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1. 发明申请

WO2009092781A3 PROCESS FOR OBTAINING MODIFIED MOLECULAR SIEVES 审中-公开
公开(公告)号：WO2009092781A3
公开(公告)日：2009-07-30
申请号：PCT/EP2009/050758
申请日：2009-01-23
申请人： TOTAL PETROCHEMICALS RESEARCH FELUY , NESTERENKO, Nikolai , VERMEIREN, Walter , VAN DONK, Sander , MINOUX, Delphine
发明人： NESTERENKO, Nikolai , VERMEIREN, Walter , VAN DONK, Sander , MINOUX, Delphine
IPC分类号： B01J27/16 , B01J29/06 , B01J29/40 , C07C1/20 , C07C4/06
摘要： The invention covers a process for obtaining an alkaline earth or rare earth metal-P-modified molecular sieve (M-P-modified molecular sieve) comprising the following steps: a), selecting at least one molecular sieve selected from one of: - a P-modified molecular sieve which contains at least 0.3 wt% of P obtained by dealuminating a molecular sieve in a steaming step, followed by a leaching step using an acid solution containing a source of P - a molecular sieve which is modified with P during step b) by dealuminating the molecular sieve in a steaming step, followed by a leaching step using an acid solution containing a source of P thereby introducing at least 0.3 wt % of P b). contacting said molecular sieve with an alkaline earth or rare earth metal-containing compound (M-containing compound) to introduce at least 0.05 wt% of the alkaline earth or rare earth metal to the molecular sieve. The invention also covers a catalyst composite comprising: a), at least 10 wt % of a M-P-modified molecular sieve comprising at least 0.05 % by weight of an alkaline earth or rare earth metal (M) and at least 0.3 wt% of P, b). optionally metal phosphate, c). optionally matrix material, and d). optionally binder. The catalyst of the invention can also be used in a process for making an olefin product from an oxygen-containing, halogenide-containing or sulphur-containing organic feedstock wherein said oxygen-containing, halogenide-containing or sulphur-containing organic feedstock is contacted in the XTO reactor with the catalyst composite according to the invention under conditions effective to convert the oxygen-containing, halogenide-containing or sulphur-containing organic feedstock to olefin products (the XTO reactor effluent). The catalyst composite of the invention can also be used in addition or alternatively in an OCP process.

2. 发明申请

WO2009098262A1 DEHYDRATION OF ALCOHOLS ON CRYSTALLINE SILICATES 审中-公开
标题翻译：酒精在水溶性硅酸盐上的脱水
公开(公告)号：WO2009098262A1
公开(公告)日：2009-08-13
申请号：PCT/EP2009/051329
申请日：2009-02-05
申请人： TOTAL PETROCHEMICALS RESEARCH FELUY , MINOUX, Delphine , NESTERENKO, Nikolai , VERMEIREN, Walter , VAN DONK, Sander , DATH, Jean-Pierre
发明人： MINOUX, Delphine , NESTERENKO, Nikolai , VERMEIREN, Walter , VAN DONK, Sander , DATH, Jean-Pierre
IPC分类号： C07C1/24 , C07C11/04
CPC分类号： C07C1/24 , B01J29/40 , B01J2229/16 , B01J2229/36 , B01J2229/37 , B01J2229/42 , C07C2529/40 , Y02P20/52 , C07C11/04
摘要： The present invention relates to a process for the dehydration of at least an alcohol to make at least an olefin, comprising: introducing in a reactor a stream (A) comprising at least an alcohol, optionally water, optionally an inert component, contacting said stream with a catalyst in said reactor at conditions effective to dehydrate at least a portion of the alcohol to make an olefin, recovering from said reactor an olefin containing stream (B), Wherein the catalyst is : • a crystalline silicate having a ratio Si/AI of at least about 100, or • a dealuminated crystalline silicate, or • a phosphorus modified zeolite, the WHSV of the alcohols is at least 2 h -1 , the temperature ranges from 280°C to 500°C. It relates also to the same process as above but wherein the catalyst is a phosphorus modified zeolite and at any WHSV. The partial pressure of the alcohol in the dehydration reactor advantageously ranges from 1.2 to 4 bars absolute (0.12 MPa to 0.4 MPa), the temperature of the dehydration reactor ranges advantageously from 300°C to 400°C and the alcohol is selected among ethanol, propanol, butanol and phenylethanol.
摘要翻译：本发明涉及一种使至少一种醇脱水以制备至少一种烯烃的方法，其包括：在反应器中引入至少包含醇，任选的水，任选的惰性组分的物流（A）在有效使至少一部分醇脱水以制备烯烃的条件下在所述反应器中的催化剂，从所述反应器回收含烯烃的物流（B），其中所述催化剂是：具有比例Si / Al的结晶硅酸盐至少约100个，或脱铝结晶硅酸盐或磷改性沸石，醇的WHSV为至少2h -1，温度范围为280℃至500℃。它还涉及与上述相同的方法，但是其中催化剂是磷改性沸石并且在任何WHSV下。脱水反应器中的醇的分压有利地在1.2至4巴绝对压力（0.12MPa至0.4MPa）的范围内，脱水反应器的温度有利地为300℃至400℃，醇选自乙醇，丙醇，丁醇和苯乙醇。

3. 发明申请

WO2009016156A1 CRACKING OF OLEFINS ON PHOSPHORUS MODIFIED MOLECULAR SIEVES. 审中-公开
标题翻译：烯烃改性磷酸酯改性分子筛的破碎。
公开(公告)号：WO2009016156A1
公开(公告)日：2009-02-05
申请号：PCT/EP2008/059886
申请日：2008-07-28
申请人： TOTAL PETROCHEMICALS RESEARCH FELUY , NESTERENKO, Nikolai , VERMEIREN, Walter , MINOUX, Delphine , VAN DONK, Sander
发明人： NESTERENKO, Nikolai , VERMEIREN, Walter , MINOUX, Delphine , VAN DONK, Sander
IPC分类号： B01J29/06 , B01J29/18 , B01J29/40 , C07C4/06 , C07C4/10 , C10G11/05
CPC分类号： C10G11/05 , B01J29/06 , B01J29/18 , B01J29/40 , B01J29/65 , B01J29/70 , B01J2229/16 , B01J2229/18 , B01J2229/36 , B01J2229/37 , B01J2229/40 , C10G2300/1088 , C10G2300/807 , C10G2400/20 , C10G2400/22
摘要： The present invention provides a process for the catalytic cracking of an olefin-rich feedstock which is selective towards light olefins in the effluent, the process comprising contacting a hydrocarbon feedstock containing one or more olefins, with a catalyst made of a phosphorus-modified zeolite (A), to produce an effluent with an olefin content of lower molecular weight than that of the feedstock, wherein said phosphorous modified zeolite (A) is made by a process comprising in that order: selecting a zeolite with low Si/AI ratio (advantageously lower than 30) among H+ or NH 4 + -form of MFI, MEL, FER, MOR, clinoptilolite, said zeolite having been made preferably without direct addition of organic template; steaming at a temperature ranging from 400 to 870°C for 0.01-200h; leaching with an aqueous acid solution containing the source of P at conditions effective to remove a substantial part of Al from the zeolite and to introduce at least 0.3 wt% of P; separation of the solid from the liquid; an optional washing step or an optional drying step or an optional drying step followed by a washing step; a calcination step. Said cracking of an olefin-rich feedstock is often referred in the following description and claims as OCP (Olefin Cracking Process). The catalyst made of a P-modified zeolite (A) can be the P-modified zeolite (A) itself or it can be the P-modified zeolite (A) formulated into a catalyst by combining with other materials that provide additional hardness or catalytic activity to the finished catalyst product. The zeolite with low Si/AI ratio has been made previously with or without direct addition of an organic template. The zeolite can be made with the help of seeds techniques but without template, the seeds could have been made with a template which means that the zeolite is made without direct addition of a template.
摘要翻译：本发明提供了一种对在流出物中对轻质烯烃有选择性的富烯烃原料的催化裂化方法，该方法包括使含有一种或多种烯烃的烃原料与由磷改性沸石制成的催化剂 A），以产生烯烃含量低于原料的分子量的流出物，其中所述的磷改性沸石（A）通过以下方法制备：选择具有低Si / Al比的沸石（有利地低于30）MFI，MEL，FER，MOR，斜发沸石的H +或NH4 +形式，所述沸石优选不直接添加有机模板; 在400〜870℃的温度范围内蒸煮0.01〜200h; 在有效从沸石中除去大部分Al并引入至少0.3wt％P的条件下，用含有P源的酸性水溶液浸出; 从液体中分离固体; 任选的洗涤步骤或任选的干燥步骤或任选的干燥步骤，随后进行洗涤步骤; 煅烧步骤。富烯烃原料的所述裂化在下列说明书和权利要求书中通常称为OCP（烯烃裂化方法）。由P型改性沸石（A）制成的催化剂可以是P型改性沸石（A）本身，也可以是通过与提供额外硬度或催化剂的其它材料组合而配制成催化剂的P型改性沸石（A）对成品催化剂产品的活性。具有低Si / Al比的沸石先前已经或没有直接添加有机模板而被制备。沸石可以借助于种子技术制成，但是没有模板，种子可以用模板制成，这意味着沸石是在没有直接添加模板的情况下制成的。

4. 发明申请

WO2011089235A1 DEHYDRATION OF ALCOHOLS ON A CRYSTALLINE SILICATE OF LOW Si/Al RATIO 审中-公开
标题翻译：醇在低Si / Al比例的晶体硅酸中的脱水
公开(公告)号：WO2011089235A1
公开(公告)日：2011-07-28
申请号：PCT/EP2011/050855
申请日：2011-01-21
申请人： TOTAL PETROCHEMICALS RESEARCH FELUY , MINOUX, Delphine , NESTERENKO, Nikolai , ADAM, Cindy , VAN DONK, Sander , VERMEIREN, Walter
发明人： MINOUX, Delphine , NESTERENKO, Nikolai , ADAM, Cindy , VAN DONK, Sander , VERMEIREN, Walter
IPC分类号： C07C1/24 , C07C11/04
CPC分类号： C07C1/24 , B01J29/65 , B01J29/90 , B01J2229/16 , B01J2229/36 , C07C2529/65 , C07C2529/70 , C07C2529/85 , C23C18/00 , C25D7/0664 , C25D17/00 , Y02P20/52 , Y02P20/584 , C07C11/04
摘要： The present invention (in a first embodiment) relates to a process for the dehydration of an alcohol having at least 2 carbon atoms to make the corresponding olefin, comprising: introducing in a reactor a stream (A) comprising at least an alcohol, optionally water, optionally an inert component, contacting said stream with a catalyst in said reactor at conditions effective to dehydrate at least a portion of the alcohol to make an olefin, recovering from said reactor an olefin containing stream (B), wherein, the catalyst is a crystalline silicate of the group FER, MWW, EUO, MFS, ZSM- 48, MTT or TON having Si/Al under 100, or a dealuminated crystalline silicate of the group FER, MWW, EUO, MFS, ZSM-48, MTT or TON having Si/Al under 100, or a phosphorus modified crystalline silicate of the group FER, MWW, EUO, MFS, ZSM-48, MTT or TON having Si/Al under 100, the WHSV of the alcohol is at least 4 h -1 and/or the temperature ranges from 320°C to 600°C.
摘要翻译：本发明（在第一实施方案中）涉及使具有至少2个碳原子的醇脱水以制备相应烯烃的方法，包括：在反应器中引入至少包含醇，任选的水任选的惰性组分，在所述反应器中使所述料流与催化剂接触的条件下，使所述醇的至少一部分脱水以制备烯烃，从所述反应器回收含烯烃流（B），其中所述催化剂为具有Si / Al低于100的组FER，MWW，EUO，MFS，ZSM-48，MTT或TON的结晶硅酸盐，或FER，MWW，EUO，MFS，ZSM-48，MTT或TON组的脱铝结晶硅酸盐 Si / Al低于100，或具有Si / Al低于100的FER，MWW，EUO，MFS，ZSM-48，MTT或TON的磷改性结晶硅酸盐，醇的WHSV为至少4h -1 和/或温度范围为320℃至600℃。

5. 发明申请

WO2009098269A1 PROCESS TO MAKE OLEFINS FROM ETHANOL 审中-公开
标题翻译：从乙醇制备油脂的方法
公开(公告)号：WO2009098269A1
公开(公告)日：2009-08-13
申请号：PCT/EP2009/051342
申请日：2009-02-05
申请人： TOTAL PETROCHEMICALS RESEARCH FELUY , MINOUX, Delphine , NESTERENKO, Nikolai , VERMEIREN, Walter , VAN DONK, Sander , GRASSO, Giacomo
发明人： MINOUX, Delphine , NESTERENKO, Nikolai , VERMEIREN, Walter , VAN DONK, Sander , GRASSO, Giacomo
IPC分类号： C07C11/06 , C07C11/04 , C07C1/24 , C07C4/06
CPC分类号： C07C11/04 , C07C1/24 , C07C4/06 , C07C11/06
摘要： The present invention relates to a process for the conversion of ethanol to make essentially ethylene and propylene, comprising : a) introducing in a reactor (A) (also called the first low temperature reaction zone) a stream comprising ethanol, optionally water, optionally an inert component, b) contacting said stream with a catalyst (A1) in said reactor (A) at conditions effective to dehydrate at least a portion of the ethanol to essentially ethylene, c) recovering from said reactor an effluent comprising : essentially ethylene, minor amounts of various hydrocarbons, water, optionally unconverted ethanol and the optional inert component of step a), d) fractionating said effluent of step c) to remove water, unconverted ethanol, optionally the inert component, and optionally the whole or a part of the various hydrocarbons to get a stream (D) comprising essentially ethylene and optionally the inert component, e) introducing at least a part of said stream (D) mixed with a stream (D1 ) comprising olefins having 4 carbon atoms or more (C4+ olefins) in a OCP reactor (also called the second high temperature reaction zone) under the condition that the mixture (D)+(D1) comprises at least 10wt% of C4+ olefins, f) contacting said stream comprising at least a part of (D) and the stream (D1 ) in said OCP reactor with a catalyst which is selective towards light olefins in the effluent, to produce an effluent with an olefin content of lower molecular weight than that of the feedstock, g) fractionating said effluent of step f) to produce at least an ethylene stream, a propylene stream and a fraction consisting essentially of hydrocarbons having 4 carbon atoms or more, optionally recycling ethylene in whole or in part at the inlet of the OCP reactor of step f), or at the inlet of the reactor (A) or in part at the inlet of the OCP reactor of step f) and in part at the inlet of the reactor (A), optionally recycling the fraction consisting essentially of hydrocarbons having 4 carbon atoms or more at the inlet of the OCP reactor.
摘要翻译：本发明涉及一种将乙醇转化成基本上乙烯和丙烯的方法，其包括：a）在反应器（A）（也称为第一低温反应区）中引入包含乙醇，任选的水，任选地，惰性组分，b）在有效将至少一部分乙醇脱水至基本上乙烯的条件下，使所述料流与所述反应器（A）中的催化剂（A1）接触; c）从所述反应器回收包含：基本上乙烯，次要的流出物各种烃，水，任选未转化的乙醇和步骤a）的任选的惰性组分的量，d）将步骤c）的所述流出物分馏以除去水，未转化的乙醇，任选的惰性组分，以及任选的全部或部分各种烃以得到基本上包含乙烯和任选的惰性组分的物流（D），e）将至少一部分与流（D1）com混合的所述物流（D）在混合物（D）+（D1）包含至少10重量％的C 4 +烯烃的条件下，在OCP反应器（也称为第二高温反应区）中具有4个碳原子或更多个（C 4 +烯烃）使所述OCP反应器中包含至少一部分（D）和物流（D1）的物流与流出物中的轻质烯烃选择性的催化剂接触，以产生具有低于原料，g）对步骤f）的所述流出物进行分馏以产生至少一种乙烯流，丙烯料流和基本上由具有4个碳原子或更多碳原子的烃组成的馏分，任选地在乙烯流入口处全部或部分回收乙烯 OCP反应器，或在反应器（A）的入口或部分在步骤f）的OCP反应器的入口处，部分地在反应器（A）的入口处，可任选地再循环基本上组分的馏分的碳氢化合物 OCP或更多在OCP反应器的入口处。

6. 发明申请

WO2009098267A1 PROCESS TO MAKE OLEFINS FROM ETHANOL 审中-公开
标题翻译：从乙醇制备油脂的方法
公开(公告)号：WO2009098267A1
公开(公告)日：2009-08-13
申请号：PCT/EP2009/051340
申请日：2009-02-05
申请人： TOTAL PETROCHEMICALS RESEARCH FELUY , MINOUX, Delphine , NESTERENKO, Nikolai , VERMEIREN, Walter , VAN DONK, Sander , GRASSO, Giacomo
发明人： MINOUX, Delphine , NESTERENKO, Nikolai , VERMEIREN, Walter , VAN DONK, Sander , GRASSO, Giacomo
IPC分类号： C07C1/24 , C07C11/02
CPC分类号： C10G11/05 , C07C1/20 , C07C1/24 , C07C4/06 , C07C11/06 , C07C2529/035 , C07C2529/70 , C07C2529/85 , Y02P30/42 , C07C11/04
摘要： The present invention relates to a process for the conversion of ethanol to make essentially ethylene and propylene, comprising : a) introducing in a reactor (A) (also called the first low temperature reaction zone) a stream comprising ethanol under a partial pressure at least about 0.2 MPa, optionally water, optionally an inert component; b) contacting said stream with a catalyst (A1) in said reactor (A) at conditions effective to convert at least a portion of the ethanol to essentially ethylene, propylene and olefins having 4 carbon atoms or more (C4+ olefins); c) recovering from said reactor an effluent comprising : ethylene and C4+ fraction containng mainly olefins having 4 carbon atoms or more (C4+ olefins), propylene and various hydrocarbons, water, optionally unconverted ethanol and the optional inert component of step a); d) fractionating said effluent of step c) to remove water, unconverted ethanol, optionally the inert component, optionally the propylene and optionally the whole or a part of the various hydrocarbons to get a stream (D) comprising essentially ethylene, olefins having 4 carbon atoms or more (C4+ olefins) and optionally the inert component; e) introducing at least a part of said stream (D) optionally mixed with a stream (D1) comprising olefins having 4 carbon atoms or more (C4+ olefins) in a OCP reactor (also called the second high temperature reaction zone) under the condition that said mixture (D)+(D1) comprises at least 10wt% of C4+ olefins; f) contacting said stream comprising at least a part of (D) and the optional (D1) in said OCP reactor with a catalyst which is selective towards light olefins in the effluent, to produce an effluent with an olefin content of lower molecular weight than that of the feedstock; g) fractionating said effluent of step f) to produce at least an ethylene stream, a propylene stream and a fraction consisting essentially of hydrocarbons having 4 carbon atoms or more, optionally recycling ethylene in whole or in part at the inlet of the OCP reactor of step f), or at the inlet of the reactor (A) or in part at the inlet of the OCP reactor of step f) and in part at the inlet of the reactor (A), optionally recycling the fraction consisting essentially of hydrocarbons having 4 carbon atoms or more at the inlet of the OCP reactor.
摘要翻译：本发明涉及一种将乙醇转化成基本上乙烯和丙烯的方法，包括：a）至少在部分压力下将反应器（A）（也称为第一低温反应区）引入包含乙醇的料流约0.2MPa，任选的水，任选的惰性组分; b）在有效将至少一部分乙醇转化成基本上为具有4个碳原子或更多个（C 4 +烯烃）的乙烯，丙烯和烯烃的条件下，使所述料流与所述反应器（A）中的催化剂（A1）接触; c）从所述反应器回收流出物，其包含：乙烯和C4 +馏分主要含有具有4个碳原子或更多个（C 4 +烯烃）的烯烃，丙烯和各种烃，水，任选未转化的乙醇和步骤a）的任选的惰性组分; d）将步骤c）的所述流出物分馏以除去水，未转化的乙醇，任选的惰性组分，任选的丙烯和任选的各种烃的全部或部分，以获得基本上包含乙烯，含有4个碳的烯烃原子或更多（C4 +烯烃）和任选的惰性组分; e）在OCP反应器（也称为第二高温反应区）中将至少一部分所述物流（D）任选与包含具有4个碳原子或更多个（C 4 +烯烃）的烯烃的物流（D1）所述混合物（D）+（D1）包含至少10重量％的C 4 +烯烃; f）使所述OCP反应器中包含至少一部分（D）和任选的（D1）的物流与在流出物中对轻质烯烃有选择性的催化剂接触，以产生具有低于原料的; g）将步骤f）的所述流出物分馏以产生至少一种乙烯流，丙烯料流和基本上由具有4个碳原子或更多碳原子的烃组成的馏分，任选地将乙烯全部或部分在OCP反应器的入口步骤f），或在反应器（A）的入口处或部分在步骤f）的OCP反应器的入口处，部分地在反应器（A）的入口处，可任选地再循环基本上由以下物质组成的馏分：具有在OCP反应器的入口处具有4个或更多个碳原子。

7. 发明申请

WO2009016155A2 USE OF PHOSPHORUS MODIFIED MOLECULAR SIEVES IN CONVERSION OF ORGANICS TO OLEFINS 审中-公开
标题翻译：磷酸改性分子筛在有机物转化成烯烃中的应用
公开(公告)号：WO2009016155A2
公开(公告)日：2009-02-05
申请号：PCT/EP2008/059885
申请日：2008-07-28
申请人： TOTAL PETROCHEMICALS RESEARCH FELUY , NESTERENKO, Nikolai , VERMEIREN, Walter , MINOUX, Delphine , VAN DONK, Sander
发明人： NESTERENKO, Nikolai , VERMEIREN, Walter , MINOUX, Delphine , VAN DONK, Sander
IPC分类号： C07C1/20 , C07C11/02 , B01J29/00 , B01J29/85 , C01B39/02 , C07C2/08
CPC分类号： C07C1/20 , B01J29/40 , B01J37/28 , B01J2229/18 , B01J2229/37 , C07C1/322 , C07C4/06 , C07C2529/85 , C10G2400/20 , Y02P30/42 , C07C11/02
摘要： The present invention relates to a process to make light olefins, in a combined XTO-OCP process, from an oxygen-containing, halogenide-containing or sulphur-containing organic feedstock comprising : contacting said oxygen-containing, halogenide-containing or sulphur-containing organic feedstock in the XTO reactor with a catalyst made of a P-modified zeolite (A) at conditions effective to convert at least a portion of the feedstock to form a XTO reactor effluent comprising light olefins and a heavy hydrocarbon fraction; separating said light olefins from said heavy hydrocarbon fraction; contacting said heavy hydrocarbon fraction in the OCP reactor with a catalyst made of a P-modified zeolite (A) at conditions effective to convert at least a portion of said heavy hydrocarbon fraction to light olefins; wherein said P-modified zeolite (A) is made by a process comprising in that order: selecting a zeolite (advantageously with Si/AI ratio between 4 and 500) among H + or NH 4 + -form of MFI, MEL, FER, MOR, clinoptilolite; introducing P at conditions effective to introduce advantageously at least 0.05 wt% of P; separation of the solid from the liquid if any; an optional washing step or an optional drying step or an optional drying step followed by a washing step; a calcination step.
摘要翻译：本发明涉及一种在组合的XTO-OCP方法中由含氧，含卤素或含硫有机原料制备轻质烯烃的方法，包括：将含氧的含卤素或含硫的在有效地转化至少一部分原料以形成包含轻质烯烃和重质烃馏分的XTO反应器流出物的条件下，在XTO反应器中的有机原料具有由P改性沸石（A）制成的催化剂; 将所述轻质烯烃与所述重质烃馏分分离; 在有效将至少一部分所述重质烃馏分转化为轻质烯烃的条件下，使所述OCP反应器中的所述重质烃馏分与由P-改性沸石（A）制成的催化剂接触; 其中所述P型改性沸石（A）通过以下方法制备：在MFI，MEL，FER，MOR，HNO 3的H +或NH 4 +形式中选择沸石（有利地具有4至500的Si / Al比）斜发沸石; 在有效引入至少0.05重量％的P的条件下引入P; 从液体中分离出固体物质; 任选的洗涤步骤或任选的干燥步骤或任选的干燥步骤，随后进行洗涤步骤; 煅烧步骤。

8. 发明申请

WO2009098268A1 DEHYDRATION OF ALCOHOLS IN THE PRESENCE OF AN INERT COMPONENT 审中-公开
标题翻译：酒精中存在异味组分时的脱水
公开(公告)号：WO2009098268A1
公开(公告)日：2009-08-13
申请号：PCT/EP2009/051341
申请日：2009-02-05
申请人： TOTAL PETROCHEMICALS RESEARCH FELUY , MINOUX, Delphine , NESTERENKO, Nikolai , VERMEIREN, Walter , VAN DONK, Sander
发明人： MINOUX, Delphine , NESTERENKO, Nikolai , VERMEIREN, Walter , VAN DONK, Sander
IPC分类号： C07C1/24 , C07C11/02 , C07C11/04
CPC分类号： C07C11/02 , C07C1/24 , C07C11/04
摘要： The present invention (first embodiment) relates to a process for the dehydration of at least an alcohol to make at least an olefin, comprising : a) introducing in a reactor a stream (A) comprising at least an alcohol optionally in aqueous solution and an inert component, b) contacting said stream with a catalyst in said reactor at conditions effective to dehydrate at least a portion of the alcohol to make an olefin, c) recovering from said reactor a stream (B) comprising : the inert component and at least an olefin, water and optionally unconverted alcohol, d) optionally fractionating the stream (B) to recover the unconverted alcohol and recycling said unconverted alcohol to the reactor of step a), e) optionally fractionating the stream (B) to recover the inert component and the olefin and recycling said inert component to the reactor of step a), Wherein, the inert component is selected among ethane, the hydrocarbons having from 3 to 10 carbon atoms, naphtenes and CO2, the proportion of the inert component is such as the reactor operates essentially adiabatically. The present invention also relates to a similar process as above but the catalyst is : • a crystalline silicate having a ratio Si/AI of at least 100, or • a dealuminated crystalline silicate, or • a phosphorus modified zeolite, the WHSV of the alcohol is at least 2 h -1 when the catalyst is a crystalline silicate having a ratio Si/AI of at least 100 or a dealuminated crystalline silicate. Advantageously the pressure of the dehydration reactor is high enough to help the recovery of the inert component and recycling thereof in the reactor of step a) without a gas compressor but only a pump.
摘要翻译：本发明（第一实施方案）涉及使至少一种醇脱水以制备至少一种烯烃的方法，其包括：a）在反应器中引入任选在水溶液中至少包含醇的流（A），和惰性组分，b）在有效使至少一部分醇脱水以制备烯烃的条件下使所述料流与催化剂在所述反应器中接触，c）从所述反应器回收包含惰性组分并且至少烯烃，水和任选未转化的醇，d）任选地将料流（B）分馏以回收未转化的醇并将所述未转化的醇再循环到步骤a）的反应器中，e）任选地将料流（B）分馏以回收惰性组分和烯烃，并将所述惰性组分再循环到步骤a）的反应器中，其中惰性组分选自乙烷，具有3至10个碳原子的烃，萘和CO 2，比例的惰性组分如反应器基本上绝热地进行操作。本发明还涉及上述类似的方法，但催化剂是：Si / Al比为至少100的结晶硅酸盐，或脱铝结晶硅酸盐或磷改性沸石，醇的WHSV至少为 2 h-1，当催化剂是Si / Al比为至少100的结晶硅酸盐或脱铝结晶硅酸盐时。有利地，脱水反应器的压力足够高以帮助惰性组分的回收和在步骤a）的反应器中的回收，而没有气体压缩机，而仅仅是泵。

9. 发明申请

WO2011161045A1 DEHYDRATION OF ALCOHOLS ON POISONED ACIDIC CATALYSTS 审中-公开
标题翻译：酒精在脱毒酸催化剂上的脱水
公开(公告)号：WO2011161045A1
公开(公告)日：2011-12-29
申请号：PCT/EP2011/060212
申请日：2011-06-20
申请人： TOTAL PETROCHEMICALS RESEARCH FELUY , MINOUX, Delphine , ADAM, Cindy , NESTERENKO, Nikolai , VAN DONK, Sander , DATH, Jean-Pierre , VERMEIREN, Walter
发明人： MINOUX, Delphine , ADAM, Cindy , NESTERENKO, Nikolai , VAN DONK, Sander , DATH, Jean-Pierre , VERMEIREN, Walter
IPC分类号： C07C1/24 , C07C11/04
CPC分类号： C07C1/24 , C07C2521/04 , C07C2521/06 , C07C2521/12 , C07C2529/40 , C07C2529/65 , C07C2529/82 , C07C2529/83 , C07C2529/85 , Y02P20/52 , C07C11/04
摘要： The present invention is a process for the dehydration of an alcohol having at least 2 carbon atoms to make the corresponding olefin, comprising: a) introducing in a reactor a stream (A) comprising at least an alcohol, optionally water, optionally an inert component, b) contacting said stream with an acidic catalyst in said reactor at conditions effective to dehydrate at least a portion of the alcohol to make an olefin, c) recovering from said reactor a stream (B) comprising : the inert component and at least an olefin, water and optionally unconverted alcohol, d) optionally fractionating the stream (B) to recover the unconverted alcohol and recycling said unconverted alcohol to the reactor of step a), e) optionally fractionating the stream (B) to recover the inert component, water and the olefin and optionally recycling said inert component and optionally a part of the water to the reactor of step a), wherein, f) an effective amount of a component capable to neutralize a part of the catalyst active site is introduced in stream (A) or directly in the dehydration reactor and g) optionally the temperature of the dehydration reactor is adjusted to increase the alcohol conversion or the olefin yield or both. In another embodiment at step f) an effective amount of a component capable to increase the selectivity for the desired corresponding olefin is introduced in stream (A) or directly in the dehydration reactor. The component introcuced at step f) can be chosen from the group consisting of ammonia, organic ammonium salts, hydrazine, nitriles, amines (including pyridines, pyrrols, pyrrolydones and pyrrolidines), amides, imines, di-imines, imides, cyanates, isocyanates, nitrites and nitroso compounds, aldehydes, ketones, carboxylic esters, and their corresponding thio-compounds (thiols, sulphides, disulfides).
摘要翻译：本发明是使具有至少2个碳原子的醇脱水以制备相应的烯烃的方法，其包括：a）在反应器中引入至少包含醇，任选的水，任选的惰性组分的流（A） b）使所述料流与所述反应器中的酸性催化剂接触，在有效使所述醇的至少一部分脱水以制备烯烃的条件下，c）从所述反应器回收流（B），其包含：惰性组分和至少一种烯烃，水和任选未转化的醇，d）任选地分馏流（B）以回收未转化的醇并将所述未转化的醇再循环到步骤a）的反应器中，e）任选地将流（B）分馏以回收惰性组分，水和烯烃，并且任选地将所述惰性组分和任选的一部分水再循环到步骤a）的反应器中，其中f）有效量的能够中和c的一部分反应器活性位点以流（A）或直接在脱水反应器中引入，并且g）任选地调节脱水反应器的温度以增加醇转化率或烯烃产率或两者。在步骤f）的另一个实施方案中，有效量的能够增加所需相应烯烃的选择性的组分被引入到流（A）中，或直接在脱水反应器中引入。在步骤f）中介导的组分可以选自氨，有机铵盐，肼，腈，胺（包括吡啶，吡咯，吡咯烷酮和吡咯烷），酰胺，亚胺，二亚胺，酰亚胺，氰酸酯，异氰酸酯，亚硝酸盐和亚硝基化合物，醛，酮，羧酸酯及其相应的硫代化合物（硫醇，硫化物，二硫化物）。

10. 发明申请

WO2010060981A1 PURIFICATION OF ALCOHOLS PRIOR TO THEIR USE IN THE PRESENCE OF AN ACID CATALYST 审中-公开
标题翻译：在酸性催化剂存在下使用的醇的纯化
公开(公告)号：WO2010060981A1
公开(公告)日：2010-06-03
申请号：PCT/EP2009/065951
申请日：2009-11-27
申请人： TOTAL PETROCHEMICALS RESEARCH FELUY , MINOUX, Delphine , VERMEIREN, Walter , NESTERENKO, Nikolai , VAN DONK, Sander , DATH, Jean-Pierre
发明人： MINOUX, Delphine , VERMEIREN, Walter , NESTERENKO, Nikolai , VAN DONK, Sander , DATH, Jean-Pierre
IPC分类号： C07C29/76
CPC分类号： C07C29/76 , C07C1/24 , C07C29/74 , C07C29/90 , C07C11/04 , C07C31/08
摘要： Process for the purification of an alcohol in the course of a process comprising : (1) providing a reaction zone (C) comprising an acid type catalyst; (2) providing a reaction zone (B) comprising an acid adsorbent material; (3) providing an alcohol stream comprising impurities; (4) introducing the alcohol stream of (3) into the reaction zone (B) and bringing said stream into contact with the acid adsorbent material at conditions effective to reduce the amount of impurities having an adverse effect on the acid type catalyst of the reaction zone (C); (5) recovering from step (4) an alcohol stream and introducing it into the reaction zone (C); (6) optionally introducing one or more reactants (R) into the reaction zone (C); (7) operating said reaction zone (C) at conditions effective to recover a valuable effluent.
摘要翻译：在包括以下步骤的过程中醇的纯化方法：（1）提供包含酸型催化剂的反应区（C）; （2）提供包含酸吸附材料的反应区（B）; （3）提供包含杂质的醇流; （4）将（3）的醇流引入反应区（B）中，并使所述物流与酸吸附材料接触，有效地减少对反应的酸型催化剂有不利影响的杂质的量区（C）; （5）从步骤（4）中回收醇流并将其引入反应区（C）中; （6）任选地将一种或多种反应物（R）引入反应区（C）中; （7）在有效回收有价值流出物的条件下操作所述反应区（C）。

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