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    • 1. 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.
    • 2. 发明申请
    • PROCESS FOR OBTAINING CATALYST COMPOSITES COMPRISING MEAPO AND THEIR USE IN CONVERSION OF ORGANICS TO OLEFINS
    • 获得含有MEAPO的催化剂组合物及其在有机物转化成烯烃中的用途的方法
    • WO2009092780A2
    • 2009-07-30
    • PCT/EP2009/050756
    • 2009-01-23
    • TOTAL PETROCHEMICALS RESEARCH FELUYNESTERENKO, NikolaiVERMEIREN, WalterVAN DONK, Sander
    • NESTERENKO, NikolaiVERMEIREN, WalterVAN DONK, Sander
    • B01J29/06C07C1/20B01J29/85
    • C07C1/32B01J29/005B01J29/40B01J29/85B01J2229/186B01J2229/42C07C1/20C07C1/22C07C1/26Y02P30/42C07C11/02
    • The present invention is a mixture comprising by weight 0.01 to 30% of at least one medium or large pore crystalline silicoaluminate, silicoaluminophosphate materials or silicoaluminate mesoporous molecular sieves (co-catalyst) (A) for respectively 99.99 to 70% of at least a MeAPO molecular sieve. Preferably the proportion of (A) is 1 to 15% for respectively 99 to 85% of MeAPO molecular sieves. MeAPO molecular sieves having CHA (SAPO-34) or AEI (SAPO-18) structure or mixture thereof are the most preferable. Si is the most desirable metal in MeAPO. The present invention also relates to catalysts consisting of the above mixture or comprising the above mixture. The present invention also relates to a process (hereunder referred as 'XTO 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 with the above catalyst (in the XTO reactor) under conditions effective to convert the oxygen-containing, halogenide-containing or sulphur-containing organic feedstock to olefin products (the XTO reactor effluent). The present invention also relates to a process (hereunder referred as 'combined XTO and OCP process') to make light olefins 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 the above catalyst at conditions effective to convert at least a portion of the feedstock to form an 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 at conditions effective to convert at least a portion of said heavy hydrocarbon fraction to light olefins.
    • 本发明是一种混合物,其包含0.01-30%的至少一种中孔或大孔结晶硅铝酸盐,硅铝磷酸盐物质或硅铝酸盐介孔分子筛(助催化剂)(A),分别为99.99至70%的至少一种MeAPO 分子筛。 优选地,对于99〜85%的MeAPO分子筛,(A)的比例为1〜15%。 具有CHA(SAPO-34)或AEI(SAPO-18)结构的MeAPO分子筛或其混合物是最优选的。 Si是MeAPO中最理想的金属。 本发明还涉及由上述混合物组成或包含上述混合物的催化剂。 本发明还涉及从含氧,含卤素或含硫有机原料制备烯烃产物的方法(以下称为“XTO法”),其中所述含氧,含卤素或含硫的 在有效将含氧卤化物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,有机原料与上述催化剂(在XTO反应器中)接触。 本发明还涉及从含氧,含卤化物或含硫有机原料制备轻质烯烃的方法(以下称为“组合XTO和OCP方法”),包括:使含有氧的含卤素的 或含硫有机原料在具有上述催化剂的XTO反应器中,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; 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OCP反应器中的所述重质烃馏分接触。
    • 6. 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。
    • 7. 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。
    • 8. 发明申请
    • METHOD FOR PREPARING METALLOALUMINOPHOSPHATE (MEAPO) MOLECULAR SIEVE
    • 制备金属磷酸盐(MEAPO)分子筛的方法
    • WO2008110528A1
    • 2008-09-18
    • PCT/EP2008/052813
    • 2008-03-10
    • TOTAL PETROCHEMICALS RESEARCH FELUYCENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (CNRS)VERMEIREN, WalterNESTERENKO, NikolaiPETITTO, CarolinaDI RENZO, FrancescoFAJULA, François
    • VERMEIREN, WalterNESTERENKO, NikolaiPETITTO, CarolinaDI RENZO, FrancescoFAJULA, François
    • C01B37/08B01J29/85C07C1/20C07C1/26C07C1/32
    • B01J29/84B01J29/85C01B37/06C01B37/08C07C1/20C07C1/26C07C1/322C07C2529/84C07C2529/85Y02P30/42C07C11/02
    • The present invention also relates to a method for preparing metalloaluminophosphate (MeAPO) molecular sieve said method comprising: a) forming a reaction mixture containing a texture influencing agent (TIA), an organic templating agent (TEMP), at least a reactive inorganic source of MeO 2 insoluble in the TIA, reactive sources of Al 2 O 3 and P 2 O 5 , b) crystallizing the above reaction mixture thus formed until crystals of the metalloaluminophosphate are formed, c) recovering a solid reaction product, d) washing it with water to remove the TIA and e) calcinating it to remove the organic template. In a usual embodiment said reaction mixture has a composition expressed in terms of molar oxide ratios of :TEMP/Al 2 O 3 = 0.3-5, more desirable 0.5-2 MeO 2 /Al 2 O 3 = 0.005-2.0, more desirable 0.022-0.8 P 2 O 5 /Al 2 O 3 = 0.5-2, more desirable 0.8-1.2 TIA/Al 2 O 3 = 3-30, more desirable 6-20. In a usual embodiment the metalloaluminophosphate (MeAPO) molecular sieves made with the above method have a lamellar crystal morphology having an empirical chemical composition on an anhydrous basis, after synthesis and calcination, expressed by the formula H x Me y Al z P k O 2 wherein, y+z+k=1, x
    • 本发明还涉及一种制备金属铝磷酸盐(MeAPO)分子筛的方法,所述方法包括:a)形成含有纹理影响剂(TIA),有机模板剂(TEMP),至少反应性无机源 不溶于TIA的Al 2 O 3和P 2 O 5的反应性源的MeO 2 b)使如此形成的上述反应混合物结晶直到形成金属磷酸铝的晶体,c)回收固体反应产物,d)用水洗涤以除去TIA,和e)煅烧以除去有机模板 。 在通常的实施方案中,所述反应混合物具有以摩尔氧化物比例表示的组成:TEMP / Al 2 O 3 N 3 = 0.3-5,更优选0.5-2 MeO 更优选的是0.022-0.8 P 2 O 2 O 3, 5/3/3/3/3>更优选0.8-1.2 TIA / Al 2 O 3 3〜30,更优选6〜20。 在通常的实施方案中,用上述方法制备的金属铝磷酸盐(MeAPO)分子筛具有层状晶体形态,其在合成和煅烧之后具有无水基础上的经验化学组成,由式H 其中,y + z + k = 1,x <= y;其中,y + z + k = 1,x <= y; y的值为0.0008〜0.4,更优选为0.005〜0.18; z的值为0.25至0.67,更优选为0.38至0.5525; k具有0.2至0.67范围内的值,更优选0.36至0.54,所述分子筛主要具有平板晶体形态。 在有利的实施方案中,通过本发明的方法制备的MeAPO基本上具有结构CHA或AEI或其混合物。 优选地,它们基本上具有结构SAPO 18或SAPO 34或其混合物。 本发明还涉及由通过本发明的方法制备的上述MeAPO分子筛或包含通过本发明的方法制备的上述MeAPO分子筛组成的催化剂。 本发明还涉及一种由含氧卤化物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与上述催化剂接触 有效地将含氧卤化物或含硫有机原料转化为烯烃产物的条件。