CN101180239B - 沸石催化剂和方法 - Google Patents

沸石催化剂和方法 Download PDF

Info

Publication number
CN101180239B
CN101180239B CN2006800181369A CN200680018136A CN101180239B CN 101180239 B CN101180239 B CN 101180239B CN 2006800181369 A CN2006800181369 A CN 2006800181369A CN 200680018136 A CN200680018136 A CN 200680018136A CN 101180239 B CN101180239 B CN 101180239B
Authority
CN
China
Prior art keywords
zeolite
catalyzer
zsm
phosphorus
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2006800181369A
Other languages
English (en)
Other versions
CN101180239A (zh
Inventor
A·K·高希
N·库尔卡尼
P·哈维
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saudi Basic Industries Corp
Original Assignee
Saudi Basic Industries Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saudi Basic Industries Corp filed Critical Saudi Basic Industries Corp
Publication of CN101180239A publication Critical patent/CN101180239A/zh
Application granted granted Critical
Publication of CN101180239B publication Critical patent/CN101180239B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J35/30—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C07C2/68—Catalytic processes with halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1096—Aromatics or polyaromatics
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

由含磷的ZSM-5类沸石形成催化剂。ZSM-5类沸石的二氧化硅/氧化铝的摩尔比为至少200。含磷的ZSM-5类沸石还具有沸石重量至少8wt％的磷含量，和具有多个磷物种，这通过最大值为约0-约-50ppm的至少两个31P MAS NMR峰来显示。可在芳烃烷基化中，在适合于芳烃烷基化的反应条件下，通过使该催化剂与芳烃和烷基化剂的原料接触，从而使用该催化剂。

Description

沸石催化剂和方法
本申请是2004年4月23日提交的标题为“Method ofModifying Zeolite Catalyst”的美国专利申请的部分继续，在此通过参考将其全文引入。
技术领域
本发明一般地涉及烷基化芳族化合物的方法和用于这一反应的催化剂。
背景技术
对二甲苯是一种有价值的取代芳族化合物，这是因为对它具有巨大的需求用于生产对苯二甲酸，一种在形成聚酯纤维和树脂中的主要组分。商业上它可由加氢处理石脑油(催化重整)、蒸汽裂化石脑油或瓦斯油，和甲苯歧化来生产。
在实验室研究中，用甲醇烷基化甲苯(也称为甲苯的甲基化)用于生产对二甲苯。已知在酸性催化剂上，尤其在沸石或沸石类催化剂上发生甲苯的甲基化。特别地，ZSM-5类沸石、沸石β和硅铝磷酸盐(silicaaluminophosphate)(SAPO)催化剂用于这一方法。一般地，可由甲苯的甲基化形成邻(o)-、间(m)-和对(p)-二甲苯的热动力学平衡混合物，正如以下的反应所示：
Figure S2006800181369D00011
在约500℃的反应温度下，o-、m-和p-二甲苯的热动力学平衡组合物可以分别是约25、50和25mol％。可在宽泛范围的温度下发生这种甲苯的甲基化，然而可通过吸收和异构化循环，从混合二甲苯中分离对二甲苯。可通过辅助烷基化二甲苯产物，生产诸如C9+之类的副产物和其它芳族产物。
若催化剂具有形状选择性能的话，则可在甲苯的甲基化反应中获得显著较高含量的对二甲苯。可通过改性沸石的开孔尺寸，使沸石的外表面失活或者控制沸石的酸度，从而在改性的沸石催化剂内获得形状选择性能。可在改性的ZSM-5或ZSM-5类沸石催化剂上发生甲苯的甲基化，从而得到含有比热动力学浓度显著更大量的对二甲苯的二甲苯产物。
使用磷酸和其它含磷化合物改性ZSM-5沸石催化剂，以提供形状选择性能。美国专利No.6504072例如公开了用磷(P)处理ZSM-5沸石催化剂，以控制扩散度和孔体积下降，之后剧烈地通入蒸汽，以提供对位选择性催化剂。美国专利No.4554394讨论了用气相有机基磷试剂处理ZSM-5沸石，提供对位选择性能。尽管这种磷处理过的ZSM-5催化剂可具有高的对二甲苯选择性，但它们倾向于以非常快的速度失活。例如，催化剂可在1天内丧失大于其起始活性的50％。这可能是由于在催化剂上焦炭沉积所致。
由于存在商业成功地甲基化甲苯的许多技术障碍，因此仍需要改进。
附图简述
为了更全面地理解本发明，现结合附图，参考下述说明，其中：
图1是不同H3PO4改性的ZSM-5沸石催化剂的BET表面积随改性所使用的磷用量的变化的图表；
图2是不同H3PO4改性的ZSM-5沸石催化剂的总孔体积随改性所使用的磷用量的变化的图表；
图3示出了(a)SiO2/Al2O3的摩尔比为280的NH4-ZSM-5，和(b)磷改性的ZSM-5沸石催化剂的27Al MAS-NMR图谱；
图4示出了在不同温度下干燥/焙烧，(a)在60℃下干燥(催化剂T)，(b)在250℃下干燥(催化剂U)，(c)在350℃下干燥(催化剂V)，和(d)在510℃下焙烧(催化剂W)之后，磷改性的催化剂的31PMAS-NMR图谱；
图5是对于在起始SiO2/Al2O3的摩尔比为30的H3PO4改性的ZSM-5沸石催化剂上，由甲苯的甲基化获得的液体产物物流来说，全部二甲苯的wt％和对全部二甲苯以及对p-二甲苯的选择率随改性所使用的碳用量的变化的图表；和
图6是对于在起始SiO2/Al2O3的摩尔比为280的H3PO4改性的ZSM-5沸石催化剂上，由甲苯的甲基化获得的液体产物物流来说，全部二甲苯的wt％和对全部二甲苯以及对p-二甲苯的选择率随改性所使用的磷用量的变化的图表。
详细说明
此处所使用的措辞“ZSM-5类”是指结构上与ZSM-5沸石相同的那些沸石。另外，措辞“ZSM-5”和“ZSM-5类”在此处可互换使用，以囊括彼此，且不应当在任何限制的意义上来解释。在美国专利No.3702886中公开了ZSM-5沸石催化剂及其制备方法，在此通过参考将其引入。
此处所使用的催化活性可表达为相对于加入的甲苯的摩尔数转化的甲苯的mol％，且可定义为：
mol％甲苯转化率＝[(Ti-T0)/T1]×100            (2)
其中Ti是加入的甲苯的摩尔数，和T0是未反应的甲苯的摩尔数。此处所使用的混合二甲苯的选择率可表达为：
mol％混合二甲苯的选择率＝[Xmx/(Ti-T0)]×100   (3)
其中Xmx是在产物内二甲苯的总摩尔数(o-、m-或p-)。此处所使用的对二甲苯的选择率可表达为：
mol％对二甲苯的选择率＝(Xp/Xmx)×100          (4)
其中Xp是对二甲苯的摩尔数。
用含磷化合物改性ZSM-5沸石并热处理可引起在沸石孔隙和通道内形成一些磷物种，这可导致表面积和孔体积减少。这种改性的催化剂可提供增加的对位选择性且不需要随后在高温(例如大于或等于700℃)下通入蒸汽或者额外地处理催化剂。磷改性的ZSM-5催化剂提供增加的活性和对芳烃烷基化的选择性。在一些情况下，对于特定的ZSM-5沸石催化剂来说，可在甲苯甲基化中使用期间，实现增加的催化剂活性和总的二甲苯选择率，同时仍提供高的对二甲苯选择率。
在本发明中，用含磷化合物改性ZSM-5沸石并热处理，以提供形状选择性。起始的ZSM-5沸石可以是NH4-或H-形式的沸石，这种沸石可以是粉末形式或者任何其它形式。在本发明中，ZSM-5沸石催化剂可包括在用含磷化合物改性之前，氧化硅/氧化铝的摩尔比大于2 5的那些。正如以下所述，起始ZSM-5沸石催化剂中氧化硅/氧化铝之比可对在甲苯甲基化中随后处理过的催化剂的催化剂活性和二甲苯的选择性具有影响。在一些情况下，起始ZSM-5中SiO2/Al2O3的摩尔比可以是200、280、300-1000或更大，以实现较高的活性和增加的对二甲苯选择率。
磷化合物可以是含磷的酸，例如磷酸(H3PO4)和亚磷酸(H3PO3)。对于含磷的酸来说，可使用浓度大于50wt％的酸，其中50wt％-约85wt％是合适的。磷化合物也可包括其它非酸的含磷的化合物，例如磷酸氢铵((NH4)2HPO4)。所使用的磷的用量可提供处理的催化剂0.04g P/g沸石或更大的磷含量。在一些应用中，可将用量为0.08g P/g沸石或更大，更具体地约0.09g P/g沸石到约0.10g P/g沸石或者到约0.15g P/g沸石的磷掺入到催化剂内。
可通过各种技术进行磷的处理。这可包括淤浆蒸发和湿初始(incipient)法。在淤浆蒸发中，可通过制备沸石的淤浆，和磷化合物的水溶液，从而将磷掺入到催化剂内。可利用淤浆的加热，以促进沸石催化剂的处理和蒸发液体。加热淤浆到大于或等于约25℃的温度，其中在大多数情况下70℃-约100℃是合适的。也可在这一步骤期间搅拌或搅动淤浆，以确保均匀的处理。可通过本领域公知的喷雾干燥技术，实现从沸石淤浆中蒸发液体。
在湿初始法中，添加磷化合物的水溶液，例如在没有形成淤浆的情况下，通过喷雾，干燥沸石。干燥的沸石(它最初可以是粉末形式)可与磷化合物混合，形成料团。然后可在与淤浆技术相类似的温度下加热料团，以促进水的蒸发。
可在含有氧气，典型地空气的环境内，在大于或等于250℃下，更特别地在300℃至600℃的温度下，更特别地在约400℃-约570℃下焙烧P处理过的沸石。可随着时间的流逝，典型地进行数分钟到大于或等于1小时的焙烧。也可通过随着时间流逝，逐渐增加温度，进行焙烧。
可未粘合或者用粘合剂粘合的方式使用磷改性的沸石催化剂。合适的粘合剂的实例包括诸如氧化铝、粘土和二氧化硅之类的材料。制备粘合的催化剂所使用的那些技术是本领域众所周知的。
处理过的ZSM-5沸石催化剂可提供小于或等于约0.2ml/g的总孔体积。更特别地，总的孔体积范围可以是约0.18ml/g-约0.07ml/g。ZSM-5沸石催化剂的BET表面积范围可以是小于300m2/g-约10m2/g。
磷改性的催化剂在沸石结构内含有忽略不计含量的四面体/结构Al(它在约50ppm处显示出弱的27Al-MAS NMR峰)，但该催化剂可在沸石孔隙内含有“碎片(debris)”或额外结构(extra framework)的铝(EFAl)(它在约-14ppm处显示出强的27Al-MAS NMR峰)。对于处理过的沸石催化剂来说，骨架铝与非骨架铝之比范围可以是约0.12-0.25。
磷改性的沸石催化剂含有P物种(它在约0ppm-50ppm处显示出最大的31P-MAS NMR峰)。P物种可以是游离的磷酸盐，或者键合到额外结构的Al或者AlPO/SAPO或者聚磷酸盐类物种上。
处理过的催化剂可在甲苯甲基化中用作非蒸汽加工催化剂。也可在低温或者温和的温度下蒸汽加工磷处理过的ZSM-5沸石催化剂。可通过在氢气或者其它惰性气体存在下接触催化剂与蒸汽，从而发生蒸汽加工。蒸汽加工温度范围可以是约150℃-约250℃、300℃或350℃。这可在任何芳烃烷基化反应或者引入任何反应原料之前，通过在反应器内单独或者就地实现。可进行蒸汽加工数分钟-数小时。在2005年5月5日提交的标题为“Hydrothermal Treatment ofPhosphorus-Modified Zeolite Catalysts”的悬而未决的美国专利申请序列号No.11/122919中公开了使用在温和温度下催化剂的蒸汽加工，在此通过参考引入。
改性催化剂可在烷基化反应条件下接触芳烃和烷基化剂的合适原料，进行芳烃烷基化。使用甲苯/甲醇原料，该催化剂在甲苯甲基化中使用时具有特殊的应用。也可任选地使用气体共原料。共原料气体可包括氢气或惰性气体。可使用用量为至少0.1mol/mol芳烃烷基化原料的共原料。此处所使用的措辞“烷基化原料”包括芳烃化合物和烷基化剂。此处所使用的措辞“甲基化原料”包括甲苯和甲醇原料。
除了共原料气体以外，水或蒸汽也可作为共原料与烷基化原料一起引入到反应器内。在烷基化反应启动过程中，可在有或无氢气或惰性气体作为共原料的情况下，与烷基化原料一起引入甲基化反应所使用的水或蒸汽到反应器中，或者在起始的启动之后引入甲基化反应所使用的水或蒸汽。在任何一种情况下，可添加液体水并蒸发，之后将其与共原料气体(如果有的话)和烷基化原料混合。
甲苯甲基化或者其它芳烃烷基化的反应器压力可以变化，但典型地范围为约10-约1000psig。反应器温度范围典型地可以是400-700℃。
可在进行芳烃烷基化反应常用的各种不同的反应器内进行反应。单一或者串联的多个反应器适合于进行甲苯的甲基化。
对p-二甲苯具有增加的选择性的这一改性催化剂可用于甲苯甲基化以供由甲苯和甲醇原料制备二甲苯产品。特别地，当在甲苯甲基化中使用时，该催化剂可提供大于80％、85％和90％的对二甲苯选择率。另外，在一些情况下，可实现大于90％的总的二甲苯选择率。
下述实施例起到进一步阐述本发明的作用。
实施例
催化剂的制备
催化剂A-I
起始物质是SiO2/Al2O3的摩尔比为30的NH4-ZSM-5沸石粉末。在400ml烧杯内制备含有11.63g NH4-ZSM-5沸石和50ml去离子水的含水淤浆。将烧杯置于热板上，并在使用磁搅拌棒搅拌沸石悬浮液。该悬浮液的温度维持在约90℃。逐滴添加1.08g磷酸(85wt％在水中)到烧杯内。继续加热，直到所有液体蒸发。在90℃-120℃下干燥磷酸改性的沸石至少4小时和在340℃-360℃下干燥3小时，然后在空气中，在510℃-530℃下焙烧10小时。然后粉碎焙烧的沸石，并使用20和40目的筛网筛选。通过相对于起始NH4-ZSM-5沸石粉末的用量，改变磷酸用量，制备一系列催化剂A-H(参见表1)。还(使用以上所述的相同温度曲线)，通过焙烧SiO2/Al2O3的摩尔比为30的NH4-ZSM-5沸石粉末，制备非磷的ZSM-5催化剂(催化剂I)。在表1以及在图1和2中示出了催化剂A-I的BET表面积(SA)和总的孔体积(PV)(通过N2吸收来测量)。
表1
  催化剂    水，ml 沸石粉末，g  H3PO4含量，ga P，g/g沸石a SA，m2/g   PV，ml/g
    ABCDEFGHI     10050505050505050-    46.5011.6311.6311.6411.6311.6311.6411.64-      4.001.082.524.046.018.0512.5116.010     0.02 30.0250.0580.0930.1390.1860.2790.3700   266.4259.0157.866.924.018.614.29.7357.2     0.4830.3400.2120.1890.1830.1790.0770.0790.579
a在制备中所使用的磷酸(在水中85％)或P的总量
根据表1和图1与2可看出，观察到通过使用磷酸或磷含量增加、SiO2/Al2O3的摩尔比为30的起始NH4-ZSM-5制备的沸石催化剂A-H的BET表面积(SA)和总的孔体积(PV)急剧增加。
催化剂J-O
起始物质是SiO2/Al2O3的摩尔比为280的NH4-ZSM-5沸石粉末。在400ml烧杯内制备含有12.09g NH4-ZSM-5沸石和50ml去离子水的淤浆。将烧杯置于热板上，并在使用磁搅拌棒搅拌沸石悬浮液。该悬浮液的温度维持在约90℃。逐滴添加1.08g磷酸(85wt％在水中)到烧杯内。继续加热，直到所有液体蒸发。在90℃-120℃下干燥磷酸改性的沸石至少4小时和在340℃-360℃下干燥3小时，然后在空气中，在510℃-530℃下焙烧10小时。然后粉碎焙烧的沸石，并使用20和40目的筛网筛选。通过相对于起始NH4-ZSM-5沸石粉末的用量，改变磷酸用量，制备一系列催化剂J-N(参见表2)。还(使用以上所述的相同温度曲线)，通过焙烧SiO2/Al2O3的摩尔比为280的NH4-ZSM-5沸石粉末，制备非磷的ZSM-5催化剂(催化剂O)。在表2以及在图1和2中示出了催化剂J-O的BET表面积和总的孔体积(通过N2吸收来测量)。使用SiO2/Al2O3的摩尔比为280的起始NH4-ZSM-5制备的催化剂的BET表面积(SA)和总的孔体积(PV)的下降不如通过使用SiO2/Al2O3的摩尔比为30的起始NH4-ZSM-5制备的催化剂A-J突出。
表2
  催化剂   水，ml   沸石粉末，g  H3PO4含量，ga P，g/g沸石a  SA，m2/g  PV，ml/g
    JKLMN0     505010010050-     12.0924.0948.3848.3912.09-     1.083.9515.823.77.750     0.0240.0440.0880.1230.1720   330.7299.4183.2156.2163.7375.0    0.2080.1820.1380.1130.1200.244
a在制备中所使用的磷酸(在水中85％)或P的总量
催化剂P-S
起始物质是SiO2/Al2O3的摩尔比为280的NH4-ZSM-5沸石粉末。在400ml烧杯内制备含有51.66g NH4-ZSM-5沸石和200ml去离子水的淤浆。将烧杯置于热板上，并在使用磁搅拌棒搅拌沸石悬浮液。该悬浮液的温度维持在约90℃。在50ml水内溶解9.07g磷酸氢铵(NH4)2HPO4，并将该盐溶液逐滴添加到烧杯内。继续加热，直到所有液体蒸发。在90℃-120℃下干燥磷酸氢铵改性的沸石至少4小时和在340℃-360℃下干燥3小时，然后在空气中，在510℃-530℃下焙烧10小时。然后粉碎焙烧的沸石，并使用20和40目的筛网筛选。通过相对于起始NH4-ZSM-5沸石粉末的用量，改变磷酸氢铵的用量，制备一系列催化剂P-S(参见表3)。表3中示出了催化剂P-S的BET表面积(SA)和总的孔体积(PV)(通过N2吸收来测量)。
表3
 催化剂#     水，ml   沸石粉末，g   (NH4)2HPO4含量，ga   P，g/g沸石a   SA，m2/g   PV，ml/g
 PQRS     200200200200   30.0951.6651.6648.38   2.499.0712.8518.14   0.0180.0390.0550.082   317.2278.3241.0216.2   0.2080.1790.1550.131
a在制备中所使用的磷酸氢铵或P的总量
在给定的磷含量下，通过使用磷酸制备的一系列催化剂J-N与通过使用磷酸氢铵制备的一系列催化剂P-S在表面积和孔体积之间很少或者没有差别。因此，使用磷酸或磷酸氢铵作为含磷化合物制备对二甲苯选择性催化剂不可能具有显著的差别。
催化剂T-W
起始物质是SiO2/Al2O3的摩尔比为280的NH4-ZSM-5沸石粉末。在2L烧杯内制备含有400.0g NH4-ZSM-5沸石和800ml去离子水的淤浆。将烧杯置于热板上，并在使用机械搅拌器搅拌沸石悬浮液。该悬浮液的温度维持在90℃以上。将182.5g磷酸(85wt％在水中)逐滴添加到烧杯内。继续加热，直到所有液体蒸发。将磷酸改性的沸石分成4个样品，并在不同的最大温度下干燥或者焙烧每一样品：催化剂T(在60℃下干燥)，催化剂U(在250℃下干燥)，催化剂V(在350℃下干燥)和催化剂W(在510℃下干燥)。
固态27Al MAS-NMR
采用400MHz的分光计(27Al，在104.5MHz下)，在室温下在ZSM-5沸石上记录固态幻角自旋(MAS)NMR光谱。将样品封装在氮化硅转子(Si3N4)内并在13KHz的样品旋转(约800000rpm)下旋转。使用10度的倾斜和0.5s的循环延迟以避免饱和。累积约4000-10000次扫描，以便传输信号平均值并改进信号/噪音比。没有使用质子去耦合。在化学位移尺度下，在0.0ppm处将所有光谱相对于六水合氯化铝(在管道内单独地试验)定位。这导致在氮化铝(在氮化硅转子内小的杂质)峰上104.85ppm的内标。
在SiO2/Al2O3的摩尔比为280的起始NH4-ZSM-5沸石和磷改性的沸石上记录27Al MAS-NMR。起始NH4-ZSM-5沸石样品在约55ppm处显示出强的27Al MAS-NMR峰，该峰归因于结构四面体(4配位的)铝(图3的图谱a)。共振的尖锐度和对称表明沸石是相对具有非常小晶格缺陷的晶体。结构Al造成沸石的酸度，和起始沸石样品显示出强的酸度。P改性的样品在约55-50ppm区域处显示出归于结构四面体铝(图3，图谱b)的弱峰。四面体铝峰被严重扭曲，从而表明一旦除去某些骨架铝，则存在因该结构内孔隙引起的嵌套(nested)硅烷醇。相邻峰(30-40ppm)的峰是由于可能在与氧的或3或5配位中严重扭曲但仍在骨架铝原子内导致的。在光谱内在-14ppm处最高的峰来自于当通过以上所述的磷酸盐改性方法从沸石结构中除去四面体配位结构的铝所形成的八面体配位的铝原子。
31P MAS NMR
采用400MHz的分光计(31P，在161.7MHz下)，在室温下在P/ZSM-5沸石上记录MAS NMR光谱。将样品封装在氮化硅转子(Si3N4)内并在13KHz的样品旋转(约800000rpm)下旋转。使用30度的倾斜和15s的循环延迟以避免饱和。累积约4000-10000次扫描，以便传输信号平均值并改进信号/噪音比。没有使用质子去耦合。在化学位移尺度下，将所有光谱双重地相对于在37.8ppm处的二硫化四甲基二膦和在0.0ppm处85％的磷酸(在管道内单独地试验)定位。
在不同的温度下干燥或焙烧之后，在P处理过的ZSM-5(SiO2/Al2O3，摩尔比280)上记录31P MAS-NMR。对于在60℃下干燥之后的P/ZSM-5(催化剂T，图4，图谱a)来说，观察到在约0ppm处的强峰和在约-11ppm处的弱峰。在约0ppm处的弱峰可归因于在沸石孔隙/通道内夹留的游离磷酸盐。当干燥或焙烧温度增加时，随着在约-20ppm到约-50ppm处新峰的出现，在约0ppm处的峰降低(催化剂U-W，图4，图谱b-d)。在干燥/焙烧温度变化的情况下，在约-11ppm处观察到的弱峰保持几乎不变。在约-11、约-31和约-44ppm处的峰归因于键合到各种磷物种上的磷，例如额外结构的Al、AlPO/SAPO和聚磷酸盐。显然，在干燥/焙烧过程中，在沸石内磷的状态改变。
X-射线衍射图案(XRD)
在Philips(X′Pert型号)衍射仪上，在5-55°范围内，在2°/分钟的扫描速度下，使用CuKα1射线，记录NH4-ZSM-5和P处理过的催化剂(U-W)的X-射线衍射图案(XRD)。在NH4-ZSM-5沸石P处理之后，ZSM-5的峰强下降。显然，P处理引起对起始沸石结构的一些损坏。在催化剂于250℃下干燥之后，P处理的ZSM-5催化剂在d-间距8.02、6.53和3.52埃处开始显示出新峰；当在350℃和510℃下进一步干燥/焙烧催化剂时，新峰的强度进一步增加。在下表4中列出了X-射线衍射峰。
表4
                      粉末XRD强度*
  d-间距[埃]     强度     d-间距[埃]     强度
  11.0910.009.889.688.026.686.536.335.985.69     1005542178788167     5.564.254.003.843.813.713.643.522.982.78     996503127102285
*所示的强度以任意的单元为尺度，以便大多数峰强为100。
实施例1-19
在甲苯甲基化反应中使用以上和表1-3中所述的催化剂A-I、J-O和P-S。反应各自在固定床、连续流动类型的反应器内进行。在每一情况下，在氢气(H2)流下，通过缓慢升高催化剂床温度(约5℃/分钟)到200℃，干燥催化剂至少1小时。在200℃下，甲苯和甲醇的预混甲基化原料(摩尔比2/1)加入到反应器中，和升高催化剂床的入口温度到约500℃。液体时空速度(LHSV)(以甲基化原料为基础)维持在约31hr-1，和加入并维持共原料H2气体以提供H2/(甲苯+甲醇)的摩尔比为约0.1。添加水到甲基化原料中，并气化，之后引入到反应器内。H2O/(甲苯+甲醇)的摩尔比为约0.65，和反应器压力为约20psig。在约3-4小时的时间处收集液体产物并分析。表5-7中列出了下述结果。图5是对于催化剂A-I来说的对p-二甲苯选择率和全部二甲苯的选择率的图表。图6是对于催化剂J-O来说的对p-二甲苯选择率和全部二甲苯的选择率的图表。
表5
    催化剂     A     B     C     D      E   F   G   H   I
    实施例产物分析，wt％1水甲醇二甲醚苯甲苯乙苯对二甲苯(PX)间二甲苯(MX)邻二甲苯(OX)乙基甲苯三甲基苯C10+全部芳烃产物，wt％全部二甲苯，wt％全部二甲苯的选择率，wt％对二甲苯的选择率，wt％     121.06001.3943.8207.1115.446.861.012.940.3635.1129.4183.7724.17     221.500.1001.1844.7706.8514.886.580.952.840.3633.6428.3184.1624.20     321.610.150050.54012.358.943.460.422.330.2027.7024.7589.3549.90     421.900.750054.86014.304.201.820.261.750.1622.4920.3290.3570.37     519.024.050070.2105.580.470.300.140.2206.716.3594.6387.87   618.214.640072.0004.490.260.170.110.1205.1 54.9295.5391.26   716.545.370075.3302.650.1100002.762.7610096.01   817.276.480074.1102.030.1100002.142.1410094.86   921.720.0800.4349.6305.8612.485.381.182.810.4128.5523.7283.0824.70
1流体产物物流分析
表6
催化剂  J  K  L  M  N   O
实施例产物分析，wt％1水甲醇二甲醚苯甲苯乙苯对二甲苯(PX)间二甲苯(MX)邻二甲苯(OX)乙基甲苯三甲基苯C10+全部芳烃产物，wt％全部二甲苯，wt％全部二甲苯的选择率，wt％对二甲苯的选择率，wt％  1016.330.540057.02019.553.121.560.351.390.1226.0924.2392.8780.69  1116.800.500057.76020.182.041.070.361.170.1124.9323.2993.4286.65  1219.732.390060.57015.050.760.480.320.450.2517.3116.2994.1192.39  1316.381.720064.47015.240.840.530.350.47017.4316.6195.3091.75  1415.792.130066.10013.370.960.680.330.550.0915.9815.0193.9389.07   1516.120.4500.3952.3708.5413.705.500.672.050.2031.0527.7489.3430.79
1流体产物物流分析
表7
催化剂  P  Q  R  S
实施例产物分析，wt％1水甲醇二甲醚苯甲苯乙苯对二甲苯(PX)间二甲苯(MX)邻二甲苯(OX)乙基甲苯三甲基苯C10+全部芳烃产物，wt％全部二甲苯，wt％全部二甲苯的选择率，wt％对二甲苯的选择率，wt％  1617.650.570056.17019.872.531.470.351.250.1325.6023.8793.2483.24  1716.460.850060.21018.171.760.980.361.080.1222.4720.9193.0686.90  1816.220.980061.74018.341.050.580.410.68021.0619.9794.8291.84  1916.582.270066.50013.341.060.2500014.6514.6510091.06
1流体产物物流分析
尽管仅仅以某些形式示出了本发明，但对于本领域的技术人员来说，应当不受这样限制，而是可在没有脱离本发明范围的情况下进行各种改变和改性。因此，合适的是所附权利要求应当宽泛地且与本发明范围一致的方式解释。

Claims (20)

1.一种催化剂，它包括二氧化硅与氧化铝的摩尔比为至少200的含磷的ZSM-5类沸石，该含磷的ZSM-5类沸石的磷含量为0.09gP/g-0.15gP/g沸石且具有多个磷物种，这通过最大值为0至-50ppm的至少两个31P MAS NMR峰来显示。
2.权利要求1的催化剂，其中：
存在多个磷物种，这通过最大值在0ppm、-11ppm、-31ppm或-44ppm处的至少两个31P MAS NMR峰来显示。
3.权利要求1的催化剂，其中：
存在多个磷物种，这通过最大值在0ppm、-11ppm、-31ppm或-44ppm处的至少三个31P MAS NMR峰来显示。
4.权利要求1的催化剂，其中：
存在多个磷物种，这通过最大值在0ppm、-11ppm、-31ppm和-44ppm处的31P MAS NMR峰来显示。
5.权利要求1的催化剂，其中：
含磷的ZSM-5类沸石的总孔隙体积为小于或等于0.2ml/g。
6.权利要求1的催化剂，其中：
含磷的ZSM-5沸石的BET表面积为300m2/g-10m2/g。
7.权利要求1的催化剂，其中：
含磷的ZSM-5类沸石显示出如表4所示的粉末X-射线衍射峰。
8.权利要求1的催化剂，其中：
含磷的ZSM-5类沸石的总孔隙体积为小于或等于0.18ml/g。
9.权利要求1的催化剂，其中：
沸石具有0.12-0.25的骨架铝与非骨架铝之比，这通过27AlMAS-NMR来测量。
10.芳烃烷基化的方法，该方法包括：
提供二氧化硅/氧化铝的摩尔比为至少200的含磷的ZSM-5类沸石催化剂，该含磷的ZSM-5类沸石的磷含量为0.09gP/g-0.15gP/g沸石且具有多个磷物种，这通过最大值为0至-50ppm的至少两个31P MAS NMR峰来显示；和
在适合于芳烃烷基化的反应条件下，使催化剂与含芳烃和烷基化剂的芳烃烷基化原料接触。
11.权利要求10的方法，其中：
存在多个磷物种，这通过最大值在0ppm、-11ppm、-31ppm或-44ppm处的至少两个31P MAS NMR峰来显示。
12.权利要求10的方法，其中：
存在多个磷物种，这通过最大值在0ppm、-11ppm、-31ppm或-44ppm处的至少三个31P MAS NMR峰来显示。
13.权利要求10的方法，其中：
存在多个磷物种，这通过最大值在0ppm、-11ppm、-31ppm和-44ppm处的31P MAS NMR峰来显示。
14.权利要求10的方法，其中：
含磷的ZSM-5类沸石的总孔隙体积为小于或等于0.2ml/g。
15.权利要求10的方法，其中：
含磷的ZSM-5类沸石的总孔隙体积为小于或等于0.18ml/g。
16.权利要求10的方法，其中：
磷含量为沸石重量的8％-10％。
17.权利要求10的方法，其中：
含磷的ZSM-5沸石催化剂的BET表面积为300m2/g-10m2/g。
18.权利要求10的方法，其中：
含磷的ZSM-5类沸石显示出如表4所示的粉末X-射线衍射峰。
19.权利要求10的方法，其中：
含磷的ZSM-5沸石催化剂在50ppm和-14ppm处具有27AlMAS-NMR峰。
20.权利要求10的方法，其中：
沸石具有0.12-0.25的骨架铝与非骨架铝之比，这通过27AlMAS-NMR来测量。
CN2006800181369A 2005-05-25 2006-05-24 沸石催化剂和方法 Expired - Fee Related CN101180239B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US11/136,877 2005-05-25
US11/136,877 US7399727B2 (en) 2004-04-23 2005-05-25 Zeolite catalyst and method
PCT/US2006/020110 WO2006127827A2 (en) 2005-05-25 2006-05-24 Zeolite catalyst and method

Publications (2)

Publication Number Publication Date
CN101180239A CN101180239A (zh) 2008-05-14
CN101180239B true CN101180239B (zh) 2011-03-30

Family

ID=37452794

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2006800181369A Expired - Fee Related CN101180239B (zh) 2005-05-25 2006-05-24 沸石催化剂和方法

Country Status (6)

Country Link
US (1) US7399727B2 (zh)
EP (1) EP1893530A4 (zh)
JP (1) JP5107906B2 (zh)
KR (1) KR101321217B1 (zh)
CN (1) CN101180239B (zh)
WO (1) WO2006127827A2 (zh)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7304194B2 (en) * 2005-05-05 2007-12-04 Saudi Basic Industries Corporation Hydrothermal treatment of phosphorus-modified zeolite catalysts
US7368410B2 (en) * 2005-08-03 2008-05-06 Saudi Basic Industries Corporation Zeolite catalyst and method of preparing and use of zeolite catalyst
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
US8115041B2 (en) * 2008-04-02 2012-02-14 Saudi Basic Industries Corporation Pretreatment of a phosphorus-modified zeolite catalyst for an aromatic alkylation process
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
US8062987B2 (en) 2009-10-05 2011-11-22 Saudi Basic Industries Corporation Phosphorus-containing zeolite catalysts and their method of preparation
CA2780741C (en) 2009-10-12 2023-04-04 Smith Holdings, Llc Methods and compositions for modulating gene expression using oligonucleotide based drugs administered in vivo or in vitro
DE102011013908A1 (de) 2011-03-15 2012-09-20 Süd-Chemie AG Modifizierter Katalysator zur Umwandlung von Oxygenaten zu Olefinen
SG10201602933TA (en) 2011-10-17 2016-05-30 Exxonmobil Res & Eng Co Phosphorus Modified Zeolite Catalysts
US9278342B2 (en) 2012-07-02 2016-03-08 Saudi Basic Industries Corporation Method of modifying a phosphorus-containing zeolite catalyst
MY170534A (en) 2013-01-31 2019-08-15 Exxonmobil Chemical Patents Inc Production of para-xylene
US8969643B2 (en) 2013-05-23 2015-03-03 Saudi Basic Industries Corporation Method for conversion of aromatic hydrocarbons
US9783462B2 (en) 2013-09-10 2017-10-10 Saudi Basic Industries Corporation Toluene methylation with transalkylation of heavy aromatics
US9364815B2 (en) 2013-11-07 2016-06-14 Saudi Basic Industries Corporation Method of preparing an alumina catalyst support and catalyst for dehydrogenation reactions, and its use
US10532962B2 (en) 2016-02-02 2020-01-14 Sabic Global Technologies B.V. Conversion of shale gas to aromatics
GB201615626D0 (en) * 2016-09-14 2016-10-26 Johnson Matthey Plc Alkylation process
US20230202851A1 (en) * 2020-04-13 2023-06-29 China Petroleum & Chemical Corporation Phosphorus-containing/phosphorus-modified zsm-5 molecular sieve, cracking auxiliary and cracking catalyst containing the same, process of preparing the same, and use thereof
CN113526519B (zh) * 2020-04-13 2023-01-13 中国石油化工股份有限公司 含磷的多级孔zsm-5分子筛及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5951963A (en) * 1997-03-24 1999-09-14 China Petrochemical Corporation Phosphorous containing zeolite having MFI type structure
US20050070749A1 (en) * 2003-09-30 2005-03-31 Ghosh Ashim Kumar Toluene methylation process

Family Cites Families (137)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3702886A (en) 1969-10-10 1972-11-14 Mobil Oil Corp Crystalline zeolite zsm-5 and method of preparing the same
US3962364A (en) * 1975-03-28 1976-06-08 Mobil Oil Corporation Alkylation in presence of phosphorus-modified crystalline luminosilicate catalyst
US3965207A (en) 1975-01-06 1976-06-22 Mobil Oil Corporation Selective production of para-xylene
US4049573A (en) * 1976-02-05 1977-09-20 Mobil Oil Corporation Zeolite catalyst containing oxide of boron or magnesium
US4115424A (en) 1976-12-22 1978-09-19 Monsanto Company Zeolite catalyst
US4250345A (en) 1978-01-10 1981-02-10 Mobil Oil Corporation Selective production of para-xylene
US4152364A (en) 1978-01-19 1979-05-01 Mobil Oil Corporation Selective production of para-xylene
US4444989A (en) * 1979-04-20 1984-04-24 E. I. Du Pont De Nemours And Company Methylation of toluene to para-xylene catalyzed by crystalline silica
US4278827A (en) 1980-04-07 1981-07-14 Mobil Oil Corporation Shape selective reactions with zeolite catalyst modified with group IVB metal
DE3169731D1 (en) 1980-11-04 1985-05-09 Teijin Petrochem Ind A catalyst composition containing as catalytically active components alumina and a cristalline aluminosilicate zeolite, a process for isomerizing xylenes and ethylbenzene, and use of this catalyst composition
US4704495A (en) 1980-12-29 1987-11-03 Mobil Oil Corporation Catalytic conversions using shape selective metallic catalysts
US4554394A (en) 1982-03-18 1985-11-19 Mobil Oil Corporation Organophosphorus-treated zeolite catalysts for para-selective aromatics conversion
US4409132A (en) 1982-03-18 1983-10-11 Mobil Oil Corporation Organophosphorus-treated zeolite catalysts for para-selective aromatics conversion
US5254767A (en) 1982-04-30 1993-10-19 Mobil Oil Corp. Highly siliceous porous crystalline material and its use in conversion of oxygenates
US4902406A (en) 1982-04-30 1990-02-20 Mobil Oil Corporation Synthesis of zeolite ZSM-22
US5336478A (en) 1982-04-30 1994-08-09 Mobil Oil Corp. Highly siliceous porous crystalline material
US5248841A (en) 1982-04-30 1993-09-28 Mobil Oil Corporation Hydrocarbon conversion with ZSM-22 zeolite
US5254770A (en) 1982-09-01 1993-10-19 Mobil Oil Corp. Isomerization of aromatic compounds over ZSM-22 zeolite
US4973781A (en) 1982-11-17 1990-11-27 Mobil Oil Corporation Zeolite ZSM-57 and catalysis therewith
US4914067A (en) 1983-05-02 1990-04-03 Uop Catalytic cracking catalysts and cracking process using mixed catalyst system
US4548914A (en) 1983-08-26 1985-10-22 Mobil Oil Corporation Zeolite catalysts of improved activity and para-selectivity
US4891197A (en) 1983-12-19 1990-01-02 Mobil Oil Corporation Silicophosphoaluminates and related crystalline oxides
US4694114A (en) 1984-01-11 1987-09-15 Mobil Oil Corporation Process for isomerizing alkyl aromatic hydrocarbons utilizing ZSM-23 zeolite and a hydrogenation/dehydrogenation metal
US4758328A (en) 1984-01-17 1988-07-19 Union Oil Company Of California Shock calcined aluminosilicate zeolites
US4623633A (en) 1984-01-17 1986-11-18 Union Oil Company Of California Shock calcined aluminosilicate zeolites
US4716135A (en) 1984-04-09 1987-12-29 Mobil Oil Corporation Organophosphorus-modified zeolites and method of preparation
US4638106A (en) 1984-07-13 1987-01-20 Exxon Research & Engineering Co. Two stage process for improving the catalyst life of zeolites in the synthesis of lower olefins from alcohols and their ether derivatives
US5047141A (en) 1984-07-16 1991-09-10 Mobil Oil Corporation Larger pore molecular sieves of controlled activity
US4912073A (en) 1984-07-16 1990-03-27 Mobil Oil Corp. Larger pore molecular sieves of controlled activity
US4873067A (en) 1984-08-21 1989-10-10 Mobil Oil Corporation Zeolite ZSM-57
IL73146A (en) 1984-10-02 1988-11-15 Yeda Res & Dev Catalysts and process for the production of hydrocarbons and substitution of hydrocarbons
US4891467A (en) 1984-10-15 1990-01-02 Amoco Corporation Selective synthesis of pseudocumene and durene
US4721827A (en) 1985-02-20 1988-01-26 Aristech Chemical Corportion Crystalline magnesia-silica composites and process for producing same
US4623530A (en) 1985-02-20 1986-11-18 United States Steel Corporation Crystalline magnesia-silica composites and process for producing same
JPS61221137A (ja) * 1985-03-28 1986-10-01 Teijin Yuka Kk Ｐ−キシレンの製造法
US4727209A (en) 1985-06-11 1988-02-23 Uop Inc. Hydrocarbon alkylation processes employing a phosphorus-modified alumina composite
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
US4673767A (en) 1985-11-25 1987-06-16 Amoco Corporation AMS-1B crystalline borosilicate molecular sieve-based catalyst compositions and process for toluene alkylation
US4670616A (en) 1985-11-25 1987-06-02 Amoco Corporation AMS-1B crystalline borosilicate molecular sieve-based catalyst compositions and process for toluene methylation
US4695666A (en) 1985-12-09 1987-09-22 Uop Inc. Phosphorus-containing alumina catalyst for the isomerization of aromatics
US4746763A (en) 1987-04-22 1988-05-24 Uop Inc. Process for producing aromatic compounds from C2 -C6 aliphatic hydrocarbons
US4761513A (en) 1987-07-01 1988-08-02 Uop Inc. Temperature control for aromatic alkylation process
FR2623423B1 (fr) 1987-11-23 1990-03-30 Centre Nat Rech Scient Nouveaux catalyseurs a base de zeolithes modifiees par des elements alcalins sous forme metallique, leur preparation et leur application a l'alkylation des derives alkyl-aromatiques
US4935574A (en) 1988-03-29 1990-06-19 E. I. Du Pont De Nemours And Company Preparation of para-xylene by toluene methylation
FR2629444B1 (fr) 1988-04-01 1990-12-07 Rhone Poulenc Chimie Zeolites a base de silice et d'oxyde de germanium et procede de synthese de celles-ci
US4891930A (en) * 1988-04-04 1990-01-09 Schaefer Alan W Apparatus and process for applying a cover, to a round hay bale
US4847223A (en) 1988-04-08 1989-07-11 Concordia University Superacidic catalysts for low temperature conversion of aqueous ethanol to ethylene
US4861930A (en) 1988-09-28 1989-08-29 Uop Combination process for the conversion of a C2 -C6 aliphatic hydrocarbon
GB8829923D0 (en) 1988-12-22 1989-02-15 Ici Plc Zeolites
US5178748A (en) 1988-12-22 1993-01-12 Imperial Chemical Industries Catalytic reactions using zeolites
US5233102A (en) 1989-08-02 1993-08-03 E. I. Du Pont De Nemours And Company Olefin hydration
US5124299A (en) 1989-08-02 1992-06-23 E. I. Du Pont De Nemours And Company Catalysis using blends of perfluorinated ion-exchange polymers with perfluorinated diluents
US5105047A (en) 1989-08-02 1992-04-14 E. I. Du Pont De Nemours And Company Catalysis using blends of perfluorinated ion-exchange polymers with perfluorinated diluents
US5094995A (en) 1989-08-02 1992-03-10 E. I. Du Pont De Nemours And Company Supported perfluorinated ion-exchange polymers
US5043502A (en) 1990-03-16 1991-08-27 Uop Production of xylenes from light aliphatic hydrocarbons via dehydrocyclodimerization and methylation
US5173461A (en) 1990-03-21 1992-12-22 Mobil Oil Corporation Toluene disproportionation catalyst
US5534239A (en) 1990-03-23 1996-07-09 Societe Nationale Elf Aquitaine Process for the synthesis of a silica enriched crystalline aluminosilicate having the offretite structure, the aluminosilicate obtained and its use as a catalyst for the conversion of hydrocarbons
GB9013859D0 (en) 1990-06-21 1990-08-15 Ici Plc Zeolites
GB9013916D0 (en) 1990-06-22 1990-08-15 Ici Plc Zeolites
EP0466545A1 (fr) 1990-06-29 1992-01-15 Rhone-Poulenc Chimie Zéolithes à base de silice et d'oxydes d'éléments tétravalents, leur procédé de synthèse et leur application
JPH06340416A (ja) 1990-08-29 1994-12-13 Rhone Poulenc Chim シリカ及び場合によっては四価元素の酸化物を基材とするゼオライトの製造法
US5110776A (en) 1991-03-12 1992-05-05 Mobil Oil Corp. Cracking catalysts containing phosphate treated zeolites, and method of preparing the same
US5366948A (en) 1991-03-12 1994-11-22 Mobil Oil Corp. Catalyst and catalytic conversion therewith
US5456821A (en) 1991-03-12 1995-10-10 Mobil Oil Corp. Catalytic conversion with improved catalyst
US5348643A (en) 1991-03-12 1994-09-20 Mobil Oil Corp. Catalytic conversion with improved catalyst
US5231064A (en) 1991-03-12 1993-07-27 Mobil Oil Corp. Cracking catalysts comprising phosphorus and method of preparing and using the same
US5171921A (en) 1991-04-26 1992-12-15 Arco Chemical Technology, L.P. Production of olefins
US5387732A (en) 1991-10-15 1995-02-07 Fina Technology, Inc. Start-up process for improved selectivity in toluene disproportionation
US5210356A (en) 1991-12-16 1993-05-11 Fina Technology, Inc. Toluene disproportionation employing modified omega zeolite catalyst
US5227558A (en) 1992-02-10 1993-07-13 Fina Technology, Inc. Aromatic alkylation process employing steam modified zeolite beta catalyst
US5571768A (en) 1992-03-12 1996-11-05 Mobil Oil Corporation Zeolite functionalized with organosiliceous groups
US5321183A (en) 1992-03-12 1994-06-14 Mobil Oil Corp. Process for the regioselective conversion of aromatics to para-disubstituted benzenes
US5475179A (en) 1992-03-12 1995-12-12 Mobil Oil Regioselective production of para-dialkyl benzenes
US5498814A (en) 1992-03-12 1996-03-12 Mobil Oil Corp. Regioselective methylation of toluene to para-xylene
US5516736A (en) 1992-03-12 1996-05-14 Mobil Oil Corp. Selectivating zeolites with organosiliceous agents
EP0568913A3 (en) 1992-05-03 1995-03-22 Dalian Chemical Physics Inst Process for the conversion of methanol into light olefins and catalyst used therefor.
US5318696A (en) 1992-12-11 1994-06-07 Mobil Oil Corporation Catalytic conversion with improved catalyst catalytic cracking with a catalyst comprising a large-pore molecular sieve component and a ZSM-5 component
US5294578A (en) 1992-12-23 1994-03-15 Mobil Oil Corp. Supported acid catalysts, their preparation and use in organic compound conversion
US5336824A (en) 1993-01-29 1994-08-09 Fina Technology, Inc. Mordenite catalysts in toluene synthesis
US5349113A (en) 1993-02-25 1994-09-20 Mobil Oil Corp. Shape selective hydrocarbon conversion over pre-selectivated, activated catalyst
US5365003A (en) 1993-02-25 1994-11-15 Mobil Oil Corp. Shape selective conversion of hydrocarbons over extrusion-modified molecular sieve
CN1034223C (zh) 1993-03-29 1997-03-12 中国石油化工总公司 制取低碳烯烃的裂解催化剂
US5378670A (en) 1993-04-16 1995-01-03 W. R. Grace & Co.-Conn. Phosphorus zeolites/molecular sieves
US5362697A (en) 1993-04-26 1994-11-08 Mobil Oil Corp. Synthetic layered MCM-56, its synthesis and use
US5430213A (en) 1993-05-06 1995-07-04 Exxon Chemical Patents Inc. Process for producing 1,4-dienes
US5523510A (en) 1993-08-30 1996-06-04 Texaco Inc. Treated bound ferrierite zeolites for skeletal isomerization of n-olefins to iso-olefins
US5563310A (en) 1993-09-14 1996-10-08 Mobil Oil Corporation Toluene alkylation with methanol
ES2139752T3 (es) 1993-10-18 2000-02-16 Mobil Oil Corp Material cristalino poroso sintetico, mcm-58, su sintesis y uso.
EP0655277A1 (en) 1993-11-01 1995-05-31 Csir Amorphous aluminosilicate catalyst
ES2139197T3 (es) * 1994-03-31 2000-02-01 Infineum Usa Lp Reacciones de polimerizacion con catalizadores de acidos de lewis soportados.
WO1995026814A1 (en) 1994-03-31 1995-10-12 Exxon Chemical Patents Inc. Supported lewis acid catalysts derived from superacids useful for hydrocarbon conversion reactions
US5561095A (en) * 1994-03-31 1996-10-01 Exxon Chemical Patents Inc. Supported lewis acid catalysts for hydrocarbon conversion reactions
US5576256A (en) 1994-05-23 1996-11-19 Intevep, S.A. Hydroprocessing scheme for production of premium isomerized light gasoline
US5646314A (en) 1994-11-16 1997-07-08 Arco Chemical Technology, L.P. Process for titanium silicalite-catalyzed epoxidation
US5573746A (en) 1995-06-06 1996-11-12 Mobil Oil Corporation Zeolite synthesis with amino acid directing agents
US6060633A (en) * 1995-10-20 2000-05-09 Chen; Frank Joung-Yei Supported Lewis acid catalysts derived from superacids useful for hydrocarbon conversion reactions
CA2204461C (en) * 1996-05-14 2006-07-04 Thomas V. Harris Process for producing an alkylated, non-oxygen-containing aromatic hydrocarbon
ZA978671B (en) * 1996-10-02 1999-03-26 Mobil Oil Corp Selective para-xylene production by toluene methylation
US6048816A (en) * 1996-10-02 2000-04-11 Mobil Oil Corporation Catalyst and process for converting methanol to hydrocarbons
WO1998023373A1 (fr) * 1996-11-27 1998-06-04 Idemitsu Kosan Co., Ltd. Procede de production d'un catalyseur pour l'epuration des gaz d'echappement
US5925586A (en) * 1996-12-31 1999-07-20 Exxon Chemical Patents, Inc. Phosphorus modified small pore molecular sieve catalysts, and their use in the production of light olefins
US5905051A (en) * 1997-06-04 1999-05-18 Wu; An-Hsiang Hydrotreating catalyst composition and processes therefor and therewith
US5898089A (en) * 1997-07-09 1999-04-27 Phillips Petroleum Company Hydrocarbon aromatization process using a zeolite
US6034283A (en) * 1997-07-18 2000-03-07 Asahi Kasei Kogyo Kabushiki Kaisha Process for production of cyclic alcohols
US6047544A (en) * 1997-08-20 2000-04-11 Nissan Motor Co., Ltd. Engine exhaust gas purification catalyst and exhaust gas purifier
EP0903178B2 (en) * 1997-09-17 2012-05-30 China Petro-Chemical Corporation A pentasil-type molecular sieve containing composition, its preparation method and use
US6423879B1 (en) * 1997-10-02 2002-07-23 Exxonmobil Oil Corporation Selective para-xylene production by toluene methylation
NO318036B1 (no) * 1997-10-15 2005-01-24 Res Inst Petroleum Processing Katalysator for katalytisk pyrolyseprosess for fremstilling av lette olefiner og fremgangsmate for fremstilling derav
US6040257A (en) * 1997-11-07 2000-03-21 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and processes therefor and therewith
EP1044068A1 (en) * 1997-12-03 2000-10-18 Exxon Chemical Patents Inc. Catalyst comprising a zeolite partially coated with a second zeolite, its use for hydrocarbon conversion
CN1069682C (zh) * 1997-12-23 2001-08-15 中国石油化工总公司 重油催化热裂解层柱粘土催化剂及其制备
US6395664B1 (en) * 1998-02-19 2002-05-28 Uop Llc Process for reactivating a deactivated dehydrocyclodimerization catalyst with water
US5907073A (en) * 1998-02-24 1999-05-25 Fina Technology, Inc. Aromatic alkylation process
US6074975A (en) * 1998-03-03 2000-06-13 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and processes therefor and therewith
US6417421B1 (en) * 1998-03-03 2002-07-09 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and process therefor and therewith
US6080303A (en) * 1998-03-11 2000-06-27 Exxon Chemical Patents, Inc. Zeolite catalyst activity enhancement by aluminum phosphate and phosphorus
ES2224702T3 (es) * 1998-09-28 2005-03-01 Bp Corporation North America Inc. Procedimiento para la produccion de olefinas empleando un catalizador a base de pentasil zaolita.
JP3868128B2 (ja) * 1998-10-05 2007-01-17 新日本石油株式会社 軽油の水素化脱硫装置及び方法
JP3871449B2 (ja) * 1998-10-05 2007-01-24 新日本石油株式会社 軽油の水素化脱硫方法
CN1096296C (zh) * 1998-11-13 2002-12-18 中国石油化工集团公司 一种生产中间馏分油的加氢裂化催化剂及其制备
US6057485A (en) * 1998-11-17 2000-05-02 Fina Technology, Inc. Gas phase alkylation with split load of catalyst
US6090274A (en) * 1998-12-29 2000-07-18 Phillips Petroleum Company Hydrotreating catalyst composition and processes therefor and therewith
US6268305B1 (en) * 1999-02-27 2001-07-31 Fina Technology, Inc. Catalysts with low concentration of weak acid sites
US6090991A (en) * 1999-02-27 2000-07-18 Fina Technology, Inc. Gas phase alkylation method and catalyst
US6222084B1 (en) * 1999-04-09 2001-04-24 Fina Technology, Inc. Gas phase alkylation-liquid phase transalkylation process
US6699811B1 (en) * 1999-05-05 2004-03-02 Exxon Mobil Chemical Patents Inc. Tailored zeolite bound zeolite catalyst and its use for hydrocarbon conversion
US6388156B1 (en) * 1999-05-14 2002-05-14 Exxonmobil Chemical Patents Inc. Direct selective synthesis of para-xylene by reacting an aromatic compound with a methylating agent formed from CO, Co2 and H2
JP3859940B2 (ja) * 1999-08-06 2006-12-20 日産自動車株式会社 排気ガス浄化用触媒及びその製造方法
US6187982B1 (en) * 1999-10-15 2001-02-13 Mobil Oil Corporation Process for converting dienes and oxygenates to para-xylene and light olefins
US6726834B2 (en) * 1999-10-22 2004-04-27 Intevep, S.A. Process for catalytic cracking of a hydrocarbon feed with a MFI aluminisilcate composition
EP1116775A1 (en) * 2000-01-12 2001-07-18 Akzo Nobel N.V. Catalyst composition with high efficiency for the production of light olefins
JP3489048B2 (ja) * 2000-02-01 2004-01-19 日産自動車株式会社 排気ガス浄化用触媒
US6506954B1 (en) * 2000-04-11 2003-01-14 Exxon Mobil Chemical Patents, Inc. Process for producing chemicals from oxygenate
JP3904802B2 (ja) * 2000-04-26 2007-04-11 日産自動車株式会社 排気ガス浄化用触媒及びその製造方法
TWI240716B (en) * 2000-07-10 2005-10-01 Bp Corp North America Inc Pressure swing adsorption process for separating paraxylene and ethylbenzene from mixed C8 aromatics
US7285511B2 (en) * 2004-04-23 2007-10-23 Saudi Basic Industries Corporation Method of modifying zeolite catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5951963A (en) * 1997-03-24 1999-09-14 China Petrochemical Corporation Phosphorous containing zeolite having MFI type structure
US20050070749A1 (en) * 2003-09-30 2005-03-31 Ghosh Ashim Kumar Toluene methylation process

Also Published As

Publication number Publication date
JP5107906B2 (ja) 2012-12-26
WO2006127827A3 (en) 2007-10-25
EP1893530A4 (en) 2011-10-26
US20050240070A1 (en) 2005-10-27
KR20080019012A (ko) 2008-02-29
KR101321217B1 (ko) 2013-10-23
EP1893530A2 (en) 2008-03-05
US7399727B2 (en) 2008-07-15
JP2008545528A (ja) 2008-12-18
CN101180239A (zh) 2008-05-14
WO2006127827A2 (en) 2006-11-30

Similar Documents

Publication Publication Date Title
CN101180239B (zh) 沸石催化剂和方法
EP2138231B1 (en) Method of modifying zeolite catalyst
US7368410B2 (en) Zeolite catalyst and method of preparing and use of zeolite catalyst
RU2494809C2 (ru) Катализатор для каталитического крекинга углеводорода, который применяют при получении легкого олефина, и способ его получения
CN100404480C (zh) 甲苯甲基化工艺
RU2659066C2 (ru) Получение пара-ксилола
KR20080013953A (ko) 인 담지 제올라이트 촉매의 열수 처리
CN103987456A (zh) 制备磷改性的沸石催化剂的方法
CN102259018B (zh) 一种zsm-5复合分子筛及其制备方法
GB2114998A (en) Alkylation of aromatics employing silicalite catalysts
CN112844453B (zh) 一种zsm-5催化剂及其制备方法和用途
CN101514018B (zh) Zsm-5/丝光沸石/mcm-56三相共生分子筛及其合成方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20110330

Termination date: 20210524

CF01 Termination of patent right due to non-payment of annual fee