CN1441701A - 用于含氧化合物转化的含金属的小孔分子筛催化剂 - Google Patents
用于含氧化合物转化的含金属的小孔分子筛催化剂 Download PDFInfo
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- CN1441701A CN1441701A CN01812626A CN01812626A CN1441701A CN 1441701 A CN1441701 A CN 1441701A CN 01812626 A CN01812626 A CN 01812626A CN 01812626 A CN01812626 A CN 01812626A CN 1441701 A CN1441701 A CN 1441701A
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Abstract
一种热金属处理的磷酸硅铝分子筛的制备方法,包括a)提供含模板剂的磷酸硅铝分子筛;b)使含金属的溶液与所述含模板剂的磷酸硅铝分子筛混合;c)将步骤b)所得混合物加热至在120和400℃之间的温度得到热金属处理的磷酸硅铝分子筛;d)从所述含金属的溶液中分离出所述热金属处理的磷酸硅铝分子筛;和e)将所述热金属处理的磷酸硅铝分子筛焙烧提供焙烧的热金属处理的磷酸硅铝分子筛。
Description
发明领域
本发明涉及含金属的分子筛的制备方法、包含含金属的分子筛的催化剂、和使含氧化合物原料转化成产品包括烯烃的方法。特别地,本发明涉及分子筛表面用金属热浸渍的磷酸硅铝催化剂。
发明背景
传统上通过催化或蒸汽裂化由石油原料生产烯烃特别是轻烯烃。但含氧化合物正日益成为制备轻烯烃特别是乙烯和丙烯的代用原料。有前途的含氧化合物原料是醇类如甲醇和乙醇、二甲醚、甲乙醚、二乙醚、碳酸二甲酯、和甲酸甲酯。这些含氧化合物许多可由多种来源生产,包括由天然气衍生的合成气;石油液体;和碳质材料包括煤。由于这些来源相对较便宜,所以醇、醇的衍生物、和其它含氧化合物有希望成为用于生产轻烯烃的经济的非石油源。
一种烯烃生产方法是用磷酸硅铝(SAPO)分子筛催化剂使甲醇催化转化。例如US4 499 327(Kaiser)公开了用各种SAPO分子筛催化剂由甲醇制备烯烃。所述过程可在300和500℃之间的温度、0.1至100大气压之间的压力、和0.1至40hr-1之间的重时空速(WHSV)下进行。
Inui(J.Chemical Society Chem.Commun.p.205,1990)已证明甲醇与镍取代的SAPO-34而非未取代的SAPO-34接触时可提高对乙烯的选择性。在此情况下,镍取代在SAPO-34的骨架内发生。
与Kaiser和Inui的操作相反,也可在合成后即合成所述分子筛骨架之后掺入金属。例如,US5 962 762(Sun等)教导一种用掺入金属的SAPO催化剂使甲醇转化成轻烯烃的方法。通过金属水溶液(优选含镍或钴的溶液)在环境条件下与SAPO接触一夜使所述溶液吸附至SAPO分子筛上。然后使处理后的分子筛与溶液分离,干燥。US5 625 104和5 849 968(Beck等)教导一种方法,通过将沸石用有机硅或多氧硅化合物预处理然后用金属溶液处理在沸石催化剂中掺入碱土金属。US4 692 424(Le Van Mao)教导一种方法,通过加入少量锰的水溶液形成有展性的糊和在加压下挤出所述糊,在ZSM催化剂的外部反应活性部位上干混入锰离子。
尽管现有技术中为使分子筛改性做出许多努力,但仍需要寻找在甲醇至轻烯烃的转化中表现出高乙烯和/或丙烯选择性的分子筛或分子筛催化剂。
发明概述
本发明提供一种热金属处理的磷酸硅铝分子筛的制备方法,包括:
a)提供含模板剂的磷酸硅铝分子筛;
b)使含金属的溶液与所述含模板剂的磷酸硅铝分子筛混合;
c)将步骤b)所得混合物加热至在120和400℃之间的温度得到热金属处理的磷酸硅铝分子筛;
d)从所述含金属的溶液中分离出所述热金属处理的磷酸硅铝分子筛;和
e)将所述热金属处理的磷酸硅铝分子筛焙烧提供焙烧的热金属处理的磷酸硅铝分子筛。
优选地,所述金属选自第IB族金属、第IIB族金属、第VIII族金属及其混合物,最优选选自铁、钴、铜、锌及其混合物。所述金属溶液选自金属乙酸盐溶液、金属硝酸盐溶液、金属硫酸盐溶液、金属卤化物溶液及其混合物。
本发明还涉及一种焙烧的热金属处理的磷酸硅铝分子筛,可通过本发明方法获得。还涉及一种热金属处理的磷酸硅铝分子筛,其中作为金属前体的热分解产物的金属化合物沉积在所述分子筛的外表面上和/或孔内,所述金属选自第IB族金属、第IIB族金属、第VIII族金属及其混合物。
本发明还涉及一种催化剂,包含本发明的热金属处理的磷酸硅铝分子筛。
本发明还涉及一种烯烃产品的制备方法,其中使包含热金属处理的磷酸硅铝分子筛的催化剂与包含至少一种含至少一个氧原子的有机化合物(含氧化合物)的原料在适合使所述含氧化合物转化成烯烃的条件下接触。
发明详述
本发明涉及已在加热下用金属处理的磷酸硅铝分子筛。这些热金属改性的分子筛用于甲醇至轻烯烃的催化转化时,表现出比相应未改性的磷酸硅铝分子筛更高的乙烯和/或丙烯选择性。
因此,本发明的第一目的是一种热金属处理的磷酸硅铝的制备方法。该方法的第一步在于提供含模板剂的磷酸硅铝分子筛。
磷酸硅铝分子筛(SAPOs)包含[SiO2]、[AlO2]和[PO2]共角四面体单元的三维微孔晶体骨架结构。Si掺入所述结构的方式可通过29Si MASNMR测定(参见Blackwell and Patton,J.Phys.Chem.,92,3965(1988))。理想的SAPO分子筛将在所述29Si MAS NMR中在-88至-96ppm范围内的化学位移δ(Si)内出现一或多个峰,而且在-88至-115ppm范围内的化学位移δ(Si)内的总峰面积在所有峰的总峰面积的至少20%的范围内,其中δ(Si)化学位移参照外部四甲基硅烷(TMS)。
SAPO分子筛一般分为有8、10或12元环结构的微孔材料。这些环结构的平均孔径大小可在3.5-15埃的范围内。优选平均孔径小于约5埃、优选平均孔径大小在3.5至5埃范围内、更优选在3.5至4.2埃范围内的小孔SAPO分子筛。这些孔径大小是有8元环的分子筛的特征。
SAPO分子筛包括共角[SiO2]、[AlO2]和[PO2]四面体单元的分子骨架。此类骨架可使包含含氧化合物的原料转化成烯烃产品。
本发明分子筛骨架结构内的[PO2]四面体单元可由多种组合物提供。这些含磷组合物的例子包括磷酸、有机磷酸酯如磷酸三乙酯、和磷铝酸盐。使含磷组合物与活性含硅和含铝组合物在适当条件下混合形成所述分子筛。
所述骨架结构内的[AlO2]四面体单元可由多种组合物提供。这些含铝组合物的例子包括烷醇铝如异丙醇铝、磷酸铝、氢氧化铝、铝酸钠、和假勃姆石。使含铝组合物与活性含硅和含磷组合物在适当条件下混合形成所述分子筛。
所述骨架结构内的[SiO2]四面体单元可由多种组合物提供。这些含硅组合物的例子包括硅溶胶和烷氧基硅如原硅酸四乙酯。为制备磷酸硅铝分子筛,使含硅组合物与活性含铝和含磷组合物在适当条件下混合形成所述分子筛。
所述反应混合物可包含一或多种模板剂。模板剂是结构导向剂或影响结构的试剂,典型地含有氮、磷、氧、碳、氢或其组合,可还含有至少一个烷基或芳基,所述烷基或芳基中存在1至8个碳原子。两或多种模板剂的混合物可产生不同分子筛的混合物,或者当一种模板剂比另一种的导向性更强时主要产生一种分子筛。
代表性的模板剂包括四乙铵盐、环戊胺、氨甲基环己烷、哌啶、二乙胺、三乙胺、环己胺、三乙基羟乙胺、吗啉、二丙胺(DPA)、吡啶、异丙胺及其组合。优选的模板剂是二乙胺、三乙胺、环己胺、哌啶、吡啶、异丙胺、四乙铵盐、二丙胺及其混合物。所述四乙铵盐包括氢氧化四乙铵(TEAOH)、磷酸四乙铵、氟化四乙铵、溴化四乙铵、氯化四乙铵、乙酸四乙铵。优选的四乙铵盐是氢氧化四乙铵和磷酸四乙铵。用于制备SAPO-34A时特别优选的模板剂是二乙胺(DEA),用于制备SAPO-34B时特别优选的模板剂是三乙胺(TEA)。
所述SAPO分子筛通过本领域公知的水热晶化法合成。参见例如US4 440 871;4 861 743;5 096 684;和5 126 308,其制备方法全部引入本文供参考。使活性的硅、铝和磷组分与至少一种模板剂一起混合形成反应混合物。一般将所述混合物密封,加热(优选在自生压力下)至至少100℃、优选100-250℃的温度直至形成结晶产物。形成所述结晶产物可能需要约2小时至多达2周。某些情况下,搅拌、滚动或用晶体材料接种将促进所述产物的形成。
典型地,所述分子筛产物将在溶液中形成。可通过标准方法如离心分离或过滤回收。还可将所述产物洗涤、通过同样的方法回收、和干燥。作为所述晶化法的结果,所回收分子筛的孔内含有制备所述初始反应混合物中所用模板剂的至少一部分。
本发明制备热金属处理的磷酸硅铝分子筛的第二步中,在加热下用金属溶液处理所述含模板剂的磷酸硅铝晶体。
本发明优选的金属选自第IB族金属、第IIB族金属、第VIII族金属及其混合物。所述金属更优选选自铁、钴、铜、锌及其混合物,最优选选自铜、锌或其混合物。所述金属的来源是金属溶液,优选选自金属乙酸盐溶液、金属硝酸盐溶液、金属硫酸盐溶液、金属卤化物溶液及其混合物。所述金属溶液可以是水溶液或非水溶液;在后一情况下,所述溶剂可以是醇或其它极性有机溶剂。金属浓度典型地在0.01和10.0M之间,优选在0.05和5M之间,最优选在0.08和3M之间。
然后使所述含金属的溶液与所述分子筛在反应容器中混合,加热至选定温度。典型地,在120和400℃之间、优选在120和260℃之间、最优选在160和220℃之间的温度下加热所述混合物。优选在自生压力下加热所述混合物。取决于工艺温度、压力、所用金属溶液的类型、金属溶液的浓度、和所用分子筛的类型,可使用任何时间周期。对于特定温度和在自生压力下,所述反应进行几小时,典型地进行12小时。应理解本领域普通技术人员将知道如何根据这些参数改变加热混合物的时间长短。
在此阶段,得到可称为热金属处理的磷酸硅铝分子筛的物质,然后从所述含金属的溶液中分离。通常较高的工艺温度将使溶液中的一些金属配合物分解形成细沉淀金属。然后将分离出的分子筛用一或多种流体(典型地为水或醇)洗涤以除去痕量的金属溶液和松结合的沉淀金属离子。使洗涤后的分子筛干燥,例如在110℃下干燥过夜。
所述金属可沉积在磷酸硅铝分子筛的外表面上和/或孔内。不希望受限于任何理论,相信所述热金属处理过程按以下方式发生。首先,与含金属的溶液混合的分子筛有位于孔结构内的模板剂。然而,随着工艺温度升高,一些模板剂或模板剂的分解产物可能离开孔结构而完全或部分地被金属溶液置换。所述模板剂在所述含金属的溶液中可能有一些溶解度,因而所述金属配合物可置换孔内的模板剂。所述工艺温度通常高于模板剂分子的沸点或熔点,甚至在所述加热过程的升高压力下。或者,所述高工艺温度可能激发所述模板剂的分解历程。即使按此路径,在热金属处理过程中一些或所有模板剂或模板剂的分解产物可能离开分子筛孔,而可能完全或部分地被金属溶液置换。
所述含金属的分子筛洗涤和干燥后,可将所述分子筛在各种条件下焙烧或部分焙烧。典型地,本发明分子筛在用于转化反应器之前在空气中于550℃下焙烧约2至5小时。
从而得到焙烧的热金属处理的磷酸硅铝分子筛。
可选地,可通过在所述热金属处理步骤期间加入所要助金属(co-metal)的共溶液还用附加金属浸渍分子筛表面。或者,也可通过在所述第一热金属处理之后进行一或多个后续热金属处理用附加的助金属浸渍分子筛表面。
适用于本发明的SAPO分子筛包括SAPO-5、SAPO-8、SAPO-11、SAPO-16、SAPO-17、SAPO-18、SAPO-20、SAPO-31、SAPO-34、SAPO-35、SAPO-36、SAPO-37、SAPO-40、SAPO-41、SAPO-42、SAPO-44、SAPO-47、SAPO-56、及其混合物。优选SAPO-18、SAPO-34、SAPO-35、SAPO-44和SAPO-47,特别是SAPO-34,及其混合物。本文所用术语混合物与组合物同义,是不同比例的有两或多种组分的物质的组合物,不管其物理状态如何。
因此,本发明热金属改性的磷酸硅铝分子筛的制备方法是在分子筛结构形成后进行的金属处理。在分子筛已制备后掺入金属有几点优于现场掺入金属。可在掺入金属之前改变分子筛的物性如粒度和孔径大小。因而,合成后技术在分子筛的制备和筛分中提供更宽的可能性。例如,可在多种分子筛上测试一种特定的金属,或者在各种金属上测试一种特定的分子筛。而且,通过不同方法所得分子筛结构可能明显不同,反映在催化性能明显不同。
本发明的第二目的涉及一种热金属处理的磷酸硅铝分子筛,其中作为金属前体的热分解产物的金属化合物沉积在所述分子筛的外表面上和/或孔内,所述金属选自第IB族金属、第IIB族金属、第VIII族金属及其混合物。优选所述金属选自铁、钴、铜、锌、及其混合物,最优选所述金属选自铜、锌、及铜和锌的混合物。
所述金属前体选自金属乙酸盐、金属硝酸盐、金属硫酸盐或金属卤化物。沉积在分子筛外表面上和/或孔内的金属量使所述分子筛包含在0.05和20%(重)之间的金属、优选在0.05和10%(重)之间的金属、最优选在0.05和5%(重)之间的金属。
本发明热处理的磷酸硅铝分子筛适合在包含至少一种含至少一个氧原子的有机化合物(以下称为含氧化合物)至轻烯烃的转化中用作催化剂。为此,所述磷酸硅铝可与其它组分组合或混合使用。
磷铝(ALPO)分子筛可与本发明的磷酸硅铝分子筛组合使用。磷铝分子筛是可能有AlPO4骨架的微孔结晶氧化物。所述骨架内可有其它元素,典型地有约3至约10埃范围内的均匀孔度,能按大小选择分离分子物质。已报道了多于两打结构类型,包括沸石拓扑相似物。US4310440中更详细地描述了磷铝酸盐的背景和合成,引入本文供参考。优选的ALPO结构是ALPO-5、ALPO-11、ALPO-18、ALPO-31、ALPO-34、ALPO-36、ALPO-37和ALPO-46。
所述ALPOs的骨架内可还包括金属取代基。优选所述金属选自镁、锰、锌、钴及其混合物。这些材料优选表现出类似于硅铝酸盐、磷铝酸盐和氧化硅-磷铝酸盐分子筛组合物的吸附、离子交换和/或催化性能。此类物质及其制备描述在US4 567 029中,引入本文供参考。
含金属的ALPOs有MO2、AlO2和PO2四面体单元的三维微孔晶体骨架结构。人造结构的这些材料(焙烧之前含有模板剂)可通过经验化学组成(干基)表示为:
mR:(MxAlyPz)O2
其中“R”代表晶内孔体系中存在的至少一种有机模板剂;“m”代表每摩尔(MxAlyPz)O2存在“R”的摩尔数,其值为0至0.3,所有情况下其最大值都取决于模板剂的分子尺寸和所涉及的具体金属磷铝酸盐的孔体系的可用空隙体积,“x”、“y”和“z”分别代表以四面体氧化物形式存在的金属“M”(即镁、锰、锌和钴)、铝和磷的摩尔分数。
含金属的ALPOs有时缩写为MeAPO。在组合物中的金属“Me”为镁的情况下,所述组合物缩写为MAPO。类似地,ZAPO、MnAPO和CoAPO分别用于含锌、锰和钴的组合物。为识别构成所述各亚类MAPO、ZAPO、CoAPO和MnAPO的不同结构的物种,在各物种后面加上数字,定为例如ZAPO-5、MAPO-11、CoAPO-34等。
本发明SAPO分子筛还可与其它材料混合(即共混、配混)。制成后,所得组合物典型地称为SAPO催化剂,所述催化剂包含SAPO分子筛。可与所述分子筛共混的材料可以是各种惰性或催化活性材料、或各种粘合剂材料。这些材料包括组合物如高岭土和其它粘土、各种形式的稀土金属、金属氧化物、其它非沸石催化剂组分、沸石催化剂组分、氧化铝或铝溶胶、羟基氯化铝(aluminum chlorhydrol)、氧化钛、氧化锆、氧化镁、氧化钍、氧化铍、石英、氧化硅或硅溶胶、及其混合物。这些组分还可降低催化剂总成本、起吸热作用有助于在再生期间使催化剂隔热、使催化剂致密和提高催化剂强度。特别希望用于所述催化剂起吸热作用的惰性材料有约0.05至约1cal/g-℃、更优选约0.1至约0.8cal/g-℃、最优选约0.1至约0.5cal/g-℃的热容。
氧化铝粘合剂如羟基氯化铝、和/或一或多种粘土如高岭土优选与本发明分子筛组合使用。如果所述分子筛为干燥形式的,则加入流体如水形成浆液。但更通常地由前面所述结晶步骤制备保持浆液形式的分子筛之后制备所述催化剂。其它组分以干燥固体和/或浆液形式加入所述分子筛浆液中。使有特定固含量和粒度的此最终浆液混合直至所有组分相对均匀分布。然后将所述均匀混合的浆液喷雾干燥或挤出形成所述催化剂。
可包括其它分子筛材料作为所述SAPO催化剂组合物的一部分或作为需要时与所述SAPO催化剂混合的分开的分子筛催化剂。适用于本发明的小孔分子筛的结构类型包括AEI、AFT、APC、ATN、ATT、ATV、AWW、BIK、CAS、CHA、CHI、DAC、DDR、EDI、ERI、GOO、KFI、LEV、LOV、LTA、MON、PAU、PHI、RHO、ROG、THO、及其取代形式。适用于本发明的中孔分子筛的结构类型包括MFI、MEL、MTW、EUO、MTT、HEU、FER、AFO、AEL、TON、及其取代形式。这些小和中孔分子筛更详细地描述在Atlas of Zeolite Structural Types,W.M.Meier and D.H.Olsen,Butterworth Heineman,3rd ed.,1997中,其详述引入本文供参考。可与磷酸硅铝催化剂组合的优选分子筛包括ZSM-5、ZSM-34、毛沸石和菱沸石。
配制后,本发明催化剂组合物典型地包含约1至约99%、更优选约5至约90%、最优选约10至约80%(重)的分子筛。还优选所述催化剂颗粒的粒度为约20至3000μ,更优选约30至200μ,最优选约50至150μ。
所述催化剂颗粒可经各种处理达到要求的物理和化学特性。此处理包括但不限于水热处理、焙烧、酸处理、碱处理、研磨、球磨、碾磨、喷雾干燥、及其组合。
含本发明热处理分子筛的催化剂颗粒适合作为催化剂用于烃转化、特别是用于含至少一种含至少一个氧原子的有机化合物(含氧化合物)至轻烯烃的催化转化。因此,本发明第三方面涉及一种烯烃产品的制备方法,其中使本发明催化剂与包含至少一种含氧化合物的原料在适合使所述含氧化合物转化成烯烃的条件下接触。
本发明的此方面中,含有至少一种含氧化合物和可选的稀释剂或与所述含氧化合物分开加入或混合的烃的进料与含SAPO分子筛的催化剂在反应区或容积内接触。发生此接触的容积在本文中称为“反应器”,它可以是“反应器设备”或“反应系统”的一部分。所述反应系统的另一部分可以是“再生器”,它包含使所述催化剂与再生介质接触除去所述烯烃转化反应所致催化剂上的碳质沉积物(或焦炭)的容积。
本发明含氧化合物原料包含至少一种含有至少一个氧原子的有机化合物(含氧化合物),如脂族醇、醚、羰基化合物(醛、酮、羧酸、碳酸酯、和酯等)。所述含氧化合物为醇时,所述醇可包括有1至10个碳原子、更优选1至4个碳原子的脂族部分。代表性的醇包括但不限于低级直链和支链脂肪醇及其不饱和对应物。适用的含氧化合物的例子包括但不限于:甲醇;乙醇;正丙醇;异丙醇;C4-C20醇;甲乙醚;二甲醚;二乙醚;二异丙醚;甲醛;碳酸二甲酯;二甲酮;乙酸;及其混合物。优选的含氧化合物是甲醇、二甲醚、或其混合物。
本发明优选烯烃产品的制备方法可包括由烃如油、煤、焦油砂、页岩、生物体和天然气制备这些组合物的附加步骤。所述组合物的制备方法为本领域已知。这些方法包括发酵产生醇或醚,制备合成气,然后使所述合成气转化成醇或醚。合成气可通过已知方法如蒸汽转化、自热转化和部分氧化生产。
所述原料中可存在一或多种惰性稀释剂,例如基于供入反应区(或催化剂)的所有进料和稀释剂组分的总摩尔数,占1至99%(摩尔)。如本文所定义,稀释剂是在分子筛催化剂上基本不反应、主要起降低原料中含氧化合物浓度作用的组合物。典型的稀释剂包括但不限于氦、氩、氮、一氧化碳、二氧化碳、水、基本上不反应的烷属烃(尤其是链烷烃如甲烷、乙烷、和丙烷)、基本上不反应的烯属烃、基本上不反应的芳香化合物、及其混合物。优选的稀释剂是水和氮。水可以液体或蒸汽形式注入。
可还包括作为所述原料部分即共进料的烃。如本文所定义,包括在原料中的烃是与分子筛催化剂接触时转化成另一种化学排列的烃组合物。这些烃可包括烯烃、活性烷属烃、活性烷基芳烃、活性芳烃或其混合物。优选的烃共进料包括丙烯、丁烯、戊烯、C4 +烃混合物、C5 +烃混合物、及其混合物。更优选作为共进料的是C4 +烃混合物,最优选由反应产物分离和循环得到的C4 +烃混合物。
本发明方法中,可通过焦化的催化剂与再生介质接触除去全部或部分焦炭沉积物使焦化的催化剂再生。可通过停止向反应器供应进料流、引入再生介质、停止再生介质流、然后将所述进料再引入完全或部分再生的催化剂,周期性地在反应器内进行此再生。还可通过使一部分失活的催化剂排入分开的再生器中、在再生器内使焦化的催化剂再生、然后将再生的催化剂再引入反应器,周期性地或连续地在反应器外进行再生。可在适合使反应器内整个催化剂上保持要求的焦炭含量的时间和条件下进行再生。
已在反应器内与进料接触的催化剂在本文中定义为“接触原料的”催化剂。接触原料的催化剂将提供丙烷和焦炭含量明显低于新催化剂和再生催化剂的烯烃转化反应产物。随着催化剂接触更多的进料(通过在给定进料速度下延长时间或在给定时间下提高进料速度),催化剂一般将提供更少量的丙烷。
在任何给定的瞬间,反应器内的催化剂一些是新鲜的、一些是再生的、一些因尚未再生而是焦化或部分焦化的。因而,反应器内催化剂的各部分接触原料的时间长段不同。由于进料流入反应器的速度可能改变,供给催化剂各部分的进料量也可能改变。考虑到此变化,用“平均催化剂接触原料指数(ACFE指数)”定量地定义反应器内整个催化剂已接触原料的程度。
本文所用ACFE指数是进料的总重量除以送入反应器的分子筛的总重量(即不包括所述催化剂组合物的粘合剂、惰性材料等)。应在相等的时间间隔进行测量,所述时间间隔应足够长以消除催化剂或原料速度的波动,根据反应器和再生工艺步骤选择使所述系统可视为基本连续。在周期性再生的反应器系统中,所述时间间隔可在几小时至几天或更长的范围内。在基本上不断再生的反应器系统中,几分钟或几小时可能足够。
催化剂的流量可以各种方式测量。设计在反应器和再生器之间运送催化剂的设备时,给定反应器内焦炭产率、离开反应器的催化剂上的平均焦炭含量、和离开再生器的催化剂上的平均焦炭含量,则可确定催化剂流量。在催化剂连续流动的操作单元中,可采用各种测量技术.许多此类技术描述在例如Michel Louge,“ExperimentalTechniques”,Circulating Fluidized Beds,Grace,Avidan,&Knowlton,eds.,Blackie,1997(336-337)中,其描述引入本文供参考。
本发明中,确定ACFE指数中可只用送入反应器的催化剂中的分子筛。但送入反应器的催化剂可以是新鲜的或再生的或二者组合。可能在反应器设备(即通过导管、管或环形区)内从所述反应器至所述反应器循环而尚未再生或不含新鲜催化剂的分子筛不用于确定ACFE指数。
本发明一优选实施方案中,含有含氧化合物和可选的与所述含氧化合物分开加入或混合的烃的进料与含有SAPO分子筛的催化剂在反应器中在能产生烯烃的工艺条件下接触。
可使用任何标准反应器系统,包括固定床、流化床或移动床系统。优选的反应器是并流提升管反应器和接触时间短的逆流自由降落反应器。理想地,所述反应器是其中含氧化合物原料可在至少约1hr-1、优选在约1至1000hr-1范围内、更优选在约20至1000hr-1范围内、最优选在约20至500hr-1范围内的重时空速(WHSV)下与分子筛催化剂接触的。WHSV在本文中定义为含氧化合物和可选地存在于所述进料中的烃的重量/小时/所述催化剂的分子筛的重量。因为所述催化剂或所述原料可能含有起惰性物或稀释剂作用的其它材料,因此所述WHSV基于所述含氧化合物进料、可能存在的烃、和所述催化剂中所含分子筛的重量计算。
优选在所述含氧化合物处于气相时使所述含氧化合物进料与催化剂接触。所述过程也可在液相或气/液混合相进行。所述过程在液相或气/液混合相进行时,根据所述催化剂和反应条件可产生不同的进料至产品的转化率和选择性。
所述过程一般可在宽温度范围内进行。有效的操作温度范围可为200至700℃,优选300至600℃,更优选350至550℃。在所述温度范围的下端,所要烯烃产品的形成可能变得相当慢。在所述温度范围的上端,所述过程可能不形成最优量的产品。
非常希望在至少300℃的温度和低于约0.016的温度校正的归一化甲烷选择性(TCNMS)下操作。特别优选由含氧化合物制备烯烃的反应条件包括至少约20hr-1产生烯烃的WHSV和低于约0.016的TCNMS。
本文所用TCNMS定义为温度低于400℃时的归一化甲烷选择性(NMS)。所述NMS定义为甲烷的产率除以乙烯的产率,其中各产率均基于重量%测量或转换成重量%。温度为400℃或更高时,所述TCNMS由下式定义,其中T为反应器内平均温度(℃):
压力也可在宽范围内改变,包括自生压力。有效压力可以是(但不限于)至少1psia、优选至少5psia的含氧化合物分压。在较高的含氧化合物分压如大于20psia的含氧化合物分压下所述过程特别有效。优选含氧化合物分压为至少约25psia、更优选至少约30psia。对于实际设计而言,希望在不大于约500psia、优选不大于约400psia、最优选不大于约300psia的甲醇分压下操作。
含氧化合物至轻烯烃产物的转化可在各种催化反应器中进行。反应器类型包括固定床反应器、流化床反应器、和并流提升管反应器,如“Free Fall Reactor”,Fluidization Engineering,D.Kunii andO.Levenspiel,Robert E.Krieger Publishing Co.NY,1977中所述,引入本文供参考。此外,逆流自由降落式反应器也可用于所述转化过程,如US-A-4 068 136和“Riser Reactor”,Fluidizationand Fluid-Particle Systems,p48-59,F.A.Zenz and D.F.Othmo,Reinhold Publishing Corp.,NY 1960中所述,其详述也引入本文供参考。
所述连续操作的一优选实施方案中,仅从所述反应器中取出一部分催化剂,送入再生器除去所述催化反应过程中积累的焦炭沉积物。在所述再生器中,催化剂与含有氧或其它氧化剂的再生介质接触。其它氧化剂的例子包括O3、SO3、N2O、NO、NO2、N2O5、及其混合物。优选以空气形式提供O2。所述空气可用氮气、CO2或烟道气稀释,可加入水蒸汽。理想地,使所述再生器内O2浓度降至控制水平以减小所述废催化剂或失活催化剂过热或产生过热部位。所述失活的催化剂也可用H2、CO、其混合物、或其它适合的还原剂还原再生。也可采用氧化再生和还原再生的组合。
本质上,在再生过程中从所述催化剂中除去焦炭沉积,形成再生的催化剂。然后使所述再生的催化剂返回所述反应器进一步与进料接触。典型的再生温度在250-700℃的范围内,理想地在350-700℃的范围内。优选在450-700℃的温度范围内进行再生。
一实施方案中,所述反应器和再生器这样构造以致所述进料在再生催化剂返回所述反应器之前接触所述再生催化剂。另一实施方案中,所述反应器和再生器这样构造以致所述进料在再生催化剂返回所述反应器之后接触所述再生催化剂。再另一实施方案中,可使所述进料流分流以致进料接触返回所述反应器之前和返回所述反应器之后的再生催化剂。
优选所述反应器内的催化剂有对乙烯和/或丙烯的选择性有效的平均焦炭含量。优选所述催化剂上的平均焦炭含量为约2至约30%(重),更优选约2至约20%(重)。为保持此催化剂上的平均焦炭含量,可在能有效地保持要求的催化剂上焦炭含量的条件下使全体催化剂部分再生。但优选仅使一部分焦化的催化剂循环在不再生的情况下接触进料。此循环可在所述反应器内或外部完成。要被再生的焦化催化剂部分优选在能获得焦炭含量低于2%(重)、优选低于1.5%(重)、最优选低于1.0%(重)的再生催化剂的条件下再生。
为补充再生或反应过程中的任何催化剂损失,可加入新鲜催化剂。优选将所述新鲜催化剂加入从再生器中排出的再生催化剂中,然后二者一起加入所述反应器中。但所述新鲜催化剂可与再生催化剂无关地加入所述反应器中。可加入任何量的新鲜催化剂,但优选保持至少1.5的ACFE指数。
通过本发明含氧化合物至烯烃的转化反应产生的烯烃可聚合形成聚烯烃特别是聚乙烯和聚丙烯对于本领域技术人员也是显而易见的。由烯烃形成聚烯烃的方法为本领域已知。优选催化法。特别优选金属茂、齐格勒-纳塔和酸催化体系。参见例如US3 258 455;3 305 538;3 364 190;5 892 079;4 659 685;4 076 698;3 645 992;4 302565;和4 243 691,其中关于催化剂和方法的描述均引入本文供参考。一般地,这些方法涉及使所述烯烃产品与形成聚烯烃的催化剂在能形成聚烯烃产品的压力和温度下接触。
优选的形成聚烯烃的催化剂是金属茂催化剂。所述优选的操作温度范围在50和240℃之间,所述反应可在低、中或高压下进行,在约1至200bar的范围内。对于在溶液中进行的过程,可使用惰性稀释剂,优选的操作压力范围在10和150bar之间,优选的温度范围在120和230℃之间。对于气相法,优选所述温度在60至160℃的范围内,操作压力在5和50bar之间。
除聚烯烃之外,还可由所回收的烯烃形成其它烯烃衍生物。这些包括但不限于醛、醇、乙酸、线型α-烯烃、乙酸乙烯酯、二氯乙烯和氯乙烯、乙苯、环氧乙烷、枯烯、异丙醇、丙烯醛、烯丙基氯、环氧丙烷、丙烯酸、乙丙橡胶、丙烯腈、及乙烯、丙烯或丁烯的三聚物和二聚物。制备这些衍生物的方法为本领域公知,因而本文中不再论述。
结合以下实施例将更好地理解本发明,这些实施例用于说明要求保护的本发明总范围内的具体实施方案。
实施例1
用二乙胺(DEA)作模板剂水热法制备SAPO-34A。将SAPO-34A(10g)加至硝酸锌水溶液(100ml,0.1M)中。在200ml不锈钢容器中搅拌此混合物。将所述容器密封,在烘箱中于200℃和自生压力下加热12小时。过滤回收所述分子筛,水洗,在110℃下干燥过夜。然后通过在空气中加热至550℃将所述分子筛焙烧2至5小时。如此制备的分子筛标记为Zn-SAPO-34A-200。
对表1中所列其它金属重复所述步骤。所有情况下均使用金属硝酸盐,但M=Ti时除外,此时使用硫酸钛。
实施例2
重复实施例1的步骤,但金属处理温度为180℃。对表2中所列金属重复此步骤。所有情况下均使用金属硝酸盐,但M=Ti时除外,此时使用硫酸钛。此实施例中所得热金属处理的SAPOs标记为M-SAPO-34A-180,其中M用相应的金属取代。
实施例3
重复实施例1的步骤,但所用磷酸硅铝分子筛为SAPO-34B(用三乙胺作模板剂水热法制备的SAPO-34)。对表3中所列金属重复此步骤。所有情况下均使用金属硝酸盐,但M=Ti时除外,此时使用硫酸钛。此实施例中所得热金属处理的SAPOs标记为M-SAPO-34B-200,其中M用相应的金属取代。
实施例4
重复实施例3的步骤,但金属处理温度为180℃。对表4中所列金属重复此步骤。所有情况下均使用金属硝酸盐,但M=Ti时除外,此时使用硫酸钛。此实施例中所得热金属处理的SAPOs标记为M-SAPO-34B-180,其中M用相应的金属取代。
实施例5
重复实施例3的步骤,但金属处理温度为160℃。对表5中所列金属重复此步骤。所有情况下均使用金属硝酸盐,但M=Ti时除外,此时使用硫酸钛。此实施例中所得热金属处理的SAPOs标记为M-SAPO-34B-160,其中M用相应的金属取代。
实施例6
此实施例中,测试实施例1至5中制备的热金属处理的磷酸硅铝分子筛的催化性能。与未处理金属对比甲醇至轻烯烃的转化率、特别是乙烯和丙烯的选择性。试验结果示于表1至5中。
在固定床反应器(ID=1/2”石英)中用氮气(60ml/min)稀释的连续MeOH气流(WHSV=2hr1)在450℃下进行使甲醇(MeOH)转化成烯烃产品的转化反应。将实施例1-5中制备的分子筛压成片。然后将所得片粉碎成20-40目的粉末。将1.28g粉状分子筛放在反应器中,在开始MeOH进料之前在流动的N2(60ml/min)中于500℃活化1小时。用配有Paropak-QS柱和热电偶检测器的在线气相色谱仪分析反应产物。表1-5中所示试验结果概括了本发明分子筛在引入MeOH后约2分钟时的初始性能。给定试样的相对结晶度用X-射线衍射测定,所述无金属的SAPO-34A作为参考试样。使用期(min)定义为MeOH转化率降低于100%时的运行时间。
如表1-5中所示产物选择性和相应的图1-5中所示,对所述混合物进行金属处理的温度影响表面性质,从而影响所述分子筛的表面组成或至少影响所述金属在分子筛表面的沉积方式。
已充分地描述了本发明,在不背离本发明精神和范围的中,可在权利要求内的宽参数范围内完成本发明对于本领域技术人员是显而易见的。
表1.实施例1制备的M-SAPO-34A-200的MTO性能
金属 | 34/A | Al- | Fe- | Co- | Ni- | Cu- | Zn- | Cr- | Mg- | Ca- | Ba- | Ti- | La- |
相对结晶度(%) | 100 | 70 | 32 | 12 | 47 | 57 | 0 | 37 | 95 | 66 | 20 | 0 | 15 |
反应条件 | |||||||||||||
反应温度(℃) | 460 | 458 | 450 | 460 | 458 | 450 | 455 | 460 | 45 | 455 | 460 | 450 | 465 |
反应时间(min) | 2 | 2 | 3 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2.5 | 2 | 2 |
转化率(%) | 100 | 100 | 100 | 100 | 100 | 100 | 1.63 | 100 | 100 | 100 | 100 | 22.1 | 100 |
产品的分布(wt%) | |||||||||||||
CH4 | 1.03 | 1.29 | 3.08 | 1.82 | 56.61 | 3.39 | 58.33 | 1.76 | 1.73 | 1.38 | 1.94 | 89.8 | 0.96 |
C2H4 | 34.3 | 31.4 | 46.9 | 41.0 | 16.5 | 62.4 | 41.7 | 40.9 | 35.8 | 32.2 | 32.0 | 3.71 | 31.5 |
C2H6 | 1.45 | 1.82 | 2.00 | 0.71 | 8.40 | 1.63 | 0 | 1.38 | 1.38 | 0.78 | 0.84 | 1.08 | 0.98 |
C3H6 | 34.0 | 34.9 | 30.8 | 34.9 | 9.46 | 24.0 | 0 | 33.9 | 33.0 | 37.1 | 38.9 | 4.69 | 38.4 |
C3H8 | 9.98 | 10.3 | 5.50 | 3.41 | 2.94 | 2.36 | 0 | 6.0 | 7.6 | 7.0 | 7.0 | 0 | 0 |
C4H8 | 10.8 | 13.2 | 1.38 | 11.0 | 3.02 | 5.28 | 0 | 10.5 | 13.0 | 13.1 | 11.6 | 0.59 | 14.8 |
C4H10 | 1.99 | 2.43 | 1.55 | 2.01 | 0.56 | 0.98 | 0 | 1.96 | 2.4 | 2.4 | 2.1 | 0.10 | 2.7 |
C5+ | 4.51 | 4.66 | 1.96 | 4.14 | 2.47 | 0 | 0 | 3.56 | 5.0 | 6.0 | 5.6 | 0 | 10.6 |
C2=C3=选择性(wt%) | 68.3 | 66.3 | 77.6 | 75.9 | 26.0 | 86.3 | 41.7 | 74.8 | 68.8 | 69.4 | 70.9 | 8.4 | 69.9 |
使用期(min) | 40 | 45 | 45 | 32 | 49 | 34 | <2 | 29 | 78 | 57 | 36 | <2 | .56 |
表2.实施例2制备的M-SAPO-34A-180的MTO性能
金属 | 34/A | Al- | Fe- | Co- | Ni- | Cu- | Zn- | Cr- | Mg- | Ca- | Ba- | Ti- | La- |
相对结晶度(%) | 100 | 65 | 39 | 50 | 81 | 50 | 87 | 43 | 104 | 72 | 41 | 23 | 11 |
反应条件 | |||||||||||||
反应温度(℃) | 460 | 450 | 450 | 460 | 450 | 450 | 455 | 450 | 457 | 450 | 450 | 450 | 453 |
反应时间(min) | 2 | 2 | 2.5 | 2 | 2.3 | 3 | 2.4 | 2.2 | 2.4 | 2.4 | 2.2 | 2 | 2.5 |
转化率(%) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 11.0 | 100 |
产品的分布(wt%) | |||||||||||||
CH4 | 1.03 | 1.60 | 1.66 | 9.74 | 53.9 | 1.99 | 3.5 | 1.7 | 1.0 | 1.2 | 1.2 | 9.9 | 1.0 |
C2H4 | 34.3 | 23.0 | 45.3 | 48.4 | 7.4 | 50.4 | 57.9 | 29.6 | 38.2 | 34.5 | 32.4 | 46.6 | 42.5 |
C2H6 | 1.45 | 3.00 | 1.65 | 7.17 | 30.7 | 1.17 | 1. 7 | 2.0 | 1.3 | 0.87 | 0.78 | 3.8 | 1.2 |
C3H6 | 34.0 | 28.2 | 31.8 | 9.71 | 1.8 | 31.3 | 23.3 | 31.4 | 32.4 | 34.6 | 36.2 | 33.8 | 33.9 |
C3H8 | 9.98 | 19.1 | 6.73 | 15.0 | 6.1 | 4.0 | 4.1 | 14.3 | 8.9 | 8.0 | 8.4 | 4.9 | 5.02 |
C4H8 | 10.8 | 6.19 | 8.82 | 7.28 | 0 | 8.56 | 6.36 | 13.8 | 12.1 | 13.2 | 13.8 | 0 | 11.2 |
C4H10 | 1.99 | 1.14 | 1.63 | 1.35 | 0 | 1.58 | 1.17 | 2.55 | 2.24 | 2.44 | 2.55 | 0.95 | 2.06 |
C5+ | 4.51 | 7.32 | 2.41 | 1.42 | 0 | 1.01 | 2.09 | 4.64 | 3.90 | 5.19 | 4.58 | 0 | 3.12 |
C2=C3=选择性(wt%) | 68.3 | 51.2 | 77.1 | 58.1 | 9.2 | 81.7 | 81.2 | 61.0 | 70.6 | 69.1 | 68.7 | 80.3 | 76.5 |
使用期(min) | 40 | 45 | 51 | 170 | 33 | 32 | 37 | 66 | 65 | 56 | 65 | <2 | 36 |
表3.实施例3制备的M-SAPO-34B-200的MTO性能
金属 | 34/A | Al- | Fe- | Co- | Ni- | Cu- | Zn- | Cr- | Mg- | Ca- | Ba- | Ti- | La- |
相对结晶度(%) | 100 | 69 | 30 | 25 | 59 | 65 | 0 | 69 | 68 | 21 | 6 | 7 | 14 |
反应条件 | |||||||||||||
反应温度(℃) | 460 | 455 | 450 | 450 | 450 | 450 | 450 | 450 | 455 | 455 | 455 | 455 | 450 |
反应时间(min) | 2.3 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
转化率(%) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
产品的分布(wt%) | |||||||||||||
CH4 | 0.63 | 0.73 | 0.87 | 3.26 | 65.5 | 4.96 | 0.93 | 0.72 | 0.69 | 0.82 | 1.11 | 8.31 | 0.78 |
C2H4 | 37.1 | 42.7 | 45.0 | 44.7 | 14.7 | 65.4 | 47.7 | 43.3 | 41.6 | 38.4 | 32.6 | 43.0 | 37.5 |
C2H6 | 0.38 | 0.39 | 0.59 | 1.06 | 10.8 | 9.07 | 0.23 | 0.57 | 0.48 | 0.37 | 0.28 | 0.37 | 0.31 |
C3H6 | 40.2 | 39.6 | 38.1 | 29.9 | 6.41 | 19.4 | 39.5 | 38.9 | 39.2 | 43.0 | 46.5 | 38.3 | 43.1 |
C3H8 | 3.04 | 2.11 | 4.63 | 4.94 | 1.93 | 0 | 0 | 4.62 | 4.54 | 3.66 | 3.98 | 0 | 4.10 |
C4H8 | 11.9 | 9.79 | 8.30 | 9.60 | 0.70 | 1.04 | 7.61 | 8.47 | 9.59 | 9.30 | 9.72 | 7.62 | 9.97 |
C4H10 | 2.19 | 1.80 | 1.53 | 1.78 | 0.01 | 0.19 | 1.41 | 1.56 | 1.77 | 1.72 | 1.80 | 1.41 | 1.84 |
C5+ | 4.02 | 2.83 | 0.97 | 4.78 | 0 | 0 | 2.55 | 1.84 | 2.16 | 2.71 | 4.02 | 0.95 | 2.41 |
C2=C3=产选择性(wt%) | 77.2 | 82.4 | 83.1 | 74.6 | 21.1 | 84.7 | 87.3 | 82.2 | 80.8 | 81.4 | 79.1 | 81.3 | 80.6 |
使用期(min) | 210 | 143 | 32 | 35 | 33 | 31 | 32 | 32 | 62 | 30 | 34 | 34 | 61 |
表4.实施例4制备的M-SAPO-34B-180的MTO性能
金属 | 34/A | Al- | Fe- | Co- | Ni- | Cu- | Zn- | Cr- | Mg- | Ca- | Ba- | Ti- | La- |
相对结晶度(%) | 100 | 80 | 64 | 40 | 68 | 72 | 50 | 46 | 94 | 47 | 36 | 44 | 7 |
反应条件 | |||||||||||||
反应温度(℃) | 460 | 450 | 450 | 455 | 450 | 450 | 445 | 447 | 452 | 445 | 450 | 452 | 450 |
反应时间(min) | 2.3 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
转化率(%) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 79.9 | 100 |
产品的分布(wt%) | |||||||||||||
CH4 | 0.63 | 0.56 | 0.65 | 2.16 | 8.57 | 5.34 | 2.05 | 0.72 | 0.57 | 0.63 | 0.70 | 40.8 | 1.00 |
C2H4 | 37.1 | 38.1 | 44.9 | 44.7 | 47.6 | 68.3 | 57.0 | 38.6 | 40.8 | 37.6 | 35.4 | 31.9 | 39.4 |
C2H6 | 0.38 | 0.43 | 0.54 | 0.71 | 2.30 | 6.87 | 0.79 | 0.57 | 0.55 | 0.37 | 0.26 | 1.55 | 1.07 |
C3H6 | 40.2 | 41.2 | 39.7 | 38.5 | 31.5 | 18.5 | 30.5 | 40.8 | 39.0 | 42.1 | 45.4 | 18.9 | 33.8 |
C3H8 | 3.04 | 4.80 | 4.67 | 3.79 | 2.87 | 0 | 2.92 | 5.32 | 5.14 | 4.90 | 3.76 | 1.40 | 5.45 |
C4H8 | 11.9 | 10.4 | 8.04 | 8.49 | 6.06 | 0.89 | 5.71 | 10.1 | 10.0 | 10.1 | 9.60 | 4.60 | 11.7 |
C4H10 | 2.19 | 1.92 | 1.49 | 1.57 | 1.12 | 0.17 | 1.05 | 1.87 | 1.84 | 1.87 | 1.78 | 0.85 | 2.15 |
C5+ | 4.02 | 2.24 | 0 | 0 | 0 | 0 | 0 | 2.02 | 2.11 | 2.47 | 3.06 | 0 | 2.47 |
C2=C3=选择性(wt%) | 77.2 | 79.6 | 84.6 | 83.3 | 79.1 | 86.7 | 87.4 | 79.4 | 79.8 | 79.6 | 80.8 | 50.8 | 73.2 |
使用期(min) | 210 | 96 | 120 | 32 | 32 | 31 | 33 | 57 | 95 | 61 | 67 | <2 | 30 |
表5.实施例5制备的M-SAPO-34B-160的MTO性能
金属 | 34/A | Al- | Fe- | Co- | Ni- | Cu- | Zn- | Cr- | Mg- | Ca- | Ba- | Ti- | La- |
相对结晶度(%) | 100 | 94 | 63 | 82 | 93 | 75 | 93 | 66 | 97 | 68 | 70 | 50 | 5 |
反应条件 | |||||||||||||
反应温度(℃) | 460 | 450 | 450 | 450 | 448 | 450 | 450 | 450 | 450 | 450 | 450 | 450 | 450 |
反应时间(min) | 2.3 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
转化率(%) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
产品的分布(wt%) | |||||||||||||
CH4 | 0.63 | 0.59 | 0.64 | 1.03 | 4.99 | 2.30 | 1.21 | 0.67 | 0.59 | 0.53 | 0.75 | 4.57 | 1.12 |
C2H4 | 37.1 | 37.3 | 41.4 | 42.3 | 42.3 | 66.0 | 52.5 | 40.4 | 39.3 | 39.0 | 34.4 | 45.3 | 40.0 |
C2H6 | 0.38 | 0.52 | 0.52 | 0.53 | 1.53 | 2.91 | 0.52 | 0.52 | 0.47 | 0.34 | 0.30 | 2.00 | 1.02 |
C3H6 | 40.2 | 40.5 | 39.9 | 38.3 | 35.1 | 20.7 | 35.3 | 41.3 | 40.3 | 44.3 | 43.9 | 30.9 | 35.5 |
C3H8 | 3.04 | 6.24 | 5.14 | 4.05 | 4.13 | 1.56 | 2.78 | 3.93 | 4.90 | 3.96 | 4.12 | 7.19 | 4.41 |
C4H8 | 11.9 | 10.9 | 9.14 | 9.38 | 8.08 | 5.49 | 6.25 | 9.52 | 10.36 | 8.53 | 11.44 | 8.55 | 12.03 |
C4H10 | 2.19 | 2.00 | 1.69 | 1.77 | 1.49 | 1.02 | 1.16 | 1.76 | 1.92 | 1.57 | 2.11 | 1.58 | 2.22 |
C5+ | 4.02 | 2.00 | 1.55 | 2.50 | 2.41 | 0 | 0.33 | 1.93 | 1.77 | 1.83 | 2.47 | 0 | 3.78 |
C2=C3=选择性(wt%) | 77.2 | 77.8 | 81.3 | 80.5 | 77.4 | 86.7 | 87.8 | 81.7 | 79.7 | 83.2 | 78.3 | 76.1 | 75.4 |
使用期(min) | 210 | 97 | 61 | 67 | 31 | 30 | 40 | 65 | 79 | 71 | 96 | 28 | 33 |
Claims (30)
1.一种热金属处理的磷酸硅铝分子筛的制备方法,包括:
a)提供含模板剂的磷酸硅铝分子筛;
b)使含金属的溶液与所述含模板剂的磷酸硅铝分子筛混合;
c)将步骤b)所得混合物加热至在120和400℃之间的温度得到热金属处理的磷酸硅铝分子筛;
d)从所述含金属的溶液中分离出所述热金属处理的磷酸硅铝分子筛;和
e)将所述热金属处理的磷酸硅铝分子筛焙烧提供焙烧的热金属处理的磷酸硅铝分子筛。
2.权利要求1的方法,其中所述金属选自第IB族金属、第IIB族金属、第VIII族金属及其混合物。
3.上述权利要求之任一的方法,其中所述金属选自铁、钴、铜、锌及其混合物。
4.上述权利要求之任一的方法,其中所述金属选自铜、锌、或其混合物。
5.上述权利要求之任一的方法,其中步骤c)在120和260℃之间的温度下进行。
6.上述权利要求之任一的方法,其中步骤c)在160和220℃之间的温度下进行。
7.上述权利要求之任一的方法,其中步骤c)在自生压力下进行。
8.上述权利要求之任一的方法,其中所述金属溶液选自金属乙酸盐溶液、金属硝酸盐溶液、金属硫酸盐溶液、金属卤化物溶液及其混合物。
9.上述权利要求之任一的方法,其中所述含金属的溶液有在0.01和1.0M之间的金属浓度。
10.上述权利要求之任一的方法,其中所述含金属的溶液有在0.05和0.5M之间的金属浓度。
11.上述权利要求之任一的方法,其中所述含金属的溶液有在0.08和0.3M之间的金属浓度。
12.上述权利要求之任一的方法,其中所述磷酸硅铝分子筛选自SAPO-18、SAPO-34、SAPO-35、SAPO-44、SAPO-47及其混合物。
13.上述权利要求之任一的方法,其中所述磷酸硅铝分子筛选自SAPO-18、SAPO-34或其混合物。
14.上述权利要求之任一的方法,其中所述分子筛中存在的模板剂选自二乙胺、三乙胺、环己胺、哌啶、异丙胺、四乙铵盐、二丙胺、及其混合物。
15.一种焙烧的热金属处理的磷酸硅铝分子筛,可通过权利要求1至14之任一的方法获得。
16.权利要求15的焙烧的热金属处理的磷酸硅铝分子筛,其中所述焙烧的热金属处理的分子筛包含0.05至20%(重)金属。
17.权利要求15或16的焙烧的热金属处理的磷酸硅铝分子筛,其中所述焙烧的热金属处理的分子筛包含0.05至10%(重)金属。
18.一种热金属处理的磷酸硅铝分子筛,其中作为金属前体的热分解产物的金属化合物沉积在所述分子筛的外表面上和/或孔内,所述金属选自第IB族金属、第IIB族金属、第VIII族金属及其混合物。
19.权利要求18的热金属处理的磷酸硅铝分子筛,其中所述含金属的前体选自金属乙酸盐、金属硝酸盐、金属硫酸盐、金属卤化物及其混合物。
20.权利要求18或19的热金属处理的磷酸硅铝分子筛,其中所述金属选自铁、钴、铜、锌、及其混合物。
21.权利要求18至20之任一的热金属处理的磷酸硅铝分子筛,其中所述金属选自铜、锌、及其混合物。
22.权利要求18至21之任一的热金属处理的磷酸硅铝分子筛,其中所述分子筛包含0.05至20%(重)的所述金属。
23.权利要求18至22之任一的热金属处理的磷酸硅铝分子筛,其中所述分子筛包含0.05至10%(重)的所述金属。
24.权利要求18至23之任一的热金属处理的磷酸硅铝分子筛,其中所述磷酸硅铝分子筛选自SAPO-18、SAPO-34、SAPO-35、SAPO-44、SAPO-47及其混合物。
25.权利要求18至24之任一的热金属处理的磷酸硅铝分子筛,其中所述磷酸硅铝分子筛选自SAPO-18、SAPO-34或其混合物。
26.一种催化剂,包含权利要求15至17之任一的焙烧的热金属处理的磷酸硅铝分子筛或权利要求18至25之任一的热金属处理的磷酸硅铝分子筛和粘合剂。
27.权利要求26的催化剂,其中所述粘合剂选自氧化铝、羟基氯化铝、粘土及其混合物。
28.一种烯烃产品的制备方法,其中使权利要求27或28的催化剂与包含至少一种含至少一个氧原子的有机化合物(含氧化合物)的原料在适合使所述含氧化合物转化成烯烃的条件下接触。
29.权利要求28的方法,其中所述含氧化合物选自甲醇、乙醇、二甲醚、甲乙醚、二乙醚、碳酸二甲酯、甲酸甲酯及其混合物。
30.权利要求29的方法,其中所述含氧化合物是甲醇。
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Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
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US6448197B1 (en) * | 2000-07-13 | 2002-09-10 | Exxonmobil Chemical Patents Inc. | Method for making a metal containing small pore molecular sieve catalyst |
US6833127B2 (en) * | 2000-12-22 | 2004-12-21 | California Institute Of Technology | Method of removing structure directing agents from molecular sieves |
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US20060224032A1 (en) * | 2005-03-29 | 2006-10-05 | Janssen Marcel J | Protecting catalytic sites of activated porous molecular sieves |
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WO2015094696A1 (en) | 2013-12-20 | 2015-06-25 | Exxonmobil Chemical Patents Inc. | Process for converting oxygenates to aromatic hydrocarbons |
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SG11201707462TA (en) | 2015-03-31 | 2017-10-30 | Exxonmobil Chemical Patents Inc | Oxygenated hydrocarbon conversion zoned method |
JP6752964B2 (ja) * | 2017-03-31 | 2020-09-09 | 日本碍子株式会社 | Eri構造のゼオライト膜及び膜構造体 |
Family Cites Families (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US516957A (en) * | 1894-03-20 | Sash-fastener | ||
US552357A (en) * | 1895-12-31 | Door-check | ||
US4319057A (en) * | 1980-12-08 | 1982-03-09 | Grain Processing Corporation | Regeneration of molecular sieves |
US4390414A (en) | 1981-12-16 | 1983-06-28 | Exxon Research And Engineering Co. | Selective dewaxing of hydrocarbon oil using surface-modified zeolites |
DE3228984C2 (de) * | 1982-01-29 | 1984-04-26 | Kraftwerk Union AG, 4330 Mülheim | Wanderbett-, insbesondere Adsorptionsfilter |
US4859314A (en) | 1983-05-02 | 1989-08-22 | Uop | Catalytic cracking catalysts and cracking process using non-zeolitic molecular sieves |
US4912073A (en) * | 1984-07-16 | 1990-03-27 | Mobil Oil Corp. | Larger pore molecular sieves of controlled activity |
US4842714A (en) * | 1984-11-27 | 1989-06-27 | Uop | Catalytic cracking process using silicoaluminophosphate molecular sieves |
US4692424A (en) | 1985-01-03 | 1987-09-08 | The Asbestos Institute | Dry impregnated manganese zeolite |
US4681864A (en) * | 1985-07-15 | 1987-07-21 | W. R. Grace & Co. | Cracking catalyst |
US4859312A (en) * | 1987-01-12 | 1989-08-22 | Chevron Research Company | Process for making middle distillates using a silicoaluminophosphate molecular sieve |
US4861743A (en) * | 1987-11-25 | 1989-08-29 | Uop | Process for the production of molecular sieves |
US4814306A (en) * | 1987-12-29 | 1989-03-21 | Mobil Oil Corporation | Ph control by bulky organic bases during noble-metal exchange of zeolite catalysts |
US5158665A (en) | 1988-02-12 | 1992-10-27 | Chevron Research And Technology Company | Synthesis of a crystalline silicoaluminophosphate |
US4884531A (en) * | 1988-06-30 | 1989-12-05 | Mobil Oil Corporation | Operation of an internal combustion engine with a pre-engine reformer |
WO1991013132A1 (en) | 1990-03-01 | 1991-09-05 | Chevron Research Company | Synthesis of a crystalline silicoaluminophosphate |
US5100596A (en) | 1990-06-05 | 1992-03-31 | Mobil Oil Corp. | Synthesis of membrane composed of a pure molecular sieve |
US5326923A (en) * | 1990-09-26 | 1994-07-05 | Catalytica, Inc. | Method for regenerating certain acidic hydrocarbon conversion catalysts by solvent extraction |
US5248647A (en) * | 1991-02-28 | 1993-09-28 | Uop | Sapo catalysts and use thereof in methanol conversion processes |
US5155075A (en) | 1991-03-01 | 1992-10-13 | Chevron Research And Technology Company | Low temperature regeneration of coke deactivated reforming catalysts |
IL101728A (en) * | 1991-05-03 | 2007-08-19 | Univ Yale | Human Abandonment and Delta, Restrictive Areas of Effect in Tophoric Proteins, and Methods Based on Them |
US5177298A (en) * | 1991-06-18 | 1993-01-05 | Uop | Liquid phase adsorption process |
US5478787A (en) | 1991-12-26 | 1995-12-26 | Uop | Discrete molecular sieve and use |
US5240891A (en) | 1991-12-26 | 1993-08-31 | Patton Robert L | Discrete molecular sieve and use |
US5185310A (en) * | 1992-01-31 | 1993-02-09 | Mobil Oil Corp. | Activating silicoaluminophosphate compositions |
US5879655A (en) | 1992-11-02 | 1999-03-09 | Chevron Research And Technology Company | Method of making microporous non-zeolitic molecular sieves |
DE4304821A1 (de) | 1993-02-17 | 1994-08-18 | Degussa | Verfahren zum Modifizieren von Molekularsieben mittels Ionenaustausch |
US5365003A (en) | 1993-02-25 | 1994-11-15 | Mobil Oil Corp. | Shape selective conversion of hydrocarbons over extrusion-modified molecular sieve |
US5371312A (en) | 1993-04-05 | 1994-12-06 | Mobil Oil Corp. | Shape selective hydrocarbon conversions over modified catalyst |
US5403800A (en) | 1993-05-28 | 1995-04-04 | Mobil Oil Corp. | Multiple impregnation technique for the preparation of ex situ selectivated zeolite catalysts |
EP0762936A1 (en) * | 1994-06-03 | 1997-03-19 | Akzo Nobel N.V. | Hydrocracking catalyst comprising coated craking component particles |
US5817595A (en) | 1994-12-30 | 1998-10-06 | Intevep, S.A. | Catalyst for the hydroisomerization of contaminated hydrocarbon feedstock |
US5849968A (en) | 1995-06-06 | 1998-12-15 | Mobil Oil Corporation | Hydrocarbon conversion process with alkaline earth metal ion exchanged selectivated zeolite catalyst |
US5602066A (en) | 1995-06-29 | 1997-02-11 | Mobil Oil Corporation | Method of making a liquid washed selectivated zeolite catalyst |
US5744680A (en) * | 1995-08-10 | 1998-04-28 | Uop | Process for producing light olefins |
KR970015606A (ko) * | 1995-09-01 | 1997-04-28 | 윤덕용 | 폴리올레핀 중합용 메탈로센 담지촉매의 제조방법 |
US5962762A (en) | 1995-12-13 | 1999-10-05 | Sun; Hsian-Ning | Use of transition metal containing small pore molecular sieve catalysts in oxygenate conversion |
US6040264A (en) * | 1996-04-04 | 2000-03-21 | Exxon Chemical Patents Inc. | Use of alkaline earth metal containing small pore non-zeolitic molecular sieve catalysts in oxygenate conversion |
US5859314A (en) * | 1996-10-18 | 1999-01-12 | Ludwig Institute For Cancer Research | Mice with targeted tyrosine kinase, lyn, disruption |
US5932512A (en) * | 1997-08-19 | 1999-08-03 | Exxon Chemical Patents, Inc. | Fluorination of synthesized molecular sieve catalysts for increased selectivity to ethylene during conversion of oxygenates to olefins |
US6005155A (en) * | 1997-12-03 | 1999-12-21 | Exxon Chemicals Patents Inc. | Modification of molecular sieve catalyst for reduced methane production during conversion of oxygenates to olefins |
US5912393A (en) * | 1997-12-09 | 1999-06-15 | Uop Llc | Metallo aluminophosphate molecular sieve with novel crystal morphology and methanol to olefin process using the sieve |
US6127432A (en) * | 1998-01-29 | 2000-10-03 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for preparing oxygenates and catalysts therefor |
US6046373A (en) * | 1998-04-29 | 2000-04-04 | Exxon Chemical Patents Inc. | Catalytic conversion of oxygenates to olefins |
JP4168214B2 (ja) * | 1998-10-15 | 2008-10-22 | 三菱瓦斯化学株式会社 | メチルアミン製造触媒及び該触媒の製造方法 |
KR100293531B1 (ko) * | 1998-12-24 | 2001-10-26 | 윤덕용 | 이산화탄소로부터탄화수소생성을위한혼성촉매 |
WO2000069557A1 (fr) * | 1999-05-12 | 2000-11-23 | Daikin Industries, Ltd. | Catalyseurs pour la preparation d'alcools fluores et procede de preparation d'alcools fluores |
US6316683B1 (en) * | 1999-06-07 | 2001-11-13 | Exxonmobil Chemical Patents Inc. | Protecting catalytic activity of a SAPO molecular sieve |
US6448197B1 (en) * | 2000-07-13 | 2002-09-10 | Exxonmobil Chemical Patents Inc. | Method for making a metal containing small pore molecular sieve catalyst |
-
2000
- 2000-07-13 US US09/615,526 patent/US6448197B1/en not_active Expired - Lifetime
-
2001
- 2001-06-27 EP EP01952298A patent/EP1299188A2/en not_active Withdrawn
- 2001-06-27 CA CA002415730A patent/CA2415730A1/en not_active Abandoned
- 2001-06-27 WO PCT/US2001/020677 patent/WO2002005951A2/en not_active Application Discontinuation
- 2001-06-27 AU AU2001273065A patent/AU2001273065A1/en not_active Abandoned
- 2001-06-27 CN CN01812626A patent/CN1441701A/zh active Pending
- 2001-06-27 MX MXPA02012674A patent/MXPA02012674A/es unknown
-
2002
- 2002-07-30 US US10/208,324 patent/US20030018230A1/en not_active Abandoned
- 2002-08-02 US US10/211,093 patent/US6825391B2/en not_active Expired - Lifetime
-
2003
- 2003-01-09 ZA ZA200300241A patent/ZA200300241B/en unknown
- 2003-01-10 NO NO20030136A patent/NO20030136L/no not_active Application Discontinuation
- 2003-09-15 US US10/662,711 patent/US20040048734A1/en not_active Abandoned
Cited By (7)
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CN101993093B (zh) * | 2009-08-25 | 2012-10-31 | 中国科学院大连化学物理研究所 | 一种具有rho骨架结构的sapo分子筛及其制备方法 |
CN102744102A (zh) * | 2012-06-14 | 2012-10-24 | 新疆大学 | 金属改性sapo-34分子筛催化剂及制备方法和使用方法 |
CN102744102B (zh) * | 2012-06-14 | 2015-01-21 | 新疆大学 | 金属改性sapo-34分子筛催化剂及制备方法和使用方法 |
CN106984364A (zh) * | 2016-01-20 | 2017-07-28 | 中国科学院大连化学物理研究所 | 磷酸硅铝类分子筛原粉在分离/提取金属离子中的应用 |
WO2018096171A1 (en) | 2016-11-28 | 2018-05-31 | Basf Se | Catalyst composite comprising an alkaline earth metal containing cha zeolite and use thereof in a process for the conversion of oxygenates to olefins |
US11529618B2 (en) | 2016-11-28 | 2022-12-20 | Basf Se | Catalyst composite comprising an alkaline earth metal containing CHA zeolite and use thereof in a process for the conversion of oxygenates to olefins |
CN115254108A (zh) * | 2022-07-12 | 2022-11-01 | 南京工业大学 | 一种无定形硅铝封装金属氧化物催化剂的制备方法及其应用 |
Also Published As
Publication number | Publication date |
---|---|
WO2002005951A3 (en) | 2002-04-04 |
US20030018230A1 (en) | 2003-01-23 |
ZA200300241B (en) | 2004-04-08 |
MXPA02012674A (es) | 2004-07-30 |
US20030028062A1 (en) | 2003-02-06 |
CA2415730A1 (en) | 2002-01-24 |
US6448197B1 (en) | 2002-09-10 |
WO2002005951A2 (en) | 2002-01-24 |
AU2001273065A1 (en) | 2002-01-30 |
NO20030136L (no) | 2003-03-04 |
US6825391B2 (en) | 2004-11-30 |
US20040048734A1 (en) | 2004-03-11 |
EP1299188A2 (en) | 2003-04-09 |
NO20030136D0 (no) | 2003-01-10 |
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