CN1642648A - 包括分子筛的催化剂组合物、其制备及在转化方法中的应用 - Google Patents
包括分子筛的催化剂组合物、其制备及在转化方法中的应用 Download PDFInfo
- Publication number
- CN1642648A CN1642648A CNA038068079A CN03806807A CN1642648A CN 1642648 A CN1642648 A CN 1642648A CN A038068079 A CNA038068079 A CN A038068079A CN 03806807 A CN03806807 A CN 03806807A CN 1642648 A CN1642648 A CN 1642648A
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- Prior art keywords
- molecular sieve
- oxide
- carbon monoxide
- metal oxide
- olefin polymeric
- Prior art date
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 110
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 68
- 238000002360 preparation method Methods 0.000 title claims description 6
- 230000008569 process Effects 0.000 title description 11
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- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
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- 230000000737 periodic effect Effects 0.000 claims abstract description 12
- 150000001255 actinides Chemical class 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 87
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- 229910052799 carbon Inorganic materials 0.000 claims description 77
- 150000004706 metal oxides Chemical class 0.000 claims description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 67
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 53
- 239000000463 material Substances 0.000 claims description 31
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 12
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- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 4
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
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- 239000000047 product Substances 0.000 description 16
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
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- 229910052746 lanthanum Inorganic materials 0.000 description 8
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Classifications
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Abstract
本发明涉及催化剂组合物、制造它的方法、和该催化剂组合物在将原料,优选含氧化合物原料转化成一种或多种烯烃,优选乙烯和/或丙烯中的应用。该催化剂组合物包括分子筛和至少一种选自元素周期表第3族、镧系元素和锕系元素的金属氧化物。
Description
本发明涉及分子筛组合物和包含它的催化剂,并涉及这种组合物和催化剂的合成,以及这种组合物和催化剂在生产烯烃的转化方法中的应用。
常规地通过催化或蒸汽裂化方法由石油原料生产烯烃。这些裂化方法,特别是蒸汽裂化,由各种烃原料生产轻质烯烃,如乙烯和/或丙烯。乙烯和丙烯是在制造塑料和其它化工化合物的各种方法中有用的重要的商业石化产品。
石化工业一段时间以来公知,含氧化合物(oxygenate),特别是醇,可转化成轻质烯烃。优选地用于轻质烯烃生产的醇是甲醇,和优选地将含甲醇的原料转化成轻质烯烃(主要为乙烯和/或丙烯)的方法包括使原料与分子筛催化剂组合物接触。
已知有许多不同类型的分子筛可以将含有含氧化合物的原料转化成一种或多种烯烃。例如,美国专利No.5367100描述了使用沸石、ZSM-5将甲醇转化成烯烃;美国专利No.4062905讨论了使用结晶硅铝酸盐沸石,例如沸石T、ZK5、毛沸石和菱沸石,将甲醇和其它含氧化合物转化成乙烯和丙烯;美国专利No.4079095描述了使用ZSM-34将甲醇转化成烃类产品如乙烯和丙烯;和美国专利No.4310440描述了使用常表示为AlPO4的结晶铝磷酸盐由醇生产轻质烯烃。
将甲醇转化成烯烃的一些最有用的分子筛是硅铝磷酸盐(SAPO)分子筛。硅铝磷酸盐分子筛含有[SiO4]、[AlO4]和[PO4]共角四面体单元的三维微孔晶体骨架结构。在美国专利Nos.4499327、4677242、4677243、4873390、5095163、5714662和6166282中公开了SAPO分子筛的合成、将其配制成催化剂的方法和它在将原料转化成烯烃中的应用,尤其在原料是甲醇的情况下,所有这些文献在此全文引入作为参考。
当用于将甲醇转化成烯烃时,大多数分子筛(包括SAPO分子筛)会经历快速的焦化,并因此要求经常的再生,再生典型地包括将催化剂暴露于高温和蒸汽环境下。所以,目前转化甲醇的催化剂倾向于具有有限的有效寿命,因此需要提供一种具有延长的寿命的分子筛催化剂组合物,尤其当用于将甲醇转化成烯烃时。
美国专利No.4465889描述了一种在将甲醇、二甲醚或其混合物转化成富含异-C4化合物的烃类产品中使用的催化剂组合物,其包括用钍、锆、钛的金属氧化物浸渍的硅质岩分子筛。
美国专利No.6180828讨论了使用改性分子筛由甲醇和氨生产甲胺,其中例如将硅铝磷酸盐分子筛与一种或多种改性剂,如氧化锆、氧化钛、氧化钇、蒙脱石或高岭土结合。
美国专利No.5417949涉及使用分子筛和金属氧化物粘合剂,将在含氧的流出物中有毒的氮氧化物转化成氮气和水的方法,其中优选的粘合剂是二氧化钛和分子筛是硅铝酸盐。
EP-A-312981公开了使用催化剂组合物裂化含钒的烃原料物流的方法,其中所述催化剂组合物包括由包埋在无机耐火基质材料内的沸石和在含二氧化硅的载体材料上的至少一种铍、镁、钙、锶、钡或镧的氧化物(优选氧化镁)形成的物理状态混合物。
Kang和Inui在Catalysis Letters 53,第171-176页(1998)的Effects of decrease in number of acid sites located on the externalsurface of Ni-SAPO-34 crystalline catalyst by the mechanochemicalmethod(通过机械化学方法减少位于Ni-SAPO-34结晶催化剂外表面上的酸性部位数目的效果)中公开了在Ni-SAPO-34上将甲醇转化成乙烯的过程中,可通过由微球无孔二氧化硅上的MgO、CaO、BaO或Cs2O(其中最优选BaO)研磨催化剂,提高形状选择性并减少焦炭的形成。
国际公开No.WO98/29370披露了在含选自镧系、锕系、钪、钇、第4族金属、第5族金属或其组合中的金属的小孔非沸石分子筛上,将含氧化合物转化成烯烃。
一方面,本发明涉及一种催化剂组合物,它包括分子筛和至少一种选自元素周期表第3族、镧系元素和锕系元素的金属的氧化物,其中所述金属氧化物在100℃下二氧化碳的吸收量为至少0.03,并且典型的吸收量为至少0.04mg/m2金属氧化物。
优选,催化剂组合物还包括不同于所述金属氧化物的至少一种粘合剂和基质材料。
在一个实施方案中,所述金属氧化物选自氧化镧、氧化钇、氧化钪、氧化铈、氧化镨、氧化钕、氧化钐、氧化钍及其混合物。
优选,分子筛常规地包括硅铝磷酸盐。
另一方面,本发明涉及分子筛催化剂组合物,它包括第3族金属氧化物和/或镧系或锕系元素的氧化物、粘合剂、基质材料和硅铝磷酸盐分子筛。
再一方面,本发明涉及制造催化剂组合物的方法,该方法包括物理混合含分子筛的第一颗粒与含至少一种选自元素周期表第3族、镧系元素和锕系元素的金属的氧化物的第二颗粒,其中金属氧化物在100℃下的二氧化碳吸收量为至少0.03mg/m2所述金属氧化物颗粒。
优选,通过引起金属氧化物的水合前体从含金属离子的溶液中沉淀,在至少80℃的温度下水热处理该水合前体多至10天,然后在400-900℃的温度范围内焙烧该水合前体,从而生产所述第二颗粒。
在进一步的方面,本发明涉及在由分子筛和至少一种选自元素周期表第3族、镧系元素和锕系元素的金属的氧化物形成的催化剂组合物的存在下,通过将原料,如含氧化合物,常规地是醇,例如甲醇,转化成一种或多种烯烃从而生产烯烃的方法,其中所述金属氧化物在100℃下的二氧化碳吸收量为至少0.03mg/m2金属氧化物颗粒。
在一个实施方案中,催化剂组合物的寿命提高指数(LEI)大于1,如大于1.5。LEI在此处定义为该催化剂组合物对不存在活性金属氧化物情况下的相同催化剂组合物的寿命之比。
本发明涉及分子筛催化剂组合物和它将烃类原料,尤其是氧化原料转化成烯烃的用途。已发现,当用于将原料(如含氧化合物,更特别地甲醇)转化成烯烃时,结合分子筛与选自元素周期表第3族(利用在CRC Handbook of Chemistry and Physics,78th,CRC出版社,BocaRaton,Florida[1997]中所述的IUPAC格式)和/或镧系或锕系元素的活性金属氧化物,可获得具有提高的烯烃产率和/或更长寿命的催化剂组合物。另外,所得的催化剂组合物倾向于具有更高的丙烯选择性和产生较小量不想要的乙烷和丙烷,以及其它非所需的化合物,如醛和酮,特别地乙醛。
分子筛
根据IUPAC委员会关于沸石命名的规则,国际沸石协会结构委员会(Structure Commission of the International Zeolite Association)已对分子筛进行了分类。根据该分类,用三个字母的代码表示其结构已确定的骨架型沸石和沸石型分子筛,且描述于Atlas of ZeoliteFramework Types,5th版,Elsevier,London,England(2001)中,在此全部引入作为参考。
优选分子筛的非限制性实例,尤其是用于将包含含氧化合物的原料转化成烯烃的分子筛,包括骨架型AEL、AEI、BEA、CHA、EDI、FAU、FER、GIS、LTA、LTL、MER、MFI、MOR、MTT、MWW、TAM和TON。在一个优选实施方案中,在本发明催化剂组合物中使用的分子筛具有AEI拓扑结构或CHA拓扑结构、或其组合,最优选CHA拓扑结构。
结晶分子筛材料具有共角[TO4]四面体的三维、四面连接(four-connected)的骨架结构,其中T是任何四面体式配位的阳离子,如[SiO4]、[AlO4]和/或[PO4]四面体单元。此处可用的分子筛常规地包括含[AlO4]和[PO4]四面体单元(即铝磷酸盐(AlPO)分子筛)或含[SiO4]、[AlO4]和[PO4]四面体单元(即硅铝磷酸盐(SAPO)分子筛)的骨架结构。最优选,此处可用的分子筛是硅铝磷酸盐(SAPO)分子筛,或取代的、优选金属取代的SAPO分子筛。合适的金属取代基的实例是元素周期表第1族的碱金属,元素周期表第2族的碱土金属,元素周期表第3族的稀土金属,其中包括镧系,镧、铈、镨、钕、钐、铕、钆、铒、镝、钬、铒、铥、镱和镥,和钪或钇,元素周期表第4-12族的过渡金属,或任何这些金属物质的混合物。
优选,此处所使用的分子筛具有由[TO4]四面体的8元环定义的孔体系,其平均孔径小于5,如在3-5范围内,例如3-4.5,和尤其3.5-4.2。
此处可用的SAPO和AlPO分子筛的非限制性实例包括下述的一种或组合: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(美国专利No.6162415)、SAPO-47、SAPO-56、AlPO-5、AlPO-11、AlPO-18、AlPO-31、AlPO-34、AlPO-36、AlPO-37、AlPO-46,和含金属的上述分子筛。其中,尤其有用的分子筛是下述的一种或组合:SAPO-18、SAPO-34、SAPO-35、SAPO-44、SAPO-56、AlPO-18和AlPO-34,以及它们含金属的衍生物;如SAPO-18、SAPO-34、AlPO-34和AlPO-18的一种或组合,以及它们含金属的衍生物;特别是SAPO-34和AlPO-18的一种或组合,或其含金属的衍生物。
在一个实施方案中,分子筛是在一种分子筛组合物内具有两个或多个不同晶相的共生材料。特别地,在美国专利申请公开No.2002-0165089和1998年4月16日公开的国际公开No.WO 98/15496中描述了共生分子筛,这两篇文献在此全部引入作为参考。例如,SAPO-18、AlPO-18和RUW-18具有AEI骨架型结构,SAPO-34具有CHA骨架型结构。因此,此处所使用的分子筛可包括AEI和CHA骨架型的至少一个共生相,特别地在CHA骨架型对AEI骨架型的比例(根据美国专利申请公开No.2002-0165089中所披露的DIFFaX方法确定)大于1∶1的情况下。
优选地,在分子筛是硅铝磷酸盐的情况下,分子筛的Si/Al比小于或等于0.65,如0.65-0.10,优选0.40-0.10,更优选0.32-0.10,和最优选0.32-0.15。
金属氧化物
此处可用的金属氧化物是第3族金属和镧系与锕系金属的氧化物,其在100℃的二氧化碳吸收量为至少0.03mg/m2金属氧化物,如至少0.04mg/m2金属氧化物。尽管金属氧化物的二氧化碳吸收量的上限不是关键的,但一般而言此处可用的金属氧化物在100℃的二氧化碳吸收量小于10mg/m2金属氧化物,如小于5mg/m2金属氧化物。典型地,此处可用的金属氧化物具有的二氧化碳吸收量为0.05-1mg/m2金属氧化物。当与分子筛结合使用时,这种活性金属氧化物在催化转化方法,尤其在将含氧化合物转化成烯烃方面提供优势。
为了确定金属氧化物的二氧化碳吸收量,采用下述工序。通过在流动空气中加热样品到约200-500℃直到恒重,使金属氧化物样品脱水,获得“干重”。然后降低样品温度到100℃,并使二氧化碳或者连续或者脉冲地流过样品,直到获得恒重。基于样品干重,样品重量的增加(以mg/mg样品为单位)是所吸收的二氧化碳的量。
在以下报道的实施例中,使用Mettler TGA/SDTA 851热重量分析体系,在环境压力下测量二氧化碳的吸附。在流动空气中,在约500℃下使金属氧化物样品脱水1小时。然后在流动的氦气中将样品温度降低到100℃的所需吸附温度。在样品于流动氦气中达到平衡之后,使样品经历20次含10wt%二氧化碳和其余为氦气的气体混合物的独立脉冲(约12秒/次脉冲)。在吸附气体的每次脉冲之后,用流动氦气冲洗金属氧化物3分钟。基于在500℃处理之后的吸附重量,样品的重量增加(以mg/mg吸收剂为单位)为所吸附的二氧化碳量。根据以ASTM D 3663形式出版的Brunauer,Emmett和Teller(BET)方法测量样品的表面积,提供二氧化碳的吸收量(以mg二氧化碳/m2金属氧化物为单位)。
优选的第3族金属氧化物包括钪、钇和镧的氧化物,优选的镧系或锕系金属的氧化物包括铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥和钍的氧化物。最优选的活性金属氧化物是氧化钪、氧化镧、氧化钇、氧化铈、氧化镨、氧化钕及其混合物,特别是氧化镧和氧化铈的混合物。
在一个实施方案中,有用的金属氧化物是第3族金属和/或镧系和锕系金属的那些氧化物,当与分子筛在催化剂组合物中结合使用时,它们可有效延长催化剂组合物的有效寿命。通过由下述等式定义的“寿命提高指数”(LEI)来定量确定催化剂组合物寿命的延长:
LEI=与活性金属氧化物结合的催化剂的寿命/催化剂的寿命
其中在相同的条件下,以相同的方法测量催化剂或催化剂组合物的寿命,且它是所处理的原料的累积量/g催化剂组合物,直到通过催化剂组合物转化的原料转化率落到低于某一确定的含量,例如10%。不活泼的金属氧化物对催化剂组合物的寿命影响很少到不具有影响,或将缩短催化剂组合物的寿命,并因此将具有小于或等于1的LEI。本发明的活性金属氧化物是那些第3族的金属氧化物,其中包括镧系和锕系的氧化物,当其与分子筛结合使用时,提供LEI大于1的分子筛催化剂组合物。没有与活性金属氧化物结合的分子筛催化剂组合物定义其LEI等于1.0。
发现通过包括与分子筛结合的活性金属氧化物,可生产LEI从大于1到50,如1.5-20范围内的催化剂组合物。典型地,本发明的催化剂组合物显示出大于1.1的LEI值,例如在1.2-15范围内,和更特别地大于1.3,如大于1.5,如大于1.7,如大于2。
可使用各种方法制备活性金属氧化物。优选由活性金属氧化物前体,如金属盐,如硝酸盐、卤化物、硝酸化硫酸盐或醋酸盐,制备活性金属氧化物。其它金属氧化物的合适来源包括在焙烧过程中形成金属氧化物的化合物,如氯氧化物和硝酸盐。烷氧化物也是第3族金属氧化物的合适来源,例如正丙氧化钇。
在一个实施方案中,在包括至少80℃,优选至少100℃温度的条件下,水热处理第3族金属氧化物或镧系或锕系的氧化物。可在大于大气压的压力下,在密封的容器内进行水热处理。然而,处理的优选模式包括在回流条件下使用敞口容器。例如通过回流液体的作用和/或搅拌,在液体介质内搅拌第3族金属氧化物或镧系或锕系的氧化物,以促进氧化物与液体介质的有效相互作用。氧化物与液体介质的接触持续时间优选至少1小时,优选至少8小时。这一处理的液体介质优选pH为约6或更大,优选8或更大。合适的液体介质的非限制性实例包括水、氢氧化物溶液(包括NH4 +、Na+、K+、Mg2+和Ca2+的氢氧化物)、碳酸盐和碳酸氢盐溶液(包括NH4 +、Na+、K+、Mg2+和Ca2+的的碳酸盐和碳酸氢盐)、吡啶及其衍生物和烷基/羟基胺。
在另一实施方案中,通过使其中包括金属离子源,如金属盐的液体溶液,如水溶液,经历足以引起水合前体沉淀成固体氧化物材料的条件,如通过添加沉淀剂到溶液中,从而制备活泼的第3族金属氧化物或活泼的镧系或锕系的氧化物。方便地,在高于7的pH下进行沉淀,沉淀剂优选碱如氢氧化钠或氢氧化铵。
在沉淀过程中液体介质维持在通常小于或等于200℃的温度,如在0-200℃范围内。沉淀的特定温度范围是20-100℃。优选地,然后在至少80℃,优选至少100℃的温度下水热处理所得凝胶。水热处理典型地在大气压下进行。在一个实施方案中,水热处理凝胶多至10天,如多至5天,例如多至3天。
然后例如通过过滤或离心,并洗涤和干燥,水合前体到回收金属氧化物。然后可如在氧化气氛中,在至少400℃,如至少500℃,例如600-900℃,和尤其650-800℃的温度下,焙烧所得材料形成固体氧化物材料。焙烧时间典型地多至48小时,如0.5-24小时,例如1.0-10小时。在一个实施方案中,在约700℃下进行焙烧1-3小时。
催化剂组合物
本发明的催化剂组合物包括前述的任何一种分子筛和一种或多种以上所述的活性金属氧化物,以及任选地不同于活性金属氧化物的粘合剂和/或基质材料。典型地,在催化剂组合物内分子筛对活性金属氧化物的重量比范围为5wt%-800wt%,优选10wt%-600wt%,更优选20wt%-500wt%,和最优选30wt%-400wt%。
许多不同的粘合剂可用于形成本发明的催化剂组合物。可单独或结合使用的粘合剂的非限制性实例包括各类水合氧化铝、二氧化硅和/或其它无机氧化物溶胶。一种优选的含氧化铝的溶胶是水合氯化铝(aluminum chlorhydrol)。无机氧化物溶胶充当胶水,特别在热处理之后,将合成分子筛与其它材料如基质粘结在一起。当加热时,无机氧化物溶胶,优选具有低粘度的无机氧化物溶胶,转化成无机氧化物粘合剂组分。例如,氧化铝溶胶在热处理之后将转化成氧化铝粘合剂。
水合氯化铝,一种含有氯抗衡离子的羟基化铝基溶胶,其通式为AlmOn(OH)oClp·x(H2O),其中m为1-20,n为1-8,o为5-40,p为2-15,和x为0-30。在一个实施方案中,粘合剂是如G.M.Wolterman等,Stud.Surf.Sci.and Catal.,76,第105-144页(1993)中所述的Al13O4(OH)24Cl7·12(H2O)。在另一实施方案中,将一种或多种粘合剂与一种或多种其它氧化铝材料如羟基氧化铝、γ-氧化铝、勃姆石、水铝石,过渡态氧化铝如α-氧化铝、β-氧化铝、γ-氧化铝、δ-氧化铝、ε-氧化铝、κ-氧化铝和ρ-氧化铝、三氢氧化铝如三水铝石、三羟铝石、诺三水铝石、doyelite及其混合物结合。
可商购的胶态氧化铝溶胶的非限制性实例包括获自于NalcoChemical Co.,Naperville,Illinois的Nalco 8676,和获自于NyacolNano Technologies,Inc.,Ashland,Massachussetts的NyacolAL20DW。
在催化剂组合物含有基质材料的情况下,它优选不同于活性金属氧化物和任何粘合剂。基质材料典型地在降低总的催化剂成本上是有效的,在再生过程中充当热穴,使催化剂组合物致密并增加催化剂的物性如压碎强度和耐磨性。
此处可用的基质材料的非限制性实例包括一种或多种非活性的金属氧化物,其中包括氧化铍、石英、二氧化硅或溶胶,及其混合物,例如二氧化硅-氧化镁、二氧化硅-氧化锆、二氧化硅-二氧化钛、二氧化硅-氧化铝和二氧化硅-氧化铝-氧化钍。在一个实施方案中,基质材料是天然粘土,如来自蒙脱石和高岭土族的那些。这些天然粘土包括变班脱岩(sabbentonite)和被称为例如Dixie、McNamee、Georgia和Florida粘土的那些高岭土。其它基质材料的非限制性实例包括埃洛石(haloysite)、高岭石、地开石、珍珠石或富硅高岭石。基质材料如粘土,可经历公知的改性工艺如焙烧和/或酸处理和/或化学处理。
在一个优选的实施方案中,基质材料是粘土或粘土型组合物,尤其是具有低的铁或二氧化钛含量的粘土或粘土型组合物,最优选高岭土。已发现高岭土形成可泵送的高固体含量的淤浆,具有低的新生表面积,和由于它的片状结构而容易堆积在一起。基质材料,最优选高岭土,其优选的平均粒度为0.1-0.6微米,其中D90粒度分布小于1微米。
在催化剂组合物含有粘合剂或基质材料的情况下,基于催化剂组合物的总重量,催化剂组合物典型地含有1%-80%,优选约5%-60%,和更优选5%-50wt%的分子筛。
在催化剂组合物含有粘合剂和基质材料的情况下,粘合剂对基质材料的重量比典型地为1∶15到1∶5,如1∶10到1∶4,和尤其1∶6到1∶5。基于粘合剂、分子筛和基质材料的总重量,粘合剂的含量典型地为约2%-约30wt%,如约5%-约20wt%,和尤其约7%-约15wt%。
催化剂组合物的密度范围典型地为0.5-5g/cc,如0.6-5g/cc,例如0.7-4g/cc,尤其在0.8-3g/cc范围内。
催化剂组合物配方
在制造催化剂组合物过程中,首先合成分子筛,然后将其与优选处于基本上干燥、已干燥或焙烧状态下的活性金属氧化物物理混合。最优选,分子筛和活性金属氧化物在它们的焙烧状态下物理混合。可通过本领域任何已知的方法,如与混合研磨机、鼓式混合机、螺条/浆式混合器、捏合机或类似物实现紧密的物理混合。不需要且一般不优选分子筛与金属氧化物之间的化学反应。
在催化剂组合物含有基质和/或粘合剂的情况下,方便地最初将分子筛与基质和/或粘合剂一起配制成催化剂前体,然后将活性金属氧化物与所配制的前体结合。活性金属氧化物可作为未负载的颗粒添加或可与载体,如粘合剂或基质材料结合后添加。所得催化剂组合物然后可通过公知技术如喷雾干燥、造粒、挤出等形成为有用形状和大小的颗粒。
在一个实施方案中,将分子筛组合物和基质材料,以及任选地粘合剂与液体结合以形成淤浆,然后混合以产生含分子筛组合物的基本上均匀的混合物。合适的液体的非限制性实例包括水、醇、酮、醛和/或酯。最优选的液体是水。然后将分子筛组合物、粘合剂和基质材料的淤浆投入到成型装置中,如喷雾干燥器,所述成型装置将催化剂组合物形成为所要求的形状,例如微球。
一旦分子筛催化剂组合物在基本上干燥或已干燥的状态下成型,通常进行热处理如焙烧,以进一步硬化和/或活化所形成的催化剂组合物。典型的焙烧温度范围为400-1000℃,优选500-800℃,和更优选550-700℃。典型的焙烧环境是空气(它可包括少量水蒸气)、氮气、氦气、烟道气(贫氧的燃烧产物)或其中的任何结合。
在一个优选的实施方案中,在氮气中,在600-700℃的温度下加热催化剂组合物一段时间,典型地30分钟-15小时,优选1小时-约10小时,更优选约1小时-约5小时,和最优选约2小时-约4小时。
催化剂组合物的使用
以上所述的催化剂组合物可用于各种方法,其中包括例如石脑油原料裂化成轻质烯烃(美国专利No.6300537)或较高分子量(MW)的烃裂化成较低分子量(MW)的烃;例如重质石油和/或环状原料的加氢裂化;例如芳烃如二甲苯的异构化;例如一种或多种烯烃聚合生产聚合物产品;重整;氢化;脱氢;例如烃的脱蜡,以除去直链链烷烃;例如烷基芳族化合物的吸收,以分离出其异构体;例如芳烃如苯和烷基苯的烷基化;例如芳族和多烷基芳族烃的结合物的烷基转移;脱烷基化;氢化开环化;例如甲苯的歧化,以制造苯和二甲苯;例如直链和支链烯烃的低聚;和脱氢环化。
优选的方法包括将石脑油转化成高含量芳族的混合物的方法,将轻质烯烃转化成汽油、馏出液和润滑剂的方法;将含氧化合物转化成烯烃的方法;将轻质链烷烃转化成烯烃和/或芳族类物质的方法;和将不饱和烃(乙烯和/或乙炔)转化成醛的方法,所述醛用于转化成醇、酸和酯。
本发明的最优选方法是将原料转化成一种或多种烯烃的方法。典型地,原料包含一种或多种含脂族类部分的化合物,和优选一种或多种含氧化合物,以便脂族类部分含有1-约50个碳原子,优选1-20个碳原子,更优选1-10个碳原子,和最优选1-4个碳原子。
合适的含脂族类部分的化合物的非限制性实例包括醇如甲醇和乙醇;烷基硫醇如甲硫醇和乙硫醇;烷基硫如甲基硫;烷基胺如甲胺;烷基醚如二甲醚、二乙醚和甲乙醚;烷基卤如甲基氯和乙基氯;烷基酮如二甲酮;甲醛;和各种酸如醋酸。优选原料包括甲醇、乙醇、二甲醚、二乙醚或其结合,更优选甲醇和/或二甲醚,和最优选甲醇。
使用以上所述的各种原料,尤其含含氧化合物的原料,如醇,本发明的催化剂组合物可有效地将原料主要转化成一种或多种烯烃。所生产的烯烃典型地具有2-30个碳原子,优选2-8个碳原子,更优选2-6个碳原子,仍更优选2-4个碳原子,和最优选乙烯和/或丙烯。
典型地,本发明的催化剂组合物可有效地将含一种或多种含氧化合物的原料转化成含有大于50wt%,典型地大于60wt%,如大于70wt%,和优选大于80wt%烯烃的产品,基于产品中烃的总重量。此外,基于产品中烃的总重量,所生产的乙烯和/或丙烯的含量典型地大于40wt%,例如大于50wt%,优选大于65wt%,和更优选大于78wt%。典型地,基于所生产的烃产品的总重量,所生产的乙烯含量(重量百分数)大于30wt%,如大于35wt%,例如大于40wt%。另外,基于所生产的烃产品的总重量,所生产的丙烯含量(重量百分数)大于20wt%,如大于25wt%,例如大于30wt%,和优选大于35wt%。
使用本发明的催化剂组合物将含甲醇和二甲醚的原料转化成乙烯和丙烯,发现与在相同的转化条件下,但不含活性金属氧化物组分的类似催化剂组合物相比,乙烷和丙烷的产量下降大于10%,如大于20%,例如大于30%,和尤其在30%-40%范围内。
除了含氧化合物组分如甲醇以外,原料还可含有一种或多种稀释剂,稀释剂通常对于原料或分子筛催化剂组合物是非反应性的,且典型地用于降低原料的浓度。稀释剂的非限制性实例包括氦气、氩气、氮气、一氧化碳、二氧化碳、水、基本上不反应的链烷烃(特别地烷烃如甲烷、乙烷和丙烷),基本上不反应的芳族类化合物及其混合物。最优选的稀释剂是水和氮气,其中尤其优选水。
可在宽的温度范围内进行该方法,如在200-1000℃范围内,例如250-800℃,其中包括250-750℃,方便地300-650℃,优选350-600℃,和更优选350-550℃。
类似地,可在宽的压力范围内进行该方法,其中包括自生压力。典型地,在该方法中使用的除了其中的任何稀释剂以外的原料的分压范围为0.1kPa-5MPa,优选5kPa-1MPa,和更优选20kPa-500kPa。
重量时空速度(WHSV),它被定义为除了任何稀释剂以外的原料总重量/小时/催化剂组合物中的分子筛重量,范围可以是1-5000hr-1,优选2-3000hr-1,更优选5-1500hr-1,和最优选10-1000hr-1。在一个实施方案中,WHSV为至少20hr-1,和在原料含有甲醇和/或二甲醚的情况下,其范围为20-300hr-1。
方便地以固定床工艺,或更典型地以流化床工艺(其中包括湍动床工艺),如连续流化床工艺,和尤其的连续高速流化床工艺,进行本发明的方法。
在一个实际的实施方案中,以流化床工艺,使用反应器体系、再生体系和回收体系进行该方法。在该方法中,新鲜的原料、任选地一种或多种稀释剂与分子筛催化剂组合物一起被投入到反应器体系内的一个或多个提升管反应器中。在提升管反应器内原料被转化成气体流出物,该气体流出物与焦化的催化剂组合物一起进入反应器体系内的分离容器内。在该分离容器内,典型地在旋风分离器辅助下,焦化的催化剂组合物与气体流出物分离,然后供料到汽提区,典型地汽提区在分离容器的下端。在汽提区内,焦化的催化剂组合物与气体,如蒸汽、甲烷、二氧化碳、一氧化碳、氢气和/或惰性气体如氩气,优选蒸汽接触,从焦化的催化剂组合物中回收被吸附的烃,然后将焦化的吸附剂组合物引入到再生体系内。
在再生体系内,在能够燃烧焦化的催化剂组合物中的焦炭到优选小于0.5wt%的再生条件下,基于进入再生体系内的焦化的分子筛催化剂组合物的总重量,使焦化的催化剂组合物与再生介质,优选含氧气的气体接触。例如,再生条件可包括范围为450-750℃,和优选550-700℃的温度。
将从再生体系中取出的再生的催化剂组合物与新鲜分子筛催化剂组合物和/或再循环的分子筛催化剂组合物和/或原料和/或新鲜气体或液体结合,并返回到提升管反应器内。
从分离体系中取出气体流出物并流过回收体系,用于分离和纯化气体流出物中的轻质烯烃,尤其乙烯和丙烯。
在一个实际的实施方案中,本发明的方法形成由烃原料,尤其甲烷和/或乙烷生产轻质烯烃的综合方法中的一部分。该方法的第一步是使气体原料,优选与水蒸气结合的气体原料流到合成气生产区,生产合成气物流,其典型地包括二氧化碳、一氧化碳和氢气。然后,在150-450℃的温度范围内和5-10MPa的压力范围下,合成气物流通常通过与多相催化剂,典型地铜基催化剂接触,转化成含有含氧化合物的物流。在纯化之后,含有含氧化合物的物流可用作以上所述方法中供生产轻质烯烃如乙烯和/或丙烯的原料。在EP-B-0933345中描述了这一综合方法的非限制性实例,在此将其全部引入作为参考。
在任选地与以上所述的综合方法结合的另一更加全面的综合方法中,将所生产的烯烃导引到一个或多个聚合工艺中,用于生产各种聚烯烃。
为了提供对本发明,包括对其代表性优点的更好理解,提供下述实施例。
在实施例中,LEI定义为含有活性金属氧化物的分子筛催化剂组合物的寿命与不存在金属氧化物的相同分子筛寿命的比值,定义后者的LEI是1。为了测定LEI的目的,寿命定义为相对于每克分子筛,优选转化成一种或多种烯烃的含氧化合物的累积量,一直到转化率下降到其起始值的约10%。若实验结束时,转化率尚未落到其起始值的10%,则基于在实验的最后两个数据点的转化率的下降速度,通过线性外推估计寿命。
“主烯烃(prime olefin)”是对乙烯和丙烯的选择率之和。比值“C2 =/C3 =”是在试验中加权的乙烯对丙烯的选择率之比。通过用丙烯的选择率除以丙烯和丙烷的选择率之和来计算“C3纯度”。对甲烷、乙烯、乙烷、丙烯、丙烷、C4和C5+的选择率是在试验中加权的平均选择率。注意C5+仅仅由C5、C6、和C7组成。在表中选择率值之和达不到100%,这是因为它们已对焦炭进行了校正,这是公知的。
实施例A
分子筛的制备
在作为有机结构定向剂或模板剂的四乙基氢氧化铵(R1)和二丙胺(R2)存在下,使硅铝磷酸盐分子筛(表示为MSA的SAPO-34)结晶。通过最初混合适量的Condea Pural SB和去离子水形成淤浆,从而制备下述摩尔比组成的混合物:
0.2SiO2/Al2O3/P2O5/0.9R1/1.5R2/50H2O向该淤浆中添加适量磷酸(85%)。在搅拌下进行这些添加,形成均匀混合物。向这一均匀混合物中添加Ludox AS40(40%的SiO2),接着在混合下添加R1形成均匀混合物。向这一均匀混合物中添加R2,然后在不锈钢高压釜中,在搅拌下,通过在170℃加热40小时,使所得混合物结晶。这提供结晶分子筛的淤浆。然后从母液中通过过滤分离晶体。然后将该分子筛晶体与粘合剂和基质材料混合,并通过喷雾干燥形成颗粒。
实施例B
转化方法
使用由位于加热炉内的不锈钢反应器(外径1/4英寸(0.64cm))组成的微流反应器获得所列出的所有转化数据,其中汽化的甲醇被投入到所述炉膛内。反应器维持在475℃的温度和25psig(172.4kPag)的压力下。甲醇的流速使得以每克分子筛的重量为基础的甲醇流速(也称为重量时空速度(WHSV))为100h-1。收集流出反应器的产物气体并使用气相色谱法分析。催化剂的负载为50mg并用石英稀释催化剂床,使反应器内的热点最小。
实施例1
在空气中在700℃焙烧La(NO3)3·xH2O(Aldrich ChemicalCompany)样品,生产氧化镧。
实施例2
在搅拌下,在500ml蒸馏水中溶解50g La(NO3)3·xH2O(AldrichChemical Company)。通过添加浓氢氧化铵调节pH到9。然后将该淤浆放入聚丙烯瓶中并在蒸汽箱(100℃)内放置72小时。通过过滤回收所形成的产品,用过量水洗涤,并在85℃下干燥过夜。在流动空气中将这种催化剂的一部分在600℃焙烧3小时,产生氧化镧(La2O3)。
实施例3
在搅拌下,在500ml蒸馏水中溶解50g Y(NO3)3·6H2O。通过添加浓氢氧化铵调节pH到9。然后将该淤浆放入聚丙烯瓶中并在蒸汽箱(100℃)内放置72小时。通过过滤回收所形成的产品,用过量水洗涤,并在85℃下干燥过夜。在流动空气中将这种催化剂的一部分在600℃焙烧3小时,产生氧化钇(Y2O3)。
实施例4
在空气中,在700℃焙烧Sc(NO3)3·xH2O(Aldrich ChemicalCompany)样品,产生氧化钪(Sc2O3)。
实施例5
在搅拌下,在500ml蒸馏水中溶解50g Ce(NO3)3·6H2O。通过添加浓氢氧化铵调节pH到8。然后将该淤浆放入聚丙烯瓶中并在蒸汽箱(100℃)内放置72小时。通过过滤回收所形成的产品,用过量水洗涤,并在85℃下干燥过夜。在流动空气中将这种催化剂的一部分在600℃焙烧3小时,产生氧化铈(Ce2O3)。
实施例6
在搅拌下,在500ml蒸馏水中溶解50g Pr(NO3)3·6H2O。通过添加浓氢氧化铵调节pH到8。然后将该淤浆放入聚丙烯瓶中并在蒸汽箱(100℃)内放置72小时。通过过滤回收所形成的产品,用过量水洗涤,并在85℃下干燥过夜。在流动空气中将这种催化剂的一部分在600℃焙烧3小时,产生氧化镨(Pr2O3)。
实施例7
在搅拌下,在500ml蒸馏水中溶解50g Nd(NO3)3·6H2O。通过添加浓氢氧化铵调节pH到9。然后将该淤浆放入聚丙烯瓶中并在蒸汽箱(100℃)内放置72小时。通过过滤回收所形成的产品,用过量水洗涤,并在85℃下干燥过夜。在流动空气中将这种催化剂的一部分在600℃焙烧3小时,产生氧化钕(Nd2O3)。
实施例8
在搅拌下,在500ml蒸馏水中溶解39g Ce(NO3)3·6H2O和7.0gLa(NO3)3·6H2O。制备含20g浓氢氧化铵和500ml蒸馏水的另一溶液。使用喷嘴混合器以50ml/分钟的速度合并这两种溶液。通过添加浓氢氧化铵调节最终复合物的pH到约9。然后将该淤浆放入聚丙烯瓶中并在蒸汽箱(100℃)内放置72小时。通过过滤回收所形成的产品,用过量水洗涤,并在85℃下干燥过夜。在流动空气中将这种催化剂的一部分在700℃焙烧3小时,产生含标称5wt%镧的混合金属氧化物,基于混合金属氧化物的最终重量。
实施例9
在搅拌下,在500ml蒸馏水中溶解9g Ce(NO3)3·6H2O和30.0gLa(NO3)3·6H2O。制备含20g浓氢氧化铵和500ml蒸馏水的另一溶液。使用喷嘴混合器以50ml/分钟的速度合并这两种溶液。通过添加浓氢氧化铵调节最终复合物的pH到约9。然后将该淤浆放入聚丙烯瓶中并在蒸汽箱(100℃)内放置72小时。通过过滤回收所形成的产品,用过量水洗涤,并在85℃下干燥过夜。在流动空气中将这种催化剂的一部分在700℃焙烧3小时,产生含标称5wt%铈的混合金属氧化物,基于混合金属氧化物的最终重量。
实施例10
使用Mettler TGA/SDTA 851热重分析体系,在环境压力下,测量实施例1-9中氧化物的二氧化碳吸收量。在流动空气中,在500℃下,首先使金属氧化物样品脱水1小时,之后在100℃测量二氧化碳的吸收量。根据Brunauer,Emmett和Teller(BET)方法,测量样品的表面积,提供表1所列的二氧化碳的吸收量(单位:mg二氧化碳/m2金属氧化物)。
表1
样品 | 催化剂干重(mg) | 所吸附的CO2(mg) | 表面积(m2/g) | CO2吸收量(mg/m2) |
1 | 22 | 0.1846 | 40 | 0.210 |
2 | 31 | 0.6487 | 38 | 0.551 |
3 | 24 | 0.3296 | 80 | 0.172 |
4 | 20 | 0.0490 | 33 | 0.074 |
5 | 143 | 0.7714 | 57 | 0.095 |
6 | 50 | 0.3136 | 24 | 0.261 |
7 | 41 | 0.6491 | 18 | 0.880 |
8 | 130 | 0.8407 | 51 | 0.127 |
9 | 42 | 1.2542 | 46 | 0.649 |
对比例11
在该对比例11中,使用50mg不含活性金属氧化物的分子筛催化剂组合物,按照实施例B的方法测试实施例A所生产的分子筛催化剂组合物。表2和表3列出了试验结果。
实施例12
在该实施例中,使用40mg分子筛催化剂组合物和10mg藉助实施例1的硝酸盐分解生产的La2O3,按照实施例B的方法测试实施例A所生产的分子筛催化剂组合物。充分混合各组分,然后用砂子稀释,形成反应器床。表2和表3示出了该实验的结果,这些结果说明了添加La2O3、活性的第3族金属氧化物使寿命增加149%。对乙烷的选择率下降36%,和对丙烷的选择率下降32%,这说明了氢转移反应的显著下降。
实施例13
在该实施例中,使用40mg分子筛催化剂组合物和10mg藉助实施例2的沉淀生产的La2O3,按照实施例B的方法测试实施例A所生产的分子筛催化剂组合物。充分混合各组分,然后用砂子稀释,形成反应器床。表2和表3示出了该实验的结果,这些结果说明了添加经由沉淀生产的La2O3、活性的第3族金属氧化物使寿命增加340%。对乙烷的选择率下降55%,和对丙烷的选择率下降44%,这说明了氢转移反应的显著下降。
实施例14
在该实施例14中,使用40mg分子筛催化剂组合物和10mg实施例3生产的Y2O3,按照实施例B的方法测试实施例A所生产的分子筛催化剂组合物。充分混合各组分,然后用砂子稀释,形成反应器床。表2和表3示出了该实验的结果,这些结果说明了添加Y2O3、活性的第3族金属氧化物使寿命增加1090%。对乙烷的选择率下降45%,和对丙烷的选择率下降28%,这说明了氢转移反应的显著下降。
实施例15
在该实施例15中,使用40mg分子筛催化剂组合物和10mg实施例4生产的Sc2O3,按照实施例B的方法测试实施例A所生产的分子筛催化剂组合物。充分混合各组分,然后用砂子稀释,形成反应器床。表2和表3示出了该实验的结果,这些结果说明了添加Sc2O3、活性的第3族金属氧化物使寿命增加167%。对乙烷的选择率下降27%,和对丙烷的选择率下降21%,这说明了氢转移反应的显著下降。
实施例16
在该实施例16中,使用40mg分子筛催化剂组合物和10mg实施例5生产的Ce2O3,按照实施例B的方法测试实施例A所生产的分子筛催化剂组合物。充分混合各组分,然后用砂子稀释,形成反应器床。表2和表3示出了该实验的结果,这些结果说明了添加Ce2O3、活性的镧系金属氧化物使寿命增加630%。对乙烷的选择率下降50%,和对丙烷的选择率下降34%,这说明了氢转移反应的显著下降。
实施例17
在该实施例17中,使用40mg分子筛催化剂组合物和10mg实施例6生产的Pr2O3,按照实施例B的方法测试实施例A所生产的分子筛催化剂组合物。充分混合各组分,然后用砂子稀释,形成反应器床。表2和表3示出了该实验的结果,这些结果说明了添加Pr2O3、活性的镧系金属氧化物使寿命增加640%。对乙烷的选择率下降51%,和对丙烷的选择率下降38%,这说明了氢转移反应的显著下降。
实施例18
在该实施例18中,使用40mg分子筛催化剂组合物和10mg实施例7生产的Nd2O3,按照实施例B的方法测试实施例A所生产的分子筛催化剂组合物。充分混合各组分,然后用砂子稀释,形成反应器床。表2和表3示出了该实验的结果,这些结果说明了添加Nd2O3、活性的镧系金属氧化物使寿命增加340%。对乙烷的选择率下降49%,和对丙烷的选择率下降34%,这说明了氢转移反应的显著下降。
实施例19
在该实施例19中,使用40mg分子筛催化剂组合物和10mg实施例8生产的混合金属氧化物,按照实施例B的方法测试实施例A所生产的分子筛催化剂组合物。充分混合各组分,然后用砂子稀释,形成反应器床。表2和表3示出了该实验的结果,这些结果说明了添加5%LaOx/Ce2O3、由第3族氧化物改性的活性的镧系金属氧化物使寿命增加450%。对乙烷的选择率下降47%,和对丙烷的选择率下降37%,这说明了氢转移反应的显著下降。
实施例20
在该实施例20中,使用40mg分子筛催化剂组合物和10mg实施例9生产的混合金属氧化物,按照实施例B的方法测试实施例A所生产的分子筛催化剂组合物。充分混合各组分,然后用砂子稀释,形成反应器床。表2和表3示出了该实验的结果,这些结果说明了添加5%CeOx/La2O3、由镧系氧化物改性的活性的第3族金属氧化物使寿命增加260%。对乙烷的选择率下降56%,和对丙烷的选择率下降45%,这说明了氢转移反应的显著下降。
表2
实施例 | 反应器床组成 | 寿命提高指数(LEI) | 主烯烃(%) | C2 =/C3 = | C3纯度(%) |
对比例11 | 100%MSA | 1.0 | 72.99 | 0.90 | 94.1 |
12 | 80%MSA/20%La2O3 | 2.5 | 73.84 | 0.81 | 96.1 |
13 | 80%MSA/20%La2O3 | 4.4 | 73.78 | 0.74 | 96.9 |
14 | 80%MSA/20%Y2O3 | 11.9 | 73.68 | 0.76 | 96.0 |
15 | 80%MSA/20%Sc2O3 | 2.7 | 73.74 | 0.81 | 95.5 |
16 | 80%MSA/20%Ce2O3 | 7.3 | 70.51 | 0.69 | 96.3 |
17 | 80%MSA/20%Pr2O3 | 7.4 | 72.37 | 0.72 | 96.6 |
18 | 80%MSA/20%Nd2O3 | 4.4 | 72.57 | 0.71 | 96.3 |
19 | 80%MSA/20%LaOx/Ce2O3 | 5.5 | 70.64 | 0.73 | 96.4 |
20 | 80%MSA/20%CeOx/La2O3 | 3.6 | 70.52 | 0.71 | 96.9 |
表3
实施例 | 反应器床组成 | CH4 | C2 = | C2 0 | C3 = | C3 0 | C4 | C5+ |
对比例11 | 100%MSA | 2.04 | 34.50 | 0.78 | 38.49 | 2.43 | 14.01 | 3.82 |
12 | 80%MSA/20%La2O3 | 1.61 | 33.05 | 0.50 | 40.79 | 1.65 | 14.96 | 4.51 |
13 | 80%MSA/20%La2O3 | 1.38 | 31.43 | 0.35 | 42.35 | 1.37 | 15.03 | 5.51 |
14 | 80%MSA/20%Y2O3 | 1.39 | 31.85 | 0.43 | 41.83 | 1.74 | 14.43 | 5.61 |
15 | 80%MSA/20%Sc2O3 | 1.67 | 33.08 | 0.57 | 40.66 | 1.93 | 14.49 | 4.45 |
16 | 80%MSA/20%Ce2O3 | 2.05 | 28.89 | 0.39 | 41.62 | 1.61 | 15.29 | 6.83 |
17 | 80%MSA/20%Pr2O3 | 1.59 | 30.18 | 0.38 | 42.19 | 1.51 | 15.22 | 6.06 |
18 | 80%MSA/20%Nd2O3 | 1.64 | 30.2 | 0.40 | 42.37 | 1.61 | 15.13 | 5.68 |
19 | 80%MSA/20%LaOx/Ce2O3 | 2.62 | 29.85 | 0.41 | 40.80 | 1.52 | 14.07 | 7.14 |
20 | 80%MSA/20%CeOx/La2O3 | 2.13 | 29.16 | 0.34 | 41.36 | 1.34 | 14.86 | 7.92 |
Claims (18)
1.一种催化剂组合物,它包括分子筛和至少一种选自元素周期表第3族、镧系元素和锕系元素中的金属的氧化物,其中所述金属氧化物在100℃的二氧化碳吸收量为至少0.03mg/m2金属氧化物。
2.权利要求1的催化剂组合物,其中所述金属氧化物在100℃的二氧化碳吸收量为至少0.04mg/m2金属氧化物。
3.权利要求1或2的催化剂组合物,其中所述金属氧化物在100℃的二氧化碳吸收量小于10mg/mg金属氧化物/m2金属氧化物。
4.前述任何一项权利要求的催化剂组合物,它还包括不同于所述金属氧化物的至少一种粘合剂和基质材料。
5.一种分子筛催化剂组合物,它包括第3族金属氧化物和/或镧系或锕系元素的氧化物、粘合剂、基质材料和硅铝磷酸盐分子筛。
6.权利要求4或5的催化剂组合物,其中粘合剂是氧化铝溶胶和基质材料是粘土。
7.前述任何一项权利要求的催化剂组合物,其中所述金属氧化物选自氧化镧、氧化钇、氧化钪、氧化铈、氧化镨、氧化钕、氧化钐、氧化钍及其混合物。
8.前述任何一项权利要求的催化剂组合物,其中所述金属氧化物是氧化钇。
9.前述任何一项权利要求的催化剂组合物,其中分子筛包括铝磷酸盐或硅铝磷酸盐。
10.权利要求9的催化剂组合物,其中分子筛包括CHA骨架型分子筛和/或AEI骨架型分子筛。
11.一种制造催化剂组合物的方法,该方法包括物理混合含分子筛的第一颗粒和含至少一种选自元素周期表第3族、镧系元素和锕系元素的金属的氧化物的第二颗粒,其中所述金属氧化物在100℃的二氧化碳吸收量为至少0.03mg/m2金属氧化物颗粒。
12.权利要求11的方法,其中所述第一颗粒包括硅铝磷酸盐分子筛,包括氧化铝溶胶的粘合剂,和包括粘土的基质材料。
13.权利要求11或12的方法,其中通过引起所述金属氧化物的水合前体从含所述金属离子的溶液中沉淀,在至少80℃的温度下水热处理该水合前体多至10天,然后在400-900℃的温度范围内焙烧该水合前体,从而生产所述第二颗粒。
14.在催化剂组合物存在下将原料转化成一种或多种烯烃的方法,其中所述催化剂组合物包括分子筛和至少一种选自元素周期表第3族、镧系元素和锕系元素中的金属的氧化物,其中所述金属氧化物在100℃的二氧化碳吸收量为至少0.03mg/m2金属氧化物。
15.权利要求14的方法,其中催化剂组合物的寿命提高指数(LEI)大于1。
16.权利要求14或15的方法,其中分子筛是硅铝磷酸盐。
17.权利要求14-16任何一项的方法,其中原料包括甲醇和/或二甲醚。
18.在通过权利要求11-13任何一项的方法制备的催化剂组合物存在下将原料转化成一种或多种烯烃的方法。
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PCT/US2003/003951 WO2003074175A2 (en) | 2002-02-28 | 2003-02-10 | Catalyst compositions comprising molecular sieves, their preparation and use in conversion processes |
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AU2001275901A1 (en) * | 2000-07-13 | 2002-01-30 | Uop Llc | Attrition resistant catalyst for light olefin production |
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CN101239866B (zh) * | 2007-02-07 | 2010-12-01 | 中国石油化工股份有限公司 | 含氧化合物生产乙烯、丙烯的方法 |
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