CN101528663B - 在流化床反应器中用于制备芳香族胺的方法 - Google Patents

在流化床反应器中用于制备芳香族胺的方法 Download PDF

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CN101528663B
CN101528663B CN2007800390833A CN200780039083A CN101528663B CN 101528663 B CN101528663 B CN 101528663B CN 2007800390833 A CN2007800390833 A CN 2007800390833A CN 200780039083 A CN200780039083 A CN 200780039083A CN 101528663 B CN101528663 B CN 101528663B
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L·塞德曼
L·柯尼希斯曼
C·施耐德
E·施瓦布
D·施蒂策
C·利肯斯
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Abstract

本发明公开了一种在流化床反应器中通过催化氢化相应的硝基化合物制备芳香族胺的方法。在所述方法中，含有硝基化合物和氢气的气态反应混合物从形成流化床的非均相颗粒催化剂的底部流动到顶部。所述方法的特征在于在流化床中提供隔板，所述隔板将流化床分隔成多个在流化床反应器中水平布置的单元和多个在流化床反应器中垂直布置的单元。此外，单元壁是可渗透气体的且提供有确保非均相颗粒催化剂达到每升反应器容积中在垂直方向上从1到100升/小时范围内的传输速度的开口。

Description

在流化床反应器中用于制备芳香族胺的方法
本发明涉及一种在流化床反应器中通过相应的硝基化合物的催化氢化制备芳香族胺的方法，特别涉及通过硝基苯的催化氢化制备苯胺的方法。 
DE-A 2849002公开了一种用于在含钯的具有载体的催化剂上的芳香族胺催化气相氢化的方法，该方法优选在管式反应器中进行，其中采用温度保持在大约150℃到350℃的合适的传热液体将反应热除去。其缺点在于可能的有限的热量除去：用于采用传热介质除去反应热的热通量对于具有载体的固定床催化剂来说每平方米在0.5到5kW的范围内，因此在强的放热反应中，特别是硝基苯氢化为苯胺的反应中，当使用管式反应器时，反应热的除去会遇到困难。 
因此提议制备芳香族胺的氢化反应在已知它们具有良好传热性质的流化床反应器中进行。例如DE-A 1 114 820和DE A 1 133 394中描述了这种方法：根据所引用的文献，可能的氢化催化剂为元素周期表中第1和5到7族的重金属，并且还可以是铁和铂族，例如铜、钼、钨、镍、钴或它们的混合物，以及它们的氧化物、硫化物或卤化物，如果合适的话还可与硼或硼化合物一起使用。催化剂可应用于多种载体。这些催化剂具有小的颗粒尺寸，例如0.3mm，并且通过要进行氢化的初始混合物和用于氢化的必要的氢气保持涡流运动，如果合适的话，还混入惰性气体。 
主要专利DE-A 114 820中的方法在大气压力下进行，其与增补专利DE-A 1 133 194中的方法不同，该方法在至少3个标准大气压力的升高的压力下进行，且据说获得了较长的催化剂寿命。 
由于流化床良好的热移除性质，其中可获得每平方米10到100W的范围内的热通量以移除反应热，与必须以复杂的方式冷却的管式反应器相 比，流化床反应器可以相当容易的设计用于有利的等温反应模式。 
但是由于在已知的方法中通过形成不含固体的起泡，催化剂与反应物之间的接触有限，流化床反应器的缺点在于传质。结果就是，一部分芳香族硝基化合物并没有与涡流中的具有载体的催化剂接触，且它没有反应就离开了反应区。这不但会降低转化率，而且还导致进一步的缺点：例如在苯胺中未反应的硝基苯阻碍了在聚氨酯增值链中作为重要中间体的二苯基甲烷二异氰酸酯(MDI)的制备。 
因此本发明的目的在于在用于在通过在流化床反应器中相应的硝基化合物的催化氢化制备芳香族胺的方法中获得进一步的改进。 
该目的通过在流化床反应器中采用相应的硝基化合物的催化氢化制备芳香族胺的方法实现，其中含有硝基化合物和氢气的气态反应混合物从底部向上穿过非均相颗粒催化剂形成流化床，其中流化床提供有将流化床分隔成在流化床反应器中的多个水平排列的单元和在流化床反应器中的多个垂直排列的单元的内部构件，该单元具有可渗透气体的单元壁并且具有确保每升反应器容积中在垂直方向上非均相颗粒催化剂的交换数(exchange number)在1到100升/小时的范围内的开口。 
已经发现在水平方向上和垂直方向上通过内部构件的手段将流化床分隔成单元即通过单元壁封闭的中空空间是很重要的，该单元壁可以渗透气体并且具有允许在流化床反应器中在垂直方向上交换固体的开口。此外，可以为单元壁提供允许在水平方向上交换固体的开口。因此非均相颗粒催化剂可以在垂直方向上移动并且还可能在水平方向上移动通过流化床反应器，但是与不具备这些的流化床相比其在各个单元中被滞留，并且确保了以上限定的交换数。 
交换数通过使用引入到流化反应体系中的放射性标记固体示踪剂颗粒测定，例如如下所述：G.Reed的“Radioisotope techniques forproblem-solving in industrial process plants”，第9章，“Measurement ofresidence times and residence-time distribution”，第112-137页，J.S. Charlton编辑，Leonard Hill，Glasgow and London 1986 (ISBN0-249-44171-3)。根据这些放射性标记颗粒的时间和位置能够局部测定固体的运动并且衍生出交换数(G.Reed的“Radioisotope techniques forproblem-solving in industrial process plants”，第11章，“Miscellaneousradiotracer applications”，11.1，“Mixing and blending studies”，167-176页，J.S.Charlton编辑，Leonard Hill，Glasgow and London 1986 (ISBN0-249-44171-3))。 
单元的几何学的目标选择使得这些单元中非均相颗粒催化剂的停留时间能够与在特殊情况下进行的反应的特征相吻合。 
多个单元(即特别是在垂直方向上在气体从底部向上流动穿过反应器的方向上每米流化床高度上0到100个单元或10到50个单元)的串联排列限制返混并且因此改进选择性和转化率。多个单元(即在流化床反应器中在水平方向上每米10到100个单元或者10到50个单元)(即反应混合物平行或连续流动通过的单元)的另外的排列允许反应器的容量与需要相匹配。因此本发明反应器的容量基本并没有限制并且可以与特殊的需要相匹配，例如用于工业范围内的反应。 
作为封闭了容纳供应颗粒状非均相催化剂的中空空间的单元的结果，单元材料本身仅占流化床反应器横截面的有限部分，特别是仅仅为流化床反应器横截面面积的大约1到10％，并且因此并不导致现有技术中已知的内部构件的情况中与增加横截面占用相关的缺点。 
对于用于本发明过程中的流化床反应器，如通常地从底部通过气体分配器为其供应气态起始原料。在穿过反应区时，气态起始原料在通过气流流化的非均相颗粒催化剂上部分反应。部分反应的起始原料流动到下一个单元中，在那里它们进行进一步的部分反应。 
在反应区之上，存在将夹带的催化剂从气相中分离出来的固体分离装置。反应产物在根据本发明的流化床反应器的上部顶端以不含固体的形式离开。 
此外，对于根据本发明使用的流化床反应器，可以额外从底部或侧面对其供给液态起始原料。但是，这些物料必须能够在引入它们的点上立即气化以便确保催化剂的流化。 
单元的几何形状没有限制，单元可以是例如具有圆形壁的单元，特别是中空球体，或者是具有带有角的壁的单元。如果单元壁是带有角的，单元优选具有不超过50个角，优选不超过30个角，且特别优选不超过10个角。 
内部构件的单元的单元壁可渗透气体以便确保作为气相流动通过单元的结果的非均相颗粒催化剂的流态化。为了这一目的，单元壁可以由编织网孔或具有例如圆孔或其他形状孔的类似片状的材料制成。 
这里在单元壁中使用的编织网孔的平均网孔开口或优选的孔的宽度特别的为50到1mm，更优选为10到1mm且特别优选为5到1mm。 
作为流化床中的内部构件，特别优选使用这样的交叉通道填料，即具有带有褶皱的气体可渗透的金属片、伸展的金属片或编织网孔的填料，其在流化床反应器中在垂直方向上相互平行排列，并且具有这样的褶皱，即其在与垂直方向倾斜成不为0的角度的褶皱之间形成扁平面，连续的金属片、伸展的金属片或编织网孔之间的扁平面具有相同的倾斜角，但是具有相反的符号，以便形成在垂直方向上通过褶皱之间收缩限定的单元。 
交叉通道填料的实例有来自Sulzer AG，CH-8404 Winterthur的 
Figure G2007800390833D00041
CY或BX或Monz GmbH，D40723 Hilden的A3、BSH、B1或M类型的填料。 
在交叉通道填料中，由褶皱间的收缩限定的中空空间(即单元)在垂直方向上在两个连续的金属片、伸展的金属片或编织网孔之间作为这些的折叠结构的结果而形成。 
单元的平均液力直径通过放射性示踪技术测定，例如该方法为以上引用的测定交换数的参考文献中描述的方法，该平均液力直径优选在500到1mm的范围内，更优选为100到5mm且特别优选为50到5mm。 
这里以已知的方式将液力直径限定为从上面观察的单元的周长分隔开的单元的水平横截面面积的四倍。 
在流化床反应器中在垂直方向上通过放射性示踪技术测量的单元的平均高度优选为100到1mm，更优选为100到3mm且特别优选为40到5mm。 
以上交叉通道填料仅仅占用流化床反应器横截面面积的一小部分，特别为该面积的大约1到10％。 
褶皱间扁平面的向垂直方向倾斜的角度在10到80°的范围内，特别为20到70°，特别优选为30到60°。 
金属片、伸展的金属片或编织网孔中的褶皱之间的扁平面优选具有100到3mm范围内的褶皱高度，特别优选为40到5mm，且褶皱间的收缩的间隔在50到2mm的范围内，特别优选为20到3mm。 
为了获得反应温度的目标控制，热交换器可以安装在形成单元的内部构件中用于在吸热反应的情况中引入热量的目的，或者在放热反应的情况中用于除去热量。例如热交换器可以配置成平板或管状的形式并且可以垂直的、水平的或以倾斜的形式排列在流化床反应器中。 
传热面积可以与特殊的反应相匹配，在这种方法中，就热工程而言，通过根据本发明的反应器概念可以实现任何反应。 
形成单元的内部构件优选由具有非常良好的导热性的材料制成，以便不会阻碍通过单元壁的传热。因此根据本发明的反应器的传热性质对应于常规的流化床反应器的那些。 
用于形成单元的内部构件的材料还应当在反应条件下具有足够的稳定性，特别是不仅能耐化学品或热压，而且还必须考虑材料对流化的催化剂的机械攻击的耐受性。 
由于加工它们的原因，特别适用是金属、陶瓷、聚合物或玻璃材料。 
优选将内部构件配置成10到90％的流化床的容积分隔成单元。 
这里，优选在气态反应混合物的流动方向上流化床较低的区域没有内 部构件。 
将流化床分隔成单元的内部构件特别优选位于热交换器的上面。特别是这能够使剩余物的转化增加。 
作为通过形成单元的内部构件的有限的横截面的占用的结果，根据本发明的反应器在流化的颗粒催化剂的反混和排出倾向上没有任何不利之处。 
本发明通过以下附图进行说明。 
附图中： 
图1示意性显示了根据本发明使用的流化床反应器的优选实施方案，以及 
图2示意性显示了根据本发明使用的内部构件的优选实施方案。 
图1所示流化床反应器1包括不含固体的气体分配器区2、形成单元5的内部构件4和在内部构件4的区域中的热交换器3。 
在反应区上，反应器拓宽并且具有至少一个固体分离器6。箭头7表示气态起始原料的引入，箭头8表示气态产物流的排出。另外的液相起始原料可以通过虚线箭头9在侧面引入。 
图2显示了根据本发明的内部构件3的优选实施方案，其形式为这样的交叉通道填料，即其具有折叠的金属片10，其在轴向相互之间平行排列，并且具有褶皱11，其将金属片10分隔成褶皱之间的扁平面12，两个连续的金属片这样地排列，即其具有相同的倾斜角度但是其具有相反的符号，因此形成在垂直方向上通过收缩13限定出的单元5。 

Claims (14)

1.一种在流化床反应器(1)中通过相应硝基化合物的催化氢化制备芳香族胺的方法，其中含有硝基化合物和氢气的气态反应混合物(7)从底部向上穿过非均相颗粒催化剂形成的流化床，其中该流化床提供有将流化床分隔成多个在流化床反应器(1)中水平排列的单元(5)和多个在流化床反应器(1)中垂直排列的单元的内部构件(4)，该单元(5)具有可渗透气体的单元壁以及确保每升反应器容积中在垂直方向上非均相颗粒催化剂的交换数在1到100升/小时的开口，其中内部构件配置成这样的交叉通道填料，即其具有这样的折叠的可渗透气体的金属片(10)、伸展的金属片或编织网孔，即其在流化床反应器(1)中在垂直方向上相互平行排列，并且具有这样的褶皱(11)，即在褶皱(11)之间形成扁平面(12)，其与垂直方向倾斜成不为0的角度，其中连续的金属片(10)、伸展的金属片或编织网孔之间的褶皱(11)的扁平面(12)具有相同的倾斜角度，但其具有相反的符号，以使在垂直方向上通过褶皱之间的收缩限定而形成单元。
2.根据权利要求1的方法，其中芳香族胺为苯胺且相应的硝基化合物为硝基苯。
3.根据权利要求1或2的方法，其中将包含元素周期表中第1和/或5到8族的重金属的具有或不具有载体的催化剂用作催化剂。
4.根据权利要求1或2的方法，其中排列在流化床反应器(1)中的单元(5)的单元壁中的开口确保每升反应器容积中在垂直方向上非均相颗粒催化剂的交换数在10到50升/小时范围内，且每升反应器容积中在水平方向上为0或10到50升/小时。
5.根据权利要求1的方法，其中褶皱间扁平面与垂直方向的倾斜角度在10到80°范围内。
6.根据权利要求1或2的方法，其中内部构件(4)的单元(5)具有通过放射性示踪技术测量的100到5mm的液力直径。
7.根据权利要求1或2的方法，其中内部构件(4)的单元(5)具有在流化床反应器中在垂直方向上通过放射性示踪技术测量的100到3mm的平均高度。
8.根据权利要求1或2的方法，其中金属片、伸展的金属片或编织网孔中的褶皱(11)之间的扁平面(12)具有100到3mm范围内的褶皱高度，且褶皱(11)之间的收缩(13)的间隔在50到2mm范围内。
9.根据权利要求1或2的方法，其中热交换器(3)安装在内部构件(4)中。
10.根据权利要求9的方法，其中热交换器以平板或管的形式配置。
11.根据权利要求1或2的方法，其中内部构件(4)由金属、陶瓷、聚合物或玻璃材料制成。
12.根据权利要求1或2的方法，其中内部构件(4)将流化床容积的10到90％分隔成单元(5)。
13.根据权利要求11的方法，其中在气态反应混合物的流动方向上流化床的较低区域没有内部构件(4)。
14.根据权利要求9的方法，其中将流化床分隔成单元(5)的内部构件(4)位于热交换器(3)的上方。
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