CN103889574A - 磷改性的沸石催化剂 - Google Patents

磷改性的沸石催化剂 Download PDF

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CN103889574A
CN103889574A CN201280051056.9A CN201280051056A CN103889574A CN 103889574 A CN103889574 A CN 103889574A CN 201280051056 A CN201280051056 A CN 201280051056A CN 103889574 A CN103889574 A CN 103889574A
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carbon monoxide
olefin polymeric
zeolite
weight
catalyst
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T·W·比特尔
S·J·麦卡锡
B·瓦尔德鲁普
M·A·达格
K·J·希基
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ExxonMobil Technology and Engineering Co
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Abstract

粘合的磷改性催化剂组合物，包含具有至少40的二氧化硅与氧化铝摩尔比的沸石、总催化剂组合物的大约0.1重量％至大约3重量％的量的磷、和基本无铝的粘合剂。该粘合的催化剂组合物可有利地表现出下述至少一种：（a）至少340平方米/克的微孔表面积；（b）至少40的在～1000℉（～538℃）下在～100％蒸汽中蒸汽处理～96小时后的α值；和（c）在～1000℉（～538℃）下在～100％蒸汽中蒸汽处理～96小时后＜0.05的焦炭失活速率常数。该粘合的催化剂在煅烧态下还可有利地表现出（i）在～120℃和～60torr（～8kPa）下测得的＞～1.5×10-2秒-1的2,2-二甲基丁烷扩散率和（ii）＜～0.15的焦炭失活速率常数。

Description

磷改性的沸石催化剂
技术领域
本发明涉及磷改性的沸石催化剂及其在有机转化反应（例如甲醇转化成汽油和柴油沸程烃）的反应中的用途。
背景技术
磷改性是改进用于各种化学工艺（包括例如甲醇转化成烃和甲苯甲基化以产生二甲苯）的沸石催化剂的性能的已知方法。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（例如丙烷、丙烯或甲醇）与含有沸石（例如ZSM-5）的催化剂接触制造芳烃的方法。通过用磷酸根离子源（例如磷酸铵水溶液）浸渍沸石、然后煅烧，用氧化磷将沸石改性。氧化磷改性据称使沸石在芳构化反应中更具活性和/或对苯更有选择性。
此外，美国专利No.7,304,194公开了磷改性的ZSM-5催化剂的水热处理方法。该ZSM-5具有至少大约200的二氧化硅与氧化铝摩尔比、至少0.5微米的晶体粒度，并可以以非粘合形式使用或与选自氧化铝、粘土或二氧化硅的粘合剂结合。该磷改性沸石含有大约0.01g P/g沸石至大约0.15gP/g沸石，并在至少300℃的温度下煅烧以产生具有150-200平方米/克的通过N2吸附技术测得的BET表面积的催化剂。然后将该煅烧的催化剂在大约150℃至大约350℃的温度下用蒸汽处理。该蒸汽处理过的磷改性沸石据称在用作甲苯甲基化反应中的催化剂时表现出改进的对位选择性和甲醇选择性。
美国专利申请公开No.2010/0168489公开了粘合的磷改性沸石催化剂，其中将粘合剂材料在与磷改性沸石粘合之前用无机酸处理。合适的粘合剂材料据称包括无机氧化物，例如氧化铝、粘土、磷酸铝和二氧化硅-氧化铝。在任选的挤出后，将该沸石-粘合剂混合物在大约400℃或更高温度下加热以形成粘合的沸石催化剂，通常每克沸石0.01至大约0.15克磷。该催化剂特别旨在用于用甲醇将甲苯烷基化产生二甲苯，但据称也可用于MTG工艺。
用于甲醇制汽油（MTG）的现有催化剂通常使用粘合的磷改性沸石催化剂。通过沸石催化剂的微孔内的骨架铝生成的酸位点催化MTG反应，而磷的作用是稳定沸石骨架铝，以免由作为该工艺副产物生成的高温蒸汽造成脱铝。粘合剂材料的作用是辅助保持催化剂床中的催化剂粒子的完整性，但对于某些粘合剂，尤其是含氧化铝的粘合剂，磷会优先迁移到粘合剂氧化铝中和/或提高该催化剂的焦炭选择性。因此需要用于甲醇制汽油的改进的催化剂。
发明概述
一方面，本发明涉及粘合的磷改性催化剂组合物，其包含具有至少40的二氧化硅与氧化铝摩尔比的沸石、总催化剂组合物的大约0.1重量％至大约3重量％的量的磷、和基本无铝的粘合剂，其中该催化剂组合物表现出至少一种、优选至少两种下述性质：（a）至少340平方米/克的微孔表面积；（b）在～120℃的温度和～60torr（～8kPa）的2,2-二甲基丁烷压力下测量时大于1.2×10-2秒-1、例如大于1.5×10-2秒-1的2,2-二甲基丁烷扩散率；（c）至少20的、例如至少40的在～1000°F（～538℃）在～100％蒸汽中蒸汽处理～96小时后的α值；和（d）在～900°F（～482℃）下在～100％蒸汽中蒸汽处理～96小时后小于或等于0.06的焦炭失活速率常数。
便利地，该沸石的二氧化硅与氧化铝摩尔比可以为大约40至大约200。
便利地，该沸石可具有大约1至大约12的约束指数并在一个实施方案中包含ZSM-5。
便利地，该催化剂组合物可含有总催化剂组合物的大约0.5重量％至大约2重量％的量的磷。
便利地，粘合剂以总催化剂组合物的大约1重量％至大约50重量％、例如大约5重量％至大约40重量％的量存在。在一个实施方案中，粘合剂可包含或是二氧化硅。
另一方面，本发明涉及本文所述的粘合的磷改性催化剂组合物在有机转化反应（例如甲醇转化成在汽油沸程中沸腾的烃）的反应中的用途。
应该指出，本申请与美国临时申请Nos.61/548,015、61/548,038、61/548,044、61/548,052、61/548,057和61/548,064相关，它们各自在2011年10月17日提交，各自的整个内容在描述在此详述的本发明的任何部分所需的程度上经此引用并入本文。本申请还与另外五个共同待审的国际（PCT）申请相关，各自与其同日提交并要求上述美国临时专利申请的权益，分别名为“制造磷改性沸石催化剂的方法（Process for ProducingPhosphorus Modified Zeolite Catalysts）”、“制造磷改性沸石催化剂的方法（Process for Producing Phosphorus Modified Zeolite Catalysts）”、“磷改性的沸石催化剂（Phosphorus Modified Zeolite Catalysts）”、“磷改性的沸石催化剂（Phosphorus Modified Zeolite Catalysts）”和“醇选择性脱水成二烷基醚（Selective Dehydration of Alcohols to Dialkyl Ethers）”，各自的整个内容在描述在此详述的本发明的任何部分所需的程度上进一步经此引用并入本文。
附图简述
图1显示了比较在～1000°F（～538℃）下在～100％蒸汽中蒸汽处理大约96小时后实施例1-4的催化剂的标准化α值的图。
图2显示了比较通过沸石含量标准化的实施例1-3的催化剂的微孔表面积的图。
图3显示了比较实施例1-3的催化剂在大约120℃的温度和～60torr（～8kPa）的2,2-二甲基丁烷压力下的2,2-二甲基丁烷扩散率的图。
图4显示了比较在～900°F（～482℃）下在～100％蒸汽中蒸汽处理大约96小时后实施例6的催化剂的标准化α值和焦炭失活速率常数的图。
实施方案详述
在本文中描述了粘合的磷稳定化沸石催化剂组合物和它们在各种有机转化反应中、特别但不限于在甲醇转化成在汽油沸程中沸腾的烃的反应中的用途。
本催化剂组合物中所用的沸石通常具有至少40的、例如大约40至大约200的二氧化硅与氧化铝摩尔比。该沸石通常包含至少一种中孔硅铝酸盐沸石，例如具有1-12的约束指数（如美国专利No.4,016,218中所定义）。合适的沸石包括，但不一定限于ZSM-5、ZSM-11、ZSM-12、ZSM-22、ZSM-23、ZSM-35、ZSM-48等及其组合。在美国专利Nos.3,702,886和RE29,948中详细描述了ZSM-5。在美国专利No.3,709,979中详细描述了ZSM-11。在美国专利No.3,832,449中描述了ZSM-12。在美国专利No.4,556,477中描述了ZSM-22。在美国专利No.4,076,842中描述了ZSM-23。在美国专利No.4,016,245中描述了ZSM-35。在美国专利No.4,234,231中更特别描述了ZSM-48。在某些优选实施方案中，该沸石可以包含或者是ZSM-5。
当用在本催化剂组合物中时，该沸石可以有利地至少部分以氢形式存在。根据用于合成沸石的条件，变成氢形式可能涉及由例如碱（钠）形式转化沸石。这可容易地如下实现：例如通过离子交换以将沸石转化成铵形式，然后在空气或惰性气氛中、例如在大约400℃至大约700℃的温度下煅烧以将铵形式转化成活性氢形式。如果在沸石合成中使用有机结构导向剂，煅烧可另外合意地除去该结构导向剂。
可以将沸石与基本不含铝的粘合剂、通常是无机氧化物合并。在本说明书中，“基本不含铝”的粘合剂应被理解为是指通过XRF/ICP测量时含有少于10重量％的铝，例如少于7重量％、少于5重量％、少于3重量％、少于1重量％、少于0.5重量％、少于0.1重量％的铝，或没有可检出的铝的粘合剂。合适的粘合剂是二氧化硅。该粘合剂通常以总催化剂组合物的大约1重量％至大约50重量％、例如大约5重量％至大约40重量％的量存在。通常通过磨碎沸石和粘合剂的混合物、然后将该混合物挤出成催化剂丸粒实现沸石与粘合剂的合并。在例如美国专利No.4,582,815（其整个内容经此引用并入本文）中公开了使用二氧化硅粘合剂制造沸石挤出物的方法。
为了增强沸石的蒸汽稳定性而不过度损失其初始酸活性，本催化剂组合物可含有总催化剂组合物的大约0.01重量％至大约3重量％元素磷、例如大约0.05重量％至大约2重量％的量的磷。可以在沸石合成或将沸石和粘合剂配制成粘合的催化剂组合物的过程中的任何阶段将磷添加到催化剂组合物中。通常，可以通过用磷化合物的溶液喷涂和/或浸渍最终催化剂组合物（和/或其前体）实现磷添加。合适的磷化合物可包括，但不限于，次膦酸[H2PO(OH)]、膦酸[HPO(OH)2]和磷酸[PO(OH)3]、此类酸的盐和酯、卤化磷等、和它们的组合。在磷处理后，可以将该催化剂通常例如在空气中在大约400℃至大约700℃的温度下煅烧，以将磷转化成氧化物形式。
本文所用的粘合的磷稳定化沸石催化剂组合物有利地表现出下述（i）和（ii）：（i）在大约120℃的温度和大约60torr（大约8kPa）的2,2-二甲基丁烷压力下测量时大于1.5×10-2秒-1、例如至少1.7×10-2秒-1或至少2×10-2秒-1的2,2-二甲基丁烷扩散率，和（ii）煅烧后的小于0.2、例如小于大约0.15或小于大约0.12的焦炭失活速率常数。额外地或或者，本发明所用的粘合的磷稳定化沸石催化剂组合物以下述性质的至少一个、优选至少两个、或在一些实施方案中全部为特征：（a）至少340平方米/克、例如至少375平方米/克的微孔表面积；（b）至少20、例如至少40或至少60的在～1000°F（～538℃）下在～100％蒸汽中蒸汽处理～96小时后的α值；和（d）在～1000°F（～538℃）下在～100％蒸汽中蒸汽处理～96小时后小于或等于0.06、例如小于0.05或小于0.04的焦炭失活速率常数。本领域普通技术人员应该认识到，不同于性质（b）和（c），上述性质（a）在催化剂组合物的任何蒸汽处理之前测量。
在这些性质中，微孔率和2,2-二甲基丁烷扩散率取决于许多因素，包括但不限于沸石的孔径和晶体粒度和催化剂粒子表面处的沸石孔隙的可达性。制造具有所需微孔表面积和2,2-二甲基丁烷扩散率的沸石催化剂完全在沸石化学中的任何普通技术人员的专业知识内。
α值衡量与标准二氧化硅-氧化铝催化剂相比的沸石催化剂的酸活性。
在美国专利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）中描述了α试验，它们各自关于此描述经此引用并入本文。本文所用的试验的实验条件包括大约538℃的恒温和例如the Journal of Catalysis,第61卷,第395页中详细描述的可变流速。较高的α值往往对应于较活性的裂化催化剂。由于本催化剂组合物旨在用于MTG之类的反应（其中沸石可能发生沸石的水热脱铝），因此重要的是，该粘合的催化剂组合物在～1000°F（～538℃）下在～100％蒸汽中蒸汽处理～96小时后保持相当大的α值，即至少20。
焦炭失活速率常数衡量催化剂失活速率，这将在实施例中更详细解释。
本文所述的磷改性的粘合沸石催化剂特别可用于任何下述有机转化工艺：其中催化剂的水热稳定性是重要的。此类工艺的实例包括，但不一定限于重质烃流体催化裂化成汽油和柴油沸程烃、甲苯的甲基化和歧化以产生二甲苯、正链烷烃（例如C6和更高级）环化、甲醇转化成汽油和柴油沸程烃等，和它们的组合和/或集成。
另外或或者，本发明包括一个或多个下述实施方案。
实施方案1.粘合的磷改性催化剂组合物，其包含具有至少40的二氧化硅与氧化铝摩尔比的沸石、含量为总催化剂组合物的大约0.1重量％至大约3重量％的磷、和基本无铝的粘合剂，其中在至少大约1000°F（大约538℃）的温度下煅烧至少大约3小时的所述粘合的催化剂表现出：（i）在大约120℃的温度和大约60torr（大约8kPa）的2,2-二甲基丁烷压力下测量时大于1.5×10-2秒-1、例如至少1.7×10-2秒-1或至少2×10-2秒-1的2,2-二甲基丁烷扩散率和（ii）小于大约0.15的焦炭失活速率常数，且其中所述粘合的催化剂组合物进一步表现出至少一种下述性质：（a）至少340平方米/克、例如至少375平方米/克的微孔表面积；（b）至少20、例如至少40的在大约1000°F（大约538℃）下在大约100％蒸汽中蒸汽处理大约96小时后的α值；和（c）在大约1000°F（大约538℃）下在大约100％蒸汽中蒸汽处理大约96小时后小于或等于0.06、例如小于0.05或小于0.04的焦炭失活速率常数。
实施方案2.实施方案1的催化剂组合物，其中所述沸石的二氧化硅与氧化铝摩尔比为大约40至大约200。
实施方案3.任一前述实施方案的催化剂组合物，其中所述沸石具有大约1至大约12的约束指数。
实施方案4.任一前述实施方案的催化剂组合物，其中所述沸石包含ZSM-5或者是ZSM-5。
实施方案5.任一前述实施方案的催化剂组合物，其中所述粘合的催化剂组合物含有总催化剂组合物的大约0.5重量％至大约2重量％的量的磷。
实施方案6.任一前述实施方案的催化剂组合物，其中所述粘合剂以总催化剂组合物的大约1重量％至大约50重量％、例如大约5重量％至大约40重量％的量存在。
实施方案7.任一前述实施方案的催化剂组合物，其中所述粘合剂包含二氧化硅。
实施方案8.任一前述实施方案的催化剂组合物，其中在大约1000°F（大约538℃）下在大约100％蒸汽中蒸汽处理大约96小时后的α值为至少60。
实施方案9.任一前述实施方案的催化剂组合物，其中所述粘合的催化剂组合物表现出性质（a）至（c）中的至少两种。
实施方案10.任一前述实施方案的催化剂组合物，其中所述粘合的催化剂组合物表现出所有性质（a）至（c）。
实施方案11.有机化合物转化法，其包括使原料与任一前述实施方案的粘合的催化剂组合物在有机化合物转化条件下接触。
实施方案12.实施方案12的方法，其中所述有机化合物转化包括将甲醇转化成在汽油沸程中沸腾的烃。
现在参照实施例和附图更特别描述本发明。
实施例
实施例1.P改性的ZSM-5/Versal-300氧化铝催化剂的制备
在研磨机中将～80重量％合成后未经进一步处理的NaZSM-5沸石（具有约50的二氧化硅与氧化铝摩尔比，并含有其合成中所用的有机导向剂）与～20重量％VersalTM-300氧化铝粘合剂掺合。挤出该掺合物，并将所得挤出样品在氮气中在～1000°F（～538℃）下煅烧～3小时，以将有机模板分解成碳质沉积物。然后将煅烧的挤出物与硝酸铵溶液交换，以将沸石从钠形式转化成铵形式，此后将该挤出物在空气中在～1000°F（～538℃）下煅烧～3小时以将沸石从铵形式转化成氢形式。同时，通过氧化除去碳质沉积物。然后将由此获得的H-ZSM-5-Al2O3挤出物通过水性初湿含浸法用磷酸浸渍至～0.96重量％磷的目标水平。将该样品干燥，然后在空气中在～1000°F（～538℃）下煅烧～3小时。所得产物标作催化剂A并具有下表1中概括的性质。
实施例2.P改性的非粘合的ZSM-5催化剂的制备
不用粘合剂，将合成后未经进一步处理的NaZSM-5沸石样品挤出。将该样品在氮气中在～1000°F（～538℃）下煅烧～3小时，与硝酸铵溶液交换，并在空气中在～1000°F（～538℃）下煅烧～3小时。将该挤出物通过水性初湿含浸法用磷酸浸渍至～1.2重量％磷的目标水平。将该样品干燥，然后在～1000°F（～538℃）下煅烧～3小时。所得产物标作催化剂B并具有下表1中概括的性质。
实施例3.P改性的非粘合的小晶体ZSM-5催化剂的制备
不用粘合剂，将合成后未经进一步处理的小晶体NaZSM-5沸石样品挤出。该样品在氮气中在～1000°F（～538℃）下煅烧～3小时，与硝酸铵溶液交换，并在空气中在～1000°F（～538℃）下煅烧～3小时。将该挤出物通过水性初湿含浸法用磷酸浸渍至～1.2重量％磷的目标水平。将该样品干燥，然后在～1000°F（～538℃）下煅烧～3小时。所得产物标作催化剂C并具有下表1中概括的性质。
实施例4.P改性的二氧化硅粘合的ZSM-5催化剂的制备
将～80重量％合成后未经进一步处理的小晶体NaZSM-5沸石与～20重量％UltrasilTM二氧化硅的混合物挤出。将所述样品在氮气中在～1000°F（～538℃）下煅烧～3小时，与硝酸铵溶液交换，并在空气中在～1000°F（～538℃）下煅烧～3小时。将该挤出物通过水性初湿含浸法用磷酸浸渍至～0.96重量％磷的目标水平。将该样品干燥，然后在～1000°F（～538℃）下煅烧～3小时。所得产物标作催化剂D并具有下表1中概括的性质。
表1
实施例5.α测试
测试催化剂A-D的样品在～1000°F（～538℃）下在～100％H2O气氛中蒸汽处理～96小时后的正己烷裂化活性（α试验）。以α值表示的正己烷裂化活性可衡量催化剂的酸性。α值是指正己烷裂化的一级速率常数相对于二氧化硅-氧化铝标准的比率，并可以使用下述公式确定：
α=A*ln(1-X)/τ
其中：
A:包括参考速率常数&单位转化率≈-1.043
X:分数转化率
τ:停留时间=wt/(ρ*F)
ρ:填充密度[g/cm3]
F:气体流速[cm3/min]
wt:催化剂重量[g]
调节流速以保持大约5％至大约25％之间的转化率。在～4、～11、～18和～25分钟测量四个数据点。α值是在～18分钟的相对一级速率常数。
图1显示了α值，其通过进入挤出物配制物中的沸石的标称量标准化。含氧化铝的参比催化剂A表现出相对较低的α值，而无氧化铝的催化剂B、C和D表现出明显较高的α值。特别地，催化剂B、C和D在～1000°F（～538℃）下在～100％H2O气氛中处理～96小时后在正己烷裂化试验中表现出大于40的α值。令人惊讶的是，在催化剂配制物B和C中消除氧化铝粘合剂和在催化剂配制物D中用二氧化硅粘合剂替代氧化铝粘合剂使得蒸汽处理后的α值显著提高。
实施例6.微孔表面积
MTG反应通常在沸石微孔内发生。因此改进/使沸石微孔体积最大化有益于实现最大MTG活性。将催化剂A-D的样品在通过N2-BET测量微孔表面积之前在空气中在～1000°F（～538℃）下煅烧～6小时。通过挤出物中存在的沸石的含量将微孔表面积标准化，结果显示在图2中。没有添加粘合剂的配制物表现出比含有氧化铝粘合剂的参比配制物A高的微孔率。由于对MTG活性负责的酸位点被认为位于沸石微孔内，因此这一结果表明催化剂配制物B和C在MTG用途中优于含氧化铝的配制物A。结果是令人惊讶的，因为粘合剂粒子通常大于沸石的微通道的开口，因此没有预料到粘合剂渗入沸石微孔中。此外，沸石微孔被位于微通道孔口的粘合剂封堵预计在具有三维孔隙结构的沸石（例如MFI）中不会堵塞沸石微孔体积。优选的催化剂挤出物具有至少375平方米/克沸石的微孔表面积。
实施例7.2,2-二甲基丁烷扩散率
沸石的孔隙率在涉及沸石的反应中在产物选择性和焦炭形成中发挥作用。为了获得所需产物组成和/或防止焦炭形成，反应物快速扩散到沸石微孔中和产物从沸石微孔中快速扩散出来是有利的或甚至是必须的。将催化剂A-C的样品在测量2,2-二甲基丁烷（2,2-DMB）扩散率之前在空气中在～1000°F（～538℃）下煅烧～6小时。由2,2-DMB吸收速率和己烷吸收量使用下述公式计算扩散率：
D/r2=k*(2,2-DMB吸收速率/己烷吸收)
其中
D/r2:扩散率[10-6秒-1]
2,2-DMB吸收速率:[mg/g/min0.5]
己烷吸收：[mg/g]
K：比例常数
在两个单独实验中使用微量天平测量己烷和2,2-DMB吸收。在烃吸附之前，将大约50毫克催化剂样品在空气中加热～30分钟至～500℃，以除去水分和烃/焦炭杂质。对于己烷吸附，将样品冷却至～90℃，然后在～90℃下暴露于在氮气中的～100毫巴的己烷流中～40分钟。对于2,2-DMB吸附，在空气煅烧步骤后将样品冷却至～120℃，并暴露在～60torr（～8kPa）的2,2-二甲基丁烷压力下～30分钟。结果显示在图3中，从中可以看出催化剂B和C表现出比催化剂A高的2,2-DMB扩散率。在使用2,2-二甲基丁烷（22-DMB）作为烃时，优选的催化剂可有利地表现出大于1.2×10-2秒-1、例如大于1.5×10-2秒-1或大于2×10-2秒-1的烃扩散率。
实施例8.抗焦炭性
抗焦炭性可以是计划用于MTG反应的催化剂的重要性质。催化剂中的酸位点通常被认为不仅催化MTG反应，还催化焦炭形成，这最终使催化剂失活。为了确保连续过程，通常应将催化剂定期再生以除去焦炭。在α试验中保持正己烷裂化活性的能力用于衡量催化剂的结焦稳定性。
试验中所用的催化剂以与实施例1和2相同的方式制造，但在挤出物上分别含有～1.8重量％和～1.6重量％的较高的标称P载量。所得催化剂被标作催化剂A1和B1并具有下表2中所示的性质。
表2
催化剂 挤出物中的P含量，重量％ 粘合剂类型 粘合剂含量，重量％
A1 1.8 Al2O3 20
B1 1.6 无 0
分析表2中所列的样品A1和B1的抗焦炭性。将表2中的样品在～900°F（～482℃）下蒸汽处理～96小时，然后在上述α试验中评估它们的抗焦炭性。为了在正己烷裂化反应中评估催化剂的抗焦炭性，在～4、～11、～18和～25分钟测量的α值对照时间绘制，并通过下述公式中给出的指数函数拟合：
α = α 0 * e - ct 1 / 3
其中α0是在时间0的α值，且c是焦炭失活速率常数。
由于焦炭失活速率常数c可能对流速敏感，因此在四点测量过程中使流速保持恒定可能是重要的。结果显示在图4中。
催化剂A1和B1的α值分别为51和99。焦炭失活速率常数的评估表明初始α值α0分别为64和106。相应的焦炭失活速率常数分别为0.08和0.03。令人惊讶的是，表现出较高α和初始α值的样品B1以低于A1的焦炭失活常数为特征。优选催化剂B1具有较高的抗焦炭性，并以在α试验中小于0.05或小于0.04的焦炭失活速率常数为特征。
实施例9.P改性的ZSM-5/Versal-300氧化铝催化剂的制备
在研磨机中将～80重量％合成后未经进一步处理的NaZSM-5沸石（具有大约50的二氧化硅与氧化铝摩尔比，并含有其合成中所用的有机导向剂）与～20重量％VersalTM-300氧化铝粘合剂掺合。挤出该掺合物，并将所得挤出样品在氮气中在～1000°F（～538℃）下煅烧～3小时以分解有机模板。然后将煅烧的挤出物与硝酸铵溶液交换，以将沸石从钠形式转化成铵形式，此后将该挤出物在空气中在～1000°F（～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，通过氧化除去任何碳质沉积物（例如来自有机模板的分解和/或来自硝酸铵交换）。然后将由此获得的H-ZSM-5-Al2O3挤出物通过水性初湿含浸法用磷酸浸渍至～0.96重量％磷的目标水平。将该样品干燥，然后在空气中在～1000°F（～538℃）下煅烧另外～3小时。所得产物标作催化剂A”并具有下表3中概括的性质。
实施例10.P改性的非粘合的ZSM-5催化剂的制备
不用粘合剂，将合成后未经进一步处理的NaZSM-5沸石样品挤出。将该样品在氮气中在～1000°F（～538℃）下煅烧～3小时，与硝酸铵溶液交换，并在空气中在～1000°F（～538℃）下煅烧另外～3小时。将该挤出物通过水性初湿含浸法用磷酸浸渍至～1.2重量％磷的目标水平。将该样品干燥，然后在～1000°F（～538℃）下煅烧另外～3小时。所得产物标作催化剂B”并具有下表3中概括的性质。
实施例11.P改性的非粘合的小晶体ZSM-5催化剂的制备
不用粘合剂，将合成后未经进一步处理的小晶体NaZSM-5沸石样品挤出。将该样品在氮气中在～1000°F（～538℃）下煅烧～3小时，与硝酸铵溶液交换，并在空气中在～1000°F（～538℃）下煅烧另外～3小时。将该挤出物通过水性初湿含浸法用磷酸浸渍至～1.2重量％磷的目标水平。将该样品干燥，然后在～1000°F（～538℃）下煅烧另外～3小时。所得产物标作催化剂C”并具有下表3中概括的性质。
实施例12.P改性的二氧化硅粘合的ZSM-5催化剂的制备
将～80重量％合成后未经进一步处理的小晶体NaZSM-5沸石与～20重量％UltrasilTM二氧化硅的混合物挤出。将所述样品在氮气中在～1000°F（～538℃）下煅烧～3小时，与硝酸铵溶液交换，并在空气中在～1000°F（～538℃）下煅烧另外～3小时。将该挤出物通过水性初湿含浸法用磷酸浸渍至～0.96重量％磷的目标水平。将该样品干燥，然后在～1000°F（～538℃）下煅烧另外～3小时。所得产物标作催化剂D”并具有下表3中概括的性质。
对比例13.P改性的二氧化硅粘合的ZSM-5催化剂的制备
在研磨机中将～80重量％合成后未经进一步处理的NaZSM-5沸石（具有大约28的二氧化硅与氧化铝摩尔比，并含有其合成中所用的有机导向剂）与～20重量％UltrasilTM二氧化硅粘合剂掺合。挤出该掺合物，并将所得挤出样品在氮气中在～1000°F（～538℃）下煅烧～3小时。然后将煅烧的挤出物与硝酸铵溶液交换，然后在空气中在～1000°F（～538℃）下煅烧另外～3小时。将该挤出物然后通过水性初湿含浸法用磷酸浸渍至～0.96重量％磷的目标水平。将该样品干燥，然后在空气中在～1000°F（～538℃）下煅烧另外～3小时。所得产物标作催化剂E并具有下表3中概括的性质。
表3
Figure BDA0000492432700000141
实施例14.来自实施例9-13的样品的表征
对于根据实施例9-13制造并在上表3中详述的样品（分别为A”、B”、C”、D”和E），进行下述试验。根据实施例5对通过在～1000°F（～538℃）下在～100％H2O气氛中蒸汽处理～96小时的样品进行α测试。根据实施例6对煅烧样品进行微孔表面积测试。根据实施例7对于在测量前在空气中在～1000°F（～538℃）下煅烧～6小时的样品进行2,2-二甲基丁烷扩散率测试。但是，用于测量焦炭失活速率常数的抗焦炭性测试与实施例8类似但略微不同地进行：在样品在～1000°F（～538℃）下而非在～900°F（～482℃）下蒸汽处理～96小时后进行这些样品的抗焦炭性测试。另外，对煅烧样品进行这些样品的抗焦炭性测试。这些表征结果显示在下表4中。
表4
Figure BDA0000492432700000151
尽管已经参照具体实施方案描述和例示了本发明，但本领域普通技术人员会认识到，本发明可具有在本文中不一定例示的变动。因此，应该仅参考所附权利要求书确定本发明的真实范围。

Claims (14)

1.粘合的磷改性催化剂组合物，其包含具有至少40的二氧化硅与氧化铝摩尔比的沸石、含量为总催化剂组合物的大约0.1重量％至大约3重量％的磷、和基本无铝的粘合剂，其中在至少大约1000°F（大约538℃）的温度下煅烧至少大约3小时的所述粘合的催化剂表现出：
（i）在大约120℃的温度和大约60torr（大约8kPa）的2,2-二甲基丁烷压力下测量时大于1.5×10-2秒-1的2,2-二甲基丁烷扩散率，和
（ii）小于大约0.15的焦炭失活速率常数，
且其中所述粘合的催化剂组合物进一步表现出下述性质中的至少一种：
（a）至少375平方米/克的微孔表面积；
（b）至少40的在大约1000°F（大约538℃）下在大约100％蒸汽中蒸汽处理大约96小时后的α值；和
（c）在大约1000°F（大约538℃）下在大约100％蒸汽中蒸汽处理大约96小时后小于0.05的焦炭失活速率常数。
2.权利要求1的催化剂组合物，其中所述沸石的二氧化硅与氧化铝摩尔比为大约40至大约200。
3.权利要求1的催化剂组合物，其中所述沸石具有大约1至大约12的约束指数。
4.权利要求1的催化剂组合物，其中所述沸石包含ZSM-5。
5.权利要求1的催化剂组合物，其中所述粘合的催化剂组合物含有含量为总催化剂组合物的大约0.5重量％至大约2重量％的磷。
6.权利要求1的催化剂组合物，其中所述粘合剂以总催化剂组合物的大约1重量％至大约50重量％的量存在。
7.权利要求1的催化剂组合物，其中所述粘合剂以总催化剂组合物的大约5重量％至大约40重量％的量存在。
8.权利要求1的催化剂组合物，其中所述粘合剂包含二氧化硅。
9.权利要求1的催化剂组合物，其中在大约1000°F（大约538℃）下在大约100％蒸汽中蒸汽处理大约96小时后的α值为至少60。
10.权利要求1的催化剂组合物，其中在大约1000°F（大约538℃）下在大约100％蒸汽中蒸汽处理大约96小时后的焦炭失活速率常数小于0.04。
11.权利要求1的催化剂组合物，其中所述粘合的催化剂组合物表现出性质（a）至（c）中的至少两种.
12.权利要求1的催化剂组合物，其中所述粘合的催化剂组合物表现出所有性质（a）至（c）。
13.有机化合物转化法，其包括使原料与权利要求1的粘合的催化剂组合物在有机化合物转化条件下接触。
14.权利要求13的方法，其中所述有机化合物转化包括将甲醇转化成在汽油沸程中沸腾的烃。
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