CN1031391C - 从新鲜原料烃生产粗制氨合成气的方法 - Google Patents

从新鲜原料烃生产粗制氨合成气的方法 Download PDF

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CN1031391C
CN1031391C CN91102515A CN91102515A CN1031391C CN 1031391 C CN1031391 C CN 1031391C CN 91102515 A CN91102515 A CN 91102515A CN 91102515 A CN91102515 A CN 91102515A CN 1031391 C CN1031391 C CN 1031391C
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约瑟夫·R·勒布朗
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Abstract

通过蒸汽、氧化剂和大部分新鲜原料烃在一个放热催化转化段中进行反应得到甲烷含量很低的第一段转化气来生产氨合成气。剩余的新鲜原料在吸热催化转化段与蒸汽反应得到低甲烷含量的第二段转化气。第一段和第二段转化气合在一起，在吸热转化段与反应物进行间接热交换，从而提供这里需要的全部热量，然后收集起来作为粗制氨合成气。

Description

从新鲜原料烃生产粗制氨合成气的方法
本发明涉及由烃类如天然气生产氨的方法，具体地讲，它涉及生产氨合成气氢和氮的方法，由于取消了在工业实际中一般使用的火管式一段转化炉，使得减少了对燃料气体的需求。
无论在技术上还是在经济上，用于生产氨合成气的一段和二段转化的常规步骤是公知的。根据最新的观点，对于每个生产氨的装置，认为这两步是决定其“原料与燃料”需求的控制步骤，因为这两步都需要烃类燃烧产生的热量进行蒸汽与烃类的吸热反应。
工业用一段转化器是一个有许多大管的烧燃料的炉，管中装有含镍催化剂，通过此催化剂，当加入蒸汽时，大约有60％(体积)的新鲜原料烃转化为氢和氧化碳。此一段转化气中还含有未反应的蒸汽和剩余的烃类甲烷。从这个工艺的观点出发，一段转化器是一个吸热催化蒸汽转化区。
一段转化气被送入二段转化器，这个转化器一般是一个衬有耐火材料的容器，没有外部加热装置，在此容器中装有含镍催化剂。在进行二段转化时，一部分一段转化气和外供空气进行燃烧供给剩余甲烷与蒸汽进行吸热反应的热量，而空气也是最终氨合成气中氮的来源。从此工艺的观点看，二段转化器是一个放热催化蒸汽转化区，有时被称作自热转化器。
从二段转化器中出来的粗制热合成气含有氢、氮、一氧化碳、二氧化碳、未反应的蒸汽、剩余的甲烷和少量惰性气体，这里的一氧化碳随后会转化为氢。在一般情况下，热合成气和锅炉的进料水进行热交换，产生蒸汽供给用于二段转化空气、合成气和氨产品回收用冷冻的压缩装置。
尽管有这方面的应用，专业人员一直希望使用反应/换热器将二段转化器出口气体的热量用于一段转化的另一种用途，并借此来最大限度地减小通常的火管转化炉的规模。理论上讲，如果能把足够数量的一段转化量移到二段转化器中，使得能够用从放热转化阶段得到的热量平衡掉吸热转化阶段所需要的热量，就可以把火管炉去掉了。进行这样的热平衡实际上要求在二段转化器中燃烧更多的烃，因此使用了过量的空气，也就需要在以后除去多余的氮以保证在最终合成气中达到预期的氢/氮比。
为此目的而提出的各种反应/换热器都是一种高温换热器，它有许多单程的管子，管子的两端固定在管板上。虽然这种高温的设计比火管炉的操作费用低，但制造费用高。可能更重要的是，由上述热平衡问题造成的最终合成气中有大量的氮过剩使得必须在氨工厂的合成工段之前或在合成工段当中有很不经济的大型氮气脱除系统。
最近，如美国专利2,579,843中所示的通用型开口插接管反应/换热器已被考虑用于一段转化，因为它比单程换热器更简单。在使用开口插接管生产氨合成气的已知设计中，上述的热平衡问题使得不能放弃通常的火管转化炉。
因此，本发明的目的是在由放热转化步骤供应全部转化热的条件下生产氨合成气并将从放热催化转化取得的热量用于吸热转化步骤。
与传统的工艺相反，按照本发明，将大部分新鲜烃类与蒸汽和氧化剂一起引入到放热催化蒸汽转化段并由此排出一段转化气，借此来生产氨合成气。剩下的小部分新鲜烃类在吸热催化蒸汽转化段与蒸汽反应，并由此排出二段转化气，与第一段转化气合并。然后，使所得的合并气体与吸热催化蒸汽转化段中的反应物进行间接热交换，在这里合并气体放出热量，然后作为粗制氨合成气被回收。
放热催化蒸汽转化段在22至70巴之间的压力下绝热操作，这个转化段一般可具体采用已知的“二段转化器”的形状，尽管在本发明的方法中这个名称是不那么合适的。最好将55～85％(体积)的新鲜烃与蒸汽和氧化剂一起引入到放热转化段，这几种物料合在一起在下文中称作第一段混合原料。最好先将第一段混合原料中的蒸汽和烃组分合在一起，并预热到450～650℃的温度。如果选用空气作为氧化剂，则第一段混合原料中的蒸汽与C1的比值最好在1.5至3.5之间。若选用富氧空气作为氧化剂，以干燥状态计，氧化剂最好含氧25～40％(体积)，而第一段混合原料中蒸汽与C1之比最好为2.5～3.5。可用适当规模的深冷装置、膜装置或压力回转吸收装置来提供富氧空气。到底选用空气还是选用富氧空气，主要是由制氧装置的规模与成本、公用工程成本和制氨装置与全部生产装置的公用工程系统的综合化程度等控制的经济因素决定的。无论用哪种氧化剂，在把氧化剂加入到放热催化蒸汽转化段之前，最好先预热到480～720℃。
和二段转化器一样，放热催化蒸汽转化段是自热操作的，但与通常的系统不同，全部转化量中的大部分是在这一段中进行的，而且要选择自热蒸汽转化的条件，最好在在900～1100℃下生产出含氢、氧化碳、氮和低于1.0％(体积，基于干态)残余烃(即甲烷)的第一段转化气。
吸热催化蒸汽转化段也是在22～70巴的压力下操作，但通过催化剂管壁这个段被第一段转化气加热，下面就要讲这一点。这个段落最好制成一个立式反应/换热器，这个反应器具有装满催化剂的插接管，在其下端有气体通道。剩下的小部分新鲜烃与蒸汽一起在后面称作第二段混合原料，它也要被预热到450～650℃的温度，然后引入到吸热催化蒸汽转化段，并进行反应，从而在一般为825～1025℃的温度下生产出含有氢、氧化碳和含量低于4.0％(体积，基于干态)残余烃类(即甲烷)的第二段转化气。第二段转化气中蒸汽与C1的比值最好为4.0～5.0。
为了给吸热转化段提供总的热需求，要先将第一段转化气与第二段转化气合在一起，然后在吸热催化蒸汽转化段与第二段混合原料进行间接热交换，将合并的转化气冷却后作为粗制氨合成气而回收。
因为一般在565～735℃之间回收粗制氨合成气，最好与在此进行预热的新鲜原料烃进行间接热交换，从而回收合成气中的显热。
现在参见附图，在管线1中的新鲜原料烃最好用水饱和，在和管线2中的蒸汽合并后在原料/合成气换热器3中预热。在管线4中是大部分新鲜原料烃，它与分别由管线5和6中加入的补充蒸汽和氧化剂混合构成第一段混合原料，通过管线7将其引入放热催化蒸汽转化器8，在这里进行反应生成第一段转化气，通过管线9将该转化气回收。
由管线10来的小部分新鲜原料和由管线11来的补充蒸汽混合形成第二段混合原料，通过管线12将此原料通入转化换热器13的催化剂管侧，这就是吸热催化蒸汽转化段。在管子的开口端用丝网(没有画出)支承着催化剂。由催化管下口收集的第二段转化气14和管线9中的第一段转化气混合。这样混合起来的气体与在催化剂管中的第二段混合原料进行间接热交换而被冷却，然后将其作为粗制氨合成气从反应换热器13的壳侧通过管线15收集。在原料/合成气换热器3中，此粗制氨合成气进一步被冷却，通过管线16进一步回收其中的热量并在合成氨的已知步骤中进一步加工。
下表表示在放热催化蒸汽转化器8中使用空气或富氧空气作为氧化剂这两种不同情况下的有关操作条件和各段物料流的组成的说明性实例。
                                   表1
                             空气作为氧化剂
    图中标号 7 9 12 14 15
    压力(巴)温度(℃)组成(1)kgmoles/hr(2)mole％(干基)H2N2CH4H2OO2COCO2ArC2+        41592        40989        41539        40891        39616
 (1)  (2)  (1)  (2)     (1)     (2)  (1)     (2)  (1)     (2)
 2719428671588518--27257  0.856.925.4--15.2--0.80.70.2  18281942211500--59729125--  38.941.20.5----12.73.20.5--     1273711706----12--3     3.01.791.6------3.0--0.7  11447471232--187155----     74.30.43.1----12.110.1----  29721949682732--78444625--     47.631.21.1----12.67.10.4--
                                     表2
                             富氧空气作为氧化剂
   图中标号         7        9         12        14        15
   压力(巴)温度(℃)组成(1)kgmoles/hr(2)mole％(干基)H2N2CH4H2OO2COCO2ArC2+         41616        39997         41502        40939        39663
 (1)  (2)  (1)     (2)     (1)     (2)  (1)     (2)  (1)     (2)
 281339879576576--28178  1.046.630.6--20.0--1.00.60.3  1921133972719--50341417--     45.631.90.2----12.09.90.4--     1173591712----11--3     2.91.891.7------2.8--0.8  11677251199--209145----     75.10.51.6----13.59.3----  30881346323918--71255917--     53.723.40.6----12.49.70.3--

Claims (6)

1、从新鲜原料烃生产粗制氨合成气的方法，它包括：
a)将含有蒸汽、大部分新鲜原料烃和选自空气和富氧空气的氧化剂的第一段混合原料引入到放热催化蒸汽转化段，并由这里排出含有残余烃量(基于干态)低于1.0％(体积)的第一段转化气；
b)将含有蒸汽和剩余的少部分新鲜原料烃的第二段混合原料引入到吸热催化蒸汽转化段，并由这里排出含有残余烃量(基于干态)低于4.0％(体积)的第二段转化气；
c)将第一段转化气与第二段转化气合并，在吸热催化蒸汽转化段使合并的转化气与第二段混合原料进行间接热交换，借此提供吸热催化蒸汽转化段中所需的全部热量；以及
d)通过用换热器与第二段混合原料间接热交换来进一步冷却所得的冷却合并气体并将进一步冷却后的合并气体回收作为粗制氨合成气。
2、权利要求1的方法，其中所述大部分新鲜原料烃为所述新鲜原料烃按体积计的55～85％。
3、权利要求2的方法，其中所述新鲜原料烃被预热到450～650℃的温度。
4、权利要求3的方法，其中所述新鲜原料烃通过与粗制氨合成气进行间接热交换而被预热。
5、权利要求1或3的方法，其中所述氧化剂是预热到480～720℃的空气，所述第一段混合原料中蒸汽与C1的比例为1.5～3.5，所述第二段混合原料中蒸汽与C1的比例为4.0～5.0。
6、权利要求1或3的方法，其中所述氧化剂是预热到480～720℃的富氧空气，所述第一段混合原料中蒸汽与C1的比例为2.5～3.5，所述第二段混合原料中蒸汽与C1的比例为4.0～5.0。
CN91102515A 1989-12-11 1991-04-19 从新鲜原料烃生产粗制氨合成气的方法 Expired - Lifetime CN1031391C (zh)

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DE69103742T DE69103742T2 (de) 1989-12-11 1991-03-22 Autothermes Dampf-Reformierungsverfahren.
EP91104631A EP0504471B1 (en) 1989-12-11 1991-03-22 Autothermal steam reforming process
ES91104631T ES2058966T3 (es) 1989-12-11 1991-03-22 Procedimiento autotermico de reformado con vapor de agua.
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