CN102159521A - 利用双反应区方法由乙酸生产乙烯 - Google Patents
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Abstract
一种由乙酸选择性地形成乙烯的方法,该方法包括:在第一反应区中使含有乙酸和氢气的进料流与包括合适加氢催化剂的第一催化组合物在提高的温度下接触以形成包括乙醇和乙酸乙酯的中间体混合物;和随后在第二反应区中使该中间体混合物在合适的脱水和/或裂解催化剂上反应以形成乙烯。获得高于80%的乙烯选择性。
Description
优先权
本申请是基于具有相同标题的2008年7月31日提交的美国专利申请序列No.12/221,138,因此要求其优先权并且通过引用将其公开内容并入本文。
技术领域
本发明总体上涉及由乙酸生产乙烯的方法。更具体地,本发明涉及包括如下的方法:在第一反应区中利用第一催化剂组合物将乙酸进行加氢,和在第二反应区中用第二催化剂将加氢的中间体脱水或裂解从而以高选择性形成乙烯。
背景技术
长期需要将乙酸转化为乙烯的经济上可行的方法。乙烯是各种工业产品的重要商品原料;例如,然后可将乙烯转化为各种聚合物和其它单体产品。波动的天然气和原油价格促使按照常规生产的以石油或天然气为来源的乙烯的成本波动,从而当油价上升时造成对乙烯的替代来源的需求比以往更大。
据报导可在沸石催化剂上于150-300℃温度范围的气相中由各种乙基酯制备乙烯。可使用的乙基酯的类型包括甲酸、乙酸和丙酸的乙基酯。例如,参见Cognion等的美国专利No.4,620,050,其中报导了选择性是可接受的。
Knifton的美国专利No.4,270,015描述了涉及两步法获得乙烯:其中将一氧化碳和氢气的混合物(通常称作合成气)与含有2-4个碳原子的羧酸反应以形成所述羧酸的相应乙基酯,随后将该乙基酯在石英反应器中于约200℃-600℃的升高的温度下热解以获得乙烯。如此生产的乙烯含有其它烃,特别是作为杂质的乙烷。其中还报导了在460℃下将纯的丙酸乙酯热解可使乙烷的浓度达到高的值,接近5%。更重要地,报导了酯的转化率和乙烯的收率非常低。
在另一方面,Malinowski等的Bull.Soc.Chim.Belg.(1985),94(2),93-5公开了底物例如乙酸在载体材料如二氧化硅(SiO2)或二氧化钛(TiO2)上多相化的低价钛上的反应产生包括二乙基醚、乙烯和甲烷的产物混合物,其中选择性差。
WO 2003/040037公开了结晶微孔金属铝磷酸盐(ELAPO),特别是Si/Al比为0.03-017的SAPO型沸石例如SAPO-5、SAPO-11、SAPO-20、SAPO-18和SAPO-34均用作吸附剂或者由含有甲醇、乙醇、正丙醇、异丙醇、C4-C20醇、甲基乙基醚、二甲基醚、二乙基醚、二异丙基醚、甲醛、碳酸二甲酯、二甲基酮和/或乙酸的含氧原料生产烯烃所用的催化剂。类似的公开内容利用包含至少一种分子筛交互生长相的硅铝磷酸盐分子筛。据报导在该方法中含有含氧化合物的原料在反应器的反应区中于有效制备轻烯烃、特别是乙烯和丙烯的条件下接触包含分子筛的催化剂。参见Janssen的美国专利No.6,812,372。提及这样的含氧原料包括乙酸,但是该公开似乎限于甲醇或二甲基醚。此外,参见Vaughn的美国专利No.6,509,290,其还公开了将含氧原料转化为烯烃。
双金属钌-锡/二氧化硅催化剂通过使四丁基锡与负载在二氧化硅上的二氧化钌反应进行制备。据报导这些催化剂根据它们的锡/钌比(Sn/Ru)的值(content)而表现出不同的选择性。具体地,报导了乙酸乙酯氢解的选择性非常不同,这取决于催化剂中的Sn/Ru比。例如,对于单独钌在SiO2上,该反应不是选择性的:产生甲烷、乙烷、一氧化碳、二氧化碳以及乙醇和乙酸。然而,对于低的锡含量,据报导催化剂对乙酸的形成具有相当大的选择性,并同时在较高的Sn/Ru比时,乙醇是唯一检测到的产物。参见Loessard等的Studies in Surface Science and Catalysis(1989),Volume Date 1988,48(Struct.React.Surf.),591-600。
还研究了乙酸的催化还原。例如,Hindermann等的J.Chem.Res.,Synopses(1980),(11),373公开了乙酸在铁和在碱促进的铁上的催化还原。在他们的研究中他们发现乙酸在碱促进的铁上的还原取决于温度而按照至少两种不同的路径。例如,他们发现在350℃下,皮里亚(Piria)反应占主要并且产生丙酮和二氧化碳,他们还观测到分解产物甲烷和二氧化碳。然而在较低温度下这些分解产物减少。在另一方面,在300℃下观测到致使形成乙醛和乙醇的常规(normal)还原反应。
由前述明显的是,现有方法不具有对乙烯的必要选择性或者现有技术规定了除乙酸外的昂贵起始材料和/或旨在产生除乙烯外的产物。
发明内容
一种由乙酸选择性地形成乙烯的方法,该方法包括:在第一反应区中使含有乙酸和氢气的进料流与包括合适加氢催化剂的第一催化组合物在提高的温度下接触以形成优选包括乙酸、乙醇和乙酸乙酯的中间体混合物;和随后在第二反应区中使所述加氢的混合物在合适的脱水和/或裂解催化剂上反应以形成乙烯。
附图说明
下面参考单个附图更为详细地描述本发明,该图是分层固定床反应器的示意图。
具体实施方式
下面参考仅出于举例说明目的之许多实施方案详细描述了本发明。但在所附权利要求书给出的本发明精神和范围内对具体实施方案的各种修改对本领域技术人员而言是显而易见的。
除非下文加以更具体地限制,本文所使用的术语取其普通含义。除非另外指明,%及类似术语是指摩尔%。
“转化率”按基于进料中乙酸的摩尔百分数表示。
“选择性”按基于转化的乙酸的摩尔%表示。例如,如果转化率为50摩尔%且50摩尔%转化的乙酸转化为乙烯,则是指乙烯选择性为50%。使用下面方程式由气相色谱(GC)数据计算乙烯选择性:
不意欲受理论束缚,认为根据本发明的乙酸到乙烯转化为按照下面化学方程式中的一个或多个进行:
步骤1a:乙酸加氢得到乙醇。
步骤1b:乙酸加氢得到乙酸乙酯。
步骤1c:乙酸乙酯裂解得到乙烯和乙酸。
步骤2a:乙醇脱水得到乙烯。
本发明的方法可在各种构造(configuration)中使用本领域技术人员可容易地意识到的固定床反应器或流化床反应器进行实践。可使用绝热反应器,或者可使用配设有传热介质的壳式和管式反应器。在任何情形中,可以将两个反应区容置在固定床反应器内具有不同层的单一容器中或者可以将两个反应区容置在具有挡板和分隔体从而提供两个不同区的单一容器流化床系统中。或者,可使用两个容器以容置不同的反应区。在任何情形中,可以使多个具有两个区的反应器并行运转,例如,如果便利,可以使用平行设置的多个具有分层固定床的管式反应器。
图1中示意性地显示了具有分层固定床10的管式反应器。床10为在容器12中的固定床,所述容器12包括惰性颗粒状材料层构成的混合区或层14,第一反应区或层16,可选的分离区或层18,第二反应区或层20和间隔区或层22。在压力下将包括乙酸、氢气和可选惰性载气的反应混合物作为料流24给进到床10到达混合区14。随后将该料流供给(通过压降)到第一反应区或层16。反应区16包含第一催化组合物,该催化组合物包括合适的加氢催化剂,于此产生加氢乙酸中间体。合适地,第一催化组合物为颗粒状。
在加氢后,使该混合物向前移动通过可选的分离区18到达含有第二催化组合物的第二反应区或层20,所述第二催化组合物包含合适的脱水和/或裂解催化剂。
在区20中,将加氢乙酸中间体例如乙酸乙酯和乙醇脱水和/或裂解以产生乙烯,在小于容器12入口压力的压力下使该产物向前到达间隔区22,最终作为产品流26从床10出来。
在图1中所示的构造中层14、18和22都是可选的并且可以由合适大小的惰性颗粒状材料形成。在其它布置或构造中,如本领域技术人员所可意识到的,等效装置可以具有有效促进混合、分离、热传递等的任何合适设计。
在本发明方法的第一步骤中在将乙酸加氢得到乙醇中可使用本领域技术人员已知的各种加氢催化剂。合适的加氢催化剂为在合适载体上的金属催化剂。作为这类催化剂的实例,可以无任何限制地提及以下催化剂:铜、镍、铝、铬、锌和它们的混合物。典型地,可使用在合适载体上的单金属或双金属催化剂作为加氢催化剂。因此特别优选单独或与铝、铬或锌组合的铜。
本领域已知的各种催化剂载体可用于负载本发明的催化剂。这类载体的实例无任何限制地包括氧化铁、二氧化硅、氧化铝、二氧化钛、氧化锆、氧化镁、硅酸钙、碳、石墨和它们的混合物。
在本发明的实施方案中,负载型加氢催化剂的具体实例包括氧化铁、二氧化硅、氧化铝、二氧化钛、氧化锆、氧化镁、硅酸钙、碳、石墨和它们的混合物。特别地,如上所述,优选负载在氧化铁上的铜和铜-铝催化剂。
一些商购催化剂包括如下:由Sud Chemie以T-4489的名称销售的铜-铝催化剂;以T-2130、T-4427和T-4492的名称销售的铜-锌催化剂;以T-4419和G-99B的名称销售的铜-铬催化剂;和以NiSAT 310、C47-7-04、G-49和G-69的名称销售的镍催化剂;所有都由Sud Chemie销售。特别优选以T-4489的名称销售的铜-铝催化剂。
载体上金属的负载量在本发明中并非十分关键并且可在约3重量%-约10重量%范围内变动。特别优选基于载体重量计约4重量%-约6重量%的金属负载量。因此例如负载在氧化铁上的4-6重量%的铜是特别优选的催化剂。
可使用本领域已知的任何方法进行金属浸渍。典型地,在浸渍之前将载体在120℃下干燥并且成型为尺寸分布为约0.2-0.4mm的颗粒。任选地,可以将载体进行挤压、压碎和筛分以达到所需的尺寸分布。可使用将载体材料成型为所需尺寸分布的任何已知方法。
对于具有低表面积的载体,例如α-氧化铝或氧化铁,加入过量金属溶液直到完全湿润或过量液体浸渍以便获得期望的金属负载量。
如上所述,一些加氢催化剂是双金属型。通常,在这样的情形中,一种金属充当促进剂金属而其它金属为主金属。例如铜、镍、钴和铁被认为是用于制备本发明加氢催化剂的主金属。可将主金属与促进剂金属例如钨、钒、钼、铬或锌组合。然而,应当指出,有时主金属也可充当促进剂金属或反之亦然。例如,当使用铁作为主金属时镍可用作促进剂金属。类似地,铬可与铜组合用作主金属(即Cu-Cr作为主双金属金属),其可进一步与促进剂金属例如铈、镁或锌组合。
通常分两个步骤浸渍双金属催化剂。首先,加入“促进剂”金属,接着是“主”金属。每个浸渍步骤之后接着进行干燥和煅烧。双金属催化剂还可以通过共浸渍进行制备。在如上所述三金属的含Cu/Cr催化剂的情形中,可以使用相继浸渍,初始加入“促进剂”金属。第二浸渍步骤可以包括两种主要金属即Cu和Cr的共浸渍。例如,可以通过首先浸渍硝酸铈,接着共浸渍硝酸铜和硝酸铬制备在SiO2上的Cu-Cr-Ce。再次地,每个浸渍之后接着进行干燥和煅烧。在大多数情形中,可以使用金属硝酸盐溶液进行浸渍。然而,还可使用在煅烧时释放金属离子的各种其它可溶性盐。用于浸渍的其它合适金属盐的实例包括金属氢氧化物、金属氧化物、金属乙酸盐、铵基金属氧化物(ammonium metal oxide)例如六水合七钼酸铵、金属酸例如高铼酸溶液、金属草酸盐等。
在本发明方法的另一方面,可在本发明方法的第二步骤中使用任何已知的脱水催化剂。典型地,使用沸石催化剂作为脱水催化剂。虽然可使用孔径为至少约0.6nm的任何沸石,但这类沸石中优选使用的是选自丝光沸石、ZSM-5、沸石X和沸石Y的脱水催化剂。
例如在美国专利No.4,018,514中以及在D.DOMINE和J.QUOBEX的Mol.Sieves Pap.Conf.,1967,78,Soc.Chem.Ind.London中描述了大孔丝光沸石的制备。
例如在美国专利No.2,882,244中描述了沸石X和在美国专利No.3,130,007中描述了沸石Y。
在本领域中已知用于化学反应催化的各种沸石和沸石型材料。例如,Argauer的美国专利No.3,702,886公开了称作“ZSM-5沸石”的一类合成沸石,这些沸石有效用于各种烃转化过程的催化。
适合于本发明方法的沸石可以为碱性形式,部分或全部酸化形式,或者部分脱铝形式。
在本发明的方法中称作“H-ZSM-5”或“H-丝光沸石”沸石的活性催化剂由相应的“ZSM-5”沸石或“丝光沸石”沸石通过使用本领域公知的技术用氢离子置换后种沸石的大部分、通常至少约80%的阳离子进行制备。这些沸石催化剂为基本上结晶的铝硅酸盐或者呈中性形式即完好结晶结构中的二氧化硅和氧化铝的组合。在对于本发明目的而言特别优选类别的沸石催化剂中,这些沸石中SiO2与Al2O3的摩尔比为约10-60。
如前所述,乙烯通过将乙酸乙酯脱水以及分解或“裂解”为乙烯和乙酸来进行制备。这可以是利用裂解催化剂(如果需要的话)的催化反应。合适的裂解催化剂包括磺酸树脂例如上述美国专利No.4,399,305(通过引用将其公开内容并入本文)中公开的全氟磺酸树脂。如美国专利No.4,620,050(通过引用也将其公开内容并入本文)中所述,沸石也适合作为裂解催化剂。因此,在本发明的高度有效的方法中可以使用沸石催化剂同时使乙醇脱水得到乙烯并且使乙酸乙酯分解得到乙烯。
乙酸对乙烯的选择性适宜地大于10%,例如至少20%、至少40%、至少60%或至少80%。取决于副产物混合物,如果对不期望产物例如CO2的选择性保持低,则可期望在中度选择性下操作。
优选地,对于本发明方法的目的,合适的加氢催化剂是在氧化铁上的铜或由Sud Chemie以T-4489的商品名销售的铜-铝催化剂,并且脱水催化剂为H-丝光沸石。在本发明方法的该实施方案中,在氧化铁载体上或在双金属铜-铝催化剂中的铜负载量典型地为约3重量%-约10重量%,优选地其为约4重量%-约6重量%。
在本发明的一个实施方案中,优选分层的加氢和脱水催化剂。优选地,催化剂床的顶层为加氢催化剂而底层为脱水催化剂。
在本发明方法的另一方面,在刚好足以克服穿过催化床的压降的压力下进行加氢和脱水。
可以在很多种条件下于气态或液态中进行反应。优选地,在气相中进行反应。可以使用例如约200℃-约375℃,优选约250℃-约350℃的反应温度。压力对于该反应通常并非关键并且可以使用低于大气压、大气压或超过大气压的压力。然而,在大多数情形中,反应压力可为约1-30绝对大气压。
虽然该反应每摩尔乙酸消耗2摩尔氢气以产生1摩尔乙醇,但是进料流中乙酸与氢气的实际摩尔比可以在宽范围例如约100∶1-1∶100内变化。然而优选这样的比率为约1∶20-1∶2。
与本发明方法有关的所用进料可以得自任何合适的来源,包括天然气、石油、煤、生物质等。公知的是通过甲醇羰基化、乙醛氧化、乙烯氧化、氧化发酵和厌氧发酵等制备乙酸。由于石油和天然气变得更加昂贵,由替代碳源生产乙酸和中间体例如甲醇和一氧化碳的方法引起更大关注。特别受关注的是由可得自任何合适碳源的合成气体(合成气)生产乙酸。Vidalin的美国专利No.6,232,352(通过引用将其公开内容并入本文)例如教导了对用于制造乙酸的甲醇装置进行改造的方法。通过改造甲醇装置,显著降低或很大程度地消除了就新型乙酸装置而言与CO产生有关的大量资金费用。将所有或部分合成气从甲醇合成环路(loop)中分流出并将其供给到分离装置中以回收CO和氢气,然后将它们用于生产乙酸。除乙酸外,该方法还可用于生产有关本发明所用的氢气。
Steinberg等的美国专利No.RE 35,377(也通过引用并入本文)提供了通过使含碳材料例如油、煤、天然气和生物质材料转化生产甲醇的方法。该方法包括将固体和/或液体含碳材料加氢气化以获得工艺气体,将该工艺气体与另外的天然气一起蒸汽热解以形成合成气。将该合成气转化为可以羰基化为乙酸的甲醇。该方法同样产生了如上所述有关本发明所用的氢气。还参见Grady等的美国专利No.5,821,111(其公开了通过气化将废生物质转化为合成气的方法),和Kindig等的美国专利No.6,685,754,通过引用将它们的公开内容并入本文。
可以在反应温度下使乙酸气化,然后可将其以未稀释状态或者用相对惰性的载气例如氮气、氩气、氦气、二氧化碳等稀释的状态与氢气一起给进。
或者,蒸气形式的乙酸可以作为粗产物从Scates等的美国专利No.6,657,078(通过引用将其公开内容并入本文)中所述类别的甲醇羰基化单元的闪蒸容器直接取出。可以将粗蒸气产物直接给进到本发明的反应区,而不需要使乙酸和轻馏分冷凝或除去水,从而节省总处理成本。
接触或停留时间也可宽泛地变动,这取决于如乙酸的量、催化剂、反应器、温度和压力这样的变量。当使用除固定床外的催化剂体系时,典型的接触时间为几分之一秒至大于数小时,至少对于气相反应,优选的接触时间为约0.5-100秒。
典型地,该催化剂用于固定床反应器中,例如在细长管道或管子的形状中,其中典型地为蒸气形式的反应物在催化剂上通过或穿过催化剂。如果需要,也能够使用其它反应器,例如流化床或沸腾床反应器。在一些情况中,有利地使用加氢和沸石催化剂与惰性材料例如玻璃毛相结合以调节反应物料流穿过该催化剂床的压降和反应物化合物与催化剂颗粒的接触时间。
在一个优选的实施方案中还提供了由乙酸选择性地形成乙烯的方法,该方法包括:在约250℃-350℃的温度下使乙酸和氢气的进料流与选自负载在氧化铁上的铜或铜-铝催化剂的加氢催化剂接触以形成包括乙酸、乙醇和乙酸乙酯的中间体混合物;并且同时将所述混合物在选自H-丝光沸石或钠Y沸石的脱水催化剂上反应以形成乙烯。
在本发明方法的该实施方案中,优选的加氢催化剂为在氧化铁上5重量%的铜或铜-铝催化剂中5重量%的铜并且脱水催化剂为H-丝光沸石。在本发明方法的该实施方案中优选将加氢和脱水催化剂在固定床中分层并且在约300℃-350℃的温度下以及在约1-30绝对大气压的压力下于气相中进行反应,反应物的接触时间为约0.5-100秒。
下面的实施例描述了用于制备本发明方法中使用的各种催化剂的程序。
实施例A
制备在氧化铁上的5重量%铜
在氮气氛围下的烘箱中于120℃下将均匀粒径分布为约0.2mm的粉末化和过筛的氧化铁(100g)干燥过夜并然后将其冷却至室温。向其中加入硝酸铜(17g)在蒸馏水中的溶液(100ml)。在逐渐加热到110℃(>2小时,10℃/min)的烘箱中干燥所得浆料。然后在500℃(6小时,1℃/min)下煅烧浸渍的催化剂混合物。
实施例B
制备H-丝光沸石
H-丝光沸石通过铵形式丝光沸石在500-550℃下煅烧4-8小时进行制备。如果使用钠形式丝光沸石作为前体,则在煅烧之前将钠丝光沸石离子交换为铵形式。
产物的气相色谱法(GC)分析
通过在线GC进行产物分析。使用配备有1个火焰离子化检测器(FID)和2个热导检测器(TCD)的三通道集成GC来分析反应物和产物。前通道配备有FID和CP-Sil 5(20m)+WaxFFap(5m)柱子并且用于定量:
乙醛
乙醇
丙酮
乙酸甲酯
乙酸乙烯酯
乙酸乙酯
乙酸
二乙酸乙二酯
乙二醇
亚乙基二乙酸酯
三聚乙醛
中间通道配备有TCD和Porabond Q柱子并且用于定量:
CO2
乙烯
乙烷
后通道配备有TCD和Molsieve 5A柱子并且用于定量:
氦气
氢气
氮气
甲烷
一氧化碳
在反应之前,通过用单独化合物形成尖峰测定不同组分的保留时间,并且用已知组成的校准气体或者用已知组成的液体溶液对GC进行校准。这允许测定各个组分的响应因子。
实施例1
所用催化剂为在氧化铁上的铜催化剂,从Sud Chemie购买的T-4489,和通过在按照美国专利No.4,018,514制备的铝硅酸钠丝光沸石催化剂中用基于沸石重量为近500ppm的氢离子置换钠离子制得的H-丝光沸石或其中二氧化硅与氧化铝之比优选为约15∶1-约100∶1的等效物。合适的催化剂为得自Zeolyst International的CBV21A,其具有约20∶1的二氧化硅与氧化铝之比。
在由不锈钢制成具有30mm内径且能够升至控制温度的管式反应器中,安置30ml作为顶层的在氧化铁上5重量%铜的催化剂和20ml作为底层的H-丝光沸石。装料后组合催化剂床的长度近似地为约70mm。
进料液体基本上由乙酸组成。使反应进料液体蒸发并在约300℃的温度和100psig的压力下将其随同氢气和作为载气的氦气一起以2500h-1的平均总气时空速(GHSV)装入反应器中。进料流含有约6.1%-约7.3%的乙酸摩尔百分数和约54.3%-约61.5%的氢气摩尔百分数。首先将该进料流供给到加氢催化剂(顶)层,然后使具有加氢乙酸中间体的料流与脱水催化剂层接触。使来自反应器的蒸气流出物的一部分穿过气相色谱用于流出物内容物的分析。乙酸的转化率为65%,乙烯的选择性为85%。丙酮的选择性为3%,乙酸乙酯的选择性为2%,乙醇的选择性为0.6%。二氧化碳相对低;测得的所转化乙酸对CO2的选择性为4%。
实施例2
所用催化剂是按照实施例A的工序制备的在氧化铁上的5重量%铜,和按上述实施例1通过在铝硅酸钠丝光沸石催化剂中用基于沸石重量为近500ppm的氢离子置换钠离子制得的H-丝光沸石。
基本上重复实施例1中给出的程序,在约350℃的温度和100psig的压力下气化的乙酸、氢气和氦气的进料流的平均总气时空速(GHSV)为2500h-1。所得进料流含有约7.3%的乙酸摩尔百分数和约54.3%的氢气摩尔百分数。使蒸气流出物的一部分穿过气相色谱用于流出物内容物的分析。乙酸转化率为8%,乙烯的选择性为18%。
一般而言,高度期望对乙烯的选择性高于约10%;意识到的是,可将其它副产物例如乙醇或乙酸乙酯与未反应的乙酸一起再循环到反应器,尽管还可就燃料价值再处理或使用其它副产物。期望对CO2的选择性小于10%,优选5%以下。
对比例1-5
这些实施例说明了乙酸和氢气在各种催化剂上的反应,其中没有形成乙烯和/或检测到非常低的乙烯水平。
在所有这些实施例中,基本上是按照实施例1中给出的工序,不同之处在于使用表1中所列出的不同催化剂。如表1中所汇总,在所有这些对比例中仅使用一个单催化剂层。反应温度和对乙烯的选择性也列于表1中。
表1
在这些实施例中观测到包括乙醛、乙醇、乙酸乙酯、乙烷、一氧化碳、二氧化碳、甲烷、异丙醇、丙酮和水的各种其它产物。
虽然通过某些前述实施例描述了本发明,但并不理解为受此限制;而是本发明包括上文公开的总体范围。可作出各种修改和实施而不背离其精神和范围。
Claims (25)
1.一种由乙酸选择性地形成乙烯的方法,该方法包括:在第一反应区中使含有乙酸和氢气的进料流与包括合适加氢催化剂的第一催化组合物在提高的温度下接触以形成加氢的中间体混合物;和在第二反应区中使该中间体混合物在包括合适的脱水催化剂和可选的裂解催化剂的第二催化组合物上反应以形成乙烯。
2.根据权利要求1的方法,其中所述第一和第二反应区分别包括在固定床中第一催化组合物的第一层和第二催化组合物的第二层。
3.根据权利要求1的方法,其中所述第一和第二反应区在分开的容器中。
4.根据权利要求1的方法,其中基于所消耗的乙酸,对乙烯的选择性为至少20%。
5.根据权利要求1的方法,其中基于所消耗的乙酸,对乙烯的选择性为至少40%。
6.根据权利要求1的方法,其中基于所消耗的乙酸,对乙烯的选择性为至少60%。
7.根据权利要求1的方法,其中基于所消耗的乙酸,对乙烯的选择性为至少80%。
8.根据权利要求1的方法,其中在载体的加氢催化剂上进行第一反应区中的加氢,所述催化剂选自铜、镍、铝、铬、锌、钯或它们的混合物。
9.根据权利要求8的方法,其中所述载体选自氧化铁、二氧化硅、氧化铝、二氧化钛、氧化锆、氧化镁、硅酸钙、碳、石墨和它们的混合物。
10.根据权利要求8的方法,其中所述加氢催化剂选自负载在氧化铁上的铜、铜-铝催化剂、铜-锌催化剂、铜-铬催化剂和镍催化剂。
11.根据权利要求8的方法,其中所述加氢催化剂选自负载在氧化铁上的铜或铜-铝催化剂。
12.根据权利要求1的方法,其中所述第二催化组合物包含选自H-丝光沸石、ZSM-5、沸石X和沸石Y的沸石催化剂。
13.根据权利要求12的方法,其中所述沸石具有约10-60的二氧化硅与氧化铝比(SiO2/Al2O3)。
14.根据权利要求1的方法,其中所述中间体混合物包含乙醇和乙酸乙酯,所述第二催化组合物包括裂解催化剂。
15.根据权利要求1的方法,其中所述加氢催化剂为在氧化铁上的铜,脱水催化剂为H-丝光沸石。
16.根据权利要求15的方法,其中氧化铁上铜的负载量为约3重量%-约10重量%。
17.根据权利要求15的方法,其中氧化铁上铜的负载量为约4重量%-约6重量%。
18.根据权利要求1的方法,其中所述加氢催化剂为铜-铝催化剂,脱水催化剂为H-丝光沸石。
19.根据权利要求18的方法,其中铜-铝催化剂上铜的负载量为约3重量%-约10重量%。
20.根据权利要求18的方法,其中铜-铝催化剂上铜的负载量为约4重量%-约6重量%。
21.根据权利要求1的方法,其中在气相中和在约200℃-375℃的温度下加氢和转化为乙烯。
22.根据权利要求21的方法,其中在气相中和在约250℃-350℃的温度下加氢和转化为乙烯。
23.根据权利要求21的方法,其中所述进料流含有惰性载气。
24.根据权利要求21的方法,其中反应物由摩尔比为约100∶1-1∶100的乙酸和氢气构成,反应区的温度为约250℃-350℃,反应区的压力为约1-30绝对大气压。
25.根据权利要求21的方法,其中反应物由摩尔比为约1∶20-1∶2的乙酸和氢气构成,反应区的温度为约300℃-350℃,反应区的压力为约1-30绝对大气压。
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2008
- 2008-07-31 US US12/221,138 patent/US20100030002A1/en not_active Abandoned
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2009
- 2009-07-20 AU AU2009277186A patent/AU2009277186A1/en not_active Abandoned
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- 2009-07-20 EP EP09788948.9A patent/EP2318334B1/en not_active Not-in-force
- 2009-07-20 CN CN200980136279.3A patent/CN102159521B/zh not_active Expired - Fee Related
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- 2009-07-31 TW TW098125970A patent/TW201022183A/zh unknown
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105523880A (zh) * | 2014-09-29 | 2016-04-27 | 大唐国际化工技术研究院有限公司 | 一种由醋酸酯制乙烯的方法 |
CN105523880B (zh) * | 2014-09-29 | 2018-01-26 | 大唐国际化工技术研究院有限公司 | 一种由醋酸酯制乙烯的方法 |
CN114249626A (zh) * | 2020-09-24 | 2022-03-29 | 中国科学院大连化学物理研究所 | 一种烯烃的制备方法 |
Also Published As
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ZA201100794B (en) | 2012-05-01 |
EP2318334A2 (en) | 2011-05-11 |
CA2732500A1 (en) | 2010-02-04 |
TW201022183A (en) | 2010-06-16 |
JP2011529495A (ja) | 2011-12-08 |
NZ591033A (en) | 2012-11-30 |
RU2011107272A (ru) | 2012-09-10 |
AU2009277186A2 (en) | 2011-03-10 |
KR20110069773A (ko) | 2011-06-23 |
WO2010014148A3 (en) | 2010-05-20 |
US20100030002A1 (en) | 2010-02-04 |
AU2009277186A1 (en) | 2010-02-04 |
JP5530437B2 (ja) | 2014-06-25 |
AR074715A1 (es) | 2011-02-09 |
WO2010014148A2 (en) | 2010-02-04 |
HK1159076A1 (zh) | 2012-07-27 |
CN102159521B (zh) | 2014-07-09 |
EP2318334B1 (en) | 2013-07-17 |
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