CN1196330A - 通过采用催化成品、蒸汽重整生产合成气 - Google Patents

通过采用催化成品、蒸汽重整生产合成气 Download PDF

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CN1196330A
CN1196330A CN98105652A CN98105652A CN1196330A CN 1196330 A CN1196330 A CN 1196330A CN 98105652 A CN98105652 A CN 98105652A CN 98105652 A CN98105652 A CN 98105652A CN 1196330 A CN1196330 A CN 1196330A
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J·罗斯特鲁普－尼尔森
P·S·克里斯滕森
V·L·汉森
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Topsoe AS
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Abstract

一种在管式反应器中载有蒸汽重整催化剂的情况下,通过烃原料蒸汽重整,生产富一氧化碳的氢的方法,该方法(a)让预重整的烃原料过程气体任意地通过在反应器壁上载有蒸汽重整催化剂薄膜的第一管式反应器,该反应器能与来自后置的第二管式蒸汽重整反应器的热烟气进行热交换;(b)让来自第一管式反应器的物流通入具有蒸汽重整催化剂薄膜并被燃料燃烧加热的第二管式反应器,由此获得部分蒸汽重整气流和热烟气;(c)让来自第二反应器的流出物通过固定床蒸汽重整催化剂;和(d)从固定床排出富一氧化碳和氢的产品气。

Description

通过采用催化成品、蒸汽重整生产合成气
本发明涉及通过烃原料与催化成品接触、蒸汽重整生产合成气。
术语催化成品用来表示一种催化系，该催化系的催化剂层固定在另外物质表面，例如金属表面上，其它物质可用作加强催化系的载体结构。这使催化剂自身形状可设计成不具有充够机械强度。本发明催化剂系所包括的营子其内壁放置重整催化剂薄膜层。
按下列反应(1)-(3)，通过蒸汽重整由烃生产合成气，
现有技术蒸汽重整技术是采用呈各种大小形状颗粒的重整催化剂。将催化剂颗粒放置在固定床反应器(重整菅)中。重整反应是吸热式的。在普通重整器中，通常是通过对菅子外部结合辐射和对流，从营外四周向反应提供的需热量。热量是通过营壁的热传导，传递给菅内的，并通过对流传递给气相。最后，通过对流将热由气相传递给催化剂颗粒。催化剂温度可高于100℃，低于上述重整菅轴向位置上的菅内壁温度。
业已发出，当催化成品用于蒸汽重整过程，热传递更有效。通过菅内壁传导，将热传递给催化剂，这是比通过气相对流进行传递的更为有效的一种传递机理。其结果是菅内壁和催化剂温度几乎相等(温差低于5℃)。此外，从下面看出，减少菅壁厚度，可使重整器菅内外壁的的温差变小。因而有可能使催化剂温度较高、菅道温度较低。当用催化成品管代替普通重整器菅子时，所有其他条件均相同。菅外壁温度低，是所希望的、因为这可延长菅子寿命。催化剂温度高是有利的，因为反应速度随温度而增加并且反应(3)的平衡向右边移动，结果是更好利用原料。
为此，本发明提供一种在菅式反应器内载有蒸汽重整催化剂薄膜的情况下，通过对烃原料蒸汽重整，生产富一氧化碳的氢的方法，该方法包括下列步骤：
(a)让预重整的烃原料过程气任意地通过在反应器壁上载有蒸汽重整催化剂薄膜的第一菅状反应器，其能与来自第二菅状蒸汽重整反应器的热烟气进行热交换；
(b)让由第一菅状反应器的气流通过具有蒸汽重整催化剂薄膜并被燃料燃烧加热的第二菅式反应器，由此获得部分蒸汽重整气流和热烟气。
(c)让由第二反应器来的流出物通过固定床蒸汽重整催化剂，和
(d)从固定床排出富一氧化碳和氢的气体。
催化重整器菅的压降大大低于具有相同菅径的普通容器。这样有可能采用具有较小直径的反应器，并仍保持可接受的压降。菅径较小的结果是使菅子寿命增加，并耐更高温度和减少菅子材料消耗。
最后，与具有固定床重整催化剂的普通重整器相比，当采用催化成品重整器菅子时，可减少催化剂用量。
图1表示合成气生产装置的前-后部分，原料2在装置4中被预热、脱硫、与过程蒸汽6混合，并在进入绝热式预重整器8之前被进一步加热，由预重整器8流出的流料液物流在烟气管路12中排布的环路中被进一步加热，然后送往管式重整器14。在重整器中甲烷转化为氢、一氧化碳和二氧化碳。菅式重整器下游的气流处理取决于产品使用情况。
催化成品可在图1所示的二种设备中使用。
1.在进入菅式重整器14前预重整器流料液气流在预热器盘菅10中被加热。
2.菅式重整器14。
下面列出了当将催化成品使用于上述二种设备时，在图1装置中获得的结果。用作催化成品的催化剂是由Haldor TopsoeA/S购得的R6TR镍蒸汽重整催化剂。将该结果与普通容器作比较。
预热器盘菅的目的是在烟气进入菅式重整器之前利用烟气的热量预加热过程气。烟气可用来预热过程气体和预热菅式重整器(图1中未显示)的燃烧空气，然而，烟气中的热量大于可用于这些目的所需的热量。如果将烟气较大量的热量传递给过程气体，这将是有利的。这样可减少菅式重整器中所需燃料量。由于在设备中传递较少量的热量，这样可减少重整器的尺寸。
普通预热器由于冒甲烷分解形成碳的风险，而受到限制。为此，应规定可接受的菅壁温度上限值。在预热器盘菅10(如图2所示)的内菅壁6上固定一层催化成品，其结果是可减少菅壁温度和过程气体温度。这样使得盘菅中传递效率更高而不具有较高菅温。
在计算中所采用的预热盘菅包括8根菅子，其中过程气流在该菅内流动。烟气在管外流动。流动的型式是横流/并流。图2表示一种菅子的布置情况。在表1中概括了具有催化成品和不具有催化成品的二种容器。很显然，与普通容器相比较，催化成品容器的传递效率(热能)较高，为49％。催化成品容器中的催化剂厚度为1.0mm。
表1
    普通情况     催化成品情况
    菅子数目        8          8
    总有效菅长      51.6m        76.2m
    烟气内/外温度    1057℃/964℃      1057℃/912℃
  过程气体内/外温度   512℃/650℃     512℃/631℃
    甲烷转化率       0％        8.7％
    传热效率   9.69*106卡/小时   1.44*106卡/小时
有效的菅子长度是烟气通道内的菅子长度。
普通的菅式重整器包括若干根填满催化剂颗粒的菅子。过程气体在菅外流动，将菅子放置在炉内，通过燃料燃烧将其加热。
在使用催化成品容器的情况下，采用若干根菅内壁上具有催化成品层的菅子来替代填满催化剂颗粒的菅子。催化剂层的厚度为0.25mm。由于催化成品菅式重整器中的甲烷转化不如普通容器，为此，应将附加的绝热式重整固定床反应器放置在菅式反应器下流。这种反应器称之为后置重整器。在后置重整器中所采用的催化剂是从Halodor Topsoe A/S购得的RKS-2镍蒸汽重整催化剂。
下面表2中概括了这两种容器。从表中看出，与普通容器相比，催化成品容器中的催化剂消耗减少11.5系数，在菅式重整器中的菅材消耗减少24％。
表2
  普通容器 催化成品重整器 催化成品容器+后置重整器
    菅子数目     276     187
    菅长     13m     55m
    催化剂消耗     31.0t     0.63t     2.70t
菅式重整器的菅材消耗     153.6t     116.0t
    甲烷转化率     89.0％     80.7％     90.2％
图3表示了本发明方法的流程图。三角形中的数字参考以下表，在该表中，对工艺过程的所有数值进行比较。与普通容器相比，催化成品容器的燃料消耗减少7.4％。
表3
位置 普通情况 催化成品情况
1 温度(℃)压力(kg/cm2g)总干流量(Nm3/h)总流量(Nm3/h)组成(干燥摩尔％)H2COCO2CH4 51228.55785114316823.780.7421.1454.34 51228.55785114316823.780.7421.1454.34
2 温度(℃)压力(kg/cm2g)总干流量(Nm3/h)总流量(Nm3/h)组成(干燥摩尔％)H2COCO2CH4 65027.55785114316823.780.7421.1454.34 63127.46739714872034.582.6720.1642.59
3 温度(℃)压力(kg/cm2g)总干流量(Nm3/h)总流量(Nm3/h)组成(干燥摩尔％)H2COCO2CH4 92524.114153319912168.8520.248.472.44 101526.013265319410666.7620.428.244.57
4 温度(℃)压力(kg/cm2g)总干流量(Nm3/h)总流量(Nm3/h)组成(干燥摩尔％)H2COCO2CH4 在这容器中无后置重整器 93024.414258020000369.0820.358.402.17
5 T(℃)总流量(Nm3/h) 1057244672 1057234677
6 T(℃) 964 912
7 总流量(Nm3/h) 9524 8820

Claims (4)

1.一种在菅式反应器中载有蒸汽重整催化剂的情况下，通过烃原料的蒸汽重整，生产富一氧化碳的氢的方法，该方法包括下列步骤：
(a)让预重整的烃原料过程气体任意地通过在反应器壁上载有蒸汽重整催化剂薄膜的第一菅式反应器，该反应器能与来自后置的第二菅式蒸汽重整反应器的热烟气进行热交换；
(b)让第一菅式反应器的流出物流入具有蒸汽重整催化剂薄膜并被燃料燃烧加执的第二菅式反应器，由此获得部分蒸汽重整气流和热烟气；
(c)让第二反应器的流出物通过固定床蒸汽重整催化剂；和
(d)从固定床排出富一氧化碳和氢的产品气。
2.权利要求1的方法，其中固定床蒸汽重整催化剂是在绝热条件下进行操作的。
3.权利要求1的方法，其中固定床蒸汽重整催化剂放置在第二菅式反应器中。
4.权利要求1的方法，其中蒸汽重整催化剂包括镍和/或钌。
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