CN102119054A - 低级烃芳构化催化剂及芳香族化合物的制备方法 - Google Patents
低级烃芳构化催化剂及芳香族化合物的制备方法 Download PDFInfo
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Classifications
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- 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
- B01J29/48—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 containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
Abstract
本发明的目的是在使用低级烃芳构化催化剂制备芳香族化合物的方法中,改善芳香烃的收率和催化剂的活性寿命稳定性。本发明提供了一种低级烃芳构化催化剂,其可以使低级烃发生反应,制备芳香族化合物,该低级烃芳构化催化剂的平均结晶直径是500nm以下。上述催化剂的例子是其中钼负载于作为金属硅酸盐的ZSM-5沸石上的催化剂。另外,本发明还提供了芳香族化合物的制备方法,其包括将上述催化剂与含有低级烃的反应气体相接触,制备芳香族化合物。
Description
技术领域
本发明涉及以甲烷为主要成分的天然气、生物气和水合甲烷的高度利用。天然气、生物气和水合甲烷被认为是应对地球温暖化的对策中最有效的能源资源,人们越来越关心其利用技术。甲烷资源利用其本身的清洁性质,作为下一代的新型有机资源和燃料电池用的氢资源而备受注目。特别地,本发明涉及用于由低级烃例如甲烷有效地制备以苯和萘类为主要成分的芳香族化合物和高纯度的氢气的催化化学转化技术,以及涉及生产用于其的催化剂的方法,其中苯和萘类是化学制品例如塑料类的原料。
背景技术
作为由例如甲烷等低级烃制备例如苯等芳香族化合物和氢气的方法,已知有在催化剂的存在下使低级烃反应的方法。作为此时的催化剂,据报道负载于ZSM-5系列的沸石上的钼是有效的(非专利文献1)。但是,为了进一步提高芳香族化合物和氢气的制备效率,期望开发出更优异的催化剂。
沸石作为用作该反应的催化剂的结晶性金属硅酸盐的一个例子,通常具有固体酸性和用作分子筛的数埃(例如,在ZSM-5的情况中,为5~6埃)的结晶孔径。
在由低级烃生成芳香烃例如苯等的反应中,认为连续反应发生在其中活性物质负载于金属硅酸盐上的催化剂上,由此生成芳香烃。
具体地,在该连续反应的第一阶段,在所负载的活性物质、或者金属物质例如钼、钨或铼或它们的碳化物的作用下,低级烃例如甲烷等之间发生结合反应,生成碳数为2以上的直链烃。接着,在第二阶段,在用作载体的金属硅酸盐的细孔内部空间和布朗斯台德酸点的作用下,上述直链烃发生环化反应。换句话说,通过该反应,直链烃发生了形成环状的脱氢化反应,由此转化为作为例如苯等不饱和环状烃的芳香烃。通过上述连续反应,由低级烃生成了芳香烃。
现有技术
非专利文献
非专利文献1:JOURNAL OF CATALYSIS,1997,pp.165,pp.150-161
发明内容
发明要解决的课题
但是,在上述现有技术中,在由低级烃生成芳香烃的反应中,每单位体积或单位重量的金属硅酸盐的结晶表面上细孔的入口数,即细孔入口密度是扩散速率控制的重要因素。在扩散速率控制的条件下,发生了下列问题:由于沸石的细孔,分子筛不能有效发挥功能,使得随着催化剂上反应的进行,反应产物发生焦化,因此降低了催化剂的长期稳定性和反应效率。
具体地,用作该反应的催化剂的沸石具有固体酸性和用作分子筛的数埃的结晶孔径。通常沸石的结晶大小为约数μm,与结晶孔径相比,这是非常大的。因此,在沸石用作催化剂的情况下,沸石容易进入扩散速率控制状态,其中,沸石结晶内的原料和产物的扩散比其固体酸性特性更能支配反应。换句话说,由于细孔入口密度较低,在连续反应的第一阶段生成的碳数为2以上的直链烃向细孔内部扩散和浸透的机会很小,这样不能完成环化反应的直链烃就会在沸石表面焦化,由此成为催化剂的活性寿命稳定性降低和芳香烃收率降低的因素。
因此,本发明的一个目的是,提供一种低级烃芳构化催化剂,其通过使用沸石结晶大小很小的纳米级的沸石,降低了细孔中物质的扩散的影响,提高了反应效率。
解决课题的手段
达成上述目的的本发明的低级烃芳构化催化剂是使低级烃发生反应生成芳香族化合物的催化剂,其中上述催化剂的特征在于,具有500nm以下的平均结晶直径。
此外,本发明的芳香族化合物的制备方法的特征在于,使含有低级烃的反应气体与含有平均结晶直径为500nm以下的金属硅酸盐的催化剂反应,以生成芳香族化合物。
根据本发明的低级烃芳构化催化剂和芳香族化合物的制备方法,通过使结晶直径为纳米级,来增加细孔入口的密度,由此使得直链烃向细孔内部扩散和浸透的机会增多。
上述金属硅酸盐的一个例子是ZSM-5沸石,此外,钼可以负载于上述金属硅酸盐上。
发明效果
因此,根据上述的本发明,在使用低级烃芳构化催化剂的芳香族化合物的制备方法中,改善了芳香烃的收率和催化剂的活性寿命稳定性。
附图说明
[图1]显示了根据本发明的一个实施方案,在使用低级烃芳构化催化剂的低级烃的芳构化反应中,苯收率(%)的经时变化。
具体实施方式
通过将含有钼的前体负载于金属硅酸盐上,可以获得根据本发明的实施方案的低级烃芳构化催化剂。
用于该催化剂的金属硅酸盐的例子是形成含有二氧化硅和氧化铝的多孔质体的分子筛5A(UTA)、八面沸石(NaY)以及铝硅酸盐例如NaX、ZSM-5、H-ZSM-5。用于该催化剂的金属硅酸盐的另一个例子是例如含有磷酸作为主要成分的ALPO-5、VPI-5等的多孔质载体、且是特征在于具有孔径为0.6nm~1.3nm的微孔或通道的沸石载体。用于该催化剂的金属硅酸盐的再一个例子是含有二氧化硅作为主要成分和部分氧化铝作为一种成分、且特征在于筒状细孔(通道)或中孔(孔径:1nm~10nm)的中孔多孔质载体,例如FSM-16、MCM-41。
含有钼的前体的例子是仲钼酸铵、磷钼酸、12-硅钼酸;其卤化物例如氯化物、溴化物等;其矿物酸盐例如硝酸盐、硫酸盐、磷酸盐等;其碳酸盐、及其羧酸盐例如草酸盐等,等等。
将钼负载于金属硅酸盐上的一般方法如下所述:用上述的含有钼的前体的水溶液含浸金属硅酸盐载体,以使上述的前体负载于该载体上。然后在空气中将含浸后的载体进行加热处理。
该负载方法的一个具体例子如下所述:在金属硅酸盐载体上含浸负载钼酸铵,干燥后,在空气气流中,在250℃~800℃、优选400℃~700℃下将含浸后的载体进行加热处理,由此制备负载有钼的金属硅酸盐催化剂。
当加入粘合剂例如二氧化硅、氧化铝和/或粘土后,在本发明中使用的催化剂可以成型为丸状物或挤出制品。
这里,在本发明中使用的低级烃的例子是甲烷,以及碳数2-6的饱和或不饱和烃。优选地,进行反应的气体含有至少50重量%、优选至少70重量%的甲烷。除甲烷以外,该气体还可以含有碳数2~6的饱和或不饱和烃。碳数2~6的饱和或不饱和烃的例子是乙烷、乙烯、丙烷、丙烯、正丁烷、异丁烷、正丁烯、异丁烯等。
可以通过间歇式或流通式的反应形式来实施本发明的由低级烃制备芳香烃和氢气的方法中的低级烃的芳构化反应。特别地,优选通过使用固定床、移动床或流化床等的流通式反应形式来实施该反应。
在反应温度为300℃~900℃、优选450℃~800℃、且反应压力为0.01MPa~1MPa、优选0.1MPa~0.7MPa下,通过使低级烃原料与催化剂相接触来进行催化反应。
参考实施例来更详细地说明本发明。予以说明,平均结晶直径通过计算随机选自电子显微镜图的颗粒的平均值来求出。苯收率(%)通过下式(1)来定义:
苯收率(%)={(生成的苯的量)/(用于甲烷重整反应的甲烷的量)}×100......(1)
(比较例1)
在水溶液中混合量为400g的市售的平均结晶直径1μm的H型ZSM-5沸石(SiO2/Al2O3=28)作为金属硅酸盐载体,其中所述水溶液是通过将44.2g的钼酸铵溶解于1500ml的离子交换水中制备的。将含有该载体的该水溶液在室温下搅拌3小时,以使钼酸铵含浸并负载于该载体上。在干燥后,将该载体在550℃下烧结8小时,由此得到催化剂。
(实施例1)
除了使用具有不同的平均结晶直径的沸石作为金属硅酸盐载体以外,进行与比较例1同样的制备。具体地,在水溶液中混合400g的市售的平均结晶直径70-80nm的H型ZSM-5沸石(SiO2/Al2O3=28)作为金属硅酸盐载体,其中所述水溶液是通过将44.2g的钼酸铵溶解于1500ml的离子交换水中制备的。将含有该载体的该水溶液在室温下搅拌3小时,以使钼酸铵含浸并负载于该载体上。在干燥后,将该载体在550℃下烧结8小时,由此得到催化剂。
(实施例2)
除了使用具有不同的平均结晶直径的沸石作为金属硅酸盐载体以外,进行与比较例1同样的制备。具体地,在水溶液中混合400g的市售的平均结晶直径500nm的H型ZSM-5沸石(SiO2/Al2O3=28)作为金属硅酸盐载体,其中所述水溶液是通过将44.2g的钼酸铵溶解于1500ml的离子交换水中制备的。将含有该载体的该水溶液在室温下搅拌3小时,以使钼酸铵含浸并负载于该载体上。在干燥后,将该载体在550℃下烧结8小时,由此得到催化剂。
通过使用在实施例1和2以及比较例1的条件下分别制备的催化剂,由低级烃制备芳香族化合物,由此评价催化剂的催化性能。予以说明,以苯与流通过催化剂的低级烃的比率作为评价催化性能的指标。
在反应试验条件下进行用于评价各催化剂的催化性能的反应试验,所述反应试验条件为:甲烷的反应温度是780℃,压力是0.3MPa,重量时间空间速度(WHSV)是3000ml/g/h。用作低级烃原料的反应气体是含有90%甲烷和10%氩气的组合物。予以说明,为了进行该反应试验,事先进行催化剂的预处理,其中在空气气流中将催化剂升温至550℃并维持2小时;然后用含有20%甲烷和80%氢气的预处理气体替代空气,将催化剂升温至700℃并维持3小时。然后,用反应气体替代预处理气体,将催化剂升温至780℃来完成反应,由此通过评价催化剂的活性来确认该催化剂的催化性能。
氢气、氩气和甲烷通过TCD-GC装置进行分析,芳香族化合物例如苯、甲苯、二甲苯、萘等通过FID-GC装置进行分析。
分析结果如表1和图1所示。表1显示了采用各催化剂在反应开始后经过3小时时得到的苯收率(%)。图1显示了采用各催化剂时的苯收率(%)的经时变化。
[表1]
平均结晶直径 | 苯收率 | |
比较例1 | 平均结晶直径:1微米 | 2.5% |
实施例1 | 平均结晶直径:70-80nm | 6.7% |
实施例2 | 平均结晶直径:500nm | 4.6% |
从表1可以清楚地看出,比较例1的苯收率是2.5%,而实施例1的苯收率是6.7%,实施例2的苯收率是4.6%,这样随着结晶直径变小而改善了苯收率。另外,如图1所示,关于苯收率的经时变化,也揭示出结晶直径越小,越能维持高的苯收率。
如上所述,根据本发明的低级烃芳构化催化剂,通过使结晶直径为纳米大小,细孔入口的密度变高,而使直链烃向细孔内部扩散和浸透的机会增多。因此,环化反应可以平稳地进行,由此抑制了由于作为副作用的焦化而导致的细孔入口数量减少。
具体地,由于本发明适用于连续反应,可能反应的第一阶段生成的物质会变成催化剂活性降低的原因。因此,根据本发明,通过使向第二阶段的反应的机会增多,由此抑制了焦化的发生,改善了催化剂的活性寿命稳定性。
结果,在该低级烃芳构化催化剂的作用下的低级烃的芳构化反应中,改善了芳香烃的收率和催化剂的活性寿命稳定性。
权利要求书(按照条约第19条的修改)
1.低级烃芳构化催化剂,用于通过与甲烷接触而制备芳香族化合物,其特征在于,含有:
平均结晶直径为500nm以下的金属硅酸盐和所负载的钼。
2.权利要求1所述的低级烃芳构化催化剂,其特征在于,该金属硅酸盐是ZSM-5沸石。
3.芳香族化合物的制备方法,其特征在于,包括:
使甲烷与含有平均结晶直径为500nm以下的金属硅酸盐和所负载的钼的催化剂相接触。
Claims (4)
1.低级烃芳构化催化剂,用于通过与低级烃接触而制备芳香族化合物,其特征在于,含有:
平均结晶直径为500nm以下的金属硅酸盐。
2.权利要求1所述的低级烃芳构化催化剂,其特征在于,该金属硅酸盐是ZSM-5沸石。
3.权利要求1或2所述的低级烃芳构化催化剂,其特征在于,该金属硅酸盐上负载有钼。
4.芳香族化合物的制备方法,其特征在于,包括:
使低级烃与含有平均结晶直径为500nm以下的金属硅酸盐的催化剂相接触。
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GB8525404D0 (en) * | 1985-10-15 | 1985-11-20 | Exxon Chemical Patents Inc | Zeolite l |
US5242675A (en) * | 1985-10-15 | 1993-09-07 | Exxon Research & Engineering Company | Zeolite L |
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