。
在中孔性基質上沈積或併入包含鉬及矽且具有至少一個Si-O-Mo鍵序列之前驅物可在中孔性基質成型之前、期間或之後進行。
在中孔性基質上沈積或併入本發明之前驅物可藉由稱為以下之方法實施:乾法浸漬、過量浸漬、CVD(化學氣相沈積)、CLD(化學液相沈積)等,其闡述於(例如)「Catalysis by transition metal sulphides,from molecular theory to industrial application,Hervé Toulhouat及Pascal Raybaud,第137頁」中。
催化劑可根據包含以下階段之製程藉由乾法浸漬製備:a)使式(I)、(Ia)或(Ib)及/或式(II)之包含鉬及矽且具有至少一個Si-O-Mo鍵序列之前驅物溶解於一定體積之溶液中,該溶液體積對應於基於氧化物之預成型之中孔性基質之孔體積,b)利用階段a)中所獲得之溶液浸漬基於氧化物之預成型之中孔性基質,視情況使由此獲得之固體熟化,c)對階段b)結束時所獲得之固體進行乾燥、煅燒及/或蒸汽處理
之可選階段,其係在大於或等於0.1MPa或小於或等於0.1MPa之壓力下、在50℃至1000℃之溫度範圍下實施,d)對階段c)結束時所獲得之固體進行熱活化之階段,其係在大於或等於0.1MPa或小於或等於0.1MPa之壓力下、在100℃至1000℃之溫度範圍下實施。
在階段b)中視情況實施之熟化係在經控制之氛圍下及在經控制之溫度下實施,以促進該前驅物在基於氧化物之預成型之中孔性基質之整個表面上之分散。有利地,熟化係在包含於20℃與120℃之間之溫度下及包含於0.01MPa與1MPa之間之壓力下實施。
階段c)及/或d)可在氧化、還原或中性氛圍下實施。
較佳地,可選乾燥階段c)係在少於72h且較佳少於24h之時期期間在20℃至200℃、較佳50℃至150℃且較佳100℃至130℃之溫度範圍下實施。
較佳地,熱活化階段d)係在大氣壓力下於200℃至800℃、較佳350℃至650℃之溫度範圍下在中性氛圍下實施。較佳地,中性氛圍係氮,流速範圍為0.01至20Nl/h/克階段c)結束時所獲得之固體、較佳0.1至10Nl/h/克階段c)結束時所獲得之固體。
催化劑可根據包含以下階段之製程藉由過量浸漬來製備:a’)使式(I)、(Ia)或(Ib)及/或式(II)之包含鉬及矽且具有至少一個Si-O-Mo鍵序列之前驅物溶解於一定體積之溶液中,該溶液體積對應於基於氧化物之預成型之中孔性基質之孔體積之介於1.5倍與20倍之間,b’)利用階段a’)中所獲得之溶液浸漬基於氧化物之預成型之中孔性基質,過濾並回收固體,視情況使由此獲得之固體熟化,c’)對階段b’)結束時所獲得之固體進行乾燥、煅燒及/或蒸汽處理之可選階段,其係在大於或等於0.1MPa或小於或等於0.1MPa之壓
力下、在50℃至1000℃之溫度範圍下實施,d’)對階段c’)結束時所獲得之固體進行熱活化之階段,其係在大於或等於0.1MPa或小於或等於0.1MPa之壓力下、在100℃至1000℃之溫度範圍下實施。
在階段b’)中視情況實施之熟化係在經控制之氛圍下及在經控制之溫度下實施,以促進該前驅物在基於氧化物之預成型之中孔性基質之整個表面上之分散。有利地,熟化係在包含於20℃與120℃之間之溫度下及包含於0.01MPa與1MPa之間之壓力下實施。
較佳地,在階段a’)中溶解式(I)、(Ia)或(Ib)及/或式(II)之包含鉬及矽且具有至少一個Si-O-Mo鍵序列之前驅物係在一定體積之溶液中實施,該溶液體積對應於基於氧化物之預成型之中孔性基質之孔體積之介於2倍與10倍之間。
階段c’)及/或d’)可在氧化、還原或中性氛圍下實施。
較佳地,可選乾燥階段c’)係在少於72h且較佳少於24h之時期期間在20℃至200℃、較佳50℃至150℃且較佳100℃至130℃之溫度範圍下實施。
較佳地,熱活化階段d’)係在大氣壓力下於200℃至800℃、較佳350℃至650℃之溫度範圍下在中性氛圍下實施。較佳地,中性氛圍係氮,流速範圍為0.01至10Nl/h/克階段c’)結束時所獲得之固體、較佳0.1至5Nl/h/克階段c’)結束時所獲得之固體。
有機化合物(稱為有機添加劑)亦可在根據本發明之催化劑之製備期間使用。至少一種有機添加劑可藉由在用前驅物浸漬之階段(階段b或b’)之前浸漬至中孔性基質上、藉由與前驅物共浸漬或在用前驅物浸漬之後進行後浸漬來引入。
所用有機化合物或添加劑係選自熟習此項技術者已知之螯合劑、非螯合劑、還原劑及添加劑。
該等有機化合物或添加劑有利地選自視情況醚化之單、二或多元醇、羧酸(檸檬酸、乙酸等)、糖、非環狀單醣、二醣或多醣(例如葡萄糖、果糖、麥芽糖、乳糖或蔗糖)、環狀或非環狀酯、環狀或非環狀醚、酮、組合若干種該等官能基(酮、羧酸、醚、酯、醇、胺等)之化合物、冠醚、環糊精及含有至少硫或磷或氮之化合物(例如氮基乙酸、乙二胺四乙酸或二伸乙基三胺)、胺基酸及兩性離子性化合物,其單獨使用或以混合物進行使用。
浸漬及/或溶解溶劑可選自熟習此項技術者已知之任何溶劑,例如水、有機溶劑、離子液體等。亦可使用溶劑之混合物。
當前驅物係本發明之基於鉬之雜多陰離子時,較佳使用水或質子極性溶劑,例如醇:乙醇、甲醇等。
當前驅物係含有矽氧基配體之鉬配位錯合物時,較佳使用非質子有機溶劑,例如烴:戊烷、庚烷、環己烷;芳香族化合物:甲苯、二甲苯等;醚:二乙醚、四氫呋喃(THF)等。
當基於鉬之雜多陰離子類型之前驅物與含有矽氧基配體之鉬配位錯合物一起使用時,較佳使用非質子有機溶劑,例如二甲基亞碸(DMSO)、二甲基甲醯胺(DMF)或乙腈。
亦可將一或多種其他金屬元素引入至根據本發明之製程中所用之催化劑之組成中。此金屬元素可選自鋅、鎳、鈷、鎢、釩、鈮、鉭、鐵及銅。以金屬之重量相對於基於氧化物之中孔性基質之重量之%表示,此金屬元素係以包含於0.01%與10%之間、且較佳包含於0.02%與5%之間之含量引入。
此金屬元素可藉由選自鋅、鎳、鈷、鎢、釩、鈮、鉭、鐵及銅之鹽及/或氧化物、較佳鋅、鎳、鈷、鎢之鹽及/或氧化物之化合物提供。較佳地,化合物係鈷鹽、羧酸鹽、醇鹽或氧化物。較佳地,化合物係Co(NO3)2或CoO。極佳地,化合物係Co(NO3)2。
此化合物可藉由在用式(I)、(Ia)或(Ib)及/或式(II)之包含鉬及矽且具有至少一個Si-O-Mo鍵序列之根據本發明之前驅物浸漬之前浸漬至中孔性基質上、藉由與根據本發明之該(等)前驅物共浸漬來引入。
在中孔性基質上沈積或併入式(I)、(Ia)或(Ib)及/或式(II)之包含鉬及矽且具有至少一個Si-O-Mo鍵序列之該(等)前驅物亦可直接在基於氧化物之中孔性基質之合成期間進行。
所用之合成方法可係藉由沈澱或藉由蒸發之水解性或非水解性「溶膠-凝膠」方法。蒸發方法可需要使用特定合成方法,例如噴霧乾燥、薄膜之沈積等。
在藉由噴霧乾燥進行水解性溶膠-凝膠合成從而獲得具有基於氧化物之中孔結構化基質之催化劑之具體情形下,本發明之製程中所用之催化劑可根據包含以下階段之方法來製備:
a1)使式(I)、(Ia)或(Ib)及/或式(II)之包含鉬及矽且具有至少一個Si-O-Mo鍵序列之前驅物及基於至少一種元素X之氧化物之中孔性基質之前驅物在成孔劑存在下溶解於水溶液或水-有機溶液中,以形成膠質溶液,
b1)噴霧乾燥該膠質溶液以獲得球形固體元素粒子,該等球形固體元素粒子併入基於氧化物之中孔結構化基質及式(I)、(Ia)或(Ib)及/或式(II)之包含鉬及矽且具有至少一個Si-O-Mo鍵序列之前驅物,
c1)對階段b1)結束時所獲得之固體粒子進行乾燥、煅燒及/或蒸汽處理之可選階段,其係在大於或等於0.1MPa或小於或等於0.1MPa之壓力下實施,
d1)對階段c1)結束時之乾燥固體粒子進行熱活化之階段,其係在大於或等於1巴(bar)或小於或等於0.1MPa之壓力下、在100℃至1000℃之溫度範圍下實施。
較佳地,可選乾燥階段c1)係在少於72h且較佳少於24h之時期期
間在20℃至200℃、較佳50℃至150℃且較佳100℃至130℃之溫度範圍下實施。階段c1)可在氧化、還原或中性氛圍下實施。
熱活化階段d1)可在氧化、還原或中性氛圍下實施。
較佳地,熱活化階段d1)係在大氣壓力下於200℃至800℃且較佳350℃至650℃之溫度範圍下在中性氛圍下實施。較佳地,中性氛圍係氮,流速範圍為0.01至10Nl/h/克階段c1)結束時所獲得之固體、較佳0.1至5Nl/h/克階段c1)結束時所獲得之固體。
水-有機溶液意指水與有機溶劑之混合物之溶液。較佳地,水-有機溶液係水-乙醇溶液。
階段a1)中所用之成孔劑係(例如)離子或非離子表面活性劑化合物或兩者之混合物。
中孔性基質之前驅物係基於至少一種選自以下之元素X之氧化物之基質之前驅物:矽、鋁、鈦、鋯及其混合物。該(等)前驅物可係包含元素X且能夠在溶液中以反應形式釋放此元素之任何化合物。因此,基質之至少該元素X之該(等)前驅物有利地係式XZn(n=3或4)之該元素X之無機鹽,Z係鹵素、NO3或過氯酸鹽基團,較佳地Z係氯。至少該所考慮元素X之前驅物亦可係式X(OR)n之醇鹽前驅物之一者,其中R=乙基、異丙基、正丁基、第二丁基、第三丁基等或螯合前驅物,例如X(C5H8O2)n,其中n=3或4。至少該所考慮元素X之前驅物亦可係該元素X之一(或多)種氧化物或一(或多)種氫氧化物。
在其中X係鋁或鋁與矽之混合物之較佳情形下,二氧化矽及/或氧化鋁前驅物係熟習此項技術者所熟知之無機氧化物之前驅物。二氧化矽前驅物係自以下獲得:二氧化矽之任何來源且有利地式Na2SiO3之矽酸鈉前驅物、式SiCl4之氯化前驅物、式Si(OR)4之醇鹽前驅物(其中R=H、甲基、乙基)或式Si(OR)4-aCla之氯醇鹽前驅物(其中R=H、甲基、乙基,a係包含於0與4之間)。二氧化矽前驅物亦可有利地係式
Si(OR)4-aR’a之醇鹽前驅物,其中R=H、甲基、乙基且R’係烷基鏈或(例如)經硫醇、胺基、β-二酮、磺酸基官能化之烷基鏈,a係包含於0與4之間。較佳二氧化矽前驅物係四乙基正矽酸鹽(TEOS)。氧化鋁前驅物有利地係式AlZ3之鋁之無機鹽,Z係鹵素或NO3基團。較佳地,Z係氯。氧化鋁前驅物亦可係式Al2Z’3之鋁之無機鹽,Z’係硫酸鹽基團SO4。氧化鋁前驅物亦可係式Al(OR”)3之醇鹽前驅物,其中R”=乙基、異丙基、正丁基、第二丁基或第三丁基或螯合前驅物,例如乙醯基丙酮酸鋁(Al(CH7O2)3)。氧化鋁前驅物亦可係氧化鋁或氫氧化鋁,例如AlOONa。
在其中本發明之製程中所用之催化劑在上文所揭示之不同製備製程結束時係以粉末形式獲得之情形下,粉末形式可根據熟習此項技術者熟知之方法成型。因此,其可呈以下形式:粒化、壓碎或篩分之粉末、顆粒、錠劑、珠粒、輪狀物、球狀物或擠出物(可係中空或非中空之圓柱體、例如具有2、3、4或5個葉片之多葉片圓柱體、扭曲圓柱體)或環等。較佳地,該催化劑成型為擠出物。
在該成型操作期間,本發明之製程中所用之催化劑可視情況與至少一種用作黏合劑之多孔性氧化物材料混合以便產生適於本發明之製程之催化劑之物理性質(機械強度、耐磨耗性等)。
該多孔性氧化物材料優先係選自由以下各項形成之群之多孔性氧化物材料:氧化鋁、二氧化矽、二氧化矽-氧化鋁、氧化鎂、黏土、氧化鈦、氧化鋯、氧化鑭、氧化鈰、磷酸鋁及以上所提及之氧化物之至少二者之混合物。該多孔性氧化物材料亦可選自氧化鋁-氧化硼、氧化鋁-氧化鈦、氧化鋁-氧化鋯及鈦-鋯氧化物混合物。鋁酸鹽(例如鎂、鈣、鋇、錳、鐵、鈷、鎳、銅及鋅之鋁酸鹽以及混合鋁酸鹽,例如含有以上所提及之金屬之至少二者之彼等)有利地用作多孔性氧化物材料。亦可使用鈦酸鹽,例如鋅、鎳、鈷之鈦酸鹽。亦可有
利地使用氧化鋁與二氧化矽之混合物及氧化鋁與其他化合物(例如VIB族元素、磷、氟或硼)之混合物。亦可使用二八面體層狀矽酸鹽2:1類型或三八面體層狀矽酸鹽3:1類型之簡單、合成或天然黏土,例如高嶺石(kaolinite)、葉蛇紋石(antigorite)、纖維蛇紋石(chrysotile)、蒙脫石(montmorillonite)、鋁膨潤石(beidellite)、蛭石(vermiculite)、滑石(talc)、鋰膨潤石(hectorite)、皂石(saponite)、鋰皂石(laponite)。該等黏土可視情況脫層。亦可有利地使用氧化鋁與黏土之混合物及二氧化矽-氧化鋁與黏土之混合物。使用上文所提及之化合物之至少二者之各種混合物亦可適宜用作黏合劑。
視情況,至少一種有機佐劑亦在該成型階段期間混合。該有機佐劑之存在促進藉由擠出成型。該有機佐劑可有利地選自聚乙烯吡咯啶酮、纖維素聚合物及其衍生物,較佳選自纖維素醚(例如由Dow Chemical公司所銷售之Methocel)、聚乙烯醇、聚乙二醇、聚丙烯醯胺、多醣、其天然聚合物及衍生物(例如海藻酸鹽)、聚酯、聚醯胺及芳香族聚醯胺、聚醚、聚(芳基醚)、聚胺基甲酸酯、聚碸(例如聚碸醚)、雜環聚合物,較佳選自聚醯亞胺、聚醯亞胺醚、聚醯亞胺酯、聚醯亞胺醯胺及聚苯并咪唑。
該有機佐劑相對於所形成之中孔性基質之總重量之比例有利地係包含於0重量%與20重量%之間、較佳地0重量%與10重量%之間且較佳地0重量%與7重量%之間。
藉由使烯烴與上文所定義之催化劑接觸實施烯烴歧化之方法有利地係在包含於0℃與500℃之間、較佳包含於0℃與400℃之間、更佳包含於20℃與350℃之間且更佳包含於30℃與350℃之間之溫度下實施。
烯烴之歧化反應可在氣相中或液相中實施。反應可在攪拌反應
器中以分批模式實施,或藉由使烯烴試劑經過催化劑之固定床、移動床或流化床以連續模式實施。
實施本發明之製程之壓力並非關鍵。然而,對於在液相中之操作而言,有利地維持壓力至少等於在反應之溫度下反應混合物之蒸氣壓力。
較佳在溶劑不存在下實施反應。然而,反應可在溶劑(例如烴或經鹵化之脂肪族烴、環烷烴或芳香族烴)存在下進行。
能夠藉由本發明之製程中之歧化反應之烯烴可係對應於通式R1R2C=CR3R4之直鏈烯烴,其中相同或不同之R1、R2、R3及R4係氫或具有1至20個碳原子之烴基、或具有環狀結構之烯烴,該環包含3至20個碳原子。
烯烴可獨自反應,或若干種烯烴可於混合物中一起反應。根據本發明之製程具體而言係乙烯與2-丁烯之交叉歧化反應以產生丙烯,或係將丙烯轉化為乙烯與2-丁烯之混合物之逆反應。
能夠藉由歧化反應之其他烯烴係具有諸如鹵素或酯基之官能基之直鏈或環狀單烯烴或聚烯烴。該製程亦可在共歧化中利用上文所提及之烯烴之混合物。
在藉由乙烯與2-丁烯之間之歧化產生丙烯之情形下,2-丁烯可較佳地來源於在熟習此項技術者已知之均相或異相催化劑存在下乙烯之二聚化反應。舉例而言,2-丁烯可來源於在NiCl2(PBu3)2類型之鎳錯合物存在下乙烯之二聚化,藉由均相催化產生1-丁烯與2-丁烯之混合物。舉例而言,2-丁烯可來源於在NiSO4/Al2O3類型之基於鎳之異相催化劑存在下乙烯之二聚化,藉由異相催化產生1-丁烯與2-丁烯之混合物。
在藉由乙烯與2-丁烯及1-丁烯之混合物之間之歧化產生丙烯之情形下,較佳使用使1-丁烯異構化為2-丁烯之催化劑以最大化丙烯產
率。舉例而言,可使用MgO或K2O類型之氧化物催化劑使1-丁烯異構化為2-丁烯。
乙烯可有利地藉由熟習此項技術者已知之任何脫水方法藉由使生物來源之乙醇脫水來獲得,以容許產生生物來源之丙烯。
在實例中,含有矽氧基配體之錯合物配位類型之前驅物經吡啶穩定化之參(三苯基矽基氧基)氮化鉬Mo(≡N)(OSiPh3)3(吡啶)及雜多陰離子類型之前驅物磷鉬酸PMo12O40 3-.3H+及矽鉬酸SiMo12O40 4-.4H+可商業購得。
雜多陰離子前驅物鈷矽鉬酸SiCoMo11O40 4-.4H+係根據專利申請案FR 2,764,211中所述之方法來合成。
將1.5g之PMo12O40 3-.3H+.30H2O於60℃下溶解於7.3ml之蒸餾水中。在完全溶解之後,以此溶液浸漬氧化鋁(SBET=198m2/g,Vp=0.47ml/g)。將所獲得之固體在空氣及25℃下熟化24h。使所得固體在烘箱中於120℃下乾燥24h,然後於550℃及氮下活化2h。
將1.4g之SiMo12O40 4-.4H+.28H2O於60℃下溶解於7.3ml之蒸餾水中。在完全溶解之後,以此溶液浸漬氧化鋁(SBET=198m2/g,Vp=0.47ml/g)。將所獲得之固體在空氣及25℃下熟化24h。使所得固體在烘箱中於120℃下乾燥24h,然後於550℃及氮下活化2h。
將1.4g之SiCoMo11O40 4-.4H+.28H2O於60℃下溶解於7.3ml之蒸餾
水中。以此溶液浸漬氧化鋁(SBET=198m2/g,Vp=0.47ml/g)。將所獲得之固體在空氣及25℃下熟化24h。使所得固體在烘箱中於120℃下乾燥24h,然後於550℃及氮下活化2h。
實例1D(根據本發明):藉由利用SiMo
12
O
40
4-
.4H
+
.28H
2
O及Co(NO
3
)
2
之溶液乾法浸漬製備6.7%Mo+0.9%Co/Al
2
O
3
將1.4g之SiMo12O40 4-.4H+.28H2O及0.69g之Co(NO3)2.6H2O於60℃下溶解於7.3ml之蒸餾水中。以此溶液浸漬氧化鋁(SBET=198m2/g,Vp=0.47ml/g)。將所獲得之固體在空氣及25℃下熟化24h。使所得固體在烘箱中於120℃下乾燥24h,然後於550℃及氮下活化2h。
將11.6g之Mo(≡N)(OSiPh3)3(吡啶)於60℃下溶解於7.3ml之蒸餾水中。以此溶液浸漬氧化鋁(SBET=198m2/g,Vp=0.47ml/g)。將所獲得之固體在空氣及25℃下熟化24h。使所得固體在烘箱中於120℃下乾燥24h,然後於550℃及氮下活化2h。
將0.7g之SiMo12O40 4-.4H+.28H2O及5.8g之Mo(≡N)(OSiPh3)3(吡啶)於60℃下溶解於7.3ml之蒸餾水中。以此溶液浸漬氧化鋁(SBET=198m2/g,Vp=0.47ml/g)。將所獲得之固體在空氣及25℃下熟化24h。使所得固體在烘箱中於120℃下乾燥24h,然後於550℃及氮下活化2h。
於雙夾套固定床反應器中將2g在實例1A至1F中所製備之催化劑以50重量%之比例與碳化矽(SiC)混合。將雙夾套之熱傳遞流體加熱至70℃。藉助Gilson幫浦將純丙烯傳送至反應器並將壓力設置為4.5MPa。在圖1中量化表示為毫莫耳所消耗丙烯/克催化劑/小時之催化劑
生產率,其隨時間(以t表示,表示為小時h)變化。
藉由用具有Si-O-Mo鍵之基於鉬之前驅物浸漬製備之根據本發明之催化劑1B至1F之活性大於藉由用不具有Si-O-Mo鍵之基於鉬之前驅物PMo12O40 3-.3H+.30H2O浸漬製備之非根據本發明之催化劑1A之活性。
根據本發明之催化劑1B至1F之穩定性優於非根據本發明之催化劑1A之穩定性。
圖1顯示催化劑1A至1F在丙烯歧化為乙烯及2-丁烯中之活性及穩定性。
本發明係關於使用催化劑進行烯烴歧化之方法,該催化劑係自前驅物製備,該前驅物包含鉬及矽且具有至少一個Si-O-Mo鍵序列。
Claims (17)
- 一種藉由使烯烴與催化劑接觸來實施該等烯烴之歧化之方法,該催化劑包含中孔性基質及至少元素鉬及矽,該等元素係使用至少一種包含鉬及矽且具有至少一個Si-O-Mo鍵序列之前驅物併入至該基質中。
- 如請求項1之方法,其中該前驅物係含有矽氧基配體且包含至少一個Si-O-Mo鍵序列之鉬配位錯合物及/或含有至少一個Si-O-Mo鍵序列之基於鉬之雜多陰離子類型之前驅物。
- 如請求項1或2之方法,其中當該前驅物係含有矽氧基配體之鉬配位錯合物時,其對應於式(I)Mom(=Y)n(≡N)n’(X)z(=CR2)r(OSiR3)p (I)其中彼此相同或不同之Y基團係選自O、S及NR’,彼此相同或不同之X基團係選自鹵化物,例如F、Cl、Br、I;經取代或未經取代之烷基、環烷基或芳基;經取代或未經取代之環戊二烯基;烷氧基;芳氧基;矽氧基;醯胺;氫基;硝基;羧酸鹽;乙醯基丙酮酸鹽;磺酸鹽;β-雙烯酮亞胺基;吡咯亞胺;脒基;硫氰酸鹽或NR2-CS2 -基,彼此相同或不同之R基團係選自較佳包含於1與10個碳原子之間之經取代或未經取代之烷基、環烷基及芳基,或選自經取代或未經取代之烷氧基及芳氧基,彼此相同或不同之R’基團係選自經取代或未經取代之烷基、環烷基及芳基,m等於1或2,n係包含於0與4之間, n’係包含於0與2之間,z係包含於0與9之間,r係包含於0與2之間,p係包含於1與10之間。
- 如請求項2或3之方法,其中當該前驅物係含有矽氧基配體之鉬配位錯合物類型之前驅物時,其對應於式(Ia):Mom(≡N)n’(OSiR3)p (Ia)其中彼此相同或不同之R基團可選自較佳包含於1與10個碳原子之間之經取代或未經取代之烷基、環烷基及芳基,或選自經取代或未經取代之環烷基及芳基,m等於1或2,n’係包含於0與2之間,p係包含於1與10之間。
- 如請求項2或3之方法,其中當該前驅物係含有矽氧基配體之鉬配位錯合物類型之前驅物時,其對應於式(Ib)Mom(=O)n(OSiR3)p (Ib)其中彼此相同或不同之R基團可選自較佳包含於1與10個碳原子之間之經取代或未經取代之烷基、環烷基及芳基,或選自經取代或未經取代之烷氧基及芳氧基,m等於1或2,n係包含於0與4之間,p係包含於1與10之間。
- 如前述請求項中任一項之方法,其中該含有矽氧基配體之鉬配位錯合物在其配位層中含有一或多個L型配體、視情況選自以下 之多齒配體:含磷化合物、含氧化合物、含氮化合物、含氮芳香族化合物及/或含硫化合物,例如硫醚。
- 如前述請求項中任一項之方法,其中該含有矽氧基配體之鉬配位錯合物類型之前驅物係選自以下化合物:MoO(OSiMe3)CN(CS2-NEt2)2、Mo(=N-(2,6-二-iPrC6H3))(tBu)(=CHtBu)(OSi(OtBu)3)、Mo(=S)(=NiPr)(OSitBu3)2、Mo(=O)(OSitBu3)4、Mo(≡N)(OSiPh3)3(C6H5N)或Mo2(OSiMe3)6。
- 如請求項1或2之方法,其中當根據本發明之該前驅物係雜多陰離子類型之前驅物時,其對應於式(II):(SixMomMbOyHh)q-.nH2O (II)其中,x等於1或2,m大於或等於1,b大於或等於0,m+b大於或等於5,y係包含於20與50之間,h係包含於0與12之間,q係包含於3與12之間,n係包含於0與200之間;x、m、b、y、h、n及q係整數,M係選自以下各項之金屬元素:鋁、鋅、鎳、鈷、鎢、釩、鈮、鉭、鐵及銅。
- 如請求項8之方法,其中該基於鉬之雜多陰離子類型之前驅物係選自由以下各項形成之群:式Si2Mo5O23 8-. nH2O之Strandberg雜多陰離子、式SiMo6O24 8-. nH2O之Anderson雜多陰離子、式SiMo12O40 4-. nH2O之Keggin雜多陰離子、式SiMo11O39 8-. nH2O之缺位Keggin雜多陰離子、式SiMo9O34 10-. nH2O之缺位Keggin雜多 陰離子、式Si2Mo18O62 8-. nH2O之Dawson雜多陰離子、式Si5Mo30O110 20-. nH2O之Preyssler雜多陰離子。
- 如請求項8之方法,其中該基於鉬之雜多陰離子類型之前驅物係選自由以下各項形成之群:式Si2Mo4CoO23 12-. nH2O之Strandberg雜多陰離子、式SiMo5CoO24 12-. nH2O之Anderson雜多陰離子、式SiMo11CoO40 8-. nH2O之Keggin雜多陰離子、式SiMo10CoO39 12-. nH2O之缺位Keggin雜多陰離子、式SiMo8CoO34 14-. nH2O之缺位Keggin雜多陰離子、式Si2Mo17CoO62 12-. nH2O之Dawson雜多陰離子、式Si5Mo29CoO110 24-. nH2O之Preyssler雜多陰離子。
- 如前述請求項中任一項之方法,其中該中孔性基質係基於至少一種選自以下各項之元素X之氧化物之基質:矽、鋁、鈦、鋯、鎂、鑭、鈰及其混合物。
- 如前述請求項中任一項之方法,其中該催化劑係根據包含以下階段之方法藉由乾法浸漬來製備:a)使包含鉬及矽且具有至少一個Si-O-Mo鍵序列之該前驅物溶解於一定體積之溶液中,該溶液體積對應於基於氧化物之預成型之中孔性基質之孔體積,b)利用階段a)中所獲得之該溶液浸漬該基於氧化物之預成型之中孔性基質,視情況使由此獲得之固體熟化,c)對階段b)結束時所獲得之該固體進行乾燥、煅燒及/或蒸汽處理之可選階段,其係在大於或等於0.1MPa或小於或等於0.1MPa之壓力下、在50℃至1000℃之溫度範圍內實施,d)對階段c)結束時所獲得之該固體進行熱活化之階段,其係在大於或等於0.1MPa或小於或等於0.1MPa之壓力下、在100℃至1000℃之溫度範圍內實施。
- 如請求項1至11中任一項之方法,其中該催化劑係根據包含以下 階段之方法藉由過量浸漬來製備:a’)使式(I)、(Ia)或(Ib)及/或式(II)之包含鉬及矽且具有至少一個Si-O-Mo鍵序列之該前驅物溶解於一定體積之溶液中,該溶液體積對應於該基於氧化物之預成型之中孔性基質之孔體積之介於1.5倍與20倍之間,b’)利用階段a’)中所獲得之該溶液浸漬該基於氧化物之預成型之中孔性基質,過濾並回收固體,視情況使由此獲得之該固體熟化,c’)對階段b’)結束時所獲得之該固體進行乾燥、煅燒及/或蒸汽處理之可選階段,其係在大於或等於0.1MPa或小於或等於0.1MPa之壓力下、在50℃至1000℃之溫度範圍內實施,d’)對階段c’)結束時所獲得之該固體進行熱活化之階段,其係在大於或等於0.1MPa或小於或等於0.1MPa之壓力下、在100℃至1000℃之溫度範圍內實施。
- 如請求項1至11中任一項之方法,其中該催化劑係根據包含以下階段之方法來製備:a1)使包含鉬及矽且具有至少一個Si-O-Mo鍵序列之該前驅物及基於至少一種元素X之氧化物之該中孔性基質之前驅物在成孔劑存在下溶解於水溶液或水-有機溶液中,以形成膠質溶液,b1)噴霧乾燥該膠質溶液以獲得球形固體元素粒子,該等球形固體元素粒子併入該基於氧化物之中孔結構化基質及式(I)、(Ia)或(Ib)及/或式(II)之包含鉬及矽且具有至少一個Si-O-Mo鍵序列之該前驅物,c1)對階段b1)結束時所獲得之該等固體粒子進行乾燥、煅燒及/或蒸汽處理之可選階段,其係在大於或等於0.1MPa或小於或等於0.1MPa之壓力下實施, d1)對階段c1)結束時之該等乾燥固體粒子進行熱活化之階段,其係在大於或等於1巴(bar)或小於或等於0.1MPa之壓力下、在100℃至1000℃之溫度範圍內實施。
- 如前述請求項中任一項之方法,其中該歧化反應係在包含於0℃與500℃之間之溫度下實施。
- 如前述請求項中任一項之方法,其中該等烯烴係對應於通式R1R2C=CR3R4之直鏈烯烴,其中相同或不同之R1、R2、R3及R4係氫或1至20個碳原子之烴基或具有環狀結構之烯烴,該環包含3至20個碳原子。
- 如請求項15或16中任一項之方法,其中該歧化反應係乙烯與2-丁烯之交叉歧化反應,或使丙烯轉化為乙烯與2-丁烯之混合物之逆反應。
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CN (1) | CN108137439B (zh) |
FR (1) | FR3039546B1 (zh) |
RU (1) | RU2018107136A (zh) |
SA (1) | SA518390840B1 (zh) |
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FR3084363B1 (fr) * | 2018-07-25 | 2020-08-07 | Ifp Energies Now | Procede de metathese des olefines utilisant un catalyseur contenant du silicium, du molybdene et un element alcalin |
FR3084361A1 (fr) | 2018-07-25 | 2020-01-31 | IFP Energies Nouvelles | Procede de metathese des olefines utilisant un catalyseur contenant du silicium, du molybdene et du soufre |
FR3084362A1 (fr) | 2018-07-25 | 2020-01-31 | IFP Energies Nouvelles | Procede de metathese des olefines utilisant un catalyseur contenant du silicium, du molybdene et un element alcalin |
FR3103192A1 (fr) | 2019-11-15 | 2021-05-21 | IFP Energies Nouvelles | Procede de metathese des olefines utilisant un catalyseur a haute teneur en alcalin contenant du silicium, du molybdene |
CN111047671B (zh) * | 2019-12-24 | 2023-05-16 | 成都来画科技有限公司 | 一种手绘图片的绘画路径的优化方法及存储介质 |
CN111841640B (zh) * | 2020-06-30 | 2022-12-20 | 杭州师范大学 | 一种钴基有机催化剂和其制备方法及其转化co2合成苯并氮杂环的应用 |
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FR2749778B1 (fr) | 1996-06-13 | 1998-08-14 | Elf Antar France | Procede de preparation de catalyseurs d'hydrotraitement |
FR2764211B1 (fr) * | 1997-06-09 | 1999-10-08 | Elf Antar France | Procede de preparation de catalyseurs d'hydrotraitement |
FR2826880B1 (fr) * | 2001-07-04 | 2004-06-18 | Inst Francais Du Petrole | Composition amelioree de catalyseur pour la metathese des olefines |
EP1896385B1 (en) * | 2005-06-06 | 2013-08-28 | Dow Global Technologies LLC | Metathesis process for preparing an alpha, omega -functionalized olefin |
DE102007039526A1 (de) * | 2007-08-21 | 2009-02-26 | Lanxess Deutschland Gmbh | Katalysator-Systeme und deren Verwendung für Metathese-Reaktionen |
CN101230076A (zh) * | 2007-09-30 | 2008-07-30 | 赢创德固赛有限责任公司 | 含有n杂环卡宾配体的钌的同核双金属和异核双金属亚烷基配合物及其用途 |
US8362311B2 (en) * | 2009-09-30 | 2013-01-29 | Massachusetts Institute Of Technology | Highly Z-selective olefins metathesis |
FR2977890B1 (fr) * | 2011-07-15 | 2013-07-19 | IFP Energies Nouvelles | Procede de metathese des olefines utilisant un catalyseur a base d'un materiau spherique comprenant des particules metalliques oxydes piegees dans une matrice mesostructuree |
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CN108137439B (zh) | 2021-07-20 |
US20190009260A1 (en) | 2019-01-10 |
US10737254B2 (en) | 2020-08-11 |
WO2017021235A1 (fr) | 2017-02-09 |
FR3039546B1 (fr) | 2017-08-11 |
FR3039546A1 (fr) | 2017-02-03 |
RU2018107136A3 (zh) | 2019-11-29 |
CN108137439A (zh) | 2018-06-08 |
SA518390840B1 (ar) | 2021-09-21 |
RU2018107136A (ru) | 2019-08-28 |
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