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    • 31. 发明申请
    • SIMULTANEOUS DEHYDRATION AND SKELETAL ISOMERISATION OF ISOBUTANOL ON ACID CATALYSTS
    • ISOBUTANOL在酸性催化剂上的同时脱水和同位素同位素
    • WO2011113834A1
    • 2011-09-22
    • PCT/EP2011/053902
    • 2011-03-15
    • TOTAL PETROCHEMICALS RESEARCH FELUYADAM, CindyMINOUX, DelphineNESTERENKO, NikolaiVAN DONK, SanderDATH, Jean-Pierre
    • ADAM, CindyMINOUX, DelphineNESTERENKO, NikolaiVAN DONK, SanderDATH, Jean-Pierre
    • C07C1/24C07C11/00C07C11/08C07C11/09B01J29/06B01J29/40B01J29/85
    • C07C1/24B01J29/85C07C5/2518C07C5/2775C07C11/08C07C11/09C07C2521/04C07C2529/40C07C2529/65C07C2529/70Y02P20/127
    • The present invention (in a first embodiment) relates to a process for the simu ltaneou s dehyd ration and skeletal isomerisation of isobuta nol to ma ke 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 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, 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/AI higher than 10, or a dealuminated crystalline silicate of the group FER, MWW, EUO, MFS, ZSM- 48, MTT, MFI, MEL or TON having Si/AI 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/AI 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).
    • 本发明(在第一个实施方案中)涉及一种用于将异丁醇与基本相应的烯烃进行脱水和骨架异构化的方法,其具有相同数目的碳并且基本上由正丁烯和 异丁烯,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)在有效脱水和骨架异构体的条件下,将所述物流与所述反应器中的催化剂接触, 至少一部分异丁醇以制备正丁烯和异丁烯的混合物,c)从所述反应器回收料流(B),除去水,惰性组分(如果有的话)和未转化的异丁醇,以获得n 丁烯和异丁烯,其中,异丁醇的WHSV为至少1h-1,温度为200℃〜600℃,催化剂能够同时进行bu的脱水和骨架异构化 拉登。 该催化剂是具有Si / Al高于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 / AI高于10,或AEL的硅铝磷酸盐分子筛,或硅化,锆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。
    • 33. 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。
    • 35. 发明申请
    • MIXTURES OF MOLECULAR SIEVES COMPRISING MEAPO, THEIR USE IN CONVERSION OF ORGANICS TO OLEFINS.
    • 包含MEAPO的分子筛的混合物,它们在有机物转化成烯烃中的用途。
    • WO2009016154A1
    • 2009-02-05
    • PCT/EP2008/059884
    • 2008-07-28
    • TOTAL PETROCHEMICALS RESEARCH FELUYVERMEIREN, WalterNESTERENKO, Nikolai
    • VERMEIREN, WalterNESTERENKO, Nikolai
    • B01J29/00C07C1/20
    • C07C1/20B01J29/005B01J29/035B01J29/84B01J29/85C07C1/322Y02P30/42C07C11/02
    • The present invention is a mixture comprising by weight 0.01 to 28% 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 72% 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0.01-28%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72%的至少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造烯烃产物的方法(以下称为“XTO法”),其中所述含氧卤化物或含硫的 在有效地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的含卤化物或含硫有机原料制备轻质烯烃的方法(以下称为“组合的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。
    • 36. 发明申请
    • METALLOALUMINOPHOSPHATE MOLECULAR SIEVES WITH LAMELLAR CRYSTAL MORPHOLOGY AND THEIR PREPARATION
    • 金刚石磷酸酯分子筛与晶体晶体形态及其制备
    • WO2008110526A1
    • 2008-09-18
    • PCT/EP2008/052807
    • 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
    • C01B37/08C07C1/32C07C1/26C07C1/20B01J29/85
    • B01J29/85B01J29/005B01J29/84B01J35/026B01J2029/062C01B37/06C01B37/08C01B39/54C07C1/20C07C1/26C07C1/322C07C2529/85Y02P20/52Y02P30/42C07C11/04C07C11/06
    • The present invention relates to metalloaluminophosphate (MeAPO) molecular sieve with 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 = 10 and advantageously ranges from 10 to 100. In a preferred embodiment T is 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 an advantageous embodiment the MeAPO of the invention have essentially a structure CHA or AEI or a mixture thereof. Preferably they have essentially the structure SAPO 18 or SAPO 34 or a mixture thereof. The present invention also relates to catalysts consisting of the above MeAPO molecular sieves or comprising the above MeAPO molecular sieves. The present invention also relates to a process for making an olefin product from an oxygen-containing, halogenide-containing or sulphur-containing feedstock wherein said oxygen-containing, halogenide-containing or sulphur-containing feedstock is contacted with the above catalyst under conditions effective to convert the oxygen-containing, halogenide-containing or sulphur-containing feedstock to olefin products.
    • 本发明涉及具有层状晶体形态的金属铝磷酸盐(MeAPO)分子筛,其具有无水基础上的经验化学组成,在合成和煅烧之后,由式H x表示, 其中,y + z + k = 1 x <= y表示主要是平板晶体的分子筛 宽度(W)和厚度(T)的形态如下:W / T> 10,有利地在10至100的范围内。在优选实施例中,T <0.15μm,更优选<=0.10μm 更优选<=0.08μm,有利地在0.01〜0.07μm的范围内,优选为0.04〜0.07μm。 上述金属铝磷酸盐(MeAPO)分子筛可以通过以下方法制备:a)形成含有纹理影响剂(TIA),有机模板剂(TEMP),至少一种反应性无机的MeO 2 不溶于TIA的Al 2 N 3 O 3和P 2 O 5的反应性源 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。 在有利的实施方案中,本发明的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。 本发明还涉及由上述MeAPO分子筛组成或包含上述MeAPO分子筛的催化剂。 本发明还涉及一种由含氧卤化物或含硫原料制备烯烃产物的方法,其中所述含氧卤化物或含硫原料在有效的条件下与上述催化剂接触 以将含氧的含卤化物或含硫原料转化为烯烃产物。