CN103827058A - 醇转化为碳氢化合物的沸石催化 - Google Patents
醇转化为碳氢化合物的沸石催化 Download PDFInfo
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- CN103827058A CN103827058A CN201280036737.8A CN201280036737A CN103827058A CN 103827058 A CN103827058 A CN 103827058A CN 201280036737 A CN201280036737 A CN 201280036737A CN 103827058 A CN103827058 A CN 103827058A
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- alcohol
- metal
- zeolite
- hydrocarbon polymer
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Images
Classifications
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Abstract
一种用于醇转化为碳氢化合物的方法,该方法包括在至少100℃~550℃的温度下使所述醇与负载有金属的沸石催化剂接触,其中所述醇能够通过发酵工艺制造,所述金属为带正电荷的金属离子,并且所述负载有金属的沸石催化剂对于将所述醇转化为所述碳氢化合物是有催化活性的。
Description
相关申请的交叉引用
本申请要求在2011年6月15日提交的第61/497,256号美国临时申请的优先权权益。
政府支持
本发明是利用在美国能源部门资助的基本合同号为DE-AC05-00OR22725下的政府支持完成的。美国政府享有本发明中的某些权利。
技术领域
本发明涉及,通常来说,醇催化转化为碳氢化合物(hydrocarbons),以及更特别地,涉及用于该转化的基于沸石(zeolite)的催化方法。
发明背景
醇转化为碳氢化合物通常在商业上是不可行的。实际上,大多数工业醇由碳氢化合物制得。醇向碳氢化合物的转化因现行转化工艺大量的成本要求进一步受到抑制。因此,通过自然手段(例如通过生物质发酵)得到的醇将是价格明显更低廉的原料。
然而,应用现行由生物质制造的醇(即生物醇(bio-alcohols))的转化工艺的主要障碍是通常在生物质转化醇的精炼厂制造的发酵流中产生高浓度的水(并且伴随着低浓度的醇)。现行醇转化为碳氢化合物的工艺通常在这种稀释后的醇和高浓度的水下不足以或者不是高度有效地提供该转化。取而代之,现行的醇转化为碳氢化合物的转化工艺通常要求纯醇(即基本不含水)。此外,用以适应现行技术的来自发酵流的醇浓缩和/或蒸馏将是高度能量密集的,并且因此,将极大抵消因使用生物醇的最初低成本所得的收获。
发明简述
本发明涉及用于催化转化醇为碳氢化合物的方法,其中该催化转化的实现不需要在该转化反应前预先将醇纯化或浓缩。例如,通过本文所描述的方法,能够实现对醇的稀释水性溶液(正如发现于,例如,生物质发酵反应器的发酵流中)的有效转化。在具体的实施方式中,该方法包括在至少100℃至最高达550℃的温度下使醇(或醇混合物)和负载有金属的沸石催化剂接触,其中该醇能够(即能够实现)通过发酵方法制造或该醇通过发酵方法制造,该金属是带正电的金属离子,以及该负载有金属的沸石催化剂对于将醇或其混合物转化为碳氢化合物或碳氢化合物的混合物是有催化活性的。
附图简述
图1是比较纯乙醇(A)和含10%乙醇的水(B)在400℃下经Cu-ZSM-5催化转化后的碳氢化合物的分布图。这些化合物(从左到右,按箭头指示)是水、乙醛、异丁烯、2-丁烯、丙酮、1,2-二甲基-4-乙炔基苯、2-丁酮、苯、甲苯、1,3-二甲基苯炔、对二甲苯、萘和苯酚。
图2是显示在400℃下以12.5h-1的LHSV经Cu-ZSM-5催化转化后10%乙醇的产物流中碳氢化合物的分布图。这些化合物(从左到右,按箭头指示)是水、乙醛、异丁烯、2-丁烯、丙酮、2-甲基丁烯、2-甲基-2-丁烯、顺-1,2-二甲基环丙烯、3,3-二甲基环丁烯、苯、4,4-二甲基环丁烷、甲苯、1,3-二甲基苯、1-乙基-3-甲基苯、1,2,4-三甲基苯和1-乙基-4-甲基苯。
图3A、3B分别是对于V-ZSM-5催化剂,在2.93h-1的LHSV(图3A)下描绘作为温度的函数的乙醇向碳氢化合物的转化的曲线图和在275℃(图3B)下描绘作为LHSV的函数的乙醇向碳氢化合物转化的曲线图。
图4A、4B分别是对于V-ZSM-5催化剂,描绘制造后的混合原料中的碳分布的曲线图(图4A)和描绘分馏收集所得到的柴油/喷气机燃料混合原料中碳分布的曲线图(图4B)。
发明详述
在本文描述的转化方法中,在适用于影响该转化的条件(特别地,温度和催化剂的选择)下,通过使醇与负载有金属的沸石催化剂接触来催化醇转化为碳氢化合物。正如本文所使用的,术语“醇”表示包括单一醇或者两种或更多种醇的混合物,并且同样地,术语“碳氢化合物”表示包括单一碳氢化合物或者两种或更多种碳氢化合物的混合物。
本文所考虑的醇主要是可以通过发酵工艺制造的醇(即生物醇)。本文所考虑的生物醇最显著的实例包括乙醇、丁醇和异丁醇。在不同的实施方式中,该醇能够为正如在发酵流中通常发现的乙醇或丁醇或异丁醇或它们的组合。在具体的实施方式中,该醇为正如发酵流中所遇到的醇的水性溶液(即该醇为水性溶液的组分)。在发酵流中,该醇的浓度通常不超过约20体积%、15体积%、10体积%或5体积%。在一些实施方式中,发酵流直接和该催化剂接触(通常过滤以除去固体后)以影响发酵流中的醇转化。在其它的实施方式中,在发酵流与催化剂接触之前,将发酵流醇中的醇浓缩(例如,至少或者最高达30%、40%或50%)。在另一些其它的实施方式中,选择性地将发酵流中的醇从该发酵流中除去,例如通过蒸馏,以制造作为原料的基本纯相的醇(例如,浓度至少为90%或者95%的醇)。在又一些其它的实施方式中,在和催化剂接触之前,醇完全脱水成100%的醇。
正如本文所使用的,术语“约”通常表示在指定值的±0.5%、1%、2%、5%或最高达±10%的范围内。例如,约20%的浓度通常表示,以最宽的范围来讲,20±2%,其表示18~22%。此外,术语“约”可以表示测量误差(即受测量方法的限制),或者任选地,组内物理参数的偏差或者平均值。
尽管通过本方法能够制造许多种类的碳氢化合物产物,本文主要考虑的碳氢化合物通常是饱和的,并且更特别地,属于烷烃类,其可以为直链或者支链或者它们的混合物,特别是当该碳氢化合物产物是为了用作燃料。这里特别想要的烷烃包括那些包含至少4、5或者6个碳原子,以及高达12、14、16、17、18或者20个碳原子的烷烃。直链烷烃的一些实例包括正丁烷、正戊烷、正己烷、正庚烷、正辛烷、正壬烷、正癸烷、正十一烷、正十二烷、正十三烷、正十四烷、正十五烷、正十六烷、正十七烷、正十八烷、正十九烷和正二十烷。支链烷烃的一些实例包括异丁烷、异戊烷、新戊烷、异己烷、3-甲基戊烷、2,3-二甲基丁烷、2,2-二甲基丁烷、2-甲基己烷、3-甲基己烷、2,2-二甲基戊烷、2,3-二甲基戊烷、2,4-二甲基戊烷、3,3-二甲基戊烷、2-甲基庚烷和2,2,4-三甲基戊烷(异辛烷)。可以通过该方法制造的一些其它碳氢化合物产物包括烯烃(即烯,例如,乙烯、丙烯、正丁烯和/或异丁烯)和芳香类(例如,萘、苯、甲苯和/或二甲苯)。
本文特别考虑的碳氢化合物是用作燃料或者用作燃料中的混合原料的碳氢化合物的混合物。本文制造的碳氢化合物的混合物优选基本对应于(例如,在组分和/或性质方面)已知的石油化工燃料,例如石油,或者石油的分馏溜出液。石油化工燃料的一些实例包括汽油、煤油、柴油、喷气发动机燃料(jet propellant)(例如,JP-8)。正如现行使用的碳氢化合物燃料品级(grade),本文制造的碳氢化合物的混合物能够,在一些实施方式中,主要地或者单独地由烷烃、烯烃、芳香族化合物或者它们的混合物组成。尽管芳香族化合物(特别是苯)可以存在于碳氢化合物的混合物中,但是可以最小化它们的含量以符合现行的燃料标准。由所描述的方法制造的碳氢化合物原产物通常通过蒸馏分馏成不同的燃料品级,其中的每种已知在特定的沸点范围内。本方法的一个特别的优点是本发明能够制造这些基本不含通常需要在石油精炼过程中除去的污染物(例如硫醇)的燃料品级。此外,通过对催化剂和工艺条件的合适调节,能够得到碳氢化合物的选择性分布。
取决于碳氢化合物产物的最终组分,该产物能够涉及多种应用,包括,例如作为塑料、聚合物和精细化学品的前体(precursor)。本文所描述的方法能够有利地制造其多种性质中的任何存在区别的一系列碳氢化合物产物,所述性质例如,分子量(即碳氢化合物的重量分布)、饱和度或者不饱和度(例如,烷烃和烯烃的比值)和支链的或者环状的同分异构体的水平。该方法通过恰当的选择,例如,催化剂组成(例如,催化金属)、催化剂含量(例如,催化剂和醇前体的比值)、反应温度和流速(例如,LHSV),来提供这种多样性水平。
在该方法中,在醇和催化剂接触过程中使用合适的反应温度。通常,该反应温度为至少100℃且最高达550℃。在不同的实施方式中,该反应(温度)为精确地或者近似地,例如100℃、125℃、150℃、175℃、200℃、225℃、250℃、275℃、300℃、325℃、350℃、375℃、400℃、425℃、450℃、475℃、500℃、525℃或550℃,或者以上述示例性温度中任意两个为界的范围内的温度(例如,100~550℃、200~550℃、300~550℃、400~550℃、450~550℃、100~500℃、200~500℃、300~500℃、350~500℃、400~500℃、450~500℃、100~450℃、200~450℃、300~450℃、350~450℃、400~450℃、100~425℃、200~425℃、300~425℃、350~425℃、375~425℃、400~425℃、100~400℃、200~400℃、300~400℃、350~400℃和375~400℃)。
通常,在本文所描述的方法中使用约1个大气压的环境压力(即正常大气压)。然而,在一些实施方式中,可以使用提高的压力或者降低的压力。例如,在一些实施方式中,该压力可以提高至,例如,1.5、2、3、4或5个大气压,或者降低至,例如0.5、0.2或0.1个大气压。
该催化反应器能够具有本领域内已知的用于在高温下催化处理流体或者气体的任意设计,例如流化床反应器。该方法可以以连续的或者分批的模式。在具体的实施方式中,将该醇注入经加热的反应器,使得该醇快速挥发成气体,然后该气体通过该催化剂。在一些实施方式中,如果直接使用发酵流作为原料而没有纯化,那么该反应器的设计包括锅炉(boiler)单元和反应器单元。如果该发酵流经蒸馏以浓缩乙醇,那么通常不需要锅炉单元,因为该蒸馏工艺除去发酵流中的溶解固体。该锅炉单元在液体原料进入反应器单元之前使其挥发成气体,并且保留(扣住)溶解固体。
在一些实施方式中,上述的转化方法和发酵工艺相结合,其中该发酵工艺制造用作该转化工艺的原料的醇。所述的“相结合”表示将在发酵装置或区域(zone)中制造的醇送入转化装置或区域且在其中加工(其中进行上述的转化过程)。优选地,为了使制造成本最小化,该发酵工艺足够接近于转化装置或区域,或者包括用于将经制造的醇转移至转化装置或区域的合适管道,由此,不需要运送该醇。在具体的实施方式中,在发酵装置中制造的发酵流直接转移至转化装置中,在该流接触催化剂之前通常将固体从原始流中除去(通常通过过滤或沉降)。
在一些实施方式中,该发酵工艺在自动发酵装置中进行,即,其中于其它地方制造的糖类装填入发酵装置以制造醇。在其它实施方式中,该发酵工艺(装置)为更大的生物质反应器装置的一部分,即在其中将生物质分解成可发酵的糖类,然后在发酵区域加工该糖类。生物质反应器和发酵装置在本领域内已公知。生物质通常指的是木质纤维素类物质(即,植物材料),例如木材、草、叶子、纸、玉米壳、甘蔗、甘蔗渣、坚果壳。通常,生物质向醇的转化通过以下步骤进行:1)在公知的条件下预处理生物质以释放纤维素材料中的木质素和半纤维素材料;2)通过纤维素酶的作用分解纤维素材料生成可发酵的糖类材料;3)发酵该糖类材料,通常通过发酵生物的作用,例如合适的酵母菌。
在其它的实施方式中,该醇由更直接的糖源制造,例如以植物为基的糖源,例如甘蔗或者谷物淀粉(例如玉米淀粉)。通过玉米淀粉的乙醇制造(即玉米淀粉乙醇)和通过甘蔗的乙醇制造(即甘蔗乙醇)目前代表一些最大的商业的乙醇制造方法。本文期望将该转化工艺和这些大型乙醇制造方法中的任意结合在一起。
本文所使用的转化催化剂包括沸石部分和负载于该沸石的金属。本文所考虑的沸石能够是本领域内已知的在高温条件下(即,至少100℃、150℃、200℃、250℃、300℃以及更高的温度,高达例如,500℃、550℃、600℃、650℃、700℃、750℃、800℃、850℃或900℃)稳定的多孔硅铝酸盐结构中的任意。在具体的实施方式中,该沸石从至少100℃至最高达700℃是稳定的。通常,该沸石因具有结晶结构或部分结晶结构而有序。该沸石通常能够描述为包含通过共享氧原子而互相连接(即交联的)的硅酸盐(SiO2或SiO4)和铝酸盐(Al2O3或AlO4)单元的三维骨架。
该沸石能够是微孔的(即,孔径小于2μm)、介孔的(即,孔径在2~50μm内,或者其中的子区间(sub-range)内)或者它们的组合。在几个实施方式中,该沸石材料完全或者基本是微孔的。通过完全或者基本为微孔,源自微孔的孔体积能够为,例如,100%或者至少95%、96%、97%、98%、99%或99.5%,剩余的孔体积源自介孔,或者在一些实施方式中,源自大孔(孔径大于50μm)。在其它实施方式中,该沸石材料完全或者基本为介孔的。通过完全或者基本为介孔的,源自介孔的孔体积能够为,例如,100%,或者至少为95%、96%、97%、98%、99%或99.5%,剩余的孔体积为源自微孔,或者在一些实施方式中,源自大孔。在另外其它的实施方式中,该沸石材料包含大量微孔和介孔两者。通过包含大量微孔和介孔两者,源自介孔的孔体积能够为,例如高达、至少或者精确至50%、60%、70%、80%或90%,剩余的孔体积是源自微孔,或者反之亦然。
在多种实施方式中,该沸石为MFI型沸石、MEL型沸石、MTW型沸石、MCM型沸石、BEA型沸石、高岭土或八面沸石型沸石(faujasite-type ofzeolite)。一些具体沸石的实例包括ZSM类沸石(例如,ZSM-5、ZSM-8、ZSM-11、ZSM-12、ZSM-15、ZSM-23、ZSM-35、ZSM-38、ZSM-48)、X型沸石、Y型沸石、β型沸石(zeolite beta)和MCM类沸石(例如,MCM-22和MCM-49)。这些沸石的组成、结构和性质在本领域是公知的,并且已经被详细地描述,正如发现于,例如,美国专利4,721,609、4,596,704、3,702,886、7,459,413和4,427,789中,其内容以参考的方式全部在此引入。
该沸石能具有任何合适的二氧化硅-氧化铝比(即,SiO2/Al2O3或“Si/Al”)。例如,在多种实施方式中,该沸石能具有,精确地、至少、少于或高达1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90、95、100、120、150或200的Si/Al比,或者在以任意两个前述值为边界的范围内的Si/Al比。在具体的实施方式中,该沸石具有1~45的Si/Al比。
在具体的实施方式中,该沸石为ZSM-5。ZSM-5属于包含五元环(pentasil-containing)类的沸石,所有的这些沸石也考虑在内。在具体的实施方式中,该ZSM-5沸石以化学式NanAlnSi96-nO192·16H2O表示,其中0<n<27。
通常,该沸石包含一定含量的阳离子物质。正如在本领域内公知的,阳离子物质的含量通常和沸石中的铝含量是成比例的。这是因为用较低化学价的铝原子取代硅原子需要配对阳离子(countercation)的存在以建立电荷平衡。阳离子物质的一些实例包括氢离子(H+)、碱金属离子、碱土金属离子和主族金属离子。可以包含于沸石中的碱金属离子的一些实例包括锂离子(Li+)、钠离子(Na+)、钾离子(K+)、铷离子(Rb+)和铯离子(Cs+)。可以包含于沸石中的碱土金属离子的一些实例包括铍离子(Be2+)、镁离子(Mg2+)、钙离子(Ca2+)、锶离子(Sr2+)和钡离子(Ba2+)。可以包含于沸石中的主族金属离子的一些实例包括硼离子(B3+)、镓离子(Ga3+)、铟离子(In3+)和砷离子(As3+)。在一些实施方式中,包括阳离子物质的组合。该阳离子物质可以是微量的(例如不超过0.01%或0.001%),或者任选地,大量的(即,0.01%以上,以及高达,例如,沸石的0.1重量%、0.5重量%、1重量%、2重量%、3重量%、4重量%或5重量%)。在一些实施方式中,将上述阳离子物质的类别(class)或具体实例中的任意一种或多种排除在沸石之外。
上述的沸石负载有一定含量的金属。选择负载到沸石中的金属从而使得生成的负载有金属的沸石对于在上述给出的条件下将醇转化成碳氢化合物是具有催化活性的。通常,本文所考虑的金属是带正电荷的金属离子(即,金属阳离子)形式。这些金属能够是,例如,一价的、二价的、三价的、四价的、五价的或六价的。在一些实施方式中,该金属离子为(或包括)碱金属离子。在其它实施方式中,该金属为(或包括)碱土金属离子。在其它实施方式中,该金属为(或包括)过渡金属,例如一种或多种第一列、第二列或第三列的过渡金属。一些优选的过渡金属包括铜、铁、锌、钛、钒和镉。该铜离子本质上能够是一价铜(Cu+1)或二价铜(Cu+2),并且该铁离子本质上能够是二价铁(Fe+2)或三价铁(Fe+3)。钒离子可以是以它的已知氧化态中的任意,例如V+2,V+3,V+4和V+5。在其它实施方式中,该金属为(或包括)催化活性的主族金属,例如镓或铟。单一金属或者金属组合可以负载入该沸石中。在其它实施方式中,上述的任意一种或多种金属排除在该沸石之外。
该金属负载量能够为任意合适量,但是通常不超过约2.5%,其中该负载表示为以沸石重量计的金属含量。在不同的实施方式中,该金属负载量为,精确地、至少、少于或高达,例如,0.01%、0.02%、0.03%、0.04%、0.05%、0.06%、0.07%、0.08%、0.09%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%、2.1%、2.2%、2.3%、2.4%或2.5%,或者金属负载量在以任意两个上述值为界的范围内。
在本发明另外的方面中,该沸石催化剂可以包括除上述的一种或多种金属之外至少一种三价的金属。正如本文所使用的,术语“三价金属离子”定义为除铝离子(Al+3)外的三价离子。不希望受限于任何理论,认为该三价金属引入至该沸石结构中。更具体地,认为引入的三价金属离子在沸石中与合适数目的氧原子键合,即作为包含通过氧桥连接于该结构的金属阳离子的金属氧化物单元。在一些实施方式中,三价金属离子结合一种或多种其它催化活性的金属离子的存在可以导致不同于这些离子单独使用时的叠加效应的组合效应。这里主要考虑的效应是关于所形成的、醇转化为碳氢化合物的催化剂能力。
在一些实施方式中,除铝离子外只有一种类型的三价金属离子引入该沸石。在其它实施方式中,除铝离子外至少两种三价金属离子引入该沸石。在另外其它实施方式中,除铝离子外至少三种类型的三价金属离子引入该沸石。在另外其它实施方式中,确切地,除铝离子外两种或三种类型的三价金属离子引入该沸石。
该三价金属离子中的每一个能够以任意合适量包含在内,例如,精确地、至少、少于或高达,例如0.01%、0.02%、0.03%、0.04%、0.05%、0.06%、0.07%、0.08%、0.09%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%、2.1%、2.2%、2.3%、2.4%或2.5%,或者含量在以任意两个上述值为界的范围内。任选地,三价金属(不包括Al)的总含量可以限定于上述值中的任一个。在一些实施方式中,一个或者多个具体类型,或者全部,除Al外三价金属离子排除在催化剂之外。
在第一组实施方式中,至少一种三价金属离子选自三价过渡金属离子。该一种或多种过渡金属能够选自下述类型的过渡金属元素的任意部分或选定部分:元素周期表中的第IIIB族(Sc族)、第IVB族(Ti族)、第VB族(V族)、第VIB族(Cr族)、第VIIB族(Mn族)、第VIIIB族(Fe和Co族)。三价过渡金属离子的一些实例包括Sc+3、Y+3、V+3、Nb+3、Cr+3、Fe+3和Co+3。在其它实施方式中,该三价离子排除全部过渡金属离子,或者任选地,排除上述给出的任意一种、两种或多种类别的过渡金属离子或者其具体的实例。在具体的实施方式中,该三价过渡金属离子包括Sc+3或Fe+3,或者它们的组合。
在第二组实施方式中,至少一种三价金属离子选自三价主族金属离子。一种或多种该主族金属能够选自除铝外周期表中第IIIA族(B族)和/或第VA族(N族)元素中的任一部分或选定部分。三价主族金属离子的一些实例包括Ga+3、In+3、As+3、Sb+3和Bi+3。在其它实施方式中,该三价金属离子排除除铝离子外的全部主族金属离子,或者任选地,排除上述给出的任意一种、两种或多种类别的主族金属离子,或者其具体实例。在具体的实施方式中,该三价主族金属离子包括至少In3+。
在第三组实施方式中,至少一种三价金属离子选自三价镧系金属离子。本文所考虑的三价镧系金属离子的一些实例包括La+3、Ce+3、Pr+3、Nd+3、Sm+3、Eu+3、Gd+3、Tb+3、Dy+3、Ho+3、Er+3、Tm+3、Yb+3和Lu+3。在具体的实施方式中,该三价镧系金属离子选自La+3、Ce+3、Pr+3和Nd+3中的一种或组合。在更多具体的实施方式中,该三价镧系金属离子为或包括La+3。在其它实施方式中,该三价金属离子排除全部镧系金属离子,或者任选地,排除上述提供的任意一种、两种或多种类别的镧系金属离子或者其特定实例。
在第四组实施方式中,该催化剂包含至少两种选自三价过渡金属离子的三价金属离子。这里所考虑的三价过渡金属离子的一些组合包括Sc+3和一种或多种其它三价过渡金属离子的组合,或者Fe+3和一种或多种其它三价过渡金属离子的组合,或者Y+3和一种或多种其它三价过渡金属离子的组合,或者V+3和一种或多种其它三价过渡金属离子的组合。
在第五组实施方式中,该催化剂包含至少两种选自三价主族金属离子的三价金属离子。这里所考虑的一些三价主族金属离子的组合包括In+3和一种或多种其它三价主族金属离子的组合,或者Ga+3和一种或多种其它三价主族金属离子的组合,或者As+3和一种或多种其它三价主族金属离子的组合。
在第六组实施方式中,该催化剂包含至少两种选自三价镧系金属离子的三价金属离子。这里所考虑的三价镧系金属离子的一些组合包括La+3和一种或多种其它三价镧系金属离子的组合,或者Ce+3和一种或多种其它三价镧系金属离子的组合,或者Pr+3和一种或多种其它三价镧系金属离子的组合,或者Nd+3和一种或多种其它三价镧系金属离子的组合。
在第七组实施方式中,该催化剂包含至少一种三价过渡金属离子和至少一种三价镧系金属离子。例如,在具体的实施方式中,至少一种三价金属离子选自Sc+3、Fe+3、V+3和/或Y+3,而另一种三价金属离子选自La+3、Ce+3、Pr+3和/或Nd+3。
在第八组实施方式中,该催化剂包含至少一种三价过渡金属离子和至少一种三价主族金属离子。例如,在具体的实施方式中,至少一种三价金属离子选自Sc+3、Fe+3、V+3和/或Y+3,而另一种三价金属离子选自In+3、Ga+3和/或In+3。
在第九组实施方式中,该催化剂包含至少一种三价主族金属离子和至少一种三价镧系金属离子。例如,在具体的实施方式中,至少一种三价金属离子选自In+3、Ga+3和/或In+3,而另一种三价金属离子选自La+3、Ce+3、Pr+3和/或Nd+3。
在第十组实施方式中,该催化剂包含至少三种三价金属离子。至少三种三价金属离子能够选自三价过渡金属离子、三价主族金属离子和/或三价镧系金属离子。
在具体的实施方式中,一种、两种、三种或更多种三价金属离子选自Sc+3、Fe+3、V+3、Y+3、La+3、Ce+3、Pr+3、Nd+3、In+3和/或Ga+3。在更具体的实施方式中,一种、两种、三种或更多种三价金属离子选自Sc+3、Fe+3、V+3、La+3和/或In+3。
上述的沸石催化剂通常没有涂覆包含金属的膜或层。然而,正如本文所期望的,只要该膜或层基本上不会妨碍该催化剂作为转化催化剂有效地起作用,本发明也预料到涂覆包含金属的膜或层的上述沸石催化剂。通过涂覆,膜或层存在于该沸石的表面上。在一些实施方式中,该沸石的表面只表示其外表面(即,正如沸石催化剂外轮廓面积所定义的),而在其它实施方式中,该沸石的面积表示或者包括该沸石的内表面,例如沸石的孔隙或孔道内的面积。该包含金属的膜或层能够用于,例如,调整催化剂的物理特性、催化效率或催化选择性。包含金属表面的一些实例包括碱金属、碱土金属和二价过渡或主族金属的氧化物和/或硫化物,前提是该表面金属对碳氢化合物产物无污染且对转化过程无害。
本文描述的催化剂能够通过本领域已知的任意合适的方法合成。本文所考虑的方法应该优选将金属离子均匀地引入到沸石中。该沸石可以为单一类型的沸石或不同沸石材料的组合。
在具体的实施方式中,本文描述的催化剂通过,首先,用待负载的金属浸渍沸石。该浸渍步骤能够通过,例如,用一种或多种包含待负载的金属的盐的溶液处理沸石来实现。通过用包含金属的溶液处理沸石,该包含金属的溶液和沸石接触,使得该溶液被吸入到该沸石中,优选被吸入到全部的沸石体积中。通常,在制备负载有金属的沸石催化剂(例如,Cu-ZSM5或V-ZSM-5)中,使用酸沸石形式(即,H-ZSM5)或它的铵盐(例如,NH4-ZSM-5)作为起始材料,在该原始材料上进行了金属离子(例如,铜离子)置换。该金属置换工艺的详情在本领域内是公知的。
在一个实施方式中,该浸渍步骤通过用包含待负载的全部金属的溶液处理沸石来实现。在另一个实施方式中,该浸渍步骤通过用两种或更多种溶液处理沸石来实现,其中不同溶液包含不同金属或金属组合。用浸渍溶液对沸石的每一次处理对应于单独的浸渍步骤。通常,当采用多于一次浸渍步骤时,在这些浸渍步骤之间使用干燥和/或热处理步骤。
该金属浸渍溶液包含至少一种或多种待负载入沸石的金属离子,以及用于将金属离子分散入沸石的液体载体。这些金属离子通常以金属盐的形式。优选地,这些金属盐完全溶解于该液体载体。该金属盐包含一种或多种与一种或多种配对阴离子(counteranion)呈离子键合的金属离子。上述的任意一种或多种金属离子能够充当金属离子部分。该配对阴离子能够选自,例如,卤素(F-、Cl-、Br-或I-)、羧酸根(例如,甲酸根、乙酸根、丙酸根或丁酸根)、硫酸根、硝酸根、磷酸根、氯酸根、溴酸跟、碘酸根、氢氧根、β-二酮酸根(β-diketonate)(例如,乙酰丙酮酸根)和二羧酸根(例如,草酸根、丙二酸根或丁二酸根)。
在具体的实施方式中,制备该催化剂通过形成包含沸石粉末和待引入金属的浆料(slurry)。干燥和烧制(fire)该浆料以形成粉末。然后该粉末和有机和/或无机粘合剂结合并湿混合以形成糊料(paste)。能够使形成的糊料形成任意想要的形状,例如,通过挤压形成棒状、蜂巢状、针轮状(pinwheel)结构。然后将经挤压的结构干燥和烧制以形成最终的催化剂。在其它实施方式中,将沸石粉末、金属和粘合剂全部结合在一起以形成糊料,然后将其挤压和烧制。
浸渍沸石后,通常将负载有金属的沸石干燥和/或经历热处理步骤(例如烧制或焙烧步骤)。该热处理步骤起到将经浸渍的金属永久地引入沸石的作用,例如,通过取代Al+3和/或Si+4并且在沸石材料中形成金属氧化物键。在不同的实施方式中,在至少100℃、150℃、200℃、250℃、300℃、350℃、400℃、450℃、500℃、550℃、600℃、650℃、700℃、750℃或800℃的温度或者其中范围内的温度下,该热处理步骤能够实施一时间段,例如15分钟、30分钟、1小时、2小时、6小时、12小时、24小时、30小时、36小时或48小时,或者其中范围内的时间段。在一些具体的实施方式中,该热处理步骤在至少500℃的温度下实施至少两小时。在一些实施方式中,该热处理步骤包括从较低温度到较高温度和/或从较高温度到较低温度的温度斜坡(ramping)步骤。例如,该热处理步骤能够包括以1、2、5或10℃/min的速率从100~700℃的斜坡段,反之亦然。
通常,在正常的环境压力下实施用于制造负载有金属的沸石催化剂的一个或多个热处理步骤。然而,在一些实施方式中,采用升高的压力(例如,在1个大气压~2、5或10个大气压),然而在一些实施方式中,采用降低的压力(例如,在1、0.5或0.2个大气压以下)。此外,虽然通常在正常空气环境下实施热处理步骤,但是在一些实施方式中,使用增大氧气、减少氧气或惰性环境。可以包含于加工环境的一些气体包括,例如,氧气、氮气、氦、氩、二氧化碳和它们的混合物。
为了提供更具描述性的实例,按照以下的方法能够制备Cu-ZSM-5催化剂:2.664g水合醋酸铜(即,Cu(OAc)2·6H2O)溶解于600mL去离子水(0.015M),随后加入10.005g的H-ZSM-5沸石。在50℃下持续搅拌该浆料大约两小时。冷却后通过过滤收集Cu-ZSM-5(蓝颜色),用去离子水清洗,然后在大约500℃(10℃/min)、在空气中焙烧四小时。
然后,该制造的Cu-ZSM-5前体能够进一步地用另一种金属浸渍,例如铁。例如,Cu-Fe-ZSM-5能够通过以下方法制造:5g的Cu-ZSM-5悬浮于25mL的0.015M的Fe(NO3)3水性溶液中,用N2脱气,然后在约80℃下持续搅拌约两小时。过滤后得到棕色(brown)固体,留下透明无色的滤出液。然后,该产物在约500℃(2℃/min)、在空气中焙烧约两小时。所形成的Cu-Fe-ZSM-5催化剂通常包含约2.4%的Cu和0.3%的Fe。通过相似的方式大量其它金属能够负载入该沸石以制造各种不同的负载有金属的催化剂。
通常,本文描述的沸石催化剂是粉末形式的。在第一组实施方式中,至少部分的或者全部的粉末状颗粒具有小于微米的尺寸(即,纳米级颗粒)。该纳米级颗粒能够具有的颗粒尺寸为,精确地、至少、高达或小于,例如1、2、5、10、20、30、40、50、60、70、80、90、100、150、200、250、300、350、400、450、500、550、600、650、700、750、800、850、900或950纳米(nm),或者颗粒尺寸在以任意两个上述值为界的范围内。在第二组实施方式中,至少部分或全部粉末状颗粒具有等于或高于1微米的尺寸。该微米级的颗粒能够具有的颗粒尺寸为,精确地、至少、高达或小于,例如,1、2、5、10、20、30、40、50、60、70、80、90或100微米(μm),或者颗粒尺寸在以任意两个上述值为界的范围内。在一些实施方式中,催化剂的单晶或晶粒对应于上述提供的任意尺寸,而在其它实施方式中,催化剂的晶体或晶粒聚结以提供具有任意上述示例性尺寸的经聚结的晶体或晶粒。
在其它实施方式中,该沸石催化剂能够为膜、涂层或者多层膜或涂层的形式。该涂层或多重涂层的厚度能够为,例如,1、2、5、10、50或100微米,或者其中的范围内,或者高达100微米的厚度。在另外其它实施方式中,该沸石催化剂是非颗粒(即连续的)块状固体的形式。在更多其它实施方式中,该沸石催化剂能够是纤维的或以网状物(mesh)的形式。
该催化剂还能够与适用于在催化转化器中工作的载体材料混合或附着于适用于在催化转化器中工作的载体材料。该载体材料能够是粉末(例如,具有任意上述的颗粒尺寸),颗粒(例如,0.5mm或更大颗粒尺寸),块状材料,例如流入型蜂巢状单块、板状或多板状结构或者波形金属片。如果使用蜂巢状结构,那么该蜂巢状结构能够包含任意合适的蜂房密度。例如,该蜂巢状结构能够每平方英尺具有100、200、300、400、500、600、700、800或900个蜂房(蜂房/平方英尺)(或者62~140蜂房/平方厘米)或者更大。载体材料通常由耐火组合物构成,例如那些包含堇青石、莫来石、氧化铝(例如α-氧化铝、β-氧化铝或γ-氧化铝)或氧化锆,或者它们的组合的组合物。蜂巢状结构,特别地,具体地描述于,例如美国专利5,314,665、7,442,425和7,438,868,其内容通过参考的方式全部引入至本文。当使用波状的或其它类型的金属片时,这些金属片能够在顶部彼此层叠,伴随催化剂材料负载在这些片上,从而保留了允许含醇流体流出的通道。也能够使这些层状片形成结构,例如通过弯曲这些片形成圆筒。
在具体的实施方式中,该沸石催化剂为或包括负载有上述的合适的金属中的任意的五元环类组合物。在更加具体的实施方式中,该沸石催化剂为或包括,例如负载铜的ZSM5(即,Cu-ZSM5)、Fe-ZSM5、Cu,Fe-ZSM5或Cu-ZSM5和Fe-ZSM5的混合物。在其它实施方式中,该沸石催化剂为或包括,例如,Cu-La-ZSM5、Fe-La-ZSM5、Fe-Cu-La-ZSM5、Cu-Sc-ZSM5或Cu-In-ZSM5。
下面已经列出了用于解释目的和描述本发明一些具体实施方式的实施例。然而,本发明的范围不希望以任何方式受限于本文所列出的实施例。
实施例1
Cu-ZSM5催化剂的制备
从国际分子筛公司(Zeolyst International)购买SiO2/Al2O3比为23的NH4-ZSM-5(CBV-2314),并且按收到的原样使用。在500℃焙烧NH4-ZSM-5四个小时制成定量产率的H-ZSM-5。2.664g商业可得的样品Cu(OOCCH3)2·H2O溶解于600mL去离子水以制得22摩尔的溶液。将10.0g的H-ZSM-5样品加入该醋酸铜溶液并且该悬浮液在50℃下搅拌两小时。冷却后通过过滤收集蓝色固体,然后用去离子水清洗,干燥,然后在500℃下的空气中焙烧四小时以得到Cu-ZSM-5。元素分析表明样品中2.76%的Cu和3.31%的Al。
实施例2
Fe-ZSM-5催化剂的制备
12g的H-ZSM-5样品悬浮于0.02M经脱气的Fe(NO3)3水性溶液。该悬浮液室温下搅拌24小时。通过过滤收集浅粉红色固体,然后用去离子水清洗,干燥,然后在550℃下的空气中焙烧四小时以得到9.98g的Fe-ZSM-5。元素分析表明铁为776ppm。
实施例3
CuFe-ZSM-5催化剂的制备
将5g的Cu-ZSM-5样品悬浮于25mL的0.015M的Fe(NO3)3水性溶液,用N2脱气,并且在80℃下持续搅拌两小时。通过过滤从反应混合物收集棕色固体,然而丢弃透明无色的滤出液。该粉末在500℃(2℃/min)的空气中焙烧两小时以得到浅黄色的CuFe-ZSM-5粉末。元素分析:2.39%的Cu、0.40%的Fe、2.97%的Al。
实施例4
V-ZSM-5催化剂的制备
商业得到的NH4 +-ZSM-5(SiO2/Al2O3=23)作为起始材料,用V(III)Cl3水性溶液进行离子交换。具体地,首先通过将2.5g的V(III)Cl3溶解于320mL经蒸馏的水来制备0.050M的V(III)Cl3溶液。然后,向该水性溶液加入12.17g的NH4 +-ZSM-5,然后加热至80℃。搅拌8小时后,对非均质混合物进行真空过滤,并摒弃滤出液。然后在500℃下焙烧浅蓝色V-ZSM-5最初固体产物四小时,其生成浅黄色的最终固体产物。
实施例5
使用Cu-ZSM-5催化剂的醇-碳氢化合物转化性能
向催化反应器装填1.0g的Cu-ZSM-5粉末然后在干燥的氦气下将其加热至500℃并持续四小时。将该催化剂冷却至400℃,然后使用注射泵以6.8毫升每小时的速率将10%乙醇水性溶液引入反应器。该速率对应于2.5h-1的液时空速(liquid hourly space velocity,LHSV)。将后催化剂(post-catalyst)排出物(emission)收集于浸渍在液氮中的U形管中。通过加热U形管的内含物,得到含水的乳状液。将这个乳状液样品注入气相色谱-质谱联用仪(GCMS)。从GCMS得到的结果显示于图1(B)。这和当纯乙醇注入装填Cu-ZSM-5的反应器时得到的乳状液结果的图1(A)形成对比。纯乙醇和10%乙醇水性溶液的GCMS结果对比表明,当反应在上述条件下进行时,水稀释液对转化率或产物分布没有影响。
对于乙醇的水性溶液,也用12.5h-1的LHSV实施该实验。正如图2所示的,就定量转化率和产物分布而言,得到了相同的结果。2.5和12.5分钟之间的宽峰归因于水。出现在12.5分钟之后的峰认定为归因于乙醛、异丁烷、2-丁烯、丙酮、2-甲基丁烯、2-甲基-2-丁烯、顺式-1,2-二甲基环丙烯、环戊烷、3,3-二甲基环丁烯、苯、4,4-二甲基环丁烷、甲苯、1,3-二甲基苯、1-乙基-3-甲基苯、1,2,4-三甲基苯和1-乙基-4-甲基苯。
实施例6
使用V-ZSM-5催化剂的醇-碳氢化合物转化性能
向催化反应器装填1.0g的V-ZSM-5粉末,然后在干燥的氦气流动下将其加热至500℃并持续四小时。将该催化剂冷却至200℃,然后使用注射泵以5.0毫升每小时将纯乙醇引入该反应器。该速率对应于2.93h-1的LHSV。使用在线气相色谱通过逐渐将温度升高至450℃来分析后催化剂的排出物。该数据显示于图3A和图3B。结果表明,在这个用于最小化乙烯(标示为“C2”)副产物,伴随着可忽略的CO(这表明在催化剂表面上少量产物的分解)的示例中,275℃的反应温度是理想的。也监测了275℃下作为空速的函数的乙醇的转化,并且基于该结果,确定2.93h-1的LHSV是最佳的。
在浸没于液氮的冷阱中收集催化排出物。通过加热,分离开碳氢化合物层和水层。正如从显示于图4A中的碳分布曲线可以阐明的,从乙醇产生的碳氢化合物(标示为“C3-C16”)被发现是约2.47%的石蜡、10.5%的异链烷烃(iso-paraffin)、9.65%的烯烃、3.11%的萘和74.26%的芳烃的混合物。测试表明该碳氢化合物混合物的平均分子量为97.86,平均比重为0.823,总氢(total hydrogen)为10.5,以及碳氢比为8.47。经计算的研究法辛烷值和汽车辛烷值(research and motor octane numbers)分别为107.6和93.3。馏分收集允许收集适用于和内燃机或喷气机燃料混合的160~300℃的混合原料。碳的分布显示于图4B。测试表明该碳氢化合物混合物的平均分子量为129.97,平均比重为0.88,总氢为9.4,以及碳氢比为9.63。
发动机测试在经改造的装有汽门的燃料喷射的斯特曼(Sturman)可变阀驱动发动机上进行,该发动机能够使用汽油直接喷射燃料系统预热,而不需要消耗测试燃料。然后将测试燃料或合格汽油引入,并且记录性能数据,例如气缸压力和作为曲柄角(crank angle)的函数的热量释放速率。测试表明这些与本发明混合原料相关的发动机操作参数和使用合格汽油的发动机参数是相同的。
尽管这里已经表明和描述了目前所想到的本发明优选的实施方式,但是本领域技术人员可以作出各种存在于由附加的权利要求所限定的本发明范围内的变化和修改。
Claims (31)
1.一种用于转化醇为碳氢化合物的方法,该方法包括在至少100℃~550℃的温度下使所述醇与负载有金属的沸石催化剂接触,其中所述醇能够通过发酵工艺制造,所述金属为带正电荷的金属离子,并且所述负载有金属的沸石催化剂对于将所述醇转化为所述碳氢化合物是有催化活性的。
2.权利要求1的方法,其中所述醇包括乙醇。
3.权利要求1的方法,其中所述醇为水性溶液的组分。
4.权利要求1的方法,其中所述醇为浓度不超过约20%的水性溶液的组分。
5.权利要求4的方法,其中所述浓度不超过约10%。
6.权利要求1的方法,其中所述醇通过发酵工艺制造。
7.权利要求6的方法,其中当与所述负载有金属的沸石催化剂接触时,所述醇为发酵流的组分。
8.权利要求1的方法,其中所述温度为至少200℃~500℃。
9.权利要求1的方法,其中所述温度为至少350℃~500℃。
10.权利要求1的方法,其中所述温度为至少350℃~450℃。
11.权利要求1的方法,其中所述温度为至少375℃~425℃。
12.权利要求1的方法,其中所述金属选自碱金属、碱土金属、铜、铁、钒、锌、钛、镉、镓、铟和它们的组合。
13.权利要求1的方法,其中所述金属选自铜、铁和钒。
14.权利要求1的方法,其中所述沸石包括五元环沸石。
15.权利要求14的方法,其中所述五元环沸石包括ZSM5。
16.权利要求1的方法,其中所述负载有金属的沸石催化剂包括Cu-ZSM5。
17.权利要求1的方法,其中所述负载有金属的沸石催化剂包括V-ZSM5。
18.权利要求1的方法,其中所述碳氢化合物为碳氢化合物的混合物,其中所述混合物用作燃料或者燃料的混合原料组分。
19.权利要求18的方法,其中所述碳氢化合物的混合物包括含有至少四个碳原子的碳氢化合物。
20.权利要求18的方法,其中所述碳氢化合物的混合物基本对应于石油化工馏分。
21.权利要求20的方法,其中所述石油化工馏分基本对应于选自汽油、煤油、柴油和喷气发动机燃料的燃料。
22.权利要求1的方法,其中所述方法和发酵工艺结合,其中所述发酵工艺产生作为发酵流的组分的所述醇,以及使所述发酵流和所述负载有金属的沸石催化剂接触。
23.权利要求1的方法,其中所述方法和包含发酵工艺的生物质反应器结合,其中所述发酵工艺制造作为发酵流的组分的所述醇,以及使所述发酵流和所述负载有金属的沸石催化剂接触。
24.权利要求20的方法,其中所述方法进一步包括蒸馏所述碳氢化合物混合物以得到所述碳氢化合物的混合物的馏分。
25.权利要求1的方法,其中所述醇由生物质源制造。
26.权利要求25的方法,其中所述生物质源包括木质纤维素类物质。
27.权利要求6的方法,其中所述发酵工艺从生物质源制造所述醇。
28.权利要求27的方法,其中所述生物质源包括木质纤维素类物质。
29.权利要求1的方法,其中所述醇包括正丁醇或异丁醇。
30.权利要求25的方法,其中所述生物质源包括淀粉或糖。
31.权利要求6的方法,其中所述发酵工艺从以植物为基的糖源制造所述醇。
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CN107008489B (zh) * | 2017-03-09 | 2020-04-28 | 华南理工大学 | 用于木质素加氢解聚的分子筛负载钒基催化剂及其制备方法 |
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WO2012174205A1 (en) | 2012-12-20 |
CA2839399A1 (en) | 2012-12-20 |
BR112013032184A2 (pt) | 2019-09-24 |
CN103827058B (zh) | 2016-08-17 |
EP2720990A1 (en) | 2014-04-23 |
EP2720990B1 (en) | 2018-03-07 |
CA2839399C (en) | 2021-03-23 |
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US20180187091A1 (en) | 2018-07-05 |
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US11773333B2 (en) | 2023-10-03 |
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EP2720990A4 (en) | 2014-12-24 |
HUE037515T2 (hu) | 2018-09-28 |
US20170066974A1 (en) | 2017-03-09 |
US20140100404A1 (en) | 2014-04-10 |
MX348336B (es) | 2017-06-07 |
US9533921B2 (en) | 2017-01-03 |
BR112013032184B1 (pt) | 2021-05-25 |
US20140273146A1 (en) | 2014-09-18 |
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