CN1044573C - 用于甲醇氧化脱氢制备甲醛的催化剂颗粒 - Google Patents

用于甲醇氧化脱氢制备甲醛的催化剂颗粒 Download PDF

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CN1044573C
CN1044573C CN92115016A CN92115016A CN1044573C CN 1044573 C CN1044573 C CN 1044573C CN 92115016 A CN92115016 A CN 92115016A CN 92115016 A CN92115016 A CN 92115016A CN 1044573 C CN1044573 C CN 1044573C
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A·怀奥拉
M·布鲁莎
B·麦里吉
G·古比托沙
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Abstract

一种圆柱形催化剂颗粒构型，它显示一种三叶片或三角形横截面，其上有相互等距离的三个通孔，每个通孔的轴与圆柱形颗粒的轴平行。

Description

用于甲醇氧化脱氢制备甲醛的催化剂颗粒
本发明涉及一种新型催化剂颗粒。特别是涉及一种显示其横截面靠外接圆周达到至少三点接触的圆柱形催化剂颗粒。
一种用于固定床反应器的粒状催化剂通常要满足下列要求：
-对气流的阻力小(在催化剂床等高下压降小)；
-实际表面积大，即表面积对体积的比例大；
-催化剂颗粒和反应气体间的热交换系数大；
-机械强度高，以防催化剂颗粒破裂。
固定床催化过程中常用的催化剂是各种大小的球形、实心圆柱形或环状构型。先有技术中使用这些已知类型时，反应气体向催化剂颗粒内部的扩散和反应产物向颗粒内部的反扩散常常很有限。这表示在非均相体系中，反应容易以选择方式发生在催化剂的外表面，具有先有技术的已知形状的催化剂在反应中没有得到充分利用。
因此，为了达到所需的转化速率，在必须使用一定高度的管束式固定床的场合，就必须要用大量催化剂。使用先有技术中所用的那些形状的催化剂，上述要求会造成压降增加，这是因为居于催化剂颗粒之间的空隙小。而且，在产生大量热的放热反应中，如氧化性脱氢、氧化、卤化和加氢反应，由于需要催化剂和料气之间的热交换系数要高，以确保除去足量的反应热，从而避免催化剂床过热而导致损坏催化剂和/或降低催化剂的性能。在具有传统形状的催化剂的场合，为了达到高的热交换系数，就必须增加催化剂颗粒上反应气的扰动程度，但这种策略会引起压降进一步增加，结果使操作成本增加。
美国专利4441990号公开了不同于传统形状的催化剂。该专利涉及具有基本上是三角形或四边形、多叶片形横截面的管形挤出颗粒。这些催化剂具有破碎强度和压降方面改进的优点，但线果实际上与传统催化剂所得没有很大不同。
本发明的目的是提供一种催化剂颗粒构型，通过改进压降、高的表面积与体积之比和高的热交换系数，从而有可能大大改进结果。
根据本发明，达到上述目的的方法是，颗粒有至少3个通孔，通孔的轴基本上相互平行，也与颗粒的轴基本平行，通孔的轴相互间基本上等距离。
这些通孔最好有圆形横截面，在该颗粒的横截面上，它们的轴构成了基本上是等边三角形的顶点，这些顶点指向催化颗粒的横截面与外接圆周相交接的那些点。
由于这些颗粒特别的几何形状和上述特征，在工业设施通常采用的操作条件下，在相同颗粒上，反应气体的高度扰动得以实现。由于这些颗粒具有的截面积的自由表面大，对气流的阻力低，因而使压降变小。而且当量直径小[当量直径=6(体积/总表面积)]，使催化剂颗粒显示较大的实际表面积，即表面积/体积的比例较高，因而使反应气体与催化剂表面的接触改进，这有助于反应剂的转化、限制了内扩散现象，使选择性增加。事实上与使用先有技术所用催化剂相比，使用本发明的催化剂，可以每单位体积一半催化剂的量，就能获得极高的有用产物的产率。这些催化剂的堆积密度又确实很低，为0.5-0.8g/cm3。
按照本发明的第一种实施方案，催化剂颗粒显示出彼此相等的几个基本上圆柱面形的叶片，并与通孔同轴。
按照本发明的第二种实施方案，催化剂颗粒显示出带圆形角顶的基本上为三角形的横截面。
在上述两种实施方案中，孔距(其中所谓″孔距″指有关孔的轴之间的距离)与这些孔的直径之比最好处于1.15-1.5的范围，更优选1.3-1.4。
颗粒高度与孔距之比最好处于1.5-2.5的范围，更优选1.7-2.3。
根据本发明的第一种实施方案，每个叶片的弯曲半径与孔距之比，最好处于0.6-0.9的范围内，更优选0.7-0.8。这些叶片对通孔半径之比；最好处于1.4-2.4的范围内，更优选1.75-2.05。外接圆周的半径与这些圆形叶片的弯曲半径之比，最好处于1.6-2的范围内，更优选1.7-1.85。在多叶片形式的实施方案中，每个颗粒的表面积与体积之比，最好高于2.4，更优选高于2.7。
根据本发明的第二种实施方案，每个圆形角顶的弯曲半径与孔距之比，最好为0.6-0.9，更优选0.7-0.8。外接圆周的半径与每个圆形角顶的弯曲半径之比，最好为1.6-2.0，更优选1.7-1.85。在多叶片形式的实施方案中，每个颗粒的表面积与体积之比，最好高于3.1，更优选高于3.3。
根据本发明的催化剂的形状，使其可用于广泛的催化过程中，例如有机化合物的加氢或脱氢、苯类衍生物的烷基化或脱烷基化、异构化、烯烃向甲醇的转化、甲烷变成烯烃的热氧化等。
根据本发明的催化剂的特优应用——当催化剂是铁和钼的氧化物时-是在甲醛生产过程中，通过氧化性甲醇的脱氢作用的应用。根据这一方法，使用1个或几个平行的反应器，反应器由含有催化剂的多管式管束构成，并在230-450℃温度范围内操作。在这样的反应器中，反应中产生出的热通过管壁，与在管外循环着的恒温液体进行交换。反应管的内径足够小(15-25mm)，及传热流体的循环方式，使催化床能够在尽可能接近等温条件下进行操作。
在加料气体中，甲醇和氧气存在的浓度分别为低于9％和12％(体积)，在这种相互比例下，在反应器内各点上，氧含量常常高于按由反应式 所需的化学计量的浓度；在实践中，当全部甲醇已反应完毕，氧浓度还应超过4％(体积)的值；并且同时，经常低于引起混合物发生爆炸的氧浓度(Bureao of Mines Bull；279,1939,pages82-foll.)。
在反应器入口处，待氧化的甲醇的摩尔分数被限制在那样的值，该值之上时反应的放热特征就不允许发生充分的热交换，以防催化剂床发生危险的局部过热(热斑)。
在如上所述的方法类型中，催化剂的形状和大小是基本重要的，使按照本发明催化剂构型得到的优点特别大。
从下列公开的细节中，可以看到按照本发明催化剂的进一步优点和特征，这些细节仅用作说明，不是出于限制的目的。现参考附图。
图1是按照本发明的催化剂颗粒的第一种实施方案的平面图；
图2是按照本发明的催化剂颗粒的第二种实施方案的平面图；
参考这些附图，10代表圆柱形催化剂颗粒(丸粒)，它具有3个圆形通孔12，通孔的排列是以其各中心组成等边三角形顶点。
在图1所示实施方案的形式中，丸粒显示三叶片横截面，圆形叶片10a在沿丸粒侧表面排列的纵向凹槽14处相互联结。以d1为直径的通孔12与圆形叶片10a同轴，两者一起限定了壁厚s。用角″β″表示由两通孔12的中心联结线和所述一通孔的中心与由与两通孔同轴的两叶片10a限定的纵向凹槽的联结线所构成的夹角。用p表示两通孔12的距离(即它们的中心之间的距离)，用d2表示叶片10a的直径(其半径用R表示)。丸粒横截面的外接圆周的半径用R表示。丸粒的横截面的最大和最小尺寸用M1和M2表示。
参考图2所示的实施方案的形式，其中在尺寸方面，使用与图1相同的参考号和符号，催化剂丸粒表现出三角形横截面和圆形角顶16。角顶的弯曲半径用R2表示。
在表1和2中，分别报告了按图1和2所示的催化剂丸粒的尺寸参数；在表3中报告了两种传统的环形催化剂的尺寸参数，这些丸粒是按下列实施例所公开的制作技术而做成的。对某些用于甲醇的氧化性脱氢所用的这类催化剂，其物化性能列于表4。
从有关这类丸粒尺寸和形状数据中，相应于一单个丸粒的形状的实心体体积和由此决定的催化剂的堆密度，可以计算出每个丸粒的预期重量。在整个试验的当量直径的范围内，所得预期重量与实验测得重量一致。
当然，堆密度取决于制作压力、用作起始原料的粉末特性和烧结方式。
根据下列实施例所描述的步骤，在连续流动的反应器中，测定活性、选择性和压降值。操作条件和催化剂性能的结果列于表5中。该表中，还列出了用两种具有传统环形形状的不同催化剂(实例13和14)，在相同实验条件下获得的结果。
比较这些结果，人们可以清楚地推知，用相同体积的本发明的催化剂，可获得高的产率和低的压降。若人们考虑了这些新型催化剂具有低的堆密度(以g/cm3表示)，其优点就显得更大。
尤其是，即使在较低温度下，这些催化剂显示出高的活性(实例1；表5)和在较高温度下显示出高的选择性。实例1-14
用硬脂酸为内润滑剂，将Fe2(MoO4)3和MoO3的粉末仔细混合，用特定模具用压实成型方法制备如表1和2所报告的形状和尺寸的丸粒，或用传统模具制备对比例13和14(表3)的催化剂。
然后，在500-550℃范围内，将这些丸粒烧结4小时。
烧结步骤以后，控制成型条件；使获得的催化剂具有表4所列的特性。
为了测定这些催化剂可达到的活性、产率和压降值，使用一种钢反应器，该反应器内径20.4mm，高1900mm，直立安装在一个熔盐恒温浴内，恒温浴由氮气搅拌。
催化剂被包装在管形反应器固定床内，固定床高700mm。
气流流经反应器(向下流动方式)的线速度为1.5Nm/sec，总内压为950mmHg(1.25bars)，气流中含甲醇浓度6％(体积)，氧浓度为9.5％(体积)。测定向下流过反应器出口的压力，以计算压降(ΔP)。
熔盐浴的温度调节到使甲醇的转化率达＞98％。
用气相色谱法，使用两台″Fractovap″(ex Carlo Erba)气相色谱仪分析流出反应器的反应气体。一台色谱仪用Peropak-T柱分析CO2、CH2O、DME(二甲醚)、H2O、未转化的MeOH，另一台用A型分子筛柱测定O2、N2和CO。
结果列于表5。
              表1催化剂类型        A       B       C       D高度h(mm)        5.00    5.00    5.00    4.00角β(rad)        0.89    0.78    0.75    0.89孔径d1(mm)       1.70    1.70    1.70    1.70最小厚度s(mm)    0.90    0.80    0.65    0.90孔距p(mm)        2.20    2.35    2.20    2.20横截面的最大尺寸M1(mm)       5.70    5.65    5.20    5.70横截面的最小尺寸M2(mm)       5.41    5.34    4.91    5.41实心横截面表面积(mm2)                15.64   14.69   11.28   15.64侧表面积(mm2)           170.77  171.18  164.28  136.62总表面积(mm2)           202.06  200.56  186.83  167.91催化剂颗粒占据的体积(″实心空间″)(mm3)    78.22   73.46    5.38   62.58当量直径(mm)               2.32    2.20    1.81    2.24表面积与体积之比S/V(1/mm)                2.58    2.73    3.31    2.68孔距/直径比p/dl            1.29    1.38    1.29    1.29叶片直径d2(mm)             3.50    3.30    3.00    3.50d2/dl                      2.06    1.94    1.76    2.06叶片半径Rl(mm)             1.75    1.65    1.50    1.75R1/p                       0.79    0.70    0.68    0.79高度/孔距比h/p             2.27    2.13    2.27    1.82外接圆周半径R(mm)          3.02    3.01    2.77    3.02R/R1                       1.72    1.82    1.85    1.72
                      表1(续)催化剂类型                   E       F      G高度h(mm)                  4.00    4.00    4.50角β(rad)                  0.78    0.75    0.78孔径dl(mm)                 1.70    1.70    1.70最小厚度s(mm)              0.80    0.65    0.80孔距p(mm)                  2.35    2.20    2.35横截面的最大尺寸M1(mm)                 5.65    5.20    5.65横截面的最小尺寸M2(mm)             5.34    4.91      5.34实心横截面表面积(mm2)            14.69   11.28     14.69侧表面积(mm2)       136.94  131.42    154.06总表面积(mm2)       166.32  153.98    183.44催化剂颗粒占据的体积(″实心空间″)(mm3)58.76   45.11     66.11当量直径(mm)           2.12    1.76      2.16表面积与体积之比S/V(1/mm)            2.83    3.41      2.78孔距/直径比p/ddl       1.38    1.29      1.38叶片直径d2(mm)         3.30    3.00      3.30d2/d1                  1.94    1.76      1.94叶片半径R1(mm)         1.65    1.50      1.65R1/p                   0.70    0.68      0.70高度/孔距比h/p         1.70    1.82      1.91外接圆周半径R(mm)      3.01    2.77      3.01R/R1                   1.82    1.85      1.82
                        表2催化剂类型                  H       L       M高度h(mm)                 5.00    5.00    5.00孔径d1(mm)                1.70    1.70    1.70最小厚度s(mm)             0.90    0.80    0.65孔距p(mm)                 2.20    2.35    2.20横截面的最大尺寸M1(mm)                5.70    5.65    5.20横截面的最小尺寸M2(mm)                5.41    5.34    4.91实心横截面表面积(mm2)               16.46   15.77   12.25侧表面积(mm2)          168.09  167.20  160.23总表面积(mm2)          201.00  198.73  184.74催化剂颗粒占据的体积(实心空间″)(mm3)     82.29   78.84   61.27当量直径(mm)              2.46    2.38    1.99表面积与体积之比S/V(1/mm)               2.44    2.52    3.01孔距/直径比p/d1           1.29    1.38    1.29圆顶的弯曲半径R2(mm)     1.75    1.65    1.50R2/P                     0.79    0.70    0.68高度/孔距比b/p            2.27    2.13    2.27外接圆周半径R(mm)         3.02    3.01    2.77R/R2                      1.72    1.82    1.85
                       表2(续)催化剂类型                  N       P       Q高度h(mm)                 4.00    4.00    4.00孔径d1(mm)                1.70    1.70    1.70最小厚度s(mm)             0.90    0.80    0.65孔距p(mm)                 2.20    2.35    2.20横截面的最大尺寸M1(mm)                5.70    5.65    5.20横截面的最小尺寸M2(mm)                5.41    5.34    4.91实心横截面表面积(mm2)               16.46   15.77   12.25侧表面积(mm2)          134.47  133.76  128.19总表面积(mm2)          167.39  165.29  152.70催化剂颗粒占据的体积(″实心空间″)(mm3)   68.83   63.07   49.02当量直径(mm)              2.36    2.29    1.93表面积与体积之比S/V(1/mm)               2.54    2.62    3.11孔距/直径比p/d1           1.29    1.29    1.29圆顶的弯曲半径R2(mm)     1.75    1.65    1.50R2/P                     0.79    0.70    0.68高度/孔距比h/p            1.82    1.70    1.82外接圆周半径R(mm)         3.02    3.01    2.77R/R2                      1.72    1.82    1.85
                       表3催化剂类型                  X         Y高度(mm)                   3.80      5.00外径(mm)                   4.00      5.00内径(mm)                   2.00      2.50厚度(mm)                   1.00      1.25实心横截面的表面积(mm2)   9.42     14.73侧表面积(mm2)            71.63    117.81总表面积(mm2)            90.48    147.26催化剂颗粒占有空间的体积(″实心空间″)          35.81     73.63当量直径(mm)               2.38      3.00横截面的自由表面积(mm2)   3.14      4.91
                        表4
              制甲醛的催化剂的物化特性实例号催化剂类型  丸粒高  化学分析    计算温度 30个丸
                                            粒重，
                 mm  Mo,wt％ Fe,wt％ ℃      g1    R            5.00    54.5   12.5   500    3.752    B            5.00    54.5    2.5   500    4.003    B            5.00    54.5    2.5   500    4.204    B            5.00    54.5    2.5   530    4.155    B            5.00    54.5    2.5   500    4.486    G            4.50    54.5    2.5   500    3.777    E            4.00    54.5    2.5   500    3.358    B            5.00    54.5    2.5   500    3.559    B            5.00    54.5    2.5   530    3.5510   G            4.50    54.5   12.5   500    3.4211   A            5.00    54.5   12.5   500    4.0012   A            5.00    54.5   12.5   550    4.0013* X             5.00    54.5   12.5   500    1.9014* Y             5.00    54.5   12.5   500    3.90(*)：对比例
                      表4 (续)
             制甲醛的催化剂的物化特性实例号 比表面 真密度  堆密度 孔隙率 总孔隙率 平均半径A
   m2/g   g/cc    g/cc      ％  cc/g1     5.90    3.89    1.62    58.4  0.36    12202     5.90    3.90    1.75    55.1  0.32    10853     5.80    3.89    1.81    53.5  0.30    10344     4.37    3.93    1.84    53.2  0.29    13275     5.40    3.89    1.92    50.6  0.26     9636     5.45    3.95    1.79    54.7  0.31    11387     5.47    3.93    1.80    54.2  0.30    10978     4.42    3.98    1.60    59.0  0.37    16749     3.73    3.85    1.61    58.3  0.36    193010     4.16    3.87    1.75    54.8  0.31    149011     5.70    3.85    1.75    54.55 0.31    108712     3.70    3.85    1.75    55.10 0.32    173013*    5.30    3.92    1.78    55.2  0.31    117014*    5.62    3.85    1.83    53.1  0.29    1032(*)：对比例
                      表5反应器内径=20.4mm催化剂床高=700mm线速      =1.5Nm/secondMeOH浓度=6.0％(体积)氧浓度   =9.5％(体积)实例 堆密度 盐浴温度 经反应器的 转化率号     g/mm    ℃    ΔP,mmHg      ％1     0.61    265      55      98.752     0.65    270      45      98.753     0.69    275      45      98.754     0.69    290      45      99.285     0.78    280      45      99.126     0.69    270      50      98.837     0.70    270      55      99.068     0.69    280      40      98.929     0.69    300      50      98.7610     0.65    280      40      98.6111     0.69    270      45      98.7612     0.69    310      50      98.9813*    0.81    270     100      98.9814*    0.73    280      50      98.83(*)：对比例
                    表5(续)
             实验条件和结果实例    CH2O    CO     DME      CO2
摩尔产率 摩尔产率 摩尔产率 摩尔产率1    94.82    2.79    1.07      0.072    94.68    3.08    0.94      0.123    94.10    3.40    0.96      0.094    95.22    3.11    0.82      0.135    93.94    4.19    0.90      0.096    94.42    3.25    1.07      0.107    94.65    3.31    0.94      0.088    95.61    2.23    0.98      0.109    96.23    1.66    0.76      0.1210    95.54    2.02    0.92      0.1211    94.11    3.60    0.98      0.0712    96.10    2.07    0.71      0.1013*   94.59    3.25    0.98      0.1514*   92.31    5.59    0.83      0.10(*)对比例

Claims (13)

1．一种用于甲醇氧化脱氢制备甲醛的催化剂颗粒，其特征在于该催化剂颗粒由Fe2(MoO4)3和MoO3基的粉未组成，横截面靠外接圆周达到至少三点接触，有至少3个通孔，通孔的轴相互基本平行，也与颗粒的轴基本平行，通孔轴相互基本等距。
2．根据权利要求1的颗粒，其特征在于这些通孔具有圆形横截面，在颗粒的横截面上，它们的轴心限定了基本上是等边三角形的顶点，这些顶点指向催化剂颗粒的横截面与外接圆周相交接的那些点。
3．根据权利要求2的颗粒，其特征在于它显示彼此相等的几个基本上为圆柱面形的叶片，并与通孔同轴。
4．根据权利要求2的颗粒，其特征在于它具有基本上带圆形角顶的三角形横截面。
5．根据要求2-4之任一种颗粒，其特征在于孔距(p)与这些孔的直径(d1)之比处于1.15-1.5的范围内。
6．根据权利要求2-4之任一种颗粒，其特征在于颗粒的高度与孔距之比为1.5-2.5。
7．根据权利要求3的颗粒，其特征在于每个叶片的弯曲半径与孔距之比为0.6-0.9。
8．根据权利要求3的颗粒，其特征在于这些叶片的弯曲半径与通孔的半径之比为1.4-2.4。
9．根据权利要求3的颗粒，其特征在于外接圆周的半径与每个圆形角顶的弯曲半径之比最好为1.6-2.0。
10．根据权利要求3的颗粒，其特征在于每个颗粒的表面积与体积之比大于2.4。
11．根据权利要求4的颗粒，其特征在于每个圆形角顶的弯曲半径与孔距之比为0.6-0.9。
12．根据权利要求4的颗粒，其特征在于外接圆周的半径与每个圆形角顶的弯曲半径之比为1.6-2.0。
13．根据权利要求4的颗粒，其特征在于每个颗粒的表面积与体积之比高于2.44。
CN92115016A 1992-10-06 1992-12-16 用于甲醇氧化脱氢制备甲醛的催化剂颗粒 Expired - Fee Related CN1044573C (zh)

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WO2022250568A1 (ru) * 2021-05-24 2022-12-01 Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор" Катализатор окисления метанола до формальдегида и способ его получения

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ITMI922301A1 (it) 1994-04-06
JP3382983B2 (ja) 2003-03-04
ATE153880T1 (de) 1997-06-15
IT1256156B (it) 1995-11-29
EP0591572A1 (en) 1994-04-13
TW231973B (zh) 1994-10-11
CA2084870A1 (en) 1994-04-07
CA2084870C (en) 2003-07-08
ES2103870T5 (es) 2006-11-16
ITMI922301A0 (it) 1992-10-06
RU2086299C1 (ru) 1997-08-10
DK0591572T3 (da) 1997-12-29
DE69220225T2 (de) 1998-02-19
EP0591572B2 (en) 2006-04-19
EP0591572B9 (en) 2006-08-23
US5330958A (en) 1994-07-19
DE69220225D1 (de) 1997-07-10
US5326915A (en) 1994-07-05
JPH06134318A (ja) 1994-05-17
ES2103870T3 (es) 1997-10-01
GR3024108T3 (en) 1997-10-31
DE69220225T3 (de) 2006-10-05
DK0591572T4 (da) 2006-08-21
EP0591572B1 (en) 1997-06-04
CN1085124A (zh) 1994-04-13

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