CN101184710B - 磷改性沸石催化剂的水热处理 - Google Patents
磷改性沸石催化剂的水热处理 Download PDFInfo
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 141
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
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- 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
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- 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
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Abstract
一种处理ZSM-5型沸石催化剂的方法,其通过用磷化合物处理氧化硅/氧化铝摩尔比至少约200的ZSM-5沸石催化剂来进行。将磷处理的ZSM-5沸石催化剂进行煅烧和汽蒸。在低于约300℃的温度下对该催化剂进行汽蒸。该磷处理的ZSM-5沸石催化剂具有小于催化剂0.05重量%的除磷之外的任何其它金属,该金属通过使用含有所述其它金属的化合物处理该ZSM-5沸石来提供。该催化剂可用于芳族烷基化,其通过在反应器内于适合芳族烷基化的条件下,使该催化剂与芳烃和烷基化试剂进料接触来进行。在芳族烷基化反应期间将水作为共同进料引入反应器内。
Description
技术领域
本发明总体上涉及芳族化合物的烷基化和用于该烷基化的催化剂。
背景技术
对二甲苯是一种有价值的取代芳族化合物,因为非常需要将其氧化成对苯二甲酸这种在形成聚酯纤维和树脂中的主要组分。它可通过石脑油的加氢处理(催化重整),石脑油或柴油的蒸汽裂解,以及甲苯岐化而在商业上得到。
使用甲醇的甲苯的烷基化也被称作甲苯甲基化,已用于实验室研究以生产对二甲苯。已知甲苯甲基化在酸性催化剂、尤其是沸石或沸石型催化剂上进行。尤其是,ZSM-5型沸石、β沸石和硅铝磷酸盐(SAPO)催化剂已用于该工艺。通常,如下面反应所示,邻(o)二甲苯、间(m)二甲苯和对(p)二甲苯的热动力学平衡混合物可由甲苯的甲基化形成。
邻二甲苯、间二甲苯和对二甲苯的热动力学平衡组合物在约500℃的反应温度下可分别为约25、50和25摩尔%。但这种甲苯甲基化可在宽温度范围内进行。副产物如C9+和其它芳族产物可通过二甲苯产物的二次烷基化而制得。
可通过吸附和异构化的一个循环将对二甲苯从混合二甲苯中分离。由于平衡混合物的异构浓度低,必须将该循环重复几次。高纯度等级(99+%)的对二甲苯适合被氧化成对苯二甲酸。但是,这么高纯度等级的对二甲苯生产成本很高。当初始二甲苯产物中对二甲苯的浓度为约80%或更高时,可使用一种不同的利用了结晶技术的方法,并且该方法花费可较低。因此,希望对二甲苯的浓度高于平衡浓度。
如果催化剂具有择形性能,则可在甲苯甲基化反应中得到明显较高量的对二甲苯。择形性能可在改性的沸石催化剂中通过窄化沸石孔开口尺寸、钝化沸石的外表面或控制沸石酸度而得到。甲苯甲基化可在改性的ZSM-5或ZSM-5型沸石催化剂上进行,得到包含的对二甲苯量明显高于热动力学浓度的二甲苯产物。
在Kaeding等人的,使用甲醇选择性烷基化甲苯制备对二甲苯,催化杂志(Journal of Catalysis),Vol.67,第159-174页(1981)中,描述了一种通过引入5%的磷而制备ZSM-5催化剂的方法,其中催化剂用二苯基三价膦酸在甲苯中的溶液浸渍。如此改性的ZSM-5催化剂表现出的甲苯甲基化活性是在二甲苯产物中具有84-90%的对位异构体。在另一方法中,催化剂通过由水性磷酸试剂中引入8.51%的磷而改性。该催化剂表现出高达97%的对二甲苯选择性,但是该催化剂由于炭沉积而表现出在数小时内活性降低。
遗憾的是,甲苯甲基化的商业成功存在许多技术障碍,需要进行改进。
附图简要描述
为了更加全面地理解本发明,现结合附图进行以下描述,其中:
图1显示了P改性的ZSM-5在汽蒸之前(谱图a)和在610℃下汽蒸13天之后(谱图b)的27Al MAS NMR谱图。
详细描述
具体地说,本发明公开了以下内容:
1.一种处理ZSM-5型沸石催化剂的方法,包括:
用含磷化合物处理氧化硅/氧化铝摩尔比至少200的ZSM-5沸石,其中含磷化合物选自膦酸、三价膦酸、亚磷酸和五价磷酸,这些酸的盐和酯以及卤化磷;
煅烧经过磷处理的ZSM-5沸石催化剂;和
用温度150℃-300℃的蒸汽对经过磷处理的ZSM-5沸石催化剂进行汽蒸,且其中经过磷处理的ZSM-5沸石催化剂除磷之外具有小于催化剂的0.05重量%的任何其它金属,该金属由使用含所述其它金属的化合物对ZSM-5进行处理来提供。
2.上款1的方法,其中:
经过磷处理的ZSM-5沸石催化剂具有至少0.08g P/g沸石的磷含量。
3.上款1的方法,其中:
经过磷处理的ZSM-5沸石催化剂具有至少0.08g P/g沸石至0.15g P/g沸石的磷含量。
4.上款1的方法,其中:
ZSM-5沸石催化剂的氧化硅/氧化铝摩尔比至少250。
5.上款1的方法,其中:
在150℃至250℃的温度下对经过磷处理的ZSM-5沸石催化剂进行汽蒸。
6.上款1的方法,其中:
在至少300℃的温度下煅烧经过磷处理的ZSM-5沸石催化剂。
7.一种制备烷基芳族产品的方法,包括:
用含磷化合物处理具有氧化硅/氧化铝摩尔比至少200的ZSM-5沸石,其中含磷化合物选自膦酸、三价膦酸、亚磷酸和五价磷酸,这些酸的盐和酯以及卤化磷;
煅烧经过磷处理的ZSM-5沸石催化剂;和
用温度低于300℃的蒸汽对该经过磷处理的ZSM-5沸石催化剂进行汽蒸,且其中经过磷处理的ZSM-5沸石催化剂除磷之外具有小于催化剂的0.05重量%的任何其它金属,该金属由使用含有所述其它金属的化合物对ZSM-5进行处理来提供;
在反应器内于适合芳族烷基化反应的条件下,使催化剂与芳烃和烷基化试剂的加料接触;和
在芳族烷基化反应期间将水共加料引入反应器内。
8.上款7的方法,其中:
芳烃是甲苯且烷基化试剂是甲醇。
9.上款7的方法,其中:
经过磷处理的ZSM-5沸石催化剂具有至少0.08g P/g沸石的磷含量。
10.上款7的方法,其中:
经过磷处理的ZSM-5沸石催化剂具有至少0.08g P/g沸石至0.15g P/g沸石的磷含量。
11.上款7的方法,其中:
ZSM-5沸石催化剂的氧化硅/氧化铝摩尔比至少250。
12.上款7的方法,其中:
在150℃至250℃的温度下对经过磷处理的ZSM-5沸石催化剂进行汽蒸。
13.上款7的方法,其中:
在至少300℃的温度下煅烧经过磷处理的ZSM-5沸石催化剂。
14.一种制备二甲苯产品的方法,包括:
用含磷化合物处理氧化硅/氧化铝摩尔比至少250的ZSM-5沸石催化剂,以提供0.08g P/g沸石至0.15g P/g沸石的磷含量,其中含磷化合物选自膦酸、三价膦酸、亚磷酸和五价磷酸,这些酸的盐和酯以及卤化磷;
在300℃及以上的温度下煅烧经过磷处理的ZSM-5沸石催化剂;
用温度为150℃-250℃的蒸汽对该经过磷处理的ZSM-5沸石催化剂进行汽蒸,且其中经过磷处理的ZSM-5沸石催化剂除磷之外具有小于催化剂的0.05重量%的任何其它金属,该金属由使用含有所述其它金属的化合物对ZSM-5进行处理来提供;
在反应器内于适合甲苯甲基化反应的条件下,使催化剂与甲苯和甲醇的加料接触;和
在反应期间将水共加料引入反应器内。
15.上款14的方法,其中:
以每摩尔甲苯和甲醇加料0.2摩尔至小于10摩尔水的比例将共加料水加入到反应器内。
16.上款14的方法,其中:
以每摩尔甲苯和甲醇加料0.3摩尔至小于7摩尔水的比例将共加料水加入到反应器内。
17.上款14的方法,其中:
反应器的催化剂床入口温度维持在低于700℃。
18.上款14的方法,其中:
甲苯/甲醇加料具有1∶2至10∶1的甲苯/甲醇摩尔比。
用含磷化合物对ZSM-5型沸石催化剂进行改性表现出的是,得到的对二甲苯的量显著高于使用未改性催化剂的甲苯甲基化时的热动力学平衡值。这种改性表现出可提供大于80%的对二甲苯选择性。虽然这种磷处理ZSM-5催化剂可具有高的对二甲苯选择性,但它们趋于以极快的速率失活,例如,该催化剂在一天内可失去其初始活性的50%以上。这可能是由于催化剂上的炭沉积。
本文中所使用的术语“ZSM-5型”是指结构上与ZSM-5沸石相同的那些。另外,术语“ZSM-5”和“ZSM-5型”在本文中可互换地使用以相互包括并且不应以限定方式理解。本文中所使用的催化剂活性可表示为相对加入的甲苯的摩尔数而言的被转化的甲苯的%摩尔,且可定义为:
摩尔%甲苯转化率=[(Ti-T0)/Ti]×100 (2)
其中Ti是加入的甲苯的摩尔数,T0是未反应的甲苯的摩尔数。本文中所使用的混合二甲苯的选择性可表示为:
摩尔%混合二甲苯选择性=[Xmx/(Ti-T0)]×100 (3)
其中Xmx是产物中总(邻、间或对)二甲苯的摩尔数。
本文中所使用的对二甲苯的选择性可表示为:
摩尔%对二甲苯选择性=(Xp/Xmx)×100 (4)
其中Xp是对二甲苯的摩尔数。
本文中所使用的甲醇的选择性可表示为:
摩尔%甲醇选择性=[Xmx/(Mi-M0)]×100 (5)
其中,Xmx是混合二甲苯的摩尔数,Mi是加入的甲醇的摩尔数,以及M0是未反应的甲醇的摩尔数。
在美国专利No.3,702,886中描述了ZSM-5沸石催化剂和它们的制备,通过引用将其合并到本文中。在本发明中,ZSM-5沸石催化剂可包括在改性之前具有200或更高、更优选约250或更高以及还更优选约280-约1000或更高的氧化硅/氧化铝摩尔比的那些。所述沸石可具有0.5微米或更大、更优选约0.5-约5.0微米以及还更优选约0.5-1.0微米的粒径。起始ZSM-5沸石可以是NH4-ZSM-5沸石或H-ZSM-5沸石,或者是其它阳离子交换ZSM-5沸石。
可通过用含磷(P)化合物处理来对ZSM-5沸石进行改性。可对这种改性催化剂进行处理以提供约0.01g P/g沸石或更高、更优选约0.08g P/g沸石至约0.15g P/g沸石、尤其更优选约0.09g P/g沸石至约0.13g P/g沸石的磷含量。这种含磷化合物可包括例如膦酸、三价膦酸、亚磷酸和五价磷酸,这些酸的盐和酯,以及卤化磷。特别地,五价磷酸(H3PO4)和磷酸氢铵((NH4)2HPO4)特别适合用作含磷化合物,以提供给甲苯甲基化催化剂择形性能,从而得到高的对二甲苯浓度。
可通过各种技术进行所述磷处理。这可包括浆料蒸发和初湿法(wetincipient methods)。在浆料蒸发中,通过制备沸石和磷化合物水溶液的水性浆料可将磷引入到催化剂中。可采用加热浆料来促进沸石的处理和液体的蒸发。将浆料加热至70℃和更高的温度是合适的。也可在该步骤期间搅拌和搅动浆料以确保均匀处理。将浆料加热至液体几乎完全蒸发,致使产生捏塑体,可干燥或煅烧该捏塑体以形成粉末或块。
在初湿法中,可通过例如喷淋来加入磷化合物的水性溶液,干燥沸石而不形成浆料。可将初始时可以是粉末形式的所述干燥沸石与磷化合物混合以形成捏塑体。如果必要,可向混合物中加入水来促进沸石捏塑体的形成。然后可干燥或煅烧该捏塑体以磷改性的沸石粉末或颗粒。
应注意的是,ZSM-5沸石在结构上包含Al、Si和O,并且除磷之外可不包含或仅包含痕量的任何其它金属(例如B、Be、Ca、Cd、Co、Fe和Mg等),它还包括元素周期表的IA、IIA、IIIA、IVA、VA、VIA、VIIA、VIIIA、IB、IIB、IIIB、IVB或VB族的任何金属,这些金属用于提高催化剂的对位选择性。ZSM-5沸石可不进行处理以提供除磷之外的任何其它这些金属,从而提高催化剂的对位选择性。如果由任何这种处理来提供除磷之外的金属,则ZSM-5沸石可包含小于催化剂的0.05重量%的这种金属,更优选小于催化剂的0.01重量%的这种金属,以及还更优选小于催化剂的0.001重量%的这种金属。
催化剂可以是粘结或非粘结的。合适粘结剂的例子包括诸如氧化铝、粘土和氧化硅这样的材料。那些用于制备粘结催化剂的技术在本领域中是公知的。可在400℃或更高的温度下于含氧环境(通常是空气)中煅烧粘结的或非粘结的磷改性沸石催化剂。煅烧可进行通常从几分钟到一小时或更长的时间。也可随时间逐渐提高温度来进行煅烧。
煅烧的P改性ZSM-5沸石可具有150-200m2/g的BET表面积,该面积通过N2吸附技术测得。总孔容可为0.10-0.18ml/g催化剂。通过氨程序升温脱附(NH3-TPD)技术进行表征,该催化剂的酸度可显示出具有在250℃与350℃之间的峰极值的宽峰。
在低的或适度的温度下对磷处理ZSM-5沸石催化剂进行汽蒸。可通过在氢气或空气或其它惰性气体的存在下使沸石催化剂与蒸汽接触来进行汽蒸。汽蒸温度可在约150℃至约250℃、300℃或350℃的范围内。这可在任何芳族烷基化反应或引入任何反应加料之前独立地或在反应器内原位地完成。汽蒸可通过在氢气或空气或其它惰性气体的存在下接触催化剂来进行。汽蒸可进行几分钟至几小时。由27Al MAS NMR证实,对磷处理的ZSM-5沸石进行如此汽蒸没有造成铝(Al)从沸石骨架中去除。
根据本发明对磷处理的ZSM-5沸石催化剂进行汽蒸之后,可观测到催化剂在芳族烷基化反应中的催化活性和选择性得以提高。将其与在相同或相似条件下所使用的未进行汽蒸或者在较高温度下进行汽蒸的同样的磷处理ZSM-5沸石催化剂进行对比。观测到对位选择性的增加以及烷基化试剂选择性的增加。特别地,对于在甲苯甲基化反应时使用的该催化剂,观测到甲醇选择性显著提高。
在烷基化反应期间,通过向反应器中另外引入作为共加料的水或蒸汽,经适度汽蒸的磷改性ZSM-5沸石催化剂的选择性和催化活性还可获得进一步的提高。在2003年9月30日提交的共同未决美国专利申请No.10/675,780中描述了在反应期间引入蒸汽,通过引用将其合并到本文中。引入到反应器中的水可以这样的比例加入到反应器内,该比例为每摩尔芳烃和烷基化试剂约0.1或更多的水和可小于约10摩尔的水,更优选地为每摩尔芳烃和烷基化试剂约0.3至约5、6或7摩尔的水。在某些情况下,可以每摩尔芳烃和烷基化试剂约0.2至1.2摩尔的水、更尤其每摩尔芳烃和烷基化试剂约0.3至约0.9摩尔的水这样的比例将水加入。与氢共加料相结合或不结合或者与任何惰性气体的引入相结合来完成作为共加料的水(或蒸汽)的加入。可将水共加料加入到反应器内,由于该反应器内存在这些加入的水,该反应器中的条件使得基本上没有产生催化剂的结构铝的损失。
在用或不用催化剂汽蒸的、用P改性的ZSM-5催化剂进行芳族烷基化反应中,用和不用水共加料,可将甲苯和甲醇加料在引入反应器之前进行预混合,作为单一混合加料流。该加料也可包含少量的水、C9+芳族化合物和其它化合物。然而,本文中显示的液时空速是基于不包括其它任何组分的甲苯/甲醇加料。加料中甲苯/甲醇摩尔之比可为0.5-10.0,更优选为1.0-5.0。任选地,可将共加料气体与甲苯/甲醇和蒸汽一起加入。共加料气体可以包括氢气、氮气、氦气或其它惰性气体。可以相对于甲苯和甲醇而言小于约10的摩尔比来提供共加料气体。本文中所使用的反应器温度是指催化剂床入口温度,且提供了400℃-700℃的反应器温度。
在催化测试运行期间可保持反应器入口压力基本恒定。反应器入口压力可为约10psig或更高。
可在固定床、连续流动型反应器中以向下流动模式进行反应。单个反应器或者串联和/或并联的多个反应器适合进行该反应。逐渐提高反应器的温度。起初,在将加料引入反应器内时,反应器温度可为约200℃或以上。然后可将温度提高至所需温度。可以约0.1℃/min-约10℃/min的速率逐渐提高温度,以提供约400℃-约700℃的温度。
下面的实施例更好地用于说明本发明。
实施例
使用下述操作,使用ZSM-5沸石粉末作为起始物料制备磷处理的沸石催化剂A、B和C。使用磷酸来处理沸石。起始沸石粉末是SiO2/Al2O3摩尔之比为约280的NH4-ZSM-5沸石粉末。起始沸石粉末的晶体粒径为约0.5-1.0微米。
催化剂A
通过如下的浆料方法制得磷改性的ZSM-5催化剂。在2000ml的烧杯中制备包含450.0g的NH4-ZSM-5沸石和900ml的去离子水的浆料。将该烧杯放置在电热板上并使用机械(悬臂)搅拌器以250-300rpm搅拌沸石悬浮液。将悬浮液的温度缓慢升至约80-85℃,在该温度下缓慢加入磷酸。磷酸以205.2g(85重量%水溶液)的量加入到浆料中。进一步将该浆料的温度升至95-100℃并且继续加热直至所有的液体被蒸发以形成捏塑体。在对流烘箱中于空气中以如下温度程序煅烧磷酸改性的沸石:90℃-120℃下4小时;在340℃-360℃下3小时;和520℃-530℃下于空气下10小时。然后将煅烧过的沸石粉碎并使用20和40目筛网进行筛分。该磷改性的ZSM-5沸石催化剂包含9.01g P/g沸石。
催化剂B
通过如下的浸渍法制得磷改性的ZSM-5催化剂。将50.01g量的沸石粉末放入500ml烧杯中。向该烧杯中缓慢加入22.68g的H3PO4(85%水溶液)并同时剧烈搅拌。喷水以润湿沸石粉末并形成捏塑体。然后将该催化剂转移至陶瓷盘中,并在对流烘箱中于空气中以如下温度程序进行煅烧:90℃-120℃下4小时;在340℃-360℃下3小时;和510℃-530℃下于空气下10小时。然后将煅烧过的沸石粉碎并使用20和40目筛网进行筛分。该磷改性的ZSM-5沸石催化剂包含9.02g P/g沸石。
催化剂C
按如下方法制得磷改性的ZSM-5粘结催化剂。在2000ml的烧杯中制备包含450.0g的NH4-ZSM-5沸石和900ml的去离子水的浆料。将该烧杯放置在电热板上并使用机械(悬臂)搅拌器以250-300rpm搅拌沸石悬浮液。将悬浮液的温度缓慢升至约80-85℃,在该温度下缓慢加入磷酸。将重205.2g的磷酸(85重量%水溶液)加入到浆料中。进一步将该浆料的温度升至95-100℃并且继续加热直至所有的液体被蒸发以形成捏塑体。在对流烘箱中于空气中以如下温度程序煅烧磷酸改性的沸石:90℃-120℃下4小时;340℃-360℃下3小时;和510℃-520℃下于空气下10小时。然后将部分煅烧沸石粉碎并使用80目筛网进行筛分。该P/ZSM-5催化剂包含9.36g P/g沸石。然后用10重量%的氧化铝(商业级氧化铝,Alcoa,HiQ-40,拟勃姆石型氧化铝)粘结该粉末P/ZSM-5。首先用硝酸使该氧化铝胶溶,然后将其与P/ZSM-5粉末混合并剧烈混合,用水喷淋以形成捏塑体。使用与P/ZSM-5相同的煅烧温度分布煅烧该捏塑体。然后将煅烧沸石粉碎并使用20和40目筛网进行筛分。该粘结的催化剂包含8.4g P/g催化剂。
实施例1-4
在甲苯甲基化中使用催化剂A。将装量为5.4ml的催化剂A放入到1/2英寸管式反应器的中点附近。将碳化硅(SiC)层加到催化剂床的两端。在系统中于60-80psig下对反应器进行检漏。该催化剂在使用之前于200℃下在H2流中干燥至少一个小时。在实施例1和3中,未进行任何催化剂预处理而将反应器加料引入,即没有催化剂汽蒸。然而,在实施例2和4中,为了检验催化剂汽蒸的影响,首先干燥该催化剂,然后通过在200℃下使含有H2O的氢气(10-12摩尔%)流动过夜对其进行汽蒸。通过以4.5的摩尔比混合甲苯和甲醇而制得加料。以2.0-2.1hr-1的LHSV引入预混合的甲苯/甲醇。当任选向反应器加料中加入水时,以0.8的H2O/(甲苯+甲醇)摩尔比引入水(见实施例2和4)。以预定的速率将氢气加入到加料中以维持所选的7-8的H2/(甲苯+甲醇)摩尔比。将催化剂床入口温度升至约550℃。当催化剂性能达到稳定状态时,使用等式2-4计算转化率和选择性。在下面表1中显示了实施例1-4中得到的转化率和选择性。
表1
实施例5-6
就催化剂A检验催化剂汽蒸温度的影响。在所有情况中,首先在氢气流中于200℃下干燥催化剂一小时。然后通过使含有10-12摩尔%H2O的氢气在200℃、300℃或500℃下流动过夜来对该催化剂进行汽蒸。使用与实施例4相同的反应条件。结果汇总于下面表2中。
表2
实施例7-8
就催化剂B检验催化剂汽蒸的影响。在所有情况中,首先在氢气流中于200℃下干燥催化剂一小时。在实施例7中未对催化剂进行预汽蒸。在实施例8中,在干燥催化剂之后,然后通过使含有10-12摩尔%H2O的氢气在200℃下流动过夜来对其进行汽蒸。使用与实施例4相同的反应条件。结果汇总于下面表3中。
表3
实施例9-10
还就催化剂C检验了催化剂汽蒸的影响。在所有情况中,首先在氢气流中于200℃下干燥催化剂一小时。在实施例9中,未对催化剂进行预汽蒸,而在实施例10中,在干燥催化剂之后,然后通过使含有10-12摩尔%H2O的氢气在200℃下流动过夜来对其进行汽蒸。使用与实施例4相同的使用H2O共进料的反应条件。结果汇总于下面表4中。
表4
实施例11
对于P改性的ZSM-5催化剂(例如催化剂A),记录27Al MAS NMR谱图。通过将约5.4ml的筛分催化剂(20-40目)放置在不锈钢反应器内来进行汽蒸。然后在200℃在50cc/min的H2或N2流中干燥催化剂至少一小时。将气体流速增加至459cc/min,并且以0.04ml/min将液体水引入通过200℃的蒸发器。然后将反应器温度提高至所需汽蒸温度且通常继续汽蒸过夜。参考图1,未被汽蒸的催化剂的27Al MAS-NMR谱图显示出归于沸石骨架铝的在50-55ppm的弱峰。在-12ppm附近观测到强峰,该峰归于非骨架铝(EFAl)。在610℃下汽蒸(13天)后的催化剂A的27Al MAS-NMR谱图显示出骨架Al或EFAl没有变化或变化很小。
尽管仅根据本发明的某些形式对其进行说明,但对本领域技术人员来说显而易见的是,它不受如此限制,而是在不背离本发明的范围的情况下易于进行各种改变和修饰。因而正确的是,应宽泛地并且按照与本发明范围一致的方式来理解所附权利要求书。
Claims (18)
1.一种处理ZSM-5型沸石催化剂的方法,包括:
用含磷化合物处理氧化硅/氧化铝摩尔比至少200的ZSM-5沸石催化剂,其中含磷化合物选自膦酸、三价膦酸、亚磷酸和五价磷酸,这些酸的盐和酯以及卤化磷;
煅烧经过磷处理的ZSM-5沸石催化剂;和
用温度150℃-300℃的蒸汽对经过磷处理的ZSM-5沸石催化剂进行汽蒸,且其中经过磷处理的ZSM-5沸石催化剂除磷之外具有小于催化剂的0.05重量%的任何其它金属,该金属由使用含所述其它金属的化合物对ZSM-5沸石进行处理来提供,并且经过磷处理的ZSM-5沸石催化剂具有至少0.01g P/g沸石的磷含量。
2.权利要求1的方法,其中:
经过磷处理的ZSM-5沸石催化剂具有至少0.08g P/g沸石的磷含量。
3.权利要求1的方法,其中:
经过磷处理的ZSM-5沸石催化剂具有至少0.08g P/g沸石至0.15gP/g沸石的磷含量。
4.权利要求1的方法,其中:
ZSM-5沸石催化剂的氧化硅/氧化铝摩尔比至少250。
5.权利要求1的方法,其中:
在150℃至250℃的温度下对经过磷处理的ZSM-5沸石催化剂进行汽蒸。
6.权利要求1的方法,其中:
在至少300℃的温度下煅烧经过磷处理的ZSM-5沸石催化剂。
7.一种制备烷基芳族产品的方法,包括:
用含磷化合物处理具有氧化硅/氧化铝摩尔比至少200的ZSM-5沸石催化剂,其中含磷化合物选自膦酸、三价膦酸、亚磷酸和五价磷酸,这些酸的盐和酯以及卤化磷;
煅烧经过磷处理的ZSM-5沸石催化剂;和
用温度150℃-300℃的蒸汽对该经过磷处理的ZSM-5沸石催化剂进行汽蒸,且其中经过磷处理的ZSM-5沸石催化剂除磷之外具有小于催化剂的0.05重量%的任何其它金属,该金属由使用含有所述其它金属的化合物对ZSM-5沸石进行处理来提供,并且经过磷处理的ZSM-5沸石催化剂具有至少0.01g P/g沸石的磷含量;
在反应器内于适合芳族烷基化反应的条件下,使催化剂与芳烃和烷基化试剂的加料接触;和
在芳族烷基化反应期间将水共加料引入反应器内。
8.权利要求7的方法,其中:
芳烃是甲苯且烷基化试剂是甲醇。
9.权利要求7的方法,其中:
经过磷处理的ZSM-5沸石催化剂具有至少0.08g P/g沸石的磷含量。
10.权利要求7的方法,其中:
经过磷处理的ZSM-5沸石催化剂具有至少0.08g P/g沸石至0.15g P/g沸石的磷含量。
11.权利要求7的方法,其中:
ZSM-5沸石催化剂的氧化硅/氧化铝摩尔比至少250。
12.权利要求7的方法,其中:
在150℃至250℃的温度下对经过磷处理的ZSM-5沸石催化剂进行汽蒸。
13.权利要求7的方法,其中:
在至少300℃的温度下煅烧经过磷处理的ZSM-5沸石催化剂。
14.一种制备二甲苯产品的方法,包括:
用含磷化合物处理氧化硅/氧化铝摩尔比至少250的ZSM-5沸石催化剂,以提供0.08g P/g沸石至0.15g P/g沸石的磷含量,其中含磷化合物选自膦酸、三价膦酸、亚磷酸和五价磷酸,这些酸的盐和酯以及卤化磷;
在300℃及以上的温度下煅烧经过磷处理的ZSM-5沸石催化剂;
用温度为150℃-250℃的蒸汽对该经过磷处理的ZSM-5沸石催化剂进行汽蒸,且其中经过磷处理的ZSM-5沸石催化剂除磷之外具有小于催化剂的0.05重量%的任何其它金属,该金属由使用含有所述其它金属的化合物对ZSM-5沸石进行处理来提供;
在反应器内于适合甲苯甲基化反应的条件下,使催化剂与甲苯和甲醇的加料接触;和
在反应期间将水共加料引入反应器内。
15.权利要求14的方法,其中:
以每摩尔甲苯和甲醇加料0.2摩尔至小于10摩尔水的比例将共加料水加入到反应器内。
16.权利要求14的方法,其中:
以每摩尔甲苯和甲醇加料0.3摩尔至7摩尔水的比例将共加料水加入到反应器内。
17.权利要求14的方法,其中:
反应器的催化剂床入口温度维持在低于700℃。
18.权利要求14的方法,其中:
甲苯/甲醇加料具有1∶2至10∶1的甲苯/甲醇摩尔比。
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- 2006-05-05 KR KR1020077027725A patent/KR101287237B1/ko active IP Right Grant
- 2006-05-05 WO PCT/US2006/017206 patent/WO2006121770A2/en active Application Filing
- 2006-05-05 CN CN2006800150303A patent/CN101184710B/zh not_active Expired - Fee Related
- 2006-05-05 DE DE602006019226T patent/DE602006019226D1/de active Active
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Also Published As
Publication number | Publication date |
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US7304194B2 (en) | 2007-12-04 |
KR101287237B1 (ko) | 2013-07-17 |
DE602006019226D1 (de) | 2011-02-10 |
EP1877184B1 (en) | 2010-12-29 |
KR20080013953A (ko) | 2008-02-13 |
US20060252633A1 (en) | 2006-11-09 |
EP1877184A4 (en) | 2008-11-05 |
ATE493372T1 (de) | 2011-01-15 |
ES2356498T3 (es) | 2011-04-08 |
US20080009406A1 (en) | 2008-01-10 |
WO2006121770A2 (en) | 2006-11-16 |
CN101184710A (zh) | 2008-05-21 |
WO2006121770A3 (en) | 2007-12-27 |
US7576026B2 (en) | 2009-08-18 |
EP1877184A2 (en) | 2008-01-16 |
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