CN107801392B - 烃的直接胺化 - Google Patents
烃的直接胺化 Download PDFInfo
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- CN107801392B CN107801392B CN201680019991.5A CN201680019991A CN107801392B CN 107801392 B CN107801392 B CN 107801392B CN 201680019991 A CN201680019991 A CN 201680019991A CN 107801392 B CN107801392 B CN 107801392B
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- 238000000034 method Methods 0.000 claims abstract description 34
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- 239000010949 copper Substances 0.000 claims abstract description 25
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO compounds]
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- 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
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- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- B01J6/001—Calcining
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/45—Monoamines
- C07C211/46—Aniline
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Abstract
制备可以被取代的胺化的芳族烃的方法,所述方法包括在具有结晶微孔结构的催化剂的存在下使芳族烃与氨反应的步骤,其中所述催化剂包含磷酸铝钒分子筛(VAPO)和/或磷酸铝分子筛(AlPO),并且其中优选采用镍和/或铜浸渍所述催化剂,并且其中所述芳族烃可以被取代。
Description
本发明涉及在催化胺化的催化剂的存在下使用用于胺化的氨将可以被取代的烃、优选可以被取代的芳族烃直接胺化的方法。更具体而言,本发明涉及将苯直接胺化以制备苯胺。
目前使用两个独立的制备步骤来制备苯胺,即将苯硝化成硝基苯,然后氢化成苯胺。尽管这两个反应在当今的商业方法中被有效地操作,但是如果在单个工艺步骤中就可以将苯转化为苯胺,则仍然可获得显著的资本和可变成本的优势。经由催化剂将诸如苯的烃直接胺化也是本领域已知的。这样的方法描述在例如DE19634110中,其中在氧化剂的存在下将可还原的金属氧化物催化剂用于由苯形成苯胺。还描述了将催化反应物(cataloreactants)用于用氨将苯直接胺化。例如,US 2009/0292144描述了用于将苯直接胺化的混合金属氧化物催化剂的反应性,其中该催化剂通过共沉淀技术制备并且包含金属氧化物形式的Ni、Cu、Zr、Mo。催化反应物首先消耗由胺化反应产生的氢气,并驱使反应平衡朝产物的方向。然后在另外的步骤中再生该催化剂。
现有技术中描述的方法提供了其中选择性和空时收率都低的直接胺化。此外,用于直接胺化的催化剂需要在高温下活化,这不利地影响着所需的反应并刺激氨分解成氮气和氢气。该副反应不利地扰乱反应平衡,并显著地降低苯胺收率。
因此,本发明的目的是提供将可以被取代的烃直接胺化的方法,其中制备胺化烃的选择性高,而且同时实现高空时收率。此外,目的是将在用于直接胺化中的氨的分解限制在最小限度,或者氨完全不分解。
除此之外,至少部分地通过根据权利要求的方法来满足这些目的。具体而言,通过制备可以被取代的胺化的芳族烃的方法来满足这些目的,所述方法包括在具有结晶微孔结构的催化剂的存在下使芳族烃与氨反应的步骤,其中所述催化剂包含磷酸铝钒分子筛(VAPO)或磷酸铝分子筛(AlPO),优选采用镍和/或铜浸渍所述催化剂,并且其中所述芳族烃可以被取代。已经发现这些催化剂增强了胺化的性能。这些催化剂能够在氨的存在下将烃胺化,其中反应的选择性高,并且获得的胺化烃的空时收率高。此外,这些催化剂不会引起氨分解成氢气和氮气作为副反应。此外,已经发现当用氨将苯胺化时,尤其是VAPO提供高收率的苯胺。此外,可以将所述催化剂再生若干次,并且在胺化反应期间氨不会发生分解。
根据本发明,具有结晶微孔结构的催化剂意味着可以提供催化剂的X射线衍射图,并且该催化剂具有小于20Å的孔。
分子筛催化剂通常是具有由结晶硅酸铝组成的微孔结构的催化剂并且属于一类称为沸石的材料。还存在包含结晶磷酸铝和磷酸硅铝的非沸石分子筛催化剂。根据本发明的分子筛催化剂是结晶磷酸铝(AlPO)和被钒取代的磷酸铝(VAPO)。所述分子筛催化剂还可以包括其他组分,例如粘合剂、填料、例如粘土和任选的其他催化活性剂,例如稀土金属氧化物、过渡金属氧化物或贵金属组分。
根据本发明,选择性是指转化为所需的胺化烃的烃的量/份已经反应的总烃。例如,在烃是苯的情况下,选择性是指转化为苯胺的苯的量/已经反应的苯的总量。当数值较高时,选择性较好。当选择性低时,这意味着形成较多的副产物。在氨的存在下将苯转化为苯胺中的典型副产物是甲苯、苄腈、联苯和咔唑。
不受理论约束,认为在苯的胺化中钒类物质可以通过增加亲电性来活化氨,从而能够实现苯的亲核性攻击。固体催化剂中另外的骨架氧可以将产生的氢气氧化成水。以这种方式,反应平衡向产物侧移动。
在一个优选的实施方案中,采用镍和/或铜浸渍根据本发明的分子筛催化剂。更优选地,采用镍氧化物和/或铜氧化物浸渍所述分子筛催化剂。最优选地,采用镍氧化物和铜氧化物两者浸渍所述催化剂。当采用镍和铜的氧化物浸渍AlPO催化剂和VAPO催化剂时,转化的烃的收率甚至高于当不使用镍或铜的氧化物时或当仅使用镍或仅使用铜时的收率。反应的选择性也高得多。优选地,相比于所述催化剂的总重量,镍含量为1-30wt%,更优选为1-10wt%。优选地,相比于所述催化剂的总重量,铜含量为1-30wt%,更优选为1-10wt%。合适的催化剂的实例是采用7.7wt%的镍和3.8wt%的铜浸渍的VAPO载体或AlPO载体。
在另一个实施方案中,进一步处理根据本发明的分子筛催化剂。该处理可以是煅烧或还原。煅烧可以使用例如空气或氧气实施。还原可以使用例如分子氢、肼、硼氢化物盐(例如LiBH4、NaBH4)或氨进行。
在一个实施方案中,在分子氢的存在下还原所述催化剂。优选地,通过在反应器中原位还原来活化所述催化剂。优选在100℃-300℃、更优选150℃-250℃、最优选约200℃的温度下采用氢气进行还原。优选将还原进行40-150分钟,优选60-90分钟,更优选约80分钟。已经发现80分钟的还原时间可以导致收率增加。用氢气进行的还原还原了所述催化剂中的金属。
在另一个实施方案中,优选在300-800℃、更优选400-600℃、甚至更优选约500℃的温度下采用空气煅烧所述催化剂。采用空气的煅烧优选进行40-150分钟,优选50-80分钟,更优选约60分钟。用氧气进行的煅烧氧化了所述催化剂中的金属。
优选地,当所述催化剂包含VAPO时,采用分子氢还原所述催化剂。该实施方案在选择性和收率方面提供了非常好的结果。
可用于本发明方法的VAPO催化剂和AlPO催化剂具有微孔结构。优选地,所述微孔结构通过由国际沸石协会提供的选自AFI、AEL、ATO、AEI、AET、AFN、AFO、AFT、ATV、CHA、ERI、LEV、SOD和VFI的骨架类型代码限定。本发明最优选的催化剂是具有AFI、AEL或ATO的骨架类型代码的那些催化剂。对于AlPO催化剂而言,这些催化剂分别对应于AlPO-5、AlPO-11和AlPO-31,对于VAPO催化剂而言,这些催化剂分别对应于VAPO-5、VAPO-11和VAPO-31。
所述芳族烃可以被取代。取代的芳族烃可以具有一个、两个、三个或更多个取代基,它们可以相同或不同,各自替代氢原子。取代基是卤素(例如F、Cl、Br和I)、羟基、被保护的羟基、氨基、被保护的氨基、羧基、被保护的羧基、氰基、甲基磺酰基氨基、烷氧基、酰氧基、硝基和低级卤代烷基。本文中使用的术语“取代的”是指具有一个、两个、三个或更多个取代基的部分,所述取代基可以相同或不同,各自替代氢原子。取代基的实例包括但不限于卤素(例如F、Cl、Br和I)、羟基、被保护的羟基、氨基、被保护的氨基、羧基、被保护的羧基、氰基、甲基磺酰基氨基、烷氧基、烷基、芳基、芳烷基、酰氧基、硝基和低级卤代烷基。可以被取代的芳族烃的实例是苯、联苯、萘、蒽、䓛、菲(pheanthrene)、芘、茚、烷基化苯,例如甲苯、邻二甲苯、间二甲苯、对二甲苯、乙苯、邻二乙苯、间二乙苯、对二乙苯、丙苯、异丙苯、均三甲苯、羟基苯,例如苯酚、邻甲酚、间甲酚、对甲酚、二甲苯酚类;烷氧基苯,例如苯甲醚、乙氧基苯、丙氧基苯;卤代芳族化合物,例如氟苯;卤代烷基化芳族化合物,例如三氟甲基苯;含氮的芳族化合物,例如硝基苯、苯甲腈、甲苯腈、吡啶、甲基吡啶、喹诺酮、异喹啉、喹哪啶、苯胺和N-烷基化氨基芳族化合物、N,N-烷基化氨基芳族化合物,例如甲基苯胺、二甲基苯胺、邻甲苯胺、间甲苯胺、对甲苯胺。获得的产物是相应的胺化芳基胺或杂芳基胺。特别优选的芳族烃是可以根据本发明的方法转化成苯胺的苯。苯胺可以例如用于生产异氰酸酯、染料和橡胶加工化学品。
在一个实施方案中,在400-700℃、优选400-500℃的温度、最优选在约450℃的温度下进行所述胺化。优选地,在反应开始时,在50-150巴的压力、优选在70-100巴的压力、更优选在约80巴下进行所述胺化。在这些条件下,可以获得形成的胺取代的芳族化合物的更高的收率。在胺化期间,所述压力可以变化,并且可以比在胺化开始时的压力高或低0-20巴。典型地,所述压力可以以比在反应开始时的压力高或低10巴变化。
优选地,所述胺化方法以间歇工艺进行,优选以连续工艺进行。合适的反应器是搅拌槽反应器和管式反应器。
芳族烃和氨的相对量取决于进行哪种胺化反应。通常使用化学计量量的烃和氨。但是为了使平衡向产物侧移动,优选在直接胺化方法中使用一种化学计量过量的反应物。优选使用化学计量过量的氨。
所述烃和氨可以以气态或液态形式引入反应器中。优选的相态取决于所用的反应条件和所用的反应物。在由苯和氨合成的苯胺的制备中,优选将两种反应物作为液体引入反应器中。在反应器内,氨和苯是气态的和/或形成超临界混合物。
在一个实施方案中,以0.5-1.5h-1、优选0.6-1.0h-1、更优选约0.8h-1的重量时空速率进行所述胺化。重量时空速率(WHSV)是芳族烃的流速(以克/小时计)/所使用的催化剂的质量(以克计)。已经发现,在这样的WHSV下,与高于优选范围的WHSV相比,胺化产物的收率增加。
由以下通过举例的方式示例本发明的原理而不是限制本发明的范围的实施例,本发明的上述特点、特征和优点可以变得清晰可见。
参照具体的实施方案来描述本发明。
应当注意,在权利要求书中使用的术语“包括”不应被解释为限于其后列出的手段;它不排除其他要素或步骤。因此,它应被解释为指明所提及的所述特征、步骤或组件的存在,但不排除一个或多个其他特征、步骤或组件或其组的存在或加入。因此,表述“包括手段A和B的装置”的范围不应限于仅由组件A和B组成的装置。这意味着对于本发明而言,该装置的唯独相关的组件是A和B。
在整个说明书中,涉及“一种实施方案”或“一个实施方案”。这样的描述表示关于该实施方案描述的特定特征被包含在本发明的至少一个实施方案中。因此,贯穿本说明书的各个位置出现的短语“在一种实施方案中”或“在一个实施方案中”不一定都是指相同的实施方案,但是它们可以指相同的实施方案。此外,对于本领域普通技术人员而言,特定特征或特点可以以任何合适的方式被组合在一个或多个实施方案中是明显可见的。
实施例
反应器装置和实验程序
在管子的中心将600mg的催化剂(颗粒尺寸为0.2-0.6mm)装入管式反应器(长度=31cm,内径= 0.43cm),并将剩余的空间用金刚砂填充。催化剂床具有6.9cm的长度。在胺化催化反应之前已将该催化剂“原位”活化。催化剂活化已经在空气流(190ml/min)下在500℃下进行了30、60或120分钟(实施例1、实施例2、实施例4、实施例6和实施例9)或在氢气流(100%H2,以60ml/min)下在450℃下进行了90分钟(实施例3和实施例5)或在200℃下进行了60或80分钟(实施例7、实施例8、实施例10)。之后,用氮气将该反应器吹扫30分钟,并使温度达到450℃。然后经由注射泵将氨引入反应器,以达到80巴(在反应期间±10巴的波动)的内部压力。在压力平衡后,以连续地加入到该体系的1.61ml/h的氨(9.2当量,Linde 99.98%)和0.565ml/h的苯(1.0当量,Aldrich 99.9%)的流量开始反应。反应运行140或300分钟。对于每种样品而言,使用十二烷作为外部GC标准物,在-2℃下将反应器流出物收集在甲醇中,持续3分钟。然后通过气相色谱仪(具有FID检测器的VARIAN CP3800,HP5柱30m)分析样品。
VAPO催化剂的合成
根据文献(P.Concepción,J.M.LópezNieto,J.Péres-Pariente J.Mol.Catal.A: Chem.97(1995)173)制备VAPO-5载体。详细地说,将13g的正磷酸(Aldrich,85wt%)、30g的H2O miliQ和6.7g的拟薄水铝石(pseudoboehmite)(CATAPAL 70wt%Al2O3)一起搅拌2h。在搅拌下缓慢地加入7.5g的三乙胺(Aldrich 99wt%),并在搅拌下再保持2h(溶液A)。在单独的容器中,在40℃、在搅拌下将2.5g的三乙胺、10g的H2O miliQ和1.2g的V2O5(Aldrich,99.6wt%)混合约1h,直到钒盐完全溶解(溶液B)。将溶液B缓慢地加入到溶液A中并在搅拌下再保持2h。此时,获得pH为约5.6的均匀的凝胶。将该凝胶引入衬有PTFE的60ml不锈钢高压釜中,并在200℃加热16h。然后将该高压釜在冷水中淬灭,以10 000rpm离心,洗涤并在80℃下干燥。在空气中将固体在550℃下煅烧8h。为了达到煅烧温度,以2℃/min加热材料。制备的VAPO-5中的钒负载量为0.5wt%。在此之后,应用湿浸渍技术将镍和/或铜引入催化剂上。在VAPO-Ni样品中使用7wt%的镍负载量(表1中的实施例4和实施例5),详细地说,通过在40℃下的稍微加热将296mg(Ni(OAc)2(H2O)4)(Panreac,95wt%))溶解在5 ml水中,以制备盐溶液。在搅拌下将该溶液逐滴加到1g的VAPO-5上。将最终的固体在100℃下干燥12h,然后以500℃/min进行空气煅烧8h,其中加热速率为2℃/min。在VAPO-Ni,Cu样品(表1中的实施例6-实施例8)中,使用7wt%的镍负载量和3.5wt%的铜负载量。详细地说,通过在40℃下的稍微加热将 (296mg,1.19mmol)(Ni(OAc)2(H2O)4)(Panreac,95%)和(128mg,0.28mmol)Cu(NO3)4(H2O)5(Aldrich 98wt%)溶解在1.5ml水中,以制备盐溶液。然后将该盐溶液进一步用于VAPO样品的浸渍。然后将经浸渍的材料在100℃下干燥过夜,随后以500℃/min进行空气煅烧8h,其中加热速率为2℃/min。根据表中所示的条件,随后的煅烧在流体反应器(flow reactor)中“原位”进行,其中加热速率为2℃/min。
ALPO催化剂的合成
根据以下配方(receipt)制备ALPO-5:将13g的正磷酸(Aldrich,85wt%)、40g 的H2O miliQ和6.7g的拟薄水铝石(CATAPAL 70wt%Al2O3)一起搅拌2h。在此之后,在搅拌下缓慢地加入10g的三乙胺(Aldrich 99wt%),并在搅拌下再保持2h。将凝胶引入衬有PTFE的60ml不锈钢高压釜中,并在200℃下加热16h。在此之后,将该高压釜在冷却水中淬灭,以10000rpm离心,洗涤并在80℃下干燥。在空气中将固体在550℃下煅烧8h,其中加热速率为2℃/min。在此之后,应用湿浸渍技术将镍和铜引入ALPO-5样品上。合成程序与上文在VAPO-5-NiCu样品中所述的相同,除了使用ALPO-5代替VAPO-5。
对比例1
该催化剂通过共沉淀技术制备并且包含金属氧化物形式的Ni、Cu、Zr和Mo。根据US2009/0292144 A1的实施例1合成该催化剂。苯的胺化反应发生在如上所述的反应装置中。在350℃和80巴下,不形成苯胺。然而,通过将反应温度升高至450℃,获得0.43%的平均收率(参见表1中的实施例1)。形成的副产物是甲苯、苄腈、联苯和咔唑。
对比例2-5
在如上所述的反应装置和程序中使用如上所述制备的VAPO-5。
胺化反应如上文所述在专利的实验程序中发生。
VAPO-5显示出直接胺化苯的活性,并形成了苯胺(参见表1中的实施例2-5)。采用空气或氢气在反应器中原位活化催化剂并没有改变结果。
此外,在如上所述的反应装置中,使用用镍浸渍的VAPO-5(如上所述地制备)来将苯胺化。该反应如上文所述在专利的实验程序中发生。
发现通过在VAPO中引入镍,最大收率没有变化,但平均收率增加(参见表1的实施例4)。
根据本发明的实施例6-8
在如上所述的反应装置和程序中使用如上所述制备的Ni,Cu-VAPO-5。
发现通过用Ni和Cu浸渍VAPO-5,催化剂的活性增加,特别是当在200℃下用氢气还原该催化剂时。在200℃下还原60分钟,在140分钟的反应时间时收率达到1%(参见实施例7)。在200℃的相同温度下将还原时间从60分钟增加至80分钟,在160分钟的反应时间时形成3.3%的最大收率,并获得1%的平均收率。此外,反应的选择性非常高。在反应期间仅观察到痕量的咔唑、苄腈、联苯、甲苯和二苯胺。选择性的计算不包括由焦化或简单吸附在反应器内产生的苯的损失。
已经通过在500℃、在空气中原位加热2小时而再生该催化剂,然后在200℃、在氢气中还原80分钟。在每个循环之后,使用上述程序再次测试该催化剂。已经发现,成功地完成9个再生循环,而催化剂性能没有降低。
根据本发明的实施例9和10
在反应装置中使用浸渍有镍和铜的常规磷酸铝(参见上文)。合成程序和反应装置如上所述。
针对采用氢气和空气活化,AlPO材料提供几乎相同的结果。用Ni和Cu浸渍的AlPO催化剂也显示出良好的结果。
样品 | 催化剂 | WHSV | 催化剂的处理 | 反应条件 | 平均收率,最高收率 | 选择性 |
1 * | Ni,CU, Zr, Mo | 0.83h<sup>-1</sup> | 空气,在500℃下 | 450℃,80巴 | 0.43%, 0.88% | 90% |
2** | VAPO-5 | 0.83h<sup>-1</sup> | 空气,在500℃下, 2h | 450℃,80巴 | 0.05%, 0.15% | 69% |
3** | VAPO-5 | 0.83h<sup>-1</sup> | H<sub>2 </sub>,在450℃下, 1.5h | 450℃,80巴 | 0.06%, 0.15% | 63% |
4** | VAPO-Ni | 0.83h<sup>-1</sup> | 空气,在500℃下, 30 min | 450℃,80巴 | 0,09%, 0.14% | 67% |
5** | VAPO-Ni | 0.83h<sup>-1</sup> | H<sub>2</sub>,在450℃下, 1.5h | 450℃,80巴 | <0.01%, 0.03% | 67% |
6 | VAPO-Ni, Cu | 0.83h<sup>-1</sup> | 空气,在500℃下, 60 min | 450℃,80巴 | 0.06%, 0.11% | 56% |
7 | VAPO-Ni, Cu | 0.83h<sup>-1</sup> | H<sub>2</sub>,在200℃下, 60 min | 450℃,80巴 | 0.66%, 1.01% | 89% |
8 | VAPO-Ni, Cu | 0.83h<sup>-1</sup> | H<sub>2</sub>,在200℃下, 80 min | 450℃,80巴 | 0.98%, 3.31% | 92% |
9 | AlPO-Ni, Cu | 0.83h<sup>-1</sup> | 空气,在500℃下, 60 min | 450℃,80巴 | 0.85%, 1.52% | 88% |
10 | AlPO-Ni, Cu | 0.83h<sup>-1</sup> | H<sub>2</sub>,在200℃下, 80 min | 450℃,80巴 | 0.52%, 1.47% | 87% |
表1实施例1-10中的实验结果。
*对比例,根据US 2009/0292144 A1的实施例1制备的催化剂;**对比例,WHSV是重量时空速率。
Claims (14)
1.制备胺化的芳族烃的方法,所述方法包括在具有结晶微孔结构的催化剂的存在下使芳族烃与氨反应的步骤,其中所述催化剂包含磷酸铝钒分子筛(VAPO),其采用镍和铜浸渍并采用分子氢还原,和/或磷酸铝分子筛(AlPO),其采用镍和铜浸渍并通过还原或煅烧处理,并且其中所述芳族烃能被取代,
其中在150-250℃的温度下采用分子氢进行还原,
其中采用分子氢的还原进行60-90分钟,
其中在450-550℃的温度下进行采用空气的煅烧。
2.根据权利要求1的方法,其中相比于所述催化剂的总重量,镍含量为1-30wt%。
3.根据权利要求1的方法,其中相比于所述催化剂的总重量,铜含量为1-30wt%。
4.根据权利要求1-3中任一项的方法,其中所述催化剂具有由国际沸石协会提供的选自AFI、AEL、ATO、AEI、AET、AFN、AFO、AFT、ATV、CHA、ERI、LEV、SOD、VFI的骨架类型代码。
5.根据权利要求1-3中任一项的方法,其中所述芳族烃为苯。
6.根据权利要求1-3中任一项的方法,其中在350-700℃的温度下处理所述催化剂。
7.根据权利要求1-3中任一项的方法,其中在400-700℃的温度下进行胺化。
8.根据权利要求1-3中任一项的方法,其中在50-150巴的压力下进行胺化。
9.根据权利要求2的方法,其中相比于所述催化剂的总重量,镍含量为1-10wt%。
10.根据权利要求3的方法,其中相比于所述催化剂的总重量,铜含量为1-10wt%。
11.根据权利要求1的方法,其中采用分子氢的还原进行约80分钟。
12.根据权利要求4的方法,其中所述催化剂具有AFI、AEL或ATO的骨架类型代码。
13.根据权利要求7的方法,其中在400-500℃的温度下进行胺化。
14.根据权利要求8的方法,其中在70-100巴的压力下进行胺化。
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