CN103945939A - 磷改性沸石催化剂 - Google Patents

磷改性沸石催化剂 Download PDF

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CN103945939A
CN103945939A CN201280051031.9A CN201280051031A CN103945939A CN 103945939 A CN103945939 A CN 103945939A CN 201280051031 A CN201280051031 A CN 201280051031A CN 103945939 A CN103945939 A CN 103945939A
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carbon monoxide
zeolite
olefin polymeric
catalyst
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T·W·比特尔
S·J·麦卡锡
M·达格
B·瓦尔德鲁普
K·J·希基
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ExxonMobil Technology and Engineering Co
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Abstract

本发明涉及结合型磷改性催化剂组合物，所述组合物包含具有至少40的二氧化硅:氧化铝摩尔比的沸石和具有小于200m2/g的表面积的粘合剂，其中结合催化剂组合物显示出中孔孔径分布，其中小于20%的中孔在约100%蒸汽中在约1000°F(约538℃)下蒸约96小时以前具有10nm以下的尺寸，且多于60%的中孔在在约100%蒸汽中在约1000℉(约538℃)下蒸约96小时以后具有至少21nm的尺寸。

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。
另外，美国专利申请公开No.2010/0168489公开了结合型磷改性沸石催化剂，其中在与磷改性沸石结合以前将粘合剂材料用无机酸处理。认为合适的粘合剂材料包括无机氧化物，例如氧化铝、粘土、磷酸铝和二氧化硅-氧化铝。在实施例中，粘合剂材料为可作为HiQTM-40品级(具有250m2/g的表面积)由Alcoa得到的拟勃姆石型氧化铝。在任选挤出以后，将沸石-粘合剂混合物在约400℃或更高的温度下加热以形成通常0.01-0.15g磷/g沸石的结合型沸石催化剂。该催化剂特别意欲用于将甲苯用甲醇烷基化以制备二甲苯，但认为也用于MTG方法中。
在甲醇转化成汽油(MTG)中，认为该反应通过沸石催化剂的微孔内部由骨架铝产生的酸位催化。磷的作用可以是稳定沸石骨架铝以防通过作为该方法副产物产生的高温蒸汽脱铝。粘合剂材料的作用可以是帮助保持催化剂床中催化剂颗粒的完整性。然而，令人惊讶的是，现在发现结合型磷改性沸石催化剂对于MTG反应的活性可通过使用具有较低表面积(小于200m2/g)和特定中孔分布的粘合剂而增强。该结果是令人惊讶的，因为粘合剂颗粒通常可能比沸石微通道的开孔更大，因此在这种情况下，粘合剂不预先渗入沸石微孔中。此外，位于微通道的孔口处的沸石微孔被粘合剂堵塞不预期封闭有利于MTG反应的具有三维孔结构的沸石中的沸石微孔体积，如MFI沸石中的。
发明概述
一方面，本发明在于结合型磷改性催化剂组合物，所述组合物包含具有至少40，例如约40至约200的二氧化硅:氧化铝摩尔比的沸石和具有小于200m2/g，例如小于150m2/g或者小于或等于100m2/g的表面积的粘合剂，其中结合型催化剂组合物具有中孔孔径分布，其中小于20%的中孔在约100%蒸汽中在约1000℉(约538℃)下蒸约96小时以前具有10nm以下的尺寸，且多于60%的中孔在约100%蒸汽中在约1000℉(约538℃)下蒸约96小时以后具有至少21nm的尺寸。
在一些实施方案中，沸石可具有约1至约12的约束指数和/或可包含ZSM-5。
另外或者作为选择，催化剂组合物在～100%蒸汽中在～1000℉(～538℃)下蒸～96小时以后具有至少20，例如至少40的α值。
另外或者作为选择，催化剂组合物可具有至少375m2/g的微孔表面积，和/或可包含总催化剂组合物的约0.1至约3重量%，例如约0.5至约2重量%的量的磷。
另外或者作为选择，粘合剂可包含氧化铝和/或可以以总催化剂组合物的约1至约50重量%，例如约5至约40重量%的量存在。
另外或者作为选择，催化剂可具有当在～120℃的温度和～60托(～8kPa)的2,2-二甲基丁烷压力下测量时大于1×10-2sec-1的2,2-二甲基丁烷扩散系数。
另一方面，本发明可包括本文所述未结合型催化剂组合物在有机转化反应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，其各自在与此相同日期提交且要求前述美国临时专利申请的利益，且标题分别为“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显示比较实施例1-2的催化剂在～100%蒸汽中在～1000℉(～538℃)下蒸～96小时以后的标准化α值的图。
图2显示比较通过沸石含量标准化，实施例1-2的催化剂的微孔表面积的图。
图3显示比较实施例1-2的催化剂在～120℃的温度和～60托(～8kPa)的2,2-二甲基丁烷压力下的2,2-二甲基丁烷扩散系数的图。
图4显示比较实施例1-2的催化剂的中孔孔径分布的图。
图5显示比较实施例1-2的催化剂在～100%蒸汽中在～1000℉(～538℃)下蒸～96小时以后的中孔孔径分布的图。
实施方案详述
本文描述用于多种有机转化反应中的任一种，特别但不仅仅在甲醇转化成沸点在汽油沸程内的烃中的结合型磷稳定化沸石催化剂组合物。
本发明催化剂组合物中所用沸石通常可具有至少40，例如约40至约200的二氧化硅:氧化铝摩尔比。一般而言，沸石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。在某些实施方案中，沸石可包含ZSM-5、基本由ZSM-5组成，或者为ZSM-5。
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，这可能暗示从例如碱(例如钠)形式转化沸石。这可容易地通过例如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。如果有机结构导向剂用于合成沸石，则另外的煅烧可能是理想的以除去有机结构导向剂。
沸石可与粘合剂，通常氧化铝、二氧化硅或二氧化硅-氧化铝结合，可选择粘合剂以具有小于200m2/g，例如小于150m2/g或者小于或等于100m2/g的表面积。合适的粘合剂可包含或者为PuralTM200和/或VersalTM300氧化铝。一般而言，粘合剂可以以总催化剂组合物的约1至约50重量%，例如约5至约40重量%的量存在。
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%元素磷，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/或将沸石和粘合剂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，磷添加可通过将最终催化剂组合物(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次膦酸[H2PO(OH)]、膦酸[HPO(OH)2]和磷酸[PO(OH)3]、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。
本文所用结合型磷稳定化沸石催化剂组合物可通过以下性能中的至少一种，优选至少两种表征：(a)至少375m2/g的微孔表面积；(b)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1.2×10-2sec-1的2,2-二甲基丁烷扩散系数；(c)在～100%蒸汽中在～1000℉(～538℃)下蒸～96小时以后，至少20，例如至少40的α值；(d)中孔孔径分布，其中小于20%的中孔具有10nm以下的尺寸；和(e)中孔孔径分布，其中在约100%蒸汽中在约1000℉(约538℃)下蒸约96小时以后，多于60%的中孔具有至少21nm的尺寸。本领域技术人员应当理解不同于性能(c)和(e)，以上性能(a)、(b)和(d)在催化剂组合物的任何蒸以前测量。
在这些性能中，微孔孔隙率和2,2-二甲基丁烷扩散系数可由大量因素决定，包括但未必限于沸石的孔径大小和晶体大小以及催化剂颗粒表面上沸石孔的可用性。中孔孔径分布可主要由粘合剂的表面积测定。鉴于本文公开内容是关于使用较低表面积粘合剂，所以生产具有所需中孔孔径分布、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。
α值可有利地为与标准二氧化硅-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 ofCatalysis，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可包括～538℃的恒定温度和可变的流速，如theJournal of Catalysis，第61卷，第395页所述。较高的α值通常可相当于更活性的裂化催化剂。由于本发明催化剂组合物可意欲用于其中沸石可经受沸石的水热脱铝的反应如MTG中，重要的是催化剂组合物在～100%蒸汽中在～1000℉(～538℃)下蒸～96小时以后保持显著的α值，即至少20。
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.结合型磷改性催化剂组合物，其包含具有至少40，例如约40至约200的二氧化硅:氧化铝摩尔比的沸石和具有小于200m2/g，例如小于150m2/g或者小于或等于100m2/g的表面积的粘合剂，其中结合型催化剂组合物显示出中孔孔径分布，其中小于20%的中孔在约100%蒸汽中在约1000℉(约538℃)下蒸约96小时以前具有10nm以下的尺寸，且多于60%的中孔在约100%蒸汽中在约1000℉(约538℃)下蒸约96小时以后具有至少21nm的尺寸。
实施方案2.实施方案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3.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。
实施方案4.前述实施方案中任一项的催化剂组合物，其中结合型催化剂组合物在约100%蒸汽中在约1000℉(约538℃)下蒸约96小时以后显示出至少20，例如至少40的α值。
实施方案5.前述实施方案中任一项的催化剂组合物，其中结合型催化剂组合物显示出至少375m2/g的微孔表面积。
实施方案6.前述实施方案中任一项的催化剂组合物，其进一步包含总催化剂组合物的约0.1至约3重量%，例如约0.5至约2重量%的量的磷。
实施方案7.前述实施方案中任一项的催化剂组合物，其中粘合剂以总催化剂组合物的约1至约50重量%，例如约5至约40重量%的量存在。
实施方案8.前述实施方案中任一项的催化剂组合物，其中粘合剂包含氧化铝。
实施方案9.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，沸石具有大于1.2×10-2sec-1的2,2-二甲基丁烷扩散系数。
实施方案10.有机化合物转化方法，其使原料与前述实施方案中任一项的结合型催化剂组合物在有机化合物转化条件下接触。
实施方案11.实施方案10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。
现在参考实施例和附图更特别地描述本发明。
实施例
实施例1.ZSM-5/VersalTM-300氧化铝催化剂的制备
将～80重量%的所合成NaZSM-5沸石(包含用于其合成中的有机导向剂且具有汇总于下表1中的性能)的混合物在研磨机中与～20重量%VersalTM-300氧化铝粘合剂混合。其中所用VersalTM-300氧化铝显示出约250-300m2/g的表面积。
将混合物挤出并将所得挤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成含碳沉积物。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，其后将挤出物在空气中在～1000℉(～538℃)下煅烧～3小时以将沸石从铵形式转化成氢形式。同时，含碳沉积物通过氧化而除去。然后将因此所得H-ZSM-5-Al2O3挤出物借助含水初湿浸渍(aqueous incipient wetness impregnation)而用磷酸浸渍至～0.96重量%的目标磷水平。将试样干燥，然后在空气中在～1000℉(～538℃)下煅烧～3小时。所得产物标记为催化剂A且具有汇总于下表1中的性能。
实施例2.ZSM-5/PuralTM200氧化铝催化剂的制备
重复实施例1的方法，不同之处在于PuralTM200氧化铝代替作为氧化铝粘合剂。其中所用PuralTM200氧化铝显示出约90m2/g的表面积。所得产物标记为催化剂B且具有汇总于下表1中的性能。
表1
*在～100%蒸汽中在～1000℉(～538℃)下蒸～96小时以后的α值/g沸石
实施例3.α试验
MTG反应通常在酸性位催化。催化剂的酸度可倾向于随着MTG反应器中的运行时间而降低，这可能是由于沸石水热脱铝的影响。为评估催化剂经得住MTG反应器中的水热应力的能力，MTG反应器中的蒸的条件通过实验室反应器中的水热处理评估。然后通过其正己烷裂化活性而测量催化剂的酸度(α试验)。
表示为α值的正己烷裂化活性可以为催化剂酸度的度量。α值定义为正己烷裂化的第一级速率常数相对于二氧化硅-氧化铝标准的比，并可使用下式测定：
α=A*ln(1-X)/τ
其中：
A：包括参比速率常数&单位换算≈-1.043
X：转换分数
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]
调整流速以保持5-25%的转化率。在～4、～11、～18和～25分钟时取得四个数据点。α值是在～18分钟时的相对第一级速率常数。
在α试验以前，将试样在～100%H2O气氛中在～1000°F(～538℃)下蒸～96小时。α活性(值)通过挤出物制备中所用沸石的标称量标准化。结果显示于上表1和图1中，并证明含有氧化铝的参比催化剂A显示出较低的α值(18)，而含有氧化铝的催化剂挤出物B显示出显著更高的α值(47)。令人惊讶的是用不同类型的氧化铝粘合剂代替标准氧化铝粘合剂导致蒸以后α活性(值)的戏剧性提高。
实施例4.微孔表面积
MTG反应可倾向于在沸石微孔内部进行。因此，可能有利的是改进沸石微孔体积/使沸石微孔体积最大化以实现最大的MTG活性。在通过
N2-BET测量微孔表面以前，将选自催化剂A和B的试样在真空(例如至多10-4大气压，相当于至多10Pa，或者作为选择至多10-5大气压，相当于至多1Pa)下在～350℃下煅烧～4小时。微孔表面积通过存在于催化剂A和B中的沸石含量而标准化，结果显示于上表1和图2中。可以看出催化剂B显示出与包含标准氧化铝粘合剂的参比催化剂A相比更高的微孔孔隙率。由于造成MTG活性的酸位被认为位于沸石微孔中，该结果表明相对于催化剂A中的标准氧化铝粘合剂，催化剂B在MTG应用中的优点。该结果是令人惊讶的，因为粘合剂颗粒通常可比沸石的微通道的开口更大，因此粘合剂不预先渗入沸石微孔中。此外，位于微通道的孔口处的沸石微孔被粘合剂堵塞不预期封闭具有三维孔结构的沸石中的沸石微孔体积，如MFI中的。因此，改变氧化铝粘合剂的类型会导致微孔表面积提高不是显而易见的。
实施例5.2,2-二甲基丁烷扩散系数
沸石的孔隙率在涉及沸石的反应中在产物选择性和/或焦炭形成方面可起作用。反应物快速扩散到产物中和从沸石微孔中扩散出可能是理想的以得到所需产物组成和/或防止焦炭形成。在测量2,2-二甲基丁烷(2,2-DMB)扩散系数以前，将催化剂A和B的试样在空气中在～1000°F(～538℃)下煅烧～6小时。扩散系数使用下式由2,2-DMB吸收速率和己烷吸收量计算：
D/r2=k*(2,2-DMB吸收速率/己烷吸收量)
其中：
D/r2：扩散系数[10-6sec-1]
2,2-DMB吸收速率：[mg/g/min0.5]
己烷吸收量：[mg/g]
k：比例常数
己烷和2,2-DMB吸收量在两个分开的试验中使用微量天平测量。在烃吸附以前，将约50mg特定催化剂试样在空气中加热～30分钟至～500℃，以除去水分和烃/焦炭杂质。对于己烷吸附，将特定试样冷却至～90℃，随后在氮气中在～90℃下暴露于～100毫巴己烷流下～40分钟。对于2,2-DMB吸附，将特定试样在空气煅烧步骤以后冷却至～120℃，并暴露于～60托(～8kPa)的2,2-二甲基丁烷压力下～30分钟。结果显示于上表1和图2中。可以看出催化剂B显示出比催化剂A更高的2,2-DMB吸收量。用粘合剂将沸石配制成挤出物可导致孔口的阻塞或变窄。优选催化剂B的较高扩散系数表示更大的无障碍沸石通道和孔开口程度。优选的氧化铝粘合剂B显示出具有与活性沸石组分的负相互作用。用氧化铝粘合剂设计会显示出这些有利性能的挤出物是创造性的。
实施例6.中孔孔隙率
中孔孔隙率为有利于反应物扩散至沸石表面并将产物从沸石表面释放的性能。中孔孔隙率在本文中定义为具有约2nm至约50nm的直径的孔，并可由N2-BET的滞后测量。较大的孔可容许反应物和产物更快地输送至沸石表面和从沸石表面输送出来。图4显示在空气中在～1000°F(～538℃)下煅烧～6小时以后两种催化剂A和B的孔径大小分布。所煅烧的两种试样均显示出孔径大小分布曲线中在约20-25nm下的最大值。然而，催化剂A显示出从最大值延伸至降至约6nm的更窄孔的明显肩。催化剂B显示出在6nm与孔径大小分布曲线的最大值之间区域中小得多的孔隙率。从N2-孔径大小分布曲线中看，认为催化剂B可具有相对于试样A轻微增强的扩散性能。
表2比较了在空气中在～1000°F(～538℃)下煅烧～6小时以后，关于两种催化剂A和B，3-10nm孔径的孔径范围内的中孔体积与总中孔体积。中孔体积由图4所示PSD曲线在所述范围内的积分测定。
表2.催化剂A和B在煅烧以后的中孔体积
从表2中可以看出3-10nm的小中孔相对于总测量中孔体积的分数就催化剂B而言为～14%，就催化剂A而言为～38%。
图5显示在～100%H2O气氛中在～1000°F(～538℃)下蒸～6小时以后，催化剂A和催化剂B的孔径大小分布。催化剂A显示出孔径大小分布曲线中约21nm的最大值，而催化剂B具有转移至约34nm的更大孔径的最大值。
表3比较在～100%H2O气氛中在～1000°F(～538℃)下蒸～6小时以后，关于催化剂A和B，21nm以下和以上的孔径大小范围内的中孔体积。中孔体积由图5所示PSD曲线在所述范围内的积分测定。
表3.催化剂A和B在蒸以后的中孔体积
从表3中可以看出催化剂B显示出在21nm以上的范围内比催化剂B更大的孔体积。与就催化剂A而言～34%相比，较大中孔(孔径21nm以上)的分数就催化剂B而言为～79%。
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 (11)

1.结合型磷改性催化剂组合物，其包含沸石和粘合剂，其中沸石具有至少40，例如约40至约200的二氧化硅:氧化铝摩尔比，粘合剂具有小于200m2/g，例如小于150m2/g或者小于或等于100m2/g的表面积，其中结合型催化剂组合物显示出中孔孔径分布，其中小于20%的中孔在约100%蒸汽中在约1000℉(约538℃)下蒸约96小时以前具有10nm以下的尺寸，且多于60%的中孔在约100%蒸汽中在约1000℉(约538℃)下蒸约96小时以后具有至少21nm的尺寸。
2.根据权利要求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。
3.根据权利要求1或权利要求2的催化剂组合物，其中所述沸石包含ZSM-5。
4.根据前述权利要求中任一项的催化剂组合物，其中结合型催化剂组合物在约100%蒸汽中在约1000℉(约538℃)下蒸约96小时以后显示出至少20，例如至少40的α值。
5.根据前述权利要求中任一项的催化剂组合物，其中结合型催化剂组合物显示出至少375m2/g的微孔表面积。
6.根据前述权利要求中任一项的催化剂组合物，其进一步包含总催化剂组合物的约0.1至约3重量%，例如约0.5至约2重量%的量的磷。
7.根据前述权利要求中任一项的催化剂组合物，其中粘合剂以总催化剂组合物的约1至约50重量%，例如约5至约40重量%的量存在。
8.根据前述权利要求中任一项的催化剂组合物，其中粘合剂包含氧化铝或者为氧化铝。
9.根据前述权利要求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，沸石具有大于1.2×10-2sec-1的2,2-二甲基丁烷扩散系数。
10.有机化合物转化方法，其使用原料与根据前述权利要求中任一项的结合型催化剂组合物在有机化合物转化条件下接触。
11.根据权利要求10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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Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3080040A1 (en) 2013-12-13 2016-10-19 Exxonmobil Research And Engineering Company Vehicle powertrain with onboard catalytic reformer
US10159963B2 (en) 2013-12-20 2018-12-25 Exxonmobil Research And Engineering Company Catalyst for conversion of oxygenates to aromatics
WO2015094697A1 (en) 2013-12-20 2015-06-25 Exxonmobil Chemical Patents Inc. Conversion of methanol to olefins and para-xylene
CA2968890C (en) * 2014-12-22 2021-07-06 Exxonmobil Research And Engineering Company Conversion of organic oxygenates to hydrocarbons
WO2016105888A1 (en) 2014-12-22 2016-06-30 Exxonmobil Research And Engineering Company Conversion of oxygenates to aromatics
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
CA2951911A1 (en) * 2015-12-17 2017-06-17 Gilead Sciences, Inc. Tank-binding kinase inhibitor compounds
CN110023458A (zh) 2016-12-07 2019-07-16 埃克森美孚研究工程公司 用于生产芳烃的组合烯烃和氧合物转化
WO2018106396A1 (en) 2016-12-07 2018-06-14 Exxonmobil Research And Engineering Company Integrated oxygenate conversion and olefin oligomerization
KR102500247B1 (ko) 2017-01-19 2023-02-15 엑손모빌 테크놀로지 앤드 엔지니어링 컴퍼니 가변 촉매 조성물에 의한 산소화물의 탄화수소로의 전환
US11918974B2 (en) * 2018-04-30 2024-03-05 The Regents Of The University Of Colorado Functionalization of zeolites
CA3108901A1 (en) * 2018-08-27 2020-03-05 Exxonmobil Research And Engineering Company Molecular sieves and a process for making molecular sieves
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
US11084983B2 (en) 2019-01-24 2021-08-10 Exxonmobil Research And Engineering Company Fluidized bed conversion of oxygenates with increased aromatic selectivity
EP4301699A1 (en) * 2021-03-02 2024-01-10 Basf Corporation Phosphorus modified uzm-35, methods of preparation, and methods of use thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN1302228A (zh) * 1999-03-02 2001-07-04 格雷斯公司 高沸石含量和耐磨耗催化剂,其制法及用其催化的方法
US20080146826A1 (en) * 2006-12-19 2008-06-19 Kaminsky Mark P Direct epoxidation 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
US20100168489A1 (en) * 2005-12-22 2010-07-01 Saudi Basic Industries Corporation Bound phosphorus-modified zeolite catalyst, method of preparing and method of using thereof

Family Cites Families (98)

* 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
US3931349A (en) * 1974-09-23 1976-01-06 Mobil Oil Corporation Conversion of methanol to gasoline components
NZ178543A (en) * 1974-09-23 1978-04-03 Mobil Oil Corp Conversion catalyst, crystalline alumin osilicate zeolite containing phosphorus
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
US4044065A (en) 1974-09-23 1977-08-23 Mobile Oil Corporation Conversion utilizing a phosphorus-containing zeolite catalyst
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
US4143084A (en) * 1976-07-19 1979-03-06 Mobil Oil Corporation Di-alkylbenzene isomer mixtures
PL199748A1 (pl) * 1976-07-19 1978-04-24 Mobil Oil Corp Sposob selektywnego wytwarzania p-dwualkilobenzenow
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
US4590321A (en) 1985-06-12 1986-05-20 Mobil Oil Corporation Aromatization reactions with zeolites containing phosphorus oxide
US4665251A (en) 1985-06-12 1987-05-12 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
AU652222B2 (en) * 1991-03-12 1994-08-18 Mobil Oil Corporation Preparation of cracking catalysts, and cracking process using them
US5110776A (en) * 1991-03-12 1992-05-05 Mobil Oil Corp. Cracking catalysts containing phosphate treated zeolites, and method of preparing the same
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
CA2112190C (en) 1992-12-24 2000-02-22 Hiroshi Miura Process for removing nitrogen oxides from oxygen rich exhaust gas
JPH06238131A (ja) * 1992-12-24 1994-08-30 Tosoh Corp 窒素酸化物の除去方法
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
US5993642A (en) * 1994-11-23 1999-11-30 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
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
US7399727B2 (en) 2004-04-23 2008-07-15 Saudi Basic Industries Corporation Zeolite catalyst and method
US7285511B2 (en) 2004-04-23 2007-10-23 Saudi Basic Industries Corporation Method of modifying zeolite catalyst
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
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
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
TW200918486A (en) * 2007-09-18 2009-05-01 Asahi Kasei Chemicals Corp Process for production of propylene
EP2082801A1 (en) 2008-01-25 2009-07-29 Total Petrochemicals Research Feluy Process for obtaining modified molecular sieves
US8846559B2 (en) * 2008-11-03 2014-09-30 Saudi Basic Industries Corporation Stable shape-selective catalyst for aromatic alkylation and methods of using and preparing
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
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
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 (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN1302228A (zh) * 1999-03-02 2001-07-04 格雷斯公司 高沸石含量和耐磨耗催化剂,其制法及用其催化的方法
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
US20100168489A1 (en) * 2005-12-22 2010-07-01 Saudi Basic Industries Corporation Bound phosphorus-modified zeolite catalyst, method of preparing and method of using thereof
US20080146826A1 (en) * 2006-12-19 2008-06-19 Kaminsky Mark P Direct epoxidation process

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