CN103987456A - 制备磷改性的沸石催化剂的方法 - Google Patents

制备磷改性的沸石催化剂的方法 Download PDF

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CN103987456A
CN103987456A CN201280061236.5A CN201280061236A CN103987456A CN 103987456 A CN103987456 A CN 103987456A CN 201280061236 A CN201280061236 A CN 201280061236A CN 103987456 A CN103987456 A CN 103987456A
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zeolite
phosphorus
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B·瓦尔德鲁普
S·J·麦卡锡
G·曹
P·A·比伦贝格
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ExxonMobil Technology and Engineering Co
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Abstract

在制备磷改性的沸石催化剂的方法中，可使沸石晶体在不存在单独无机氧化物粘结剂或存在基本不含铝的单独无机氧化物粘结剂下成型为成型催化剂体。在将沸石晶体转化成氢形式并除去沸石晶体合成中所用的任何有机导向剂以后，可将成型催化剂体用磷化合物的水溶液处理，并可将处理的催化剂体加热以除去水并将磷化合物转化成氧化物形式。

Description

制备磷改性的沸石催化剂的方法
发明领域
本公开内容涉及制备磷改性的沸石催化剂的方法。
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、丙烯或甲醇与包含与无机氧化物粘结剂复合的沸石如ZSM-5的催化剂接触而制备芳烃的方法。催化剂通过用磷酸根离子来源，例如磷酸铵水溶液浸渍，其后煅烧产生磷氧化物而改性，其中磷氧化物的量为催化剂复合物的约0.05-50％，优选约0.7至约15重量％。
另外，美国专利No.7,662,737公开了制备结合型磷改性的沸石催化剂的方法，其中将沸石如ZSM-5(可以为NH4 +或H+形式)用磷化合物水溶液浆化，然后将水从浆料中除去以形成磷改性的沸石。然后将磷改性的预煅烧沸石与选自氧化铝、粘土、磷酸铝和/或二氧化硅-氧化铝的酸处理无机氧化物粘结剂材料混合。在任选挤出以后，将沸石-粘结剂混合物在约400℃或更高的温度下加热以形成结合型沸石催化剂，通常0.01至约0.15g磷/g沸石。该催化剂特别意欲用于将甲苯用甲醇烷基化制备二甲苯，而且据说也用于MTG方法中。制备磷改性甲苯甲基化催化剂的类似方法公开于美国专利Nos.7,368,410和7,507,685以及美国专利申请公开Nos.2007/0149384、2008/0275280和2009/0036723中。
美国专利No.7,285,511公开了改进沸石催化剂以提高其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摩尔比的无粘结剂ZSM-5型沸石和含磷化合物水溶液组成的浆料；和将水从浆料中除去以提供具有0.04g P/g沸石或更高磷含量和0.2ml/g或更小的孔体积的非蒸汽处理的磷处理的ZSM-5沸石。所得磷处理的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结剂如氧化铝、粘土或二氧化硅复合。制备磷改性的甲苯甲基化催化剂的类似方法公开于美国专利Nos.7,399,727中。
美国专利No6,504,072公开了通过使甲苯与甲醇在严格蒸汽处理的ZSM-5催化剂上反应而选择性制备对二甲苯，所述严格蒸汽处理的ZSM-5催化剂是与氧化物改进剂，优选磷氧化物组合的以控制蒸汽处理步骤期间催化剂的微孔体积减小。催化剂中磷的引入方便地通过使ZSM-5单独地或与粘结剂或基质材料组合地，与适当磷化合物的溶液接触，其后干燥和煅烧以将磷转化成氧化物形式而进行。
通过加入磷而将沸石催化剂改性的一个理想结果可以是当暴露于高温蒸汽时沸石损失其催化活性的倾向可被降低。然而，对开发其中由磷添加而产生的蒸汽稳定化可被改进/最大化的磷改性的沸石催化剂仍受到显著关注。
根据本发明，现在发现具有改进的蒸汽稳定性的沸石催化剂可通过将自结合或与基本不含铝的粘结剂结合的沸石催化剂进行磷处理而制备。
应当指出，本申请涉及各自在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，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。本申请还涉及5个其它共同未决国际(PCT)申请，其各自在与本申请相同的日期提交且要求前述美国临时专利申请的权益，并分别标题为“磷改性的沸石催化剂的制备方法”、“磷改性的沸石催化剂”、“磷改性的沸石催化剂”、“磷改性的沸石催化剂”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。
发明概述
一方面，本发明在于制备磷改性的沸石催化剂的方法，所述方法包括：(a)使合成的沸石晶体在不存在单独无机氧化物粘结剂或存在基本不含铝的单独无机氧化物粘结剂下成型为成型催化剂体；(b)将沸石晶体转化成氢形式；(c)除去沸石晶体合成中所用的任何有机导向剂；(d)将成型催化剂体用磷化合物的水溶液处理；和(e)将处理的催化剂体加热以除去水并将磷化合物转化成氧化物形式。
方便地，可使沸石晶体在包含小于5重量％，例如小于3重量％铝的单独无机氧化物粘结剂的存在下成型为成型催化剂体。
方便地，成型(a)可通过挤出进行。
在一些实施方案中，可在成型(a)以前将沸石晶体与二氧化硅粘结剂混合。
在一些实施方案中，另外地或者备选地，可在成型(a)以前进行转化(b)。
在一些实施方案中，另外地或者备选地，可在成型(a)以前进行除去(c)。
方便地，处理(d)可通过浸渍，例如用磷羟基酸(phosphorus oxyacid)的水溶液浸渍而进行。
方便地，催化剂体可包含约0.1至约3重量％的以磷的氧化物存在的元素磷。
方便地，(e)中的加热可在约350至约650℃的温度下进行约0.2至约5.0小时。
方便地，沸石可具有约20至约200，例如约20至约150的二氧化硅:氧化铝摩尔比。
方便地，沸石可包含ZSM-5，基本由ZSM-5组成或者为ZSM-5。
另一方面，本发明可在于通过本文所述方法制备的磷改性的沸石催化剂，和/或该催化剂在有机转化反应中，尤其是在甲醇转化成烃的方法中的用途。
实施方案详述
本文描述了制备磷改性的沸石催化剂的方法。在本发明方法中，磷的引入可在沸石已成型为成型催化剂体以后进行，所述成型在不存在单独无机氧化物粘结剂(自结合)或在单独无机氧化物粘结剂的存在下进行，所述在单独无机氧化物粘结剂可有利地基本不含铝。特别地，发现通过省去粘结剂或者通过使用基本不含铝的粘结剂，催化剂的热稳定性与包含相同量的磷的常规氧化铝结合型催化剂相比可被明显提高。
本发明方法可用于制备包含任何已知沸石或沸石混合物的磷改性的沸石催化剂。在一个实施方案中，本文所述催化剂可包含至少一种具有2-12的约束指数(Constraint Index，如美国专利No.4,016,218中所定义)的中孔沸石，基本由至少一种所述沸石组成或者为至少一种所述沸石。合适的中孔分子筛可包括但不限于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。
另外或者作为备选，本文所述催化剂可包含一种或多种具有小于2的约束指数的大孔沸石。合适的大孔分子筛可包括但不限于β沸石、沸石Y、超稳定Y(USY)、脱铝Y(Deal Y)、丝光沸石、ZSM-3、ZSM-4、ZSM-18、ZSM-20等及其组合。ZSM-14描述于美国专利No.3,923,636中。ZSM-20描述于美国专利No.3,972,983中。β沸石描述于美国专利Nos.3,308,069和RE28,341中。低钠超稳定Y分子筛(USY)描述于美国专利Nos.3,293,192和3,449,070中。脱铝Y沸石(Deal Y)可通过美国专利No.3,442,795中的方法制备。沸石UHP-Y描述于美国专利No.4,401,556中。丝光沸石为天然存在的材料，但也可以以合成形式得到，例如TEA-丝光沸石(即由包含四乙基铵导向剂的反应混合物合成制备)，其公开于美国专利Nos.3,766,093和3,894,104中。
进一步另外或者作为备选，本文所述催化剂可包含至少一种MCM-22族分子筛。如本文所用，术语“MCM-22族分子筛”(或者“MCM-22族的材料”或“MCM-22族材料”或“MCM-22族沸石”)包括如下中的一种或多种：
·由普通一级(first degree)结晶构建块(building block)晶胞构成的分子筛，所述晶胞具有MWW骨架拓扑。(晶胞为原子的空间排列，其如果铺展在三维空间中的话，描述晶体结构。这类晶体结构讨论于“Atlas of ZeoliteFramework Types”，第5版，2001中，通过引用将其全部内容并入本文中)；
·由普通二级构建块构成的分子筛，所述构建块为这类MWW骨架拓扑晶胞的2维平铺，从而形成一个晶胞厚度，优选一个c-晶胞厚度的单层；
·由普通二级构建块构成的分子筛，所述构建块为一个或多于一个晶胞厚度的层，其中多于一个晶胞厚度的层可由至少两层具有一个晶胞厚度的单层的堆叠、填充或结合而构成。这类二级构建块的堆叠可以为规则方式、不规则方式、无规方式或其任何组合；和
·由具有MWW骨架拓扑的晶胞的任何规则或无规2维或3维组合构成的分子筛。
MCM-22族的分子筛可包括具有如下X射线衍射图的那些分子筛，所述X射线衍射图包括12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07埃处的d间距最大值。用于表征材料的X射线衍射数据可通过使用铜的K-α双峰作为入射辐射的标准技术和装配有闪烁计数器和相关计算机的衍射仪作为收集系统而得到。
MCM-22族材料另外地或者作为备选地包括但不限于MCM-22(描述于美国专利No.4,954,325中)、PSH-3(描述于美国专利No.4,439,409中)、SSZ-25(描述于美国专利No.4,826,667中)、ERB-1(描述于欧洲专利No.0293032中)、ITQ-1(描述于美国专利No6,077,498中)、ITQ-2(描述于国际专利公开No.WO97/17290中)、MCM-36(描述于美国专利No.5,250,277中)、MCM-49(描述于美国专利No.5,236,575中)、MCM-56(描述于美国专利No.5,362,697中)、UZM-8(描述于美国专利No.6,756,030中)及其混合物。
在某些优选实施方案中，本文所述催化剂包含ZSM-5或者为ZSM-5。另外或者作为备选，本文所述催化剂可包含或者为具有约20至约200，例如约20至约150的二氧化硅:氧化铝摩尔比的沸石。
除沸石外，本发明方法中所用催化剂可包含基本不含铝的单独无机氧化物粘结剂。“基本不含”意指单独无机氧化物粘结剂应包含小于5重量％，例如小于3重量％、小于1重量％、小于0.5重量％、小于0.3重量％、小于0.1重量％、小于0.05重量％铝，或者完全不包含可测得的铝。合适的无机氧化物粘结剂的实例可包括但不必限于二氧化硅、二氧化钛、氧化锆等，及其相互的混合物以及和其它金属氧化物的混合物(这里也通常不包括氧化铝)。无机氧化物粘结剂可以以总催化剂的约5至约65重量％，例如约10至约35重量％的量存在。或者，本发明沸石催化剂可成型为成型催化剂体而不借助单独粘结剂，即催化剂可以为自结合的。关于富二氧化硅催化剂的制备的更多信息，参考美国专利No.4,582,815，通过引用将其全部内容并入本文中。
为制备所需磷改性的催化剂，可将目标沸石的合成晶体用溶剂，通常水以及如果合适的话基本不含铝的无机氧化物粘结剂制成浆料。然后使所得浆料成型为成型催化剂体，通常通过挤出进行，然后可将催化剂体用磷化合物如磷羟基酸的水溶液处理。磷处理可方便地通过浸渍进行。在磷处理以后，可将处理的催化剂体加热以除去水并将磷化合物转化成氧化物形式。加热可有利地在氧化环境如空气中在约350至约650℃的温度下进行合适的时间，例如约0.2至约5.0小时。通常，最终催化剂可包含约0.1至约3重量％的以磷氧化物存在的元素磷。
通常，但不总是，用于制备所需催化剂的所合成沸石晶体可包含用于合成沸石的有机导向剂。这类导向剂通常可阻塞沸石的孔，所以通常应在催化使用沸石以前除去。在这种情况下，尽管导向剂可在形成成型催化剂体以前除去，在一些优选实施方案中，导向剂可通过将成型催化剂体在氧化或非氧化环境(如空气)中在约400至约820℃的温度下加热合适的时间如约0.3至约3小时而除去。通常，加热除去有机导向剂可在成型催化剂体的磷处理以前进行。
另外，许多沸石合成方法可在碱性条件下在碱金属离子，尤其是钠离子的存在下进行。在这种情况下，所合成的沸石晶体通常可以为钠形式，所以应在使用以前应转化成催化活性氢形式。这种转化通常可通过与铵阳离子进行离子交换并加热以除去氨而实现，因此留下沸石的H+形式。另外，尽管可在催化剂成形以前在所合成的沸石晶体上进行这些步骤，但在一些优选实施方案中，铵交换和随后转化成氢形式可在成型催化剂体上进行。通常沸石转化成氢形式可在成型催化剂体的磷处理以前，但在除去沸石合成中所用有机导向剂以后进行。
通过本发明方法制备的磷改性ZSM-5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不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/或整合。
另外或者作为备选，本发明可包括以下实施方案中的一个或多个。
实施方案1.制备磷改性的沸石催化剂的方法，所述方法包括：(a)使沸石晶体在不存在单独无机氧化物粘结剂或存在基本不含铝的单独无机氧化物粘结剂下成型为成型催化剂体；(b)将沸石晶体转化成氢形式；(c)除去沸石晶体合成中所用的任何有机导向剂；(d)将成型催化剂体用磷化合物的水溶液处理；和(e)将处理的催化剂体加热以除去水并将磷化合物转化成氧化物形式。
实施方案2.实施方案1的方法，其中使沸石晶体在包含小于5重量％铝的单独无机氧化物粘结剂的存在下成型为成型催化剂体。
实施方案3.前述实施方案中任一项的方法，其中在成型(a)以前将沸石晶体与二氧化硅粘结剂混合。
实施方案4.前述实施方案中任一项的方法，其中成型(a)通过挤出进行。
实施方案5.前述实施方案中任一项的方法，其中在成型(a)以前进行转化(b)。
实施方案6.实施方案5的方法，其中在成型(a)以前进行除去(c)。
实施方案7.前述实施方案中任一项的方法，其中处理(d)通过浸渍，
例如用磷羟基酸的水溶液浸渍进行。
实施方案8.前述实施方案中任一项的方法，其中(e)中的加热在约350至约650℃的温度下进行约0.2至约5.0小时。
实施方案9.前述实施方案中任一项的方法，其中沸石具有约20至约200，例如约20至约150的二氧化硅:氧化铝摩尔比。
实施方案10.前述实施方案中任一项的方法，其中沸石包含ZSM-5。
实施方案11.通过前述实施方案中任一项的方法制备的磷改性的沸石催化剂。
实施方案12.有机化合物转化方法，其利用使原料与实施方案11的磷改性的沸石催化剂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
在实施例中，所用ZSM-5晶体为使用四丙基溴化铵作为结构导向剂制备的具有约50的二氧化硅:氧化铝摩尔比的所合成钠形式ZSM-5。
在实施例中，α值用于提供与标准催化剂相比，催化剂的催化裂化活性的指示，并帮助评估相对速率常数(正己烷转化率/体积催化剂/单位时间的速率)。α值基于二氧化硅-氧化铝裂化催化剂的活性，后者的α取值为1(速率常数≈0.016sec-1)。α试验描述于美国专利No.3,354,078；the Journalof Catalysis，4，527(1965)；6，278(1966)；和61，395(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在流过保持在～1000℉(～538℃)的反应器的He载气中～100托(～13kPa)己烷蒸气压力。
实施例1.在用氧化铝挤出期间将磷加入沸石中
首先将氧化铝(基于固体～200g)加入混合机中并干磨。然后加入去离子水(～100g)以将氧化铝润湿，其后加入一定量的磷酸(基于固体，分别～0、～61、～122或～183.2g)以实现目标磷含量。然后加入Na-ZSM-5晶体(基于固体～800g)和另外的去离子水，并将混合物研磨～10至30分钟以实现挤出所需的稠度。由此制得具有四种不同磷含量(分别～0、～1.7、～3.4和～4.2重量％)的混合物。然后将各混合物挤成～1/16”圆柱体。将挤出物在～250℉(～121℃)下干燥整夜(～8至16小时)，然后在氮气中在～1000℉(～538℃)下预煅烧～3小时。然后将各挤出物与1N硝酸铵水溶液交换两次。将所得交换的催化剂在～250℉(～121℃)下干燥整夜，然后在空气中在～1000℉(～538℃)下煅烧～3小时。
实施例2.将磷加入氧化铝结合型沸石
将ZSM-5(基于固体～800g)和VersalTM300氧化铝(基于固体～200g)加入混合机中并干磨。当研磨时，加入～492g去离子水以实现挤出所需的稠度。然后将混合物挤成～1/16”圆柱体。将挤出物在～250℉(～121℃)下干燥整夜(～8至16小时)，然后在氮气中在～1000℉(～538℃)下预煅烧～3小时。然后将挤出物与1N硝酸铵水溶液交换两次。将交换的催化剂在～250℉(～121℃)下干燥整夜，然后在空气中在～1000℉(～538℃)下煅烧～3小时。然后使用磷酸水溶液将挤出物借助初始润湿以～2、～4或～6重量％磷的目标含量(实际含量如下表1所述)浸渍。然后将浸渍的晶体在～250℉(～121℃)下干燥整夜，然后在空气中在～1000℉(～538℃)下煅烧～3小时。
实施例3.将磷加入二氧化硅结合型沸石中
将ZSM-5(基于固体～800g)和UltrasilTMVN3SP二氧化硅(基于固体～100g)加入混合机中并干磨。然后将LudoxTM-40二氧化硅(～100g)加入混合物中，其后加入～60g的～50重量％苛性碱(NaOH)溶液。当研磨时，加入～85g去离子水以实现挤出所需的稠度。然后将混合物挤成～1/16”圆柱体。将挤出物在～250℉(～121℃)下干燥整夜(～8至16小时)，然后在氮气中在～1000℉(～538℃)下预煅烧～3小时。然后将挤出物与1N硝酸铵水溶液交换两次。将交换的催化剂在～250℉(～121℃)下干燥整夜，然后在空气中在～1000℉(～538℃)下煅烧～3小时。然后使用磷酸水溶液将挤出物借助初始润湿以～2、～4或～6重量％磷的目标含量(实际含量如下表1所述)浸渍。然后将浸渍的晶体在～250℉(～121℃)下干燥整夜，然后在空气中在～1000℉(～538℃)下煅烧～3小时。
实施例4.将磷加入自结合型沸石中
将ZSM-5晶体(基于固体～1.4kg)加入混合机中并干磨。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水混合的～28g的～50重量％苛性碱(NaOH)溶液加入混合物中并研磨另外～5分钟。然后将混合物挤成～1/10”四叶形(quadralobes)。将挤出物在～250℉(～121℃)下干燥整夜(～8至16小时)，然后在氮气中在～1000℉(～538℃)下预煅烧～3小时。然后将挤出物与1N硝酸铵水溶液交换两次。将交换的催化剂在～250℉(～121℃)下干燥整夜，然后在空气中在～1000℉(～538℃)下煅烧～3小时。然后使用磷酸水溶液将挤出物借助初始润湿以～2、～4或～6重量％磷的目标含量(实际含量如下表1所述)浸渍。然后将浸渍的晶体在～250℉(～121℃)下干燥整夜，然后在空气中在～1000℉(～538℃)下煅烧～3小时。
实施例5：P稳定的催化剂的己烷裂化活性的测量
分析实施例1-4的含ZSM-5的挤出物的磷含量并在～1000℉(～538℃)和～14.7psia蒸汽分压下蒸汽处理～96小时。然后在例行α试验中以己烷裂化测量筛分所制得的和蒸汽处理过的催化剂的酸性活性。来自实施例1-4的挤出物的α值和磷含量显示于下表1中。结果显示，来自实施例1和2的含氧化铝的催化剂在蒸汽处理以后具有比来自实施例3和4的二氧化硅结合型和自结合型催化剂低得多的α活性。与在蒸汽处理以后保持～14和～11α值的不具有P的相同催化剂相比，具有约0.8重量％P的二氧化硅结合型和自结合型催化剂在蒸汽处理以后保留～110α值。
表1
催化剂 磷，重量％ α值(制得的) α值(蒸汽处理过的)
实施例1a 0.0 ～300 ～13
实施例1b ～1.7 ～270 ～5.3
实施例1c ～3.4 ～250 ～12
实施例1d ～4.2 ～240 ～19
实施例2a 0.0 ～320 ～13
实施例2b ～2.7 ～340 ～22
实施例2c ～4.2 ～210 ～38
实施例2d ～5.3 ～160 ～79
实施例3a 0.0 ～580 ～14
实施例3b ～0.8 ～240 ～110
实施例3c ～1.6 ～170 ～96
实施例3d ～2.4 ～99 ～26
实施例4a 0.0 ～540 ～11
实施例4b ～0.84 ～290 ～110
实施例4c ～1.67 ～160，～210 ～85
实施例4d ～2.47 ～70 ～47、～29
尽管本发明已通过参考特定实施方案进行了描述和和说明，本领域技术人员理解本发明本身适用于本文未举例说明的变化方案。为此，则应仅参见所附权利要求书来确定本发明的真实范围。

Claims (13)

1.制备磷改性的沸石催化剂的方法，所述方法包括：
(a)使沸石晶体在不存在单独无机氧化物粘结剂或存在基本不含铝的单独无机氧化物粘结剂下成型为成型催化剂体；
(b)将沸石晶体转化成氢形式；
(c)除去沸石晶体合成中所用的任何有机导向剂；
(d)将成型催化剂体用磷化合物的水溶液处理；和
(e)将处理的催化剂体加热以除去水并将磷化合物转化成氧化物形式。
2.根据权利要求1的方法，其中使沸石晶体在包含小于5重量％铝的单独无机氧化物粘结剂的存在下成型为成型催化剂体。
3.根据权利要求1或2的方法，其中在成型(a)以前将沸石晶体与二氧化硅粘结剂混合。
4.根据前述权利要求中任一项的方法，其中成型(a)通过挤出进行。
5.根据前述权利要求中任一项的方法，其中在成型(a)以前进行转化(b)。
6.根据权利要求5的方法，其中在成型(a)以前进行除去(c)。
7.根据前述权利要求中任一项的方法，其中处理(d)通过浸渍，例如用磷羟基酸的水溶液浸渍而进行。
8.根据前述权利要求中任一项的方法，其中(e)中的加热在约350至约650℃的温度下进行约0.2至约5.0小时。
9.根据前述权利要求中任一项的方法，其中沸石具有约20至约200，例如约20至约150的二氧化硅:氧化铝摩尔比。
10.根据前述权利要求中任一项的方法，其中沸石包含ZSM-5。
11.通过前述权利要求中任一项的方法制备的磷改性的沸石催化剂。
12.有机化合物转化的方法，其利用使原料与权利要求11的磷改性的沸石催化剂在有机化合物转化条件下接触。
13.根据权利要求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。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110876956A (zh) * 2018-09-06 2020-03-13 中国科学院大连化学物理研究所 一种用于乙醇脱水制乙烯反应zsm-11分子筛催化剂的改性方法

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150167588A1 (en) 2013-12-13 2015-06-18 Exxonmobil Research And Engineering Company Enhanced methane formation in reforming catalysts
WO2015094698A1 (en) 2013-12-20 2015-06-25 Exxonmobil Chemical Patents Inc. Process for converting oxygenates to aromatic hydrocarbons
EP3102552A1 (en) 2013-12-20 2016-12-14 ExxonMobil Research and Engineering Company Method for oxygenate conversion
WO2016105888A1 (en) 2014-12-22 2016-06-30 Exxonmobil Research And Engineering Company Conversion of oxygenates to aromatics
EP3237575A1 (en) * 2014-12-22 2017-11-01 ExxonMobil Research and Engineering Company Conversion of organic oxygenates to hydrocarbons
CN106146236B (zh) * 2015-05-15 2019-06-18 内蒙古丰汇化工有限公司 由甲醇两步法制备烃类产品的方法
BR112017002594A2 (pt) * 2015-12-17 2017-12-19 Gilead Sciences Inc compostos inibidores de cinase de ligação de tank
KR20190093620A (ko) 2016-12-07 2019-08-09 엑손모빌 리서치 앤드 엔지니어링 컴퍼니 방향족 생성을 위한 조합된 올레핀 및 산소화물 전환
EP3551729B1 (en) 2016-12-07 2022-08-03 ExxonMobil Technology and Engineering Company Integrated oxygenate conversion and olefin oligomerization
WO2018136242A1 (en) 2017-01-19 2018-07-26 Exxonmobil Research And Engineering Company Conversion of oxygenates to hydrocarbons with variable catalyst composition
US11918974B2 (en) * 2018-04-30 2024-03-05 The Regents Of The University Of Colorado Functionalization of zeolites
CN112585092A (zh) * 2018-08-27 2021-03-30 埃克森美孚研究工程公司 分子筛和制造分子筛的方法
US11084983B2 (en) 2019-01-24 2021-08-10 Exxonmobil Research And Engineering Company Fluidized bed conversion of oxygenates with increased aromatic selectivity
WO2022187320A1 (en) * 2021-03-02 2022-09-09 Basf Corporation Phosphorus modified uzm-35, methods of preparation, and methods of use thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4044065A (en) * 1974-09-23 1977-08-23 Mobile Oil Corporation Conversion utilizing a phosphorus-containing zeolite catalyst
US5573990A (en) * 1992-05-03 1996-11-12 Dalian Institute Of Chemical Physics Process for the conversion of methanol to light olefins and catalyst for such process
CN101500969A (zh) * 2005-08-03 2009-08-05 沙特基础工业公司 沸石催化剂和沸石催化剂的制备方法与用途
US20100113850A1 (en) * 2008-11-03 2010-05-06 Ashim Kumar Ghosh Stable Shape-Selective Catalyst for Aromatic Alkylation and Methods of Using and Preparing
CN101772476A (zh) * 2007-09-18 2010-07-07 旭化成化学株式会社 制造丙烯的方法
WO2010133436A1 (en) * 2009-05-19 2010-11-25 Shell Internationale Research Maatschappij B.V. Process for the manufacture of a formulated oxygenate conversion catalyst, formulated oxygenate conversion catalyst and process for the preparation of an olefinic product

Family Cites Families (97)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6503410A (zh) 1963-02-21 1965-09-20
US3442795A (en) 1963-02-27 1969-05-06 Mobil Oil Corp Method for preparing highly siliceous zeolite-type materials and materials resulting therefrom
USRE28341E (en) 1964-05-01 1975-02-18 Marshall dann
US3308069A (en) 1964-05-01 1967-03-07 Mobil Oil Corp Catalytic composition of a crystalline zeolite
US3354078A (en) 1965-02-04 1967-11-21 Mobil Oil Corp Catalytic conversion with a crystalline aluminosilicate activated with a metallic halide
US3293192A (en) 1965-08-23 1966-12-20 Grace W R & Co Zeolite z-14us and method of preparation thereof
US3702886A (en) 1969-10-10 1972-11-14 Mobil Oil Corp Crystalline zeolite zsm-5 and method of preparing the same
US3709979A (en) 1970-04-23 1973-01-09 Mobil Oil Corp Crystalline zeolite zsm-11
US3832449A (en) 1971-03-18 1974-08-27 Mobil Oil Corp Crystalline zeolite zsm{14 12
US3766093A (en) 1972-01-07 1973-10-16 Mobil Oil Corp Treatment of organic cationcontaining zeolites
US3894104A (en) 1973-08-09 1975-07-08 Mobil Oil Corp Aromatization of hetero-atom substituted hydrocarbons
US4016245A (en) 1973-09-04 1977-04-05 Mobil Oil Corporation Crystalline zeolite and method of preparing same
CA1040187A (en) 1973-09-07 1978-10-10 Mobil Oil Corporation Method of preparing a crystalline aluminosilicate zeolite
US3941871A (en) 1973-11-02 1976-03-02 Mobil Oil Corporation Crystalline silicates and method of preparing the same
US3923636A (en) 1974-06-03 1975-12-02 Texaco Inc Production of lubricating oils
US3906054A (en) * 1974-09-23 1975-09-16 Mobil Oil Corp Alkylation of olefins
US3972832A (en) 1974-09-23 1976-08-03 Mobil Oil Corporation Phosphorus-containing zeolite catalyst
NZ178543A (en) * 1974-09-23 1978-04-03 Mobil Oil Corp Conversion catalyst, crystalline alumin osilicate zeolite containing phosphorus
US3931349A (en) * 1974-09-23 1976-01-06 Mobil Oil Corporation Conversion of methanol to gasoline components
US3972983A (en) 1974-11-25 1976-08-03 Mobil Oil Corporation Crystalline zeolite ZSM-20 and method of preparing same
US4016218A (en) 1975-05-29 1977-04-05 Mobil Oil Corporation Alkylation in presence of thermally modified crystalline aluminosilicate catalyst
CA1064890A (en) 1975-06-10 1979-10-23 Mae K. Rubin Crystalline zeolite, synthesis and use thereof
PL199748A1 (pl) * 1976-07-19 1978-04-24 Mobil Oil Corp Sposob selektywnego wytwarzania p-dwualkilobenzenow
US4143084A (en) * 1976-07-19 1979-03-06 Mobil Oil Corporation Di-alkylbenzene isomer mixtures
US4035430A (en) * 1976-07-26 1977-07-12 Mobil Oil Corporation Conversion of methanol to gasoline product
EP0007126A1 (en) * 1978-07-06 1980-01-23 Union Carbide Corporation Cumene synthesis process
US4234231A (en) 1978-12-06 1980-11-18 Mobil Oil Corporation Method for restoring a leached formation
US4197413A (en) * 1978-12-14 1980-04-08 Mobil Oil Corporation Production of 3-methylphenol
US4423266A (en) * 1980-10-08 1983-12-27 Mobil Oil Corporation Extending isomerization catalyst life by treating with phosphorous and/or steam
US4356338A (en) * 1979-07-27 1982-10-26 Mobil Oil Corporation Extending catalyst life by treating with phosphorus and/or steam
US4401556A (en) 1979-11-13 1983-08-30 Union Carbide Corporation Midbarrel hydrocracking
US4400571A (en) * 1981-04-27 1983-08-23 Uop Inc. Hydrocarbon isomerization process
DE3117135A1 (de) 1981-04-30 1982-11-18 Bayer Ag, 5090 Leverkusen Kristallines alumosilicat, verfahren zu dessen herstellung sowie dessen verwendung zur katalytischen umwandlung von methanol und/oder dimethylether in kohlenwasserstoffe
US4429176A (en) * 1982-02-08 1984-01-31 Mobil Oil Corporation Active zeolite catalysts of improved stability
US4409132A (en) * 1982-03-18 1983-10-11 Mobil Oil Corporation Organophosphorus-treated zeolite catalysts for para-selective aromatics conversion
US4404414A (en) * 1982-09-28 1983-09-13 Mobil Oil Corporation Conversion of methanol to gasoline
DE3370469D1 (en) * 1982-11-16 1987-04-30 Hoechst Ag Aluminium silicates with a zeolite structure and process for their preparation
DK149326C (da) 1984-01-10 1986-09-15 Haldor Topsoe As Fremgangsmaade til fremstilling af katalysatorer til anvendelse ved ethersyntese
US4556477A (en) 1984-03-07 1985-12-03 Mobil Oil Corporation Highly siliceous porous crystalline material ZSM-22 and its use in catalytic dewaxing of petroleum stocks
JPS6115848A (ja) * 1984-06-30 1986-01-23 Agency Of Ind Science & Technol リン酸カルシウム変性ゼオライト型触媒による低級オレフインの製造方法
US4582815A (en) 1984-07-06 1986-04-15 Mobil Oil Corporation Extrusion of silica-rich solids
US4560542A (en) * 1984-12-06 1985-12-24 Exxon Research And Engineering Co. Method for the preparation of zeolites using a low water low alkali metal content gel
US4665249A (en) * 1984-12-19 1987-05-12 Mobil Oil Corporation Method for feeding an MTG conversion reactor
US4665251A (en) 1985-06-12 1987-05-12 Mobil Oil Corporation Aromatization reactions with zeolites containing phosphorus oxide
US4590321A (en) 1985-06-12 1986-05-20 Mobil Oil Corporation Aromatization reactions with zeolites containing phosphorus oxide
US4826667A (en) 1986-01-29 1989-05-02 Chevron Research Company Zeolite SSZ-25
US4954325A (en) 1986-07-29 1990-09-04 Mobil Oil Corp. Composition of synthetic porous crystalline material, its synthesis and use
IT1205681B (it) 1987-05-26 1989-03-31 Eniricerche Spa Materiale sintetico cristallino poroso contenente ossidi di silicio e boro
US5250277A (en) 1991-01-11 1993-10-05 Mobil Oil Corp. Crystalline oxide material
GB9101456D0 (en) * 1991-01-23 1991-03-06 Exxon Chemical Patents Inc Process for producing substantially binder-free zeolite
US5110776A (en) * 1991-03-12 1992-05-05 Mobil Oil Corp. Cracking catalysts containing phosphate treated zeolites, and method of preparing the same
AU652222B2 (en) * 1991-03-12 1994-08-18 Mobil Oil Corporation Preparation of cracking catalysts, and cracking process using them
US5171921A (en) * 1991-04-26 1992-12-15 Arco Chemical Technology, L.P. Production of olefins
JPH04371231A (ja) * 1991-06-18 1992-12-24 N E Chemcat Corp 排気ガス浄化用触媒
US5236575A (en) 1991-06-19 1993-08-17 Mobil Oil Corp. Synthetic porous crystalline mcm-49, its synthesis and use
CN1039392C (zh) 1992-09-22 1998-08-05 中国科学院大连化学物理研究所 甲醇转化为轻烯烃的催化剂和反应工艺
JPH06238131A (ja) * 1992-12-24 1994-08-30 Tosoh Corp 窒素酸化物の除去方法
AU668614B2 (en) * 1992-12-24 1996-05-09 Tosoh Corporation Process for removing nitrogen oxides from oxygen rich exhaust gas
US5362697A (en) 1993-04-26 1994-11-08 Mobil Oil Corp. Synthetic layered MCM-56, its synthesis and use
US5457078A (en) * 1993-11-29 1995-10-10 Mobil Oil Corporation Manufacture of improved zeolite Beta catalyst
WO1996016004A2 (en) * 1994-11-23 1996-05-30 Exxon Chemical Patents Inc. Hydrocarbon conversion process using a zeolite bound zeolite catalyst
CN1049406C (zh) * 1995-10-06 2000-02-16 中国石油化工总公司 具有mfi结构含磷和稀土的分子筛
ES2124154B1 (es) 1995-11-08 1999-12-01 Univ Politecnica De Valencia C Metodo de preparaciion y propiedades cataliticas de un solido microporoso con alta superficie externa.
ES2105982B1 (es) 1995-11-23 1998-07-01 Consejo Superior Investigacion Zeolita itq-1
KR0165014B1 (ko) * 1996-03-11 1999-01-15 선우현범 섬유상 제올라이트 zsm-5 및 그 제조 방법
US6423879B1 (en) 1997-10-02 2002-07-23 Exxonmobil Oil Corporation Selective para-xylene production by toluene methylation
US6417421B1 (en) 1998-03-03 2002-07-09 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and process therefor and therewith
US6187983B1 (en) * 1998-04-29 2001-02-13 Exxon Chemical Patents Inc Converting oxygenates to olefins in the presence of electromagnetic energy
US20020049133A1 (en) * 1999-03-02 2002-04-25 Michael S. Ziebarth High zeolite content and attrition resistant catalyst, methods for preparing the same and catalyzed processes therewith
US6835863B2 (en) * 1999-07-12 2004-12-28 Exxonmobil Oil Corporation Catalytic production of light olefins from naphtha feed
EP1116519A1 (en) 2000-01-12 2001-07-18 Akzo Nobel N.V. Solid-state phosphorous activation of crystalline porous silicates
US7125818B2 (en) * 2002-10-08 2006-10-24 Exxonmobil Research & Engineering Co. Catalyst for wax isomerate yield enhancement by oxygenate pretreatment
US6756030B1 (en) 2003-03-21 2004-06-29 Uop Llc Crystalline aluminosilicate zeolitic composition: UZM-8
US7060864B2 (en) 2003-09-30 2006-06-13 Saudi Basic Industries Corporation Toluene methylation process
CN1257769C (zh) 2003-10-31 2006-05-31 中国石油化工股份有限公司 一种含磷和金属组分的mfi结构分子筛及其应用
US7285511B2 (en) 2004-04-23 2007-10-23 Saudi Basic Industries Corporation Method of modifying zeolite catalyst
US7399727B2 (en) * 2004-04-23 2008-07-15 Saudi Basic Industries Corporation Zeolite catalyst and method
US7375048B2 (en) * 2004-04-29 2008-05-20 Basf Catalysts Llc ZSM-5 additive
KR100632563B1 (ko) * 2004-09-10 2006-10-09 에스케이 주식회사 접촉 분해용 고체산 촉매 및 이를 이용하여 전범위납사로부터 경질 올레핀을 선택적으로 제조하는 공정
US7304194B2 (en) 2005-05-05 2007-12-04 Saudi Basic Industries Corporation Hydrothermal treatment of phosphorus-modified zeolite catalysts
CN100391610C (zh) 2005-08-15 2008-06-04 中国石油化工股份有限公司 含分子筛的催化裂解流化床催化剂
BRPI0505365A (pt) 2005-12-01 2007-09-25 Petroleo Brasileiro Sa processo de obtenção de zeólitas mais resistentes à desativação hidrotérmica
US7662737B2 (en) 2005-12-22 2010-02-16 Saudi Basic Industries Corporation Bound phosphorus-modified zeolite catalyst, method of preparing and method of using thereof
CN101134172B (zh) 2006-08-31 2010-10-27 中国石油化工股份有限公司 一种烃类转化催化剂
CN1915821A (zh) * 2006-09-06 2007-02-21 北京盛大京泰化学研究所 一种磷改性的zsm－5分子筛的制备方法
EP2025402A1 (en) 2007-07-31 2009-02-18 Total Petrochemicals Research Feluy Phosphorus modified molecular sieves, their use in conversion of organics to olefins
US7563740B2 (en) 2006-12-19 2009-07-21 Lyondell Chemical Technology, L.P. Direct epoxidation process
EP2036873A1 (en) * 2007-09-12 2009-03-18 Total Petrochemicals Research Feluy Use of phosphorus modified molecular sieves in conversion of organics to olefins
JP5355910B2 (ja) * 2008-03-13 2013-11-27 旭化成ケミカルズ株式会社 シリカ成形体
EP2082801A1 (en) 2008-01-25 2009-07-29 Total Petrochemicals Research Feluy Process for obtaining modified molecular sieves
CN101723775B (zh) * 2008-11-04 2013-05-22 杭州林达化工技术工程有限公司 甲醇或/和二甲醚制烃类的方法和设备
CN101492349B (zh) * 2009-03-13 2011-11-09 清华大学 一种节能环保型甲醇脱水联产燃精二甲醚的生产工艺
US8062987B2 (en) * 2009-10-05 2011-11-22 Saudi Basic Industries Corporation Phosphorus-containing zeolite catalysts and their method of preparation
CN102049293B (zh) * 2009-10-27 2012-11-14 中国石油化工股份有限公司 Zsm-5/a1po4-5双结构分子筛和甲醇制汽油的催化剂和方法
US8906224B2 (en) * 2009-12-23 2014-12-09 Exxonmobil Research And Engineering Company Sweet or sour service catalytic dewaxing in block mode configuration
TWI473651B (zh) * 2010-11-25 2015-02-21 Asahi Kasei Chemicals Corp Silica shaped body, method for producing the same, and production method of propylene using silica molded body
JP2012139640A (ja) * 2010-12-28 2012-07-26 Jx Nippon Oil & Energy Corp 単環芳香族炭化水素製造用触媒および単環芳香族炭化水素の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4044065A (en) * 1974-09-23 1977-08-23 Mobile Oil Corporation Conversion utilizing a phosphorus-containing zeolite catalyst
US5573990A (en) * 1992-05-03 1996-11-12 Dalian Institute Of Chemical Physics Process for the conversion of methanol to light olefins and catalyst for such process
CN101500969A (zh) * 2005-08-03 2009-08-05 沙特基础工业公司 沸石催化剂和沸石催化剂的制备方法与用途
CN101772476A (zh) * 2007-09-18 2010-07-07 旭化成化学株式会社 制造丙烯的方法
US20100113850A1 (en) * 2008-11-03 2010-05-06 Ashim Kumar Ghosh Stable Shape-Selective Catalyst for Aromatic Alkylation and Methods of Using and Preparing
WO2010133436A1 (en) * 2009-05-19 2010-11-25 Shell Internationale Research Maatschappij B.V. Process for the manufacture of a formulated oxygenate conversion catalyst, formulated oxygenate conversion catalyst and process for the preparation of an olefinic product

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GUOLIANG ZHAO等: "Effect of phosphorus on HZSM-5 catalyst for C4-olefin cracking reactions to produce propylene", 《JOURNAL OF CATALYSIS》 *
曾昭槐: "《择形催化》", 31 May 1994, 中国石化出版社 *
毛东森等: "分子筛晶粒大小及磷改性对ZSM-5催化甲醇转化制丙烯的影响甲醇转化制丙烯的影响", 《石油学报（石油加工）》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110876956A (zh) * 2018-09-06 2020-03-13 中国科学院大连化学物理研究所 一种用于乙醇脱水制乙烯反应zsm-11分子筛催化剂的改性方法
CN110876956B (zh) * 2018-09-06 2021-08-27 中国科学院大连化学物理研究所 一种用于乙醇脱水制乙烯反应zsm-11分子筛催化剂的改性方法

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ZA201403600B (en) 2018-11-28
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Application publication date: 20140813