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1.发明申请Use of Phosphorus Modified Molecular Sieves in Conversion of Organics to Olefins 有权使用磷改性分子筛将有机物转化为烯烃公开(公告)号：US20100261944A1
公开(公告)日：2010-10-14
申请号：US12671220
申请日：2008-07-28
IPC分类号： C07C1/00
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/Al ratio between 4 and 500) among H+ or NH4+-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：使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，使用具有P型改性沸石（A）的催化剂在XTO反应器中的有机原料; 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-改性沸石（A）通过以下顺序制备：在MFI，MEL，FER，MOR，斜发沸石的H +或NH4 +形式中选择沸石（有利地为Si / Al比在4和500之间） ; 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。
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公开(公告)号：US09249066B2
公开(公告)日：2016-02-02
申请号：US13701774
申请日：2011-06-20
申请人： Delphine Minoux , Cindy Adam , Nikolai Nesterenko , Sander Van Donk , Jean-Pierre Dath , Walter Vermeiren
发明人： Delphine Minoux , Cindy Adam , Nikolai Nesterenko , Sander Van Donk , Jean-Pierre Dath , Walter Vermeiren
IPC分类号： C07C1/24
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： A dehydration process may include introducing in a reactor an alcohol, and contacting the alcohol with an acidic catalyst to dehydrate the alcohol to make a corresponding olefin. The process may include recovering from the reactor the olefin and water. In the process, an effective amount of a component capable to neutralize a part of the catalyst active site may be introduced. The component may include ammonia, organic ammonium salts, hydrazine, nitriles, amines, amides, imines, di-imines, imides, cyanates, isocyanates, nitrites and nitroso compounds, aldehydes, ketones, carboxylic esters, and their corresponding thio-compounds.
摘要翻译： 脱水方法可以包括在反应器中引入醇，并将醇与酸性催化剂接触以使醇脱水以制备相应的烯烃。 该方法可以包括从反应器中回收烯烃和水。 在该方法中，可以引入有效量的能够中和一部分催化剂活性部位的成分。 该组分可包括氨，有机铵盐，肼，腈，胺，酰胺，亚胺，二亚胺，酰亚胺，氰酸酯，异氰酸酯，亚硝酸酯和亚硝基化合物，醛，酮，羧酸酯及其相应的硫代化合物。
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3.发明授权Simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts 有权酸催化剂上异丁醇的同时脱水和骨架异构化公开(公告)号：US09233886B2
公开(公告)日：2016-01-12
申请号：US13582759
申请日：2011-03-15
CPC分类号： C07C1/24 , B01J29/85 , C07C5/2518 , C07C5/2775 , C07C11/08 , C07C11/09 , C07C2521/04 , C07C2529/40 , C07C2529/65 , C07C2529/70 , Y02P20/127
摘要： The present invention (in a first embodiment) relates to a process for the simultaneous dehydration and skeletal isomerization of isobutanol to make substantially corresponding olefins, having the same number of carbons and consisting essentially of a mixture of n-butenes and iso-butene, said process comprising: a) introducing in a reactor a stream (A) comprising isobutanol, optionally water, optionally an inert component, b) contacting said stream with a catalyst in said reactor at conditions effective to dehydrate and skeletal isomerize at least a portion of the isobutanol to make a mixture of n-butenes and iso-butene, c) recovering from said reactor a stream (B), removing water, the inert component if any and unconverted isobutanol if any to get a mixture of n-butenes and iso-butene, Wherein, the WHSV of the isobutanol is at least 1 h−1 or the temperature is from 200° C. to 600° C. and the catalyst is capable to make simultaneously the dehydration and skeletal isomerization of butene. The catalyst is a crystalline silicate of the group FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON having Si/Al higher than 10, or a dealuminated crystalline silicate of the group FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON having Si/Al higher than 10, or a phosphorus modified crystalline silicate of the group FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON having Si/Al higher than 10, or a silicoaluminaphosphate molecular sieve of the group AEL, or a silicated, zirconated or titanated or fluorinated alumina. Advantageously the stream (B) is fractionated in a step d) to produce a n-butenes stream (N) and to remove the essential part of isobutene optionally recycled with stream (A) to the dehydration/isomerization reactor of step b).
摘要翻译： 本发明（在第一实施方案中）涉及同时脱水和骨架异构化异丁醇以制备具有相同数目的碳并基本上由正丁烯和异丁烯组成的基本相应的烯烃的方法，所述方法 方法包括：a）在反应器中引入包含异丁醇，任选的水，任选的惰性组分的物流（A），b）在所述反应器中使所述物流与催化剂接触，所述条件有效脱水并骨架异构化至少一部分 异丁醇以制备正丁烯和异丁烯的混合物，c）从所述反应器回收流（B），除去水，惰性组分（如果有的话）和未转化的异丁醇，以获得正丁烯和异丁烯的混合物， 丁烯，其中异丁醇的WHSV为至少1h-1或温度为200℃至600℃，催化剂能够同时进行b的脱水和骨架异构化 utene。 该催化剂是具有Si / Al大于10的FER，MWW，EUO，MFS，ZSM-48，MTT，MFI，MEL或TON的结晶硅酸盐，或FER，MWW，EUO等的脱铝结晶硅酸盐， 具有Si / Al大于10的MFS，ZSM-48，MTT，MFI，MEL或TON，或FER，MWW，EUO，MFS，ZSM-48，MTT，MFI，MEL或TON的磷改性结晶硅酸盐，其具有 Si / Al高于10，或AEL的硅铝磷酸盐分子筛，或硅化，锆酸化或钛酸化或氟化氧化铝。 有利地，在步骤d）中将流（B）分馏以产生正丁烯料流（N），并除去任选与料流（A）一起循环的异丁烯的主要部分至步骤b）的脱水/异构化反应器。
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4.发明授权Process to make propylene from isobutanol by dehydration and subsequent cracking 有权通过脱水和随后开裂从异丁醇制备丙烯的方法公开(公告)号：US09079813B2
公开(公告)日：2015-07-14
申请号：US13813107
申请日：2011-07-08
IPC分类号： C07C1/22 , C07C1/24 , C07C4/06 , C10G3/00 , C12P5/02 , C12P7/16 , B01J21/04 , B01J29/40 , B01J29/65
CPC分类号： C07C1/24 , B01J21/04 , B01J29/40 , B01J29/65 , C07C4/06 , C07C2521/04 , C07C2529/40 , C07C2529/65 , C07C2529/85 , C10G3/44 , C10G3/49 , C10G2300/1014 , C10G2300/201 , C10G2300/4081 , C10G2400/20 , C10G2400/22 , C12P5/026 , C12P7/16 , Y02E50/10 , Y02P20/52 , Y02P30/20 , Y02P30/42 , C07C11/08 , C07C11/06
摘要： A process for conversion of isobutanol to make propylene can include dehydrating the isobutanol to produce butenes. The process can include cracking the butenes to produce propylene.
摘要翻译： 异丁醇转化成丙烯的方法可以包括使异丁醇脱水以制备丁烯。 该方法可以包括裂解丁烯以产生丙烯。
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5.发明授权Purification of alcohols prior to their use in the presence of an acid catalyst 有权醇在使用前在酸催化剂存在下进行纯化公开(公告)号：US09000236B2
公开(公告)日：2015-04-07
申请号：US13131407
申请日：2009-11-27
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剂材料接触，有效地减少对反应的酸型催化剂具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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公开(公告)号：US20130217935A1
公开(公告)日：2013-08-22
申请号：US13813170
申请日：2011-07-08
IPC分类号： C07C1/22
CPC分类号： C07C1/22 , B01J29/40 , B01J2229/42 , C07C1/20 , C07C1/24 , C07C4/06 , C07C2529/40 , C10G3/44 , C10G3/49 , C10G3/62 , C10G2300/1014 , C10G2300/1022 , C10G2300/201 , C10G2300/4081 , C10G2400/20 , C12P5/026 , C12P7/16 , Y02E50/10 , Y02P20/52 , Y02P30/42 , C07C11/02 , C07C11/06 , C07C11/08 , C07C11/04
摘要： The present invention relates to a process for making essentially ethylene and propylene comprising: a) providing an alcohol mixture (A) comprising about 20 w % to 100% isobutanol, b) introducing in a reactor (A) a stream comprising the mixture (A) mixed with methanol or dimethyl ether or mixture thereof, optionally water, optionally an inert component, c) contacting said stream with a catalyst (A1) in said reactor (A), the MTO reactor, at conditions effective to convert at least a part of the alcohol mixture (A) and at least a part of the methanol and/or dimethyl ether to olefins, d) recovering from said reactor (A) an effluent comprising: ethylene, propylene, butene, water, optionally unconverted alcohols, various hydrocarbons, and the optional inert component of step b), e) fractionating said effluent of step d) to produce at least an ethylene stream, a propylene stream, a fraction consisting essentially of hydrocarbons having 4 carbon atoms or more, water and the optional inert component of step a), optionally recycling ethylene in whole or 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 reactor (A).
摘要翻译： 本发明涉及一种基本上制备乙烯和丙烯的方法，包括：a）提供包含约20重量％至100重量％异丁醇的醇混合物（A），b）在反应器（A）中引入包含混合物（A ）与甲醇或二甲醚或其混合物，任选的水，任选的惰性组分混合，c）使所述流与所述反应器（A）中的催化剂（A1），所述MTO反应器在有效地转化至少一部分 的醇混合物（A）和至少一部分甲醇和/或二甲醚至烯烃，d）从所述反应器（A）回收包含乙烯，丙烯，丁烯，水，任选未转化的醇，各种烃 和步骤b）的任选的惰性组分，e）将步骤d）的所述流出物分馏以产生至少一种乙烯流，丙烯料流，基本上由具有4个或更多个碳原子的烃组成的馏分，水和任选的惰性 com 步骤a）的方法，任选地在反应器（A）的入口处全部或部分地回收乙烯，任选地在反应器（A）的入口处循环基本上由具有4个或更多个碳原子的烃组成的馏分。
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7.发明申请PURIFICATION OF ALCOHOLS PRIOR TO THEIR USE IN THE PRESENCE OF AN ACID CATALYST 有权在酸性催化剂存在下使用醇类物质的纯化公开(公告)号：US20110313213A1
公开(公告)日：2011-12-22
申请号：US13131407
申请日：2009-11-27
IPC分类号： C07C29/74
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剂材料接触，有效地减少对反应的酸型催化剂具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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公开(公告)号：US20110124934A1
公开(公告)日：2011-05-26
申请号：US12994570
申请日：2009-02-24
申请人： Metin Bulut , Pierre Jacobs , Delphine Minoux , Nikolai Nesterenko , Jean-Pierre Dath , Sander Van Donk
发明人： Metin Bulut , Pierre Jacobs , Delphine Minoux , Nikolai Nesterenko , Jean-Pierre Dath , Sander Van Donk
CPC分类号： C01B37/005 , B01J29/40 , B01J29/42 , B01J29/48 , C01B39/02 , C01B39/38 , C01P2002/72
摘要： The present invention provides a method for preparing a metallosilicate of MFI type, wherein organic templates, seeding techniques, using low aliphatic alcohols miscible with water or homogeneous starting solutions are not required.The present invention relates to a process for making a crystalline metallosilicate with high Si/Metal ratio comprising:a) providing an aqueous medium comprising OH− anions and a metal source, b) providing an aqueous medium comprising an inorganic water insoluble source of silicon, c) optionally providing a non aqueous liquid medium comprising optionally an organic source of silica, d) mixing the medium a), b) and the optional c) at conditions effective to crystallize the desired metallosilicate, e) recovering the desired metallosilicate, wherein in the mixture a)+b)+c), before crystallization, the ratio Si org/Si inorganic is
摘要翻译： 本发明提供了一种制备MFI型金属硅酸盐的方法，其中不需要使用与水混合的低脂肪醇或均相起始溶液的有机模板，接种技术。 本发明涉及一种制备具有高Si /金属比的结晶金属硅酸盐的方法，其包括：a）提供包含OH-阴离子和金属源的水性介质，b）提供包含无机水不溶性硅源的水性介质， c）任选地提供包含任选的二氧化硅有机源的非水液体培养基，d）在有效使结晶期望的金属硅酸盐的条件下混合培养基a），b）和任选的c），e）回收所需的金属硅酸盐，其中 混合物a）+ b）+ c），在结晶之前，Si org / Si无机物的比例<0.3，有利地<0.2，优选为0，OH- / SiO 2的摩尔比为至少0.3，有利地为0.3至0.62， 优选为0.31〜0.61，更优选为0.32〜0.61，非常优选为0.33〜0.6，基本上不存在模板。 在另一个实施方案中，在回收所需的金属硅酸盐之前，插入步骤e），f）和g）步骤：e）将反应混合物a）+ b）+ c）冷却至约室温，f）将反应混合物的pH降低 至少0.1，优选0.3至4，更优选0.5至3，g）使所得到的步骤f）的混合物在有效继续所需金属硅酸盐结晶的条件下进行。
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公开(公告)号：US20110105815A1
公开(公告)日：2011-05-05
申请号：US12864995
申请日：2009-02-05
IPC分类号： C07C1/24
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 10 wt % 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.
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公开(公告)号：US09180439B2
公开(公告)日：2015-11-10
申请号：US12811219
申请日：2009-01-23
CPC分类号： C07C1/20 , B01J27/16 , B01J29/06 , B01J29/061 , B01J29/40 , B01J29/405 , B01J37/0201 , B01J37/0207 , B01J37/024 , B01J37/28 , B01J2229/16 , B01J2229/186 , B01J2229/36 , B01J2229/37 , C07C4/06 , C07C2523/02 , C07C2527/14 , C07C2529/06 , C07C2529/40 , C07C2529/82 , C07C2529/85 , C08F110/02 , C10G2400/20 , Y02P30/42 , C07C11/02
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.
摘要翻译： 本发明涉及一种获得碱土金属或稀土金属-P改性分子筛（M-P改性分子筛）的方法，包括以下步骤：a）。 选择至少一种分子筛，其选自以下之一中的一种分子筛：P-改性分子筛，其含有至少0.3重量％的通过在蒸汽步骤中脱模分子筛获得的P，然后使用含有源的 P是在步骤b）期间用P改性的分子筛，通过在蒸汽步骤中脱分解分子筛，然后使用含有P源的酸溶液进行浸出步骤，从而引入至少0.3重量％的P b）。 使所述分子筛与含碱土金属或稀土金属的化合物（含M化合物）接触，以将至少0.05重量％的碱土金属或稀土金属引入分子筛中。 本发明还涉及一种催化剂复合材料，其包含：a）。 至少10重量％的M-P改性分子筛包含至少0.05重量％的碱土金属或稀土金属（M）和至少0.3重量％的P，b）。 任选的金属磷酸盐，c）。 任选的基质材料，和d）。 可选粘合剂。 本发明的催化剂也可以用于从含氧，含卤素或含硫有机原料制备烯烃产物的方法，其中所述含氧卤化物或含硫有机原料接触 在具有将含氧，含卤素或含硫有机原料转化为烯烃产物（XTO反应器流出物）的条件下，具有根据本发明的催化剂复合材料的XTO反应器。 本发明的催化剂复合材料也可以在OCP方法中加入或替代地使用。
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