CN104114277B - 磷改性沸石催化剂 - Google Patents

磷改性沸石催化剂 Download PDF

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CN104114277B
CN104114277B CN201280051136.4A CN201280051136A CN104114277B CN 104114277 B CN104114277 B CN 104114277B CN 201280051136 A CN201280051136 A CN 201280051136A CN 104114277 B CN104114277 B CN 104114277B
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catalyst composition
zeolite
catalyst
phosphorus
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CN104114277A (zh
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S·J·麦卡锡
T·W·比特尔
M·A·达格
K·J·希基
B·瓦尔德鲁普
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ExxonMobil Technology and Engineering Co
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Abstract

未结合型催化剂组合物包含沸石和磷，磷的量为总催化剂组合物的约0.01至约3重量%的量。在～1000℉(～538℃)下煅烧至少～3小时，催化剂组合物可显示出(i)当在～120℃和～60托(～8kPa)下测量时，>1.5×10‑2sec‑1的2,2‑二甲基丁烷扩散系数，(ii)<～0.15的焦炭减活速率常数，和(iii)至少10的α值，且进一步显示出如下至少一项：(a)>0.2ml/g的中孔孔隙率；(b)至少375m2/g的微孔表面积；和(c)在～1000℉(～538℃)下在～100%蒸汽中蒸～96小时以后<0.05的焦炭减活速率常数。

Description

磷改性沸石催化剂
发明领域
本公开内容涉及磷改性沸石催化剂和它们在有机转化反应如甲醇转化成汽油和柴油沸程烃中的用途。
发明背景
磷改性是改进沸石催化剂在多种化学方法（包括例如甲醇转化成烃和甲苯甲基化以制备二甲苯）中的性能的已知方法。例如，美国专利Nos.4,590,321和4,665,251公开了通过使一种或多种非芳族化合物如丙烷、丙烯或甲醇与包含沸石如ZSM-5的催化剂与耐受方法中所用温度和其它条件的粘合剂或基体材料一起接触而制备芳烃的方法。通过将沸石用磷酸根离子来源如磷酸铵水溶液浸渍，其后煅烧而将沸石用磷氧化物改性。认为磷氧化物改性赋予沸石在芳香化反应中更多的活性和/或苯选择性。
美国专利Nos.6,423,879和6,504,072公开了选择性制备对二甲苯的方法，所述方法包括使甲苯与甲醇在包含多孔结晶材料的催化剂的存在下反应，所述多孔结晶材料具有当在120℃的温度和60托(8kPa)的2,2二甲基丁烷压力下测量时约0.1-15sec-1的2,2二甲基丁烷扩散参数。多孔结晶材料优选为中孔沸石，特别是ZSM-5，其已在至少950℃的温度下蒸过且与约0.05至约20重量%的至少一种氧化物改进剂，优选的磷氧化物结合以控制蒸步骤期间材料的微孔体积降低。多孔结晶材料通常与粘合剂或基体材料（优选二氧化硅或高岭粘土）结合。
美国专利No.7,304,194公开了磷改性ZSM-5催化剂的水热处理方法。在该方法中，将具有至少约250的二氧化硅/氧化铝摩尔比和至少约0.08至约0.15g P/g沸石的磷含量的ZSM-5在至少300℃的温度下煅烧，然后与蒸汽在约150至约250℃的温度下接触。认为蒸过的磷改性沸石作为催化剂用于甲苯甲基化反应中时显示出改进的对-选择性和甲醇选择性。蒸过的磷改性沸石可以以未结合形式或与粘合剂材料如氧化铝、粘土和二氧化硅结合用作催化剂。
另外，美国专利No.7,285,511公开了将沸石催化剂改性以提高它在甲苯甲基化反应中的对二甲苯选择性的方法，其中该方法包括形成基本由具有约250至约1000的SiO2/Al2O3摩尔比的无粘合剂ZSM-5型沸石和含磷化合物水溶液组成的淤浆；和从淤浆中除去水以提供具有0.04g P/g沸石或更多的磷含量和0.2ml/g或更小的孔体积的非蒸磷处理ZSM-5沸石。所得磷处理ZSM-5可以以未结合形式用作甲苯甲基化催化剂，或者可与粘合剂如氧化铝、粘土或二氧化硅化合。
在某些有机转化方法如甲醇转化成汽油和柴油沸程烃中，催化剂的水热稳定性是极其重要的，因为沸石的蒸汽脱铝是不可逆的且可戏剧性地降低催化剂寿命。然而，尽管磷改性在增强沸石水热稳定性方面是有效的，现在发现加入粘合剂以改进最终催化剂的粘结强度可负面影响磷改性的效用。因此，用某些粘合剂，尤其是含氧化铝粘合剂，磷可优先迁移至粘合剂氧化铝中，因此可提高催化剂的焦炭选择性。根据本发明，现在确定未结合型磷改性沸石催化剂组合物，其在甲醇转化反应中可倾向于显示与其它磷改性组合物相比较高的蒸汽稳定性和较低的焦炭减活速率。因此，本发明催化剂组合物在用于甲醇转化成汽油和柴油沸程烃中和/或其中存在高温蒸汽的其它方法中特别有吸引力。
概述
一方面，本发明在于未结合型催化剂组合物，所述组合物包含沸石和磷，其量为总催化剂组合物的约0.1至约3重量%，组合物具有至少20的α值，和以下性能中的至少一种，优选至少两种：
(a)大于0.2ml/g的中孔孔隙率；
(b)至少375m2/g的微孔表面积；
(c)当在～120℃的温度和～60托(～8kPa)的2,2-二甲基丁烷压力下测量时，大于1×10-2sec-1的2,2-二甲基丁烷扩散系数；
(d)在～100%蒸汽中在～1000℉(～538℃)下蒸～96小时以后，小于或等于0.06的焦炭减活速率常数。
方便地，催化剂组合物可具有至少40，例如至少75的α值。
方便地，催化剂组合物可具有大于0.3ml/g的中孔孔隙率和至少380m2/g的微孔表面积。
在一个实施方案中，催化剂组合物可具有当在～120℃的温度和～60托(～8kPa)的2,2-二甲基丁烷压力下测量时，大于1.25×10-2sec-1，例如大于1.5×10-2sec-1的2,2-二甲基丁烷扩散系数。
通常，催化剂组合物可具有小于或等于0.05的焦炭减活速率常数。
在一个实施方案中，催化剂组合物的沸石可具有约1至约12的约束指数。方便地，沸石可具有约40至约200的沸石的二氧化硅:氧化铝摩尔比，且通常包含ZSM-5或者可以为ZSM-5。
在一个实施方案中，催化剂组合物可包含总催化剂组合物的约0.01至约2重量%的量的磷。
另一方面，本发明可在于本文所述未结合型催化剂组合物在有机转化反应，例如甲醇转化成沸点在汽油沸程内的烃中的用途。
应当指出，本申请与各自在2011年10月17日提交的美国临时申请Nos.61/548,015、61/548,038、61/548,044、61/548,052、61/548,057和61/548,064有关，通过引用将其各自的全部内容并入本文中至描述本文所述本发明的任何部分所需的程度。本申请还与5个其它共同未决国际(PCT)申请有关，其各自在与其相同日期提交且要求前述美国临时专利申请的利益，并分别标题为“磷改性沸石催化剂的制备方法”、“磷改性沸石催化剂的制备方法”、“磷改性沸石催化剂”、“磷改性沸石催化剂”和“醇选择性脱水成二烷基醚”，通过引用将其各自的全部内容进一步并入本文中至描述本文所述本发明的任何部分所需的程度。
附图简述
图1为比较实施例1-6的煅烧催化剂压出物的α值的图。
图2为比较实施例1-6的煅烧催化剂压出物在～100%蒸汽中在～1000℉(～538℃)下蒸～96小时以后的α值的图。
图3为比较实施例4-6的煅烧催化剂压出物的α、α0和焦炭减活速率常数值的图。
图4为比较实施例4-6的煅烧催化剂压出物在在～100%蒸汽中在～1000℉(～538℃)下蒸～96小时以后的α、α0和焦炭减活速率常数值的图。
实施方案详述
本文描述未结合型磷稳定化沸石催化剂组合物和它在多种有机转化反应中，特别是，但不仅仅是在甲醇转化成沸点在汽油沸程内的烃中的用途。作为选择，在一些情况下，本发明催化剂组合物可称为自结合。术语“未结合”和“自结合”意欲是同义的，且意指本发明催化剂组合物可有利地不含通常与沸石催化剂结合以增强它们的物理性能的任何无机氧化物粘合剂如氧化铝和/或二氧化硅。
本发明催化剂组合物中所用沸石通常可包含至少一种具有1-12的约束指数的中孔铝硅酸盐沸石(如美国专利No.4,016,218中所定义)。合适的沸石可包括但不限于ZSM-5、ZSM-11、ZSM-12、ZSM-22、ZSM-23、ZSM-35、ZSM-48等及其组合。ZSM-5详细描述于美国专利Nos.3,702,886和RE29,948中。ZSM-11详细描述于美国专利No.3,709,979中。ZSM-12描述于美国专利No.3,832,449中。ZSM-22描述于美国专利No.4,556,477中。ZSM-23描述于美国专利No.4,076,842中。ZSM-35描述于美国专利No.4,016,245中。ZSM-48更特别地描述于美国专利No.4,234,231中。在优选实施方案中，沸石可包含ZSM-5或者为ZSM-5。
沸石的化学组成未必是关键的，但沸石可有利地包含足够的铝以提供在任何蒸以前具有至少10，例如至少20或至少50的初始α值的磷稳定化沸石催化剂。α值可以为与标准二氧化硅-氧化铝催化剂相比，沸石催化剂的酸活性的度量。α试验描述于美国专利No.3,354,078；the Journal of Catalysis，第4卷，第527页(1965)；第6卷，第278页(1966)；和第61卷，第395页(1980)中，通过引用将其各自关于该描述的内容并入本文中。其中所用试验的实验条件包括～538℃的恒定温度和可变的流速，如the Journal of Catalysis，第61页，第395页所详细描述的。较高的α值相当于更活性的裂化催化剂。在某些实施方案中，具有所需活性的沸石可具有约40至约200的二氧化硅:氧化铝摩尔比。
当用于本发明催化剂组合物中时，沸石可有利地至少部分以氢形式存在。取决于用于合成沸石的条件，这可能要求从例如碱(钠)形式转化沸石。这可容易地通过离子交换以将沸石转化成铵形式，其后在空气或惰性气氛中，例如在约400至约700℃的温度下煅烧以将铵形式转化成活性氢形式而实现。
为增强沸石的蒸汽稳定性而不过多地损失其初始酸活性，本发明催化剂组合物可包含总催化剂组合物的约0.01至约3重量%，例如约0.05至约2重量%元素磷的量的磷。磷可在沸石合成和/或沸石配制成催化剂组合物期间的任何阶段加入催化剂组合物中。一般而言，磷添加可通过将催化剂组合物(和/或其前体)用磷化合物溶液喷雾和/或浸渍而实现。合适的磷化合物可包括但不限于膦酸、三价膦酸、含磷酸(phosphorus acid)和磷酸、这类酸的盐和酯、磷卤化物等及其组合。在磷处理以后，通常可将催化剂在例如空气中在约400至约700℃的温度下煅烧以将磷转化成氧化物形式。
催化剂组合物可使用其原始结晶形式和/或在例如通过压出而配制成催化剂颗粒的磷处理沸石。在不存在粘合剂下制备沸石压出物的方法例如公开于美国专利No.4,582,815中，通过引用将其全部内容并入本文中。
除α值外，本文所用磷稳定化沸石催化剂组合物可有利地显示出如下两种：(i)当在约120℃的温度和约60托(约8kPa)的2,2-二甲基丁烷压力下测量时，大于1.5×10-2sec-1，例如至少1.7×10-2sec-1或至少2×10-2sec-1的2,2-二甲基丁烷扩散系数，和(ii)所煅烧的，小于0.2，例如小于约0.15或小于约0.12的焦炭减活速率常数。另外或者作为选择，本文所用磷稳定化沸石催化剂组合物可通过如下性能中的至少一种，优选至少两种，在一些实施方案所有进行表征：(a)大于0.2ml/g，例如大于0.3ml/g的中孔孔隙率；(b)至少375m2/g，例如至少380m2/g的微孔表面积；和(c)在～100%蒸汽中在约1000℉(约538℃)下蒸约96小时以后，小于或等于0.06，例如小于或等于0.05、小于0.05、小于或等于0.04或小于0.04的焦炭减活速率常数。本领域技术人员应当理解不同于性能(c)，以上性能(a)和(b)在催化剂组合物的任何蒸以前测量。
在这些性能中，中孔孔隙率和2,2-二甲基丁烷扩散系数可由大量因素决定，包括对于给定沸石的晶体大小。微孔表面积可通过沸石的孔径大小和催化剂颗粒表面上沸石孔的可用性测定。制备具有所需最小中孔孔隙率、微孔表面积和2,2-二甲基丁烷扩散系数的沸石催化剂应在沸石化学中技术人员的专长内。
焦炭减活速率常数可以为当经受例行α试验时催化剂减活速率的度量且定义于实施例中。
本文所述磷改性沸石催化剂可特别用于其中催化剂的水热稳定性重要的任何有机转化方法中。这类方法的实例包括但未必限于重质烃流化催化裂化成汽油和柴油沸程烃、甲苯的甲基化和歧化以制备二甲苯、正链烷烃(例如C6和更高)环化、甲醇转化成汽油和柴油沸程烃等及其组合和/或联合。
另外或者作为选择，本发明可包括以下实施方案中的一个或多个。
实施方案1.未结合型催化剂组合物，其包含沸石和磷，磷的量为总催化剂组合物的约0.01至约3重量%，其中在至少约1000℉(约538℃)的温度下煅烧至少约3小时，未结合型催化剂显示出：(i)当在约120℃的温度和约60托(约8kPa)的2,2-二甲基丁烷压力下测量时，大于1.5×10-2sec-1的2,2-二甲基丁烷扩散系数，(ii)小于约0.15的焦炭减活速率常数，和(iii)至少10的α值，且其中未结合型催化剂组合物进一步显示出如下性能中的至少一种：(a)大于0.2ml/g的中孔孔隙率；(b)至少375m2/g的微孔表面积；和(c)在约100%蒸汽中在约1000℉(约538℃)下蒸约96小时以后，小于0.05的焦炭减活速率常数。
实施方案2.实施方案1的催化剂组合物，其中煅烧后的α值为至少20，例如至少50。
实施方案3.前述实施方案中任一项的催化剂组合物，其中中孔孔隙率大于0.3ml/g。
实施方案4.前述实施方案中任一项的催化剂组合物，其中微孔表面积为至少380m2/g。
实施方案5.前述实施方案中任一项的催化剂组合物，其中当在约120℃的温度和约60托(约8kPa)的2,2-二甲基丁烷压力下测量时，2,2-二甲基丁烷扩散系数为至少1.7×10-2sec-1，例如至少2×10-2sec-1。
实施方案6.前述实施方案中任一项的催化剂组合物，其中在约100％蒸汽中在约1000℉(约538℃)的温度下蒸约96小时后焦炭减活速率常数小于或等于0.04，例如小于0.04。
实施方案7.前述实施方案中任一项的催化剂组合物，其中组合物具有所述性能(a)-(c)中的至少两种，例如所述性能(a)-(c)中的所有三种。
实施方案8.前述实施方案中任一项的催化剂组合物，权利要求1的催化剂组合物，其中所述沸石具有约1至约12的约束指数。
实施方案9.前述实施方案中任一项的催化剂组合物，其中所述沸石包含ZSM-5或者为ZSM-5。
实施方案10.前述实施方案中任一项的催化剂组合物，其中沸石的二氧化硅:氧化铝摩尔比为约40至约200。
实施方案11.前述实施方案中任一项的催化剂组合物，其中磷以总催化剂组合物的约0.05至约2重量%的量存在。
实施方案12.有机化合物转化的方法，其使用原料与前述实施方案中任一项的催化剂组合物在有机化合物转化条件下接触。
实施方案13.实施方案12的方法，其中所述有机化合物转化包括甲醇转化成沸点在汽油沸程内的烃。
现在参考以下非限定性实施例和附图更特别地描述本发明。
实施例
实施例1-3.自结合型ZSM-5催化剂的制备
将ZSM-5晶体(基于固体，～1.4kg)加入混合机中并干研磨。然后在研磨期间加入约190g去离子水。在约10分钟以后，将与约450g去离子水混合的～28g～50重量%苛性碱溶液加入混合物中并研磨另外～5分钟。然后将混合物压出成～1/10”四叶片。将压出物在下～250℉(～121℃)干燥过夜(～8-16小时)，然后在氮气中在～1000℉(～538℃)下煅烧～3小时。然后将压出物与1N硝酸铵溶液交换两次。将交换的晶体在～250℉(～121℃)下干燥过夜，然后在空气中在～1000℉(～538℃)下煅烧～3小时。使用所述程序将三种不同的ZSM-5晶体自结合。使用氮孔隙率测定法和感应耦合等离子体(ICP)元素分析分析这些催化剂，结果汇总于下表1中。
实施例4-6.磷加入自结合型ZSM-5催化剂中
将实施例1-3的自结合型催化剂各自使用磷酸溶液借助初始润湿而用～1.2重量%磷浸渍。然后将浸渍的催化剂在～250℉(～121℃)下干燥过夜(～8-16小时)，然后在空气中在～1000℉(～538℃)下煅烧～3小时。再次使用氮孔隙率测定法和ICP元素分析分析所得含P催化剂，结果也汇总于下表1中。
实施例7-12.自结合型ZSM-5催化剂的蒸汽减活
将实施例1-6的催化剂在～1000℉(～538℃)下在～100%蒸汽中蒸约96小时。再次使用氮孔隙率测定法和ICP元素分析分析所得蒸过的催化剂，结果进一步汇总于下表1中。
实施例13.2,2-二甲基丁烷吸着
表示为特性扩散时间的倒数的烃扩散系数D/r2通过实施例1-12的催化剂各自的2,2-二甲基丁烷(2,2-DMB)吸收速率测定。在烃吸附以前，将约50mg试样在空气中加热至～500℃，例如以除去水分和任何烃或焦炭杂质。对于2,2-DMB吸附，在空气煅烧步骤以后将试样冷却至～120℃，然后暴露于在氮气中的～60托(～8kPa)2,2-DMB流下。结果也汇总于表1中。
实施例14.α试验
在标准条件(～100托，或～13kPa，流过保持在～1000℉或～538℃下的反应器的He载气中的己烷蒸气压力)下的例行α试验中以己烷裂化筛分实施例1-12的催化剂，以用于酸活性。在试验期间，调整流速以实现约5至约15%的转化率。在相对恒定流量下在～4、～11、～18和～25分钟时取得四个数据点。α值表示对于正己烷裂化，在～18分钟时的第一级速率常数相对于二氧化硅-氧化铝标准的比。
α值如下测定：
α=A*ln(1-X)/τ
其中A-参比速率常数
X-转换分数
τ-停留时间。
然后将四个α值作为时间的函数绘出，并通过指数函数拟合以测定焦炭减活速率：
α=αo*exp(-ct1/3)
其中αo-在时间=0时测量的α0
c-焦炭减活速率常数
t-时间，min
α试验结果也汇总于表1中和图1-4中。从这些结果中可以看出无磷催化剂和含磷催化剂的初始α值与催化剂中的游离铝的量大略成比例。游离铝在本文中定义为总铝减去磷含量。
可以看出实施例1-3的非磷稳定化催化剂显示出高初始α值(分别为～1100、～540和～410)，但实施例7-9的它们蒸过的对应物显示出α值的显著降低(分别降至～7、～14和～4)。
对于实施例4-6的磷稳定化催化剂，尽管初始α值比它们的无磷对应物稍微更低(分别为～700、～200和～160)，实施例10-12的蒸过的变体显示出比其蒸过的无磷对应物更好的α值(分别为～58、～95和～100)保持力。
从图3和4中可以看出，对于实施例7-12的蒸过的催化剂，具有至少20的Si/Al2比、至少10,00010-6sec-1的煅烧2,2-DMB扩散系数和至少0.2ml/g的中孔孔隙率的磷稳定化自结合型ZSM-5催化剂显示出蒸时的α值保持力和低焦炭减活速率的最佳组合。如图4所示，实施例11的催化剂显示出基本无焦炭减活。
实施例15.P-改性ZSM-5/Versal-300氧化铝催化剂的制备
将～80重量%的所合成NaZSM-5沸石(具有约50的二氧化硅:氧化铝摩尔比且包含用于其合成中的有机导向剂)的混合物在研磨机中与～20重量%VersalTM-300氧化铝粘合剂混合。将混合物压出并将所得压出物试样在氮气中在～1000℉(～538℃)下煅烧～3小时以使有机模板分解。然后将煅烧的压出物与硝酸铵溶液交换以将沸石从钠形式转化成铵形式，其后将压出物在空气中在～1000℉(～538℃)下煅烧另外～3小时以将沸石从铵形式转化成氢形式。同时，任何含碳沉积物(例如来自有机模板分解和/或来自硝酸铵交换的)通过氧化而除去。然后将因此所得H-ZSM-5-Al2O3压出物借助含水初湿浸渍(aqueous incipientwetness impregnation)而用磷酸浸渍至～0.96重量%磷的目标水平。将试样干燥，然后在空气中在～1000℉(～538℃)下煅烧另外～3小时。所得产物标记为催化剂A”且具有汇总于下表2中的性能。
实施例16.P改性的未结合型ZSM-5催化剂的制备
将所合成的NaZSM-5沸石试样压出而不使用粘合剂。将试样在氮气中在～1000℉(～538℃)下煅烧～3小时，与硝酸铵溶液交换，并在空气中在～1000℉(～538℃)下煅烧另外～3小时。将压出物借助含水初湿浸渍而用磷酸浸渍至～1.2重量%磷的目标水平。将试样干燥，然后在～1000℉(～538℃)下煅烧另外～3小时。所得产物标记为催化剂B”且具有汇总于下表2中的性能。
实施例17.P改性的未结合型小晶体ZSM-5催化剂的制备
将所合成的小晶体NaZSM-5沸石试样压出而不使用粘合剂。将试样在氮气中在～1000℉(～538℃)下煅烧～3小时，与硝酸铵溶液交换，并在空气中在～1000℉(～538℃)下煅烧另外～3小时。将压出物借助含水初湿浸渍而用磷酸浸渍至～1.2重量%磷的目标水平。将试样干燥，然后在～1000℉(～538℃)下煅烧另外～3小时。所得产物标记为催化剂C”且具有汇总于下表2中的性能。
实施例18.P改性的二氧化硅结合型ZSM-5催化剂的制备
将～80重量%所合成的小晶体NaZSM-5沸石的混合物与～20重量%UltrasilTM二氧化硅一起压出。将试样在氮气中在～1000℉(～538℃)下煅烧～3小时，与硝酸铵溶液交换，并在空气中在～1000℉(～538℃)下煅烧另外～3小时。将压出物借助含水初湿浸渍而用磷酸浸渍至～0.96重量%磷的目标水平。将试样干燥，然后在～1000℉(～538℃)下煅烧另外～3小时。所得产物标记为催化剂D”且具有汇总于下表2中的性能。
实施例19.P改性的二氧化硅结合型ZSM-5催化剂的制备
将～80重量%所合成的NaZSM-5沸石(具有约28的二氧化硅:氧化铝摩尔比且包含用于其合成中的有机导向剂)的混合物在研磨机中与～20重量%UltrasilTM二氧化硅粘合剂混合。将混合物压出并将所得压出物试样在氮气中在～1000℉(～538℃)下煅烧～3小时。然后将煅烧的压出物与硝酸铵溶液交换，然后在空气中在～1000℉(～538℃)下煅烧另外～3小时。然后将压出物借助含水初湿浸渍而用磷酸浸渍至～0.96重量%磷的目标水平。将试样干燥，然后在空气中在～1000℉(～538℃)下煅烧另外～3小时。所得产物标记为催化剂E且具有汇总于下表2中的性能。
表2
催化剂 Si/Al2 粘合剂类型 粘合剂含量重量% P(重量%，基于沸石)
A” ～50 Al2O3 ～20 ～1.0
B” ～50 N/A 0 ～1.2
C” ～50 N/A 0 ～1.2
D” ～50 SiO2 ～20 ～1.0
E ～28 SiO2 ～20 ～1.0
实施例20.微孔表面积
MTG反应通常在沸石微孔内部进行。因此，有利的是改进/最大化沸石微孔体积以实现最大的MTG活性。在通过N2-BET测量微孔表面积以前，将来自实施例15-19的催化剂试样A”、B”、C”、D”和E在空气中在～1000℉(～538℃)下煅烧～6小时。微孔表面积通过存在于压出物中的沸石含量而标准化。优选的催化剂压出物显示出至少375m2/g沸石的微孔表面积。实施例21.来自实施例15-19的试样的表征
对于根据实施例15-19制备且详述于上表2中的试样(分别为A”、B”、C”、D”和E)，进行以下试验。α试验和耐焦化试验(为测量焦炭减活速率常数)根据实施例14在通过在～100%H2O气氛中在～1000℉(～538℃)下蒸～96小时处理的试样上进行。但是，对于这些试样，在煅烧的试样(未蒸)上，还进行耐焦化试验。根据实施例20对煅烧的试样进行微孔表面积实验。根据实施例13对试样进行2,2-二甲基丁烷扩散系数试验，所述试样在测量以前在空气中在～1000℉(～538℃)下煅烧～6小时。这些表征的结果显示于下表3中。
表3
尽管通过参考特定实施方案描述和阐述了本发明，本领域技术人员理解本发明本身适用于本文未必阐述的变化方案。为此，则应仅参考所附权利要求书以确定本发明的真实范围。

Claims (15)

1.未结合型催化剂组合物，其包含ZSM-5沸石和磷，磷的量为总催化剂组合物的0.01至3重量％，其中在至少1000℉的温度下煅烧至少3小时，未结合型催化剂显示出：
(i)当在120℃的温度和60托的2,2-二甲基丁烷压力下测量时，大于1.5×10-2sec-1的2,2-二甲基丁烷扩散系数，
(ii)小于0.15的焦炭减活速率常数，和
(iii)至少10的α值，
且其中未结合型催化剂组合物进一步显示出在100％蒸汽中在1000℉下蒸96小时以后小于0.05的焦炭减活速率常数。
2.根据权利要求1的催化剂组合物，其中α值为至少20。
3.根据权利要求2的催化剂组合物，其中α值为至少50。
4.根据权利要求1-3中任一项的催化剂组合物，其中未结合型催化剂组合物进一步显示出大于0.2ml/g的中孔孔隙率。
5.根据权利要求4的催化剂组合物，其中中孔孔隙率大于0.3ml/g。
6.根据权利要求1-3和5中任一项的催化剂组合物，其中未结合型催化剂组合物进一步显示出至少375m2/g的微孔表面积。
7.根据权利要求6的催化剂组合物，其中微孔表面积为至少380m2/g。
8.根据权利要求1-3、5和7中任一项的催化剂组合物，其中当在120℃的温度和60托的2,2-二甲基丁烷压力下测量时，2,2-二甲基丁烷扩散系数为至少1.7×10-2sec-1。
9.根据权利要求8的催化剂组合物，其中当在120℃的温度和60托的2,2-二甲基丁烷压力下测量时，2,2-二甲基丁烷扩散系数为至少2×10-2sec-1。
10.根据权利要求1-3、5、7和9中任一项的催化剂组合物，其中在100％蒸汽中在1000℉下蒸96小时以后，焦炭减活速率常数小于或等于0.04。
11.根据权利要求10的催化剂组合物，其中在100％蒸汽中在1000℉下蒸96小时以后，焦炭减活速率常数小于0.04。
12.根据权利要求1-3、5、7、9和11中任一项的催化剂组合物，其中所述沸石具有1至12的约束指数。
13.根据权利要求1-3、5、7、9和11中任一项的催化剂组合物，其中沸石的二氧化硅:氧化铝摩尔比为40至200。
14.根据权利要求12的催化剂组合物，其中沸石的二氧化硅:氧化铝摩尔比为40至200。
15.根据权利要求1-3、5、7、9、11和14中任一项的催化剂组合物，其中磷以总催化剂组合物的0.05至2重量％的量存在。
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