CN101528338B - 用于进行气相反应的流化床反应器 - Google Patents

用于进行气相反应的流化床反应器 Download PDF

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CN101528338B
CN101528338B CN2007800390937A CN200780039093A CN101528338B CN 101528338 B CN101528338 B CN 101528338B CN 2007800390937 A CN2007800390937 A CN 2007800390937A CN 200780039093 A CN200780039093 A CN 200780039093A CN 101528338 B CN101528338 B CN 101528338B
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L·塞德曼
D·施蒂策
T·格拉斯勒
M·卡彻斯
C·施耐德
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Abstract

本申请公开了一种用于进行气相反应的流化床反应器。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其顶部，其中流化床中排列有隔板。所述流化床反应器的特征在于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以及多个在流化床反应器中垂直布置的单元，该单元壁是气体可渗透的且提供有确保非均相颗粒催化剂达到每升反应器体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

用于进行气相反应的流化床反应器
本发明涉及一种用于进行气相反应的流化床反应器，其中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向上流动通过，且内部构件排列在流化床中。 
流化床反应器以已知的方式用于进行气相反应，其中添加了或未添加惰性载体气体的一种或多种气态起始原料从底部向上穿过非均相颗粒催化剂床，该催化剂床被精细分割的开且通过气体保持悬浮作为流化床。经常使用的是具有在1到1000μm范围内的平均直径的固体颗粒，特别是1到500μm或1到200μm。 
流化床的特征在于固体颗粒之间有限的距离造成气体形成气泡。因为流化的催化剂颗粒导致的优异的固体混合确保了非常好的传热性质，流化床反应器特别适用于以已知的方式进行具有大量反应热量的放热反应或吸热反应。 
在流化床反应器中，气相的停留时间、传质和传热通过取决于气相的流动速率和流化床催化剂的固体性质的流化的状态决定。 
但是，流化床反应器具有的缺点在于传质，因为催化剂和反应物之间的接触由于其中没有固体存在的气泡的形成而受到限制。 
发现流化床反应器特别不利于进行停留时间为关键的且缺乏选择性的反应。由于对流的固体在流化床中返混，对应于产率和选择性的反作用，形成的产物可以进一步在流化床反应器的入口区反应形成副产物和后续产物。因此对流化床中大量的内部构件和它们对流化床反应器性质的影响进行考察。例如在Handbook of Fluidization and Fluid Particle Systems，Marcel Dekker-Verlag，New York-Basel，2003，175-199中提供了综述。 
例如内部构件可以是放置在流化床中的管子以便减小气泡的尺寸和 对流的固体的返混。管子可以垂直或水平对齐，管子的间隔比气泡的平均尺寸小。这里的缺点在于高度占用的反应器的横截面并且导致增加的流化床催化剂反混和流出倾向。 
分隔板同样可以水平或垂直对齐。但是，对反应器的经济装填不可缺少的相对高气体的速率下的分隔板的水平排列导致形成严重削弱传热的气垫(参见以上引用的手册，第190页，与第190到191页左列上描述的内容相关的图15a到d)。特别是在流化床中较低的区域还会变得缺乏固体催化剂，因为增加的横截面面积的占用，因此必须考虑传热的显著恶化。垂直的内部构件，例如管的垂直排特别还具有的缺点在于这些管排不能产生对于许多应用足够的气泡尺寸的减小。 
对停留时间性质和传质的改进还可以通过流化床中规则的或不规则的填料的床的方法实现。传质可以改进且在形成填料的床的成型体之间的窄缝中最优化停留时间分布。但是，这里还发现采用填料的床，较高的交叉横截面占用在增加催化剂的反混和流出倾向方面是不利的。 
根据这一点，本发明的目的在于在具有内部构件的流化床反应器中获得进一步的改进，特别是在停留时间性质方面，固体局部停留明显更久，即与气体流动相比大约为10的2次方或更长，并且避免了上述缺点。 
特别是还可以使用具有内部构件的流化床反应器进行工业级别的处理。 
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合固体的形式离开。 
此外，对于本发明的流化床反应器，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。 
通过本发明的方法制备的芳香族胺优选为苯胺且因此相应的硝基化合物优选为硝基苯。 
作为催化剂，有可能使用用于芳香族胺氢化的已知的、颗粒状的、具有或不具有载体的催化剂，特别是含有元素周期表中第一和/或第五到八族重金属的催化剂，优选为铜、钯、钼、钨、镍和钴元素中的一种或几种。 
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、拉制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，连续排列的金属片、拉制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 DEST_PATH_GSB00000888965300011
CY或BX或Monz GmbH，D40723Hilden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排列的金属片、拉制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、拉制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。 
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。 
本发明的流化床反应器特别适用于进行以下反应：氢化反应，特别是Fischer-Tropsch反应，由苯制备环己烯/环己烷，由腈、四氢呋喃进行不含氨的氢化，由马来酸酐制备BDO和由甲烷制备苯，脱氢反应，例如从乙烷制备乙烯，从丙烷制备丙烯，从丁烷制备丁烯，从乙基苯制备苯乙烯或由十二烷制备十二烯，部分氧化反应，例如从正丁烷或raffinate II制备马来酸酐，从萘或邻二甲苯制备邻苯二甲酸酐，从丙烯或丙烷制备丙烯醛或丙烯酸，从β-甲基皮考啉制备烟酸，从乙二醇制备乙二醛，从乙醇制备乙酸，从甲醇制备甲醛，从甲醇制备甲酸或从乙烷制备乙酸，环氧化反应，特别是乙烯形成环氧乙烷，氨基氧化反应，特别是由丙烯制备丙烯腈，由异丁烷制备甲基丙烯腈或者由二甲苯制备苯甲腈，以及进一步的反应，特别是由乙炔和乙酸制备乙酸乙酯，甲烷的氯化，苯酚和甲醇形成甲酚和2，6-二甲苯酚的反应，甲醇形成汽油，1-丁烯复分解形成1-十二烯或由脲制备三聚氰胺。 
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4的内部构件3和在内部构件3的区域中的热交换器5。 
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褶皱之间的分隔成扁平面12，两个连续排列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4。 

Claims (28)

1.一种适合用于进行气相反应的流化床反应器，其中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向上流动通过，且内部构件排列在流化床中，其中内部构件将流化床分隔为多个在流化床反应器中水平排列的单元和多个在流化床反应器中垂直排列的单元，单元具有可渗透气体的单元壁并具有确保在垂直方向上每升反应器体积中非均相颗粒催化剂的交换数在1到100升/小时范围内的开口，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或编织网孔，即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，即在褶皱之间形成扁平面，其与垂直方向倾斜成不为0的角度，其中连续排列的金属片或编织网孔的褶皱之间的扁平面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的流化床反应器，其中金属片为拉制金属片。
3.根据权利要求1的流化床反应器，其中排列在流化床反应器中的单元的单元壁中的开口确保了每升反应器体积中在水平方向上非均相颗粒催化剂的交换数在100升/小时范围内。
4.根据权利要求2的流化床反应器，其中排列在流化床反应器中的单元的单元壁中的开口确保了每升反应器体积中在水平方向上非均相颗粒催化剂的交换数在100升/小时范围内。
5.根据权利要求1-4中任一项的流化床反应器，其中排列在流化床反应器中的单元的单元壁中的开口确保了每升反应器体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体积中在水平方向上其在10到50升/小时范围内。
6.根据权利要求1或2的流化床反应器，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。 
7.根据权利要求6的流化床反应器，其中褶皱间扁平面与垂直方向的倾斜角度在20到70°范围内。
8.根据权利要求6的流化床反应器，其中褶皱间扁平面与垂直方向的倾斜角度在30到60°范围内。
9.根据权利要求1-4中任一项的流化床反应器，其中内部构件的单元具有通过放射性示踪技术测量的100到5mm的液力直径。
10.根据权利要求1-4中任一项的流化床反应器，其中内部构件的单元具有通过放射性示踪技术测量的50到5mm的液力直径。
11.根据权利要求1-4中任一项的流化床反应器，其中内部构件的单元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。
12.根据权利要求5的流化床反应器，其中内部构件的单元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。
13.根据权利要求6的流化床反应器，其中内部构件的单元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。
14.根据权利要求8的流化床反应器，其中内部构件的单元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。
15.根据权利要求9的流化床反应器，其中内部构件的单元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。
16.根据权利要求1-4中任一项的流化床反应器，其中内部构件的单元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40到5mm的平均高度。
17.根据权利要求5的流化床反应器，其中内部构件的单元具有在 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40到5mm的平均高度。
18.根据权利要求6的流化床反应器，其中内部构件的单元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40到5mm的平均高度。
19.根据权利要求8的流化床反应器，其中内部构件的单元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40到5mm的平均高度。
20.根据权利要求1-4中任一项的流化床反应器，其中金属片或编织网孔中的褶皱之间的扁平面具有100到3mm范围内的褶皱高度，且褶皱之间的收缩的间隔在50到2mm范围内。
21.根据权利要求9的流化床反应器，其中金属片或编织网孔中的褶皱之间的扁平面具有100到3mm范围内的褶皱高度，且褶皱之间的收缩的间隔在50到2mm范围内。
22.根据权利要求11的流化床反应器，其中金属片或编织网孔中的褶皱之间的扁平面具有100到3mm范围内的褶皱高度，且褶皱之间的收缩的间隔在50到2mm范围内。
23.根据权利要求1-4中任一项的流化床反应器，其中金属片或编织网孔中的褶皱之间的扁平面具有40到5mm范围内的褶皱高度，且褶皱之间的收缩的间隔在20到3mm范围内。
24.根据权利要求9的流化床反应器，其中金属片或编织网孔中的褶皱之间的扁平面具有40到5mm范围内的褶皱高度，且褶皱之间的收缩的间隔在20到3mm范围内。
25.根据权利要求11的流化床反应器，其中金属片或编织网孔中的褶皱之间的扁平面具有40到5mm范围内的褶皱高度，且褶皱之间的收缩的间隔在20到3mm范围内。
26.根据权利要求1或2的流化床反应器，其中热交换器安装在内 部构件中。
27.根据权利要求26的流化床反应器，其中热交换器以平板或管的形式配置。
28.根据权利要求1-4中任一项的流化床反应器，其中内部构件由金属、陶瓷、聚合物或玻璃材料制成。 
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US8038950B2 (en) 2011-10-18
US20100021354A1 (en) 2010-01-28
PL2066436T3 (pl) 2012-12-31
EP2066436B1 (de) 2012-07-18
CN101528338A (zh) 2009-09-09
PT2066436E (pt) 2012-08-06
JP2010503530A (ja) 2010-02-04

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