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    • 2. 发明申请
    • PROCESS TO MAKE OLEFINS FROM ISOBUTANOL
    • 从ISOBUTANOL制造OLEFINS的过程
    • WO2012016786A1
    • 2012-02-09
    • PCT/EP2011/061582
    • 2011-07-08
    • TOTAL PETROCHEMICALS RESEARCH FELUYADAM, CindyMINOUX, DelphineNESTERENKO, NikolaiVAN DONK, SanderDATH, Jean-Pierre
    • ADAM, CindyMINOUX, DelphineNESTERENKO, NikolaiVAN DONK, SanderDATH, Jean-Pierre
    • C07C1/20C07C4/06C07C11/06
    • C07C1/24C07C1/20C07C1/22C07C2/12C07C4/06C07C11/06C07C29/00C07C2529/40C07C2529/85C08F210/02C08F210/06C12P7/16Y02P30/42
    • The present invention relates to a process for the conversion of an alcohols mixture (A) comprising about 20 w% to 100% isobutanol to make essentially propylene, comprising: a) introducing in a reactor (A) a stream comprising the mixture (A), mixed with astream (D1) comprising olefins having 4 carbon atoms or more (C4+ olefins), optionally water, optionally an inert component, b) contacting said stream with a catalyst (A1) at a temperature above 500°C in said reactor (A) at conditions effective to dehydrate at least a part of the isobutanol and other alcohols, if any, and make a cracking, c) recovering from said reactor (A) an effluent comprising : ethylene, propylene, water, optionally unconverted alcohols of the mixture (A), various hydrocarbons, and the optional inert component of step a), d) fractionating said effluent of step c) 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).
    • 本发明涉及一种将包含约20%至100%异丁醇的醇混合物(A)转化成基本上丙烯的方法,其包括:a)在反应器(A)中引入包含混合物(A)的料流, 与包含具有4个或更多碳原子的烯烃(C 4 +烯烃),任选的水,任选的惰性组分的流动(D1)混合,b)在所述反应器(500℃)中使所述料流与催化剂(A1)在500℃以上接触 A)在有效使所述异丁醇和其它醇的至少一部分脱水的条件下(如果有的话)和破裂,c)从所述反应器(A)回收包含乙烯,丙烯,水,任选未转化的醇 混合物(A),各种烃和步骤a)的任选的惰性组分,d)将步骤c)的所述流出物分馏以产生至少一种乙烯料流,丙烯料流,基本上由具有4个碳原子的烃组成的馏分或 更多,水和th 任选地在反应器(A)的入口处全部或部分地循环乙烯,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, 。
    • 3. 发明申请
    • PROCESS FOR MAKING CRYSTALLINE METALLOSILICATES
    • 制备晶体金属硅酸盐的方法
    • WO2009146954A1
    • 2009-12-10
    • PCT/EP2009/052169
    • 2009-02-24
    • TOTAL PETROCHEMICALS RESEARCH FELUYBULUT, MetinJACOBS, PierreMINOUX, DelphineNESTERENKO, NikolaiDATH, Jean-PierreVAN DONK, Sander
    • BULUT, MetinJACOBS, PierreMINOUX, DelphineNESTERENKO, NikolaiDATH, Jean-PierreVAN DONK, Sander
    • B01J29/40C01B39/36C10G11/05C01B39/40
    • B01J29/40B01J2229/62C01B37/005C01B39/02C01B39/023C01B39/38C01B39/40C07C2/864C07C2529/70C10G29/205C10G2300/70Y02P20/52C07C15/08
    • The present invention relates to a process for making a crystalline metallosilicate composition and comprising crystallites having an inner part (the core) and an outer part (the outer layer or shell) such that : the ratio Si/Metal is higher in the outer part than in the inner part, the crystallites have a continuous distribution of metal and silicon over the crystalline cross-section, said process comprising : a) providing an aqueous medium comprising OH - anions and a metal source, b) providing an aqueous medium comprising an inorganic source of silicon and optionally a templating agent, 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 partly crystallize the desired metallosilicate, e) cooling down the reaction mixture a)+b)+c) to about room temperature, f) decreasing the pH of the reaction mixture by at least 0.1 preferably by 0.3 to 4, more preferably by 0.5 to 3, g) subjecting the resulting mixture of step f) at conditions effective to continue the crystallization of the desired metallosilicate, h) recovering the desired metallosilicate, wherein at step d) in the mixture a)+b)+c), before crystallization, the ratio Si org/Si inorganic is - /SiO 2 is at least 0.3, advantageously from 0.3 to 0.62, preferably from 0.31 to 0.61, more preferably from 0.32 to 0.61, very preferably from 0.33 to 0.6.
    • 本发明涉及一种制备结晶金属硅酸盐组合物的方法,包括具有内部(芯)和外部(外层或外壳)的微晶,使得外部部分的Si /金属比高于 在内部,微晶在结晶横截面上具有金属和硅的连续分布,所述方法包括:a)提供包含OH-阴离子和金属源的水性介质,b)提供包含无机的水性介质 硅源和任选的模板剂,c)任选地提供包含任选的二氧化硅有机源的非水性液体介质,d)在有效地使所需金属硅酸盐部分结晶的条件下,将介质a),b)和任选的c) 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 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; h)回收所需的金属硅酸盐,其中在混合物中的步骤d)a)+ b)+ c) 在结晶之前,Si org / Si无机物的比率为 - / SiO 2为至少0.3,有利地为0.3至0.62,优选为0.31至0.61,更优选为0.32至0.61,非常优选为0.33至0.6。
    • 4. 发明申请
    • PROCESS FOR OBTAINING MODIFIED MOLECULAR SIEVES
    • WO2009092781A3
    • 2009-07-30
    • PCT/EP2009/050758
    • 2009-01-23
    • TOTAL PETROCHEMICALS RESEARCH FELUYNESTERENKO, NikolaiVERMEIREN, WalterVAN DONK, SanderMINOUX, Delphine
    • NESTERENKO, NikolaiVERMEIREN, WalterVAN DONK, SanderMINOUX, Delphine
    • B01J27/16B01J29/06B01J29/40C07C1/20C07C4/06
    • 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.
    • 5. 发明申请
    • PRODUCTION OF PROPYLENE VIA SIMULTANEOUS DEHYDRATION AND SKELETAL ISOMERISATION OF ISOBUTANOL ON ACID CATALYSTS FOLLOWED BY METATHESIS
    • 通过METATHESIS的酸性催化剂同时脱水和异构异丙醇生产丙烯
    • WO2011113836A1
    • 2011-09-22
    • PCT/EP2011/053905
    • 2011-03-15
    • TOTAL PETROCHEMICALS RESEARCH FELUYVERMEIREN, WalterADAM, CindyMINOUX, Delphine
    • VERMEIREN, WalterADAM, CindyMINOUX, Delphine
    • C07C1/24C07C11/00C07C11/08C07C11/09B01J29/06B01J29/40B01J29/85C07C6/04C07C11/06
    • C07C1/24C07C5/2506C07C5/2708C07C6/04C07C7/14866C07C7/14891C07C7/177C07C2521/04C07C2521/08C07C2523/28C07C2523/30C07C2523/36C07C2523/75C07C2529/40C07C2529/70Y02P20/127Y02P20/52C07C11/06C07C11/09C07C11/08
    • The present invention relates to a process for the production of propylene in which in a first step isobutanol is subjected to a simultaneous dehydration and skeletal isomerisation to make substantially corresponding olefins, having the same number of carbons and consisting essentially of a mixture of n-butenes and iso-butene and in a second step n-butenes are subjected to methathesis, 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 isomerise 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, d) fractionating said mixture 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), e) sending the stream (N) to a methathesis reactor and contacting stream (N) with a catalyst in said methathesis reactor, optionally in the presence of ethylene, at conditions effective to produce propylene, f) recovering from said methathesis reactor a stream (P) comprising essentialy propylene, unreacted n-butenes, heavies, optionally unreacted ethylene, g) fractionating stream (P) to recover propylene and optionally recycling unreacted n-butenes and unreacted ethylene to the methathesis reactor.
    • 本发明涉及一种生产丙烯的方法,其中在第一步中异丁醇同时进行脱水和骨架异构化以制备具有相同数目的碳的基本上相应的烯烃并且基本上由正丁烯的混合物组成 所述方法包括: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)使所述物流与一种或多种异丁烯接触, 在有效脱水和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的条件下,在所述反应器中的催化剂,c)从所述反应器回收流(B),除去水,惰性组分 如果有任何和未转化的异丁醇,以获得正丁烯和异丁烯的混合物,d)分馏所述混合物以产生正丁烯流(N)并除去i的重要部分 任选地将物流(A)再循环到所述步骤b)的脱水/异构化反应器中的丁酸丁酯,e)将所述物流(N)送入复分解反应器,并在所述复分解反应器中将催化剂(N)与催化剂接触,任选地在 乙烯,在有效生产丙烯的条件下,f)从所述复分解反应器回收包含必需丙烯,未反应的正丁烯,重质,任选未反应的乙烯的流(P),g)分馏流(P)以回收丙烯并任选地循环未反应 正丁烯和未反应的乙烯。
    • 7. 发明申请
    • DEHYDRATION OF ALCOHOLS ON CRYSTALLINE SILICATES
    • 酒精在水溶性硅酸盐上的脱水
    • WO2009098262A1
    • 2009-08-13
    • PCT/EP2009/051329
    • 2009-02-05
    • TOTAL PETROCHEMICALS RESEARCH FELUYMINOUX, DelphineNESTERENKO, NikolaiVERMEIREN, WalterVAN DONK, SanderDATH, Jean-Pierre
    • MINOUX, DelphineNESTERENKO, NikolaiVERMEIREN, WalterVAN DONK, SanderDATH, Jean-Pierre
    • C07C1/24C07C11/04
    • C07C1/24B01J29/40B01J2229/16B01J2229/36B01J2229/37B01J2229/42C07C2529/40Y02P20/52C07C11/04
    • 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.
    • 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。
    • 8. 发明申请
    • CRACKING OF OLEFINS ON PHOSPHORUS MODIFIED MOLECULAR SIEVES.
    • 烯烃改性磷酸酯改性分子筛的破碎。
    • WO2009016156A1
    • 2009-02-05
    • PCT/EP2008/059886
    • 2008-07-28
    • TOTAL PETROCHEMICALS RESEARCH FELUYNESTERENKO, NikolaiVERMEIREN, WalterMINOUX, DelphineVAN DONK, Sander
    • NESTERENKO, NikolaiVERMEIREN, WalterMINOUX, DelphineVAN DONK, Sander
    • B01J29/06B01J29/18B01J29/40C07C4/06C07C4/10C10G11/05
    • C10G11/05B01J29/06B01J29/18B01J29/40B01J29/65B01J29/70B01J2229/16B01J2229/18B01J2229/36B01J2229/37B01J2229/40C10G2300/1088C10G2300/807C10G2400/20C10G2400/22
    • 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.
    • 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。