CN1827523B - 用于合成气制造的方法 - Google Patents
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Abstract
一种用于获得与氨合成压力相对应的预定高压的合成气(GS)的方法,其中氢和氮的摩尔比是3/1,该方法包括以下步骤:将天然气的连续流与水蒸气一起供给到一段转化步骤(RP),并与过量空气一起供给到后续的二段转化步骤(RS),从而获得气流(GF),所述气流(GF)包括氢、相对所述摩尔比过量的氮、不需要的物质如杂质和惰性气体,并将所述气流在分离器单元(S)中进行净化步骤,包括低温精馏,获得包括摩尔比为3/1的氢和氮的合成气(GS)连续流,并进行后续压缩步骤,直到氨合成所需的压力值。
Description
技术领域
本发明在其最全面的方面中涉及用于制造氨的合成气制造的方法,其中将天然气例如甲烷的连续流用水蒸气进行转化步骤(一段转化),然后用过量空气进行转化的步骤(二段转化),然后进行净化步骤,包括将在所述二段转化步骤制造的气流的低温精馏。
特别地,本发明涉及上述类型的方法的低温精馏步骤,以在预定的压力下获得纯合成气。
背景技术
为了获得用于氨生产的合成气(H2+N2),天然气,特别是甲烷(CH4)的连续流首先用水蒸气,然后用过量空气进行转化处理(分别称为一段转化和二段转化,这是公知的。
这样获得的并主要包括氢、氮、一氧化碳和二氧化碳、氩和水的气体产物通过低温精馏来净化,这将在下述的说明中变得清晰。
在二段转化步骤中,为了促进从一段转化来的气体产物的燃烧,供给相对确定氢和氮之间所需的3/1摩尔比率所必须的量过量的空气。
通常,在二段转化中使用的上面所述过量空气是为了确定氢和氮之间的摩尔比率为2.5-2/1,因此,气流包括等于相对氨合成中所需的氮量的摩尔数的40%-50%的氮余量。
然后通常将过量的氮在上面所述的低温净化步骤中取走。
为了达到允许低温净化的温度值,所述的温度值通常为约120℃的值,通过简单的热交换不足以冷却来自二段转化的气流,但是冷却相当急剧的增加是必须的,并且这通常是通过所述气流的适当膨胀来获得的。
尽管从不同的视点来看是有利的,此类型的方法也不是没有缺点,主要的缺点在于来自二段转化的气流的上面所述的膨胀步骤。
事实上,对于后续的氨合成,合成气必须在预定的和非常精确的高压下,原因在于膨胀中损耗的压力随后必须在压缩步骤中恢复。
这样的压力的必要恢复指的是由特别低压值(通常通过上面所述膨胀所确定为约20巴)的气态流体的压缩,以及这负面地影响了整个方法的成本效率。
发明内容
本发明的问题在于,提供一种上述考虑类型的方法,以获得适于用于氨制造中的合成气,即在在预定的压力下的合成气,其中氢和氮摩尔比为3/1,并且其中可以完全进行来自二段转化的气流的低温净化,从而克服参照现有技术所提及的缺点。
此问题通过根据本发明的用于合成气制造的方法来解决,其中将天然气如甲烷的连续流用水蒸气进行一段转化步骤,以及用过量空气进行后续二段转化步骤,从而获得包括氢、氮、碳氧化物、氩、水和类似杂质的气体流,以及其中将所述气体流进行净化步骤,包括在分离器单元中的低温精馏,从而获得包括摩尔比为3/1的氢和氮的合成气的连续流,以及进行后续压缩步骤直到用于氨合成所需的压力值,其中,该方法包括另外的步骤:
-连续地分离这样获得的所述合成气的一部分,并膨胀所述的部分,从而获得冷却部分;
-将所述冷却部分以与将要净化的所述气流成换热关系地放置。
优选地,将合成气的所述部分在合成气流的压缩步骤之后分离。
有利地,上面所述的换热在上面所述的分离器单元之内发生。
还有利地,合成气的所述部分的分离量为合成气流的流量的10%和25%之间,优选分离量等于流量的20%。
根据本发明的方法的特征和优点将从其实施方案的详细描述变得清楚,所述的详细描述是在下面参照用于指示而非限定的目的的附图而进行的。
附图说明
在这样的附图中:
-图1显示了按照本发明根据第一实施方案用于获得合成气的方法的示意图;
-图2显示了按照本发明根据另一实施方案用于获得合成气的方法的示意图。
具体实施方式
参照图1,现在将描述根据本发明的方法的一个实施方案,所述的方法用于获得在预定的高压力值(通常在25-30巴之间)下的合成气GS,所述的包括特别适于在氨(NH3)制造中的3/1摩尔比的氢(H2)和氮(N2)的量。
在固定的操作条件中,将甲烷(CH4)的气流与水蒸气一起连续地送到第一常规转化步骤,或者一段转化RP,然后与过量空气一起送到第二常规转化步骤,或者二段转化RS。
然后,将来自二段转化RS的输出中的包括氢、氮、杂质和惰性气体如碳氧化物、水、氩的气流GF在分离器单元S中进行净化步骤,所述的净化步骤包括低温精馏,从其获得如下输出:作为初馏物,包括3/1摩尔比的氢和氮的合成气GS;以及作为尾馏物,分别包括上面所述的杂质和惰性气体的流I。
有利地包括分馏塔的分离器单元S可以备选地由适于获得包括低温精馏物的净化物的以下组成:包括冷却塔和回流冷凝器的组件,或者公知为Braun Purifier TM的净化器,或者类似的公知装置。
在上面所述的分离器装置S的输出中,将合成气GS送至在各压缩机C中的压缩步骤,由此得到压缩到压力值接近氨合成压力的合成气。
根据本发明,将上面所述合成气GS的部分GR从压缩流分离,然后送至膨胀器E中的膨胀步骤,在所述膨胀器中,将其膨胀,直到压力值基本上等于压缩机C的入口(吸入)压力,即大约25-30巴,在这样的膨胀步骤之后,获得合成气的冷却部分。
如此,将合成气这样的冷却部分GR送到换热步骤(在图1的实例中是与将要净化的气流GF间接地)。这样的换热对气流GF提供获得低温净化所必须的冷却。
优选地,这样的换热步骤在上面所述的分离器单元S中发生,其中冷却部分GR在膨胀步骤之后被输送。
优选地,合成气的上面所述部分GR的分离量为合成气GS流的流量的10%和25%之间,更优选地,所述分离量等于流量的20%。
这样的分离部分,在上面所述换热之后,与来自分离器单元S的输出中的合成气GS结合,并与其一起送到压缩步骤。
根据图1的实例的一个备选实施方案(未表现),合成气的冷却部分GR和将要净化的气流GF之间的换热步骤可以是直接型,即,其中冷气GR与将要净化的气流GF混合。
参照图2,示意性地显示了根据本发明用于获得合成气的方法的第二实施方案。在此图中,操作上类似于所述方法(图1)的第一实施方案那些的要素用相同的参考数字指示,并且为了简洁,不再重复其详细描述。
根据所述方法的此另一实施方案,中来自分离器单元S的输出中,将上面所述合成气GS的部分GR在压缩机C中的压缩步骤的上游分离。然后,将所述部分GR送至在膨胀器E’中的膨胀步骤,在所述膨胀器E’中,将其从约25-30巴的压力膨胀,直到例如10和15巴之间的值,在这样的膨胀之后,获得合成气的冷却部分GR。
与图1的实例相似的方式,然后,将这样冷却的合成气的所述部分GR送到换热步骤(与将要净化的气流GF间接地),优选地在上面所述的分离器单元S中。这样的换热对气流GF提供了获得低温净化物所必须的冷却。
在上面所述的换热之后,将分离的部分GR送至在各压缩机C’中的压缩步骤,在所述压缩机C’中,将其压缩至与来自二段转化RS的输出中的气流GF的压力基本上相同的压力值(例如25-30巴)。然后,将合成气的压缩部分GR与所述气流GF结合,并与其一起,将其送至分离器单元S中的净化步骤。
根据本发明的所述方法的主要优点在于:在将气流保持在高压力值下的同时,能够将要进行净化的气流GF冷却到从而允许有效低温净化的温度值的可能性。
因此,用来区得对应于氨制造压力的压力值下的合成气的后续压缩步骤应当更加便宜,所述的压缩步骤必须将合成气从初始高压值进行压缩。
这成为可能归功于这样的事实:为了获得将要净化的气流GF的冷却,不需要进行其整体膨胀,而净化的合成气GS的分离部分GR的膨胀以及其与将要净化的气流GF的热交换。
有利地,根据本发明的方法允许将空气流供给到二段转化RS,从而在将要净化的气流GF中确定低于在现有技术中所描述的过量的氮,同时允许有效的低温净化。
特别地,这样的过量相对上面所述的氢和氮之间的摩尔比在10摩尔%和25摩尔%之间,优选等于15摩尔%。
还有利地,根据本发明的方法适于用在工业装置改造的情况下,换言之,在用于合成气生产并包括低温净化的现有装置的容量的增加的情况下。
在改造的情况下,在装置的初始操作(其已经在现有技术中进行了说明)中根据本发明的方法的作用,实现了对装置进行有限改变而增加容量的优点。
考虑到装置中的容量的增加,应当认为,如果根据公知的方法来进行操作,就必须介入到在对应的膨胀器或者涡轮机上的膨胀步骤中,从而将其与必须膨胀具有更大流量的气流的更大容量的设备进行替换。
实施根据本发明的方法,膨胀器不必用更大容量的膨胀器进行替换,相反,用基本较小的容量的膨胀器替换,因此成本更为有效,因为其用于对净化的合成气的部分GR进行膨胀。
此外,考虑到必须将供给到二段转化的气流压缩到约35巴的压力值,应当认为,尽管容量增加,用较低量的空气操作,节省了压缩功,显然所述压缩功与将要压缩的空气流的流量成比例。
另一个优点可以清楚看到:如果认为在低温净化步骤中所需的能量消耗相对容量的增加基本不变,因为这样的增加通过必须由将要净化的气流中取走的少量的氮所补偿。
当然,为了满足可能发生和特定的要求,普通技术人员可以对上述的发明进行多种修改,所有的修改被本发明后附权利要求所限定的范围所覆盖。
Claims (7)
1.用于获得与氨合成压力相对应的预定高压的合成气(GS)的方法,其中氢和氮的摩尔比是3/1,该方法包括以下步骤:将天然气的连续流与水蒸气一起供给到一段转化步骤(RP),并与过量空气一起供给到后续的二段转化步骤(RS),从而获得气流(GF),所述气流(GF)包括氢、相对所述摩尔比过量的氮和不需要的物质,并且其中将所述气流在分离器单元(S)中进行净化步骤,包括低温精馏,从而获得包括摩尔比为3/1的氢和氮的合成气(GS)连续流,并进行后续压缩步骤,直到氨合成所需的压力值,其中,该方法包括另外的步骤:
-在所述后续压缩步骤之前或之后,连续地分离所述包括摩尔比为3/1的氢和氮的合成气(GS)连续流的一部分,并膨胀所述部分,从而获得冷却部分;
-将所述冷却部分以与将要净化的所述气流(GF)成换热关系地放置。
2.根据权利要求1的方法,其中,将合成气的所述部分在合成气(GS)流的压缩步骤之后分离。
3.根据权利要求1的方法,其中,将合成气的所述部分在合成气(GS)流的所述压缩步骤的上游分离,以及其中一旦已经用将要净化的所述气流(GF)进行了所述换热,将所述冷却部分进行压缩步骤(C’)至与将要净化的所述气流(GF)的压力基本上相同的压力值,并进行后续步骤,其中将所述压缩部分与所述将要净化的气流(GF)结合,并与其一起,将其送至在所述分离器单元(S)中的所述净化步骤。
4.根据上面所述权利要求任何一项的方法,其中,所述换热在所述分离器单元(S)之内发生。
5.根据权利要求1至3中任何一项的方法,其中,合成气的所述部分的分离量为合成气(GS)流流量的10%和20%之间。
6.根据权利要求1至3中任何一项的方法,其中,所述将要净化的气流(GF)含有相对所述摩尔比过量10摩尔%至25摩尔%的氮。
7.根据权利要求1至3中任何一项的方法,其中,在用于合成气生产的现有装置改造之后使用所述方法,在所述装置中,实施相应的方法,该方法包括含有相对于所述摩尔比过量的氮的气流的净化步骤,包括低温精馏。
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EP2135841A1 (en) * | 2008-06-20 | 2009-12-23 | Ammonia Casale S.A. | Process for the production of syngas for ammonia synthesis |
EP2159192A1 (en) * | 2008-08-28 | 2010-03-03 | Ammonia Casale S.A. | Process for the production of ammonia synthesis gas with improved cryogenic purification |
EP2284125A1 (en) * | 2009-08-13 | 2011-02-16 | Ammonia Casale S.A. | Process for revamping an ammonia plant with nitrogen-based washing of a purge stream |
CN104876185B (zh) * | 2015-05-15 | 2017-01-04 | 大连理工大学 | 膜分离富氧空气强化二段转化炉的布朗合成氨造气工艺 |
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DE1122087B (de) * | 1959-06-03 | 1962-01-18 | Linde S Eismaschinen Ag Zweign | Verfahren und Einrichtung zum Zerlegen von Gasgemischen in einer Tieftemperaturtrennanlage |
US6025403A (en) * | 1997-07-07 | 2000-02-15 | Mobil Oil Corporation | Process for heat integration of an autothermal reformer and cogeneration power plant |
US6190632B1 (en) * | 1999-02-25 | 2001-02-20 | Praxair Technology, Inc. | Method and apparatus for the production of ammonia utilizing cryogenic rectification |
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GB1156003A (en) * | 1965-10-22 | 1969-06-25 | Braun & Co C F | Ammonia Synthesis Gas Purification Process and Apparatus. |
DE1567715A1 (de) * | 1966-12-03 | 1970-07-02 | Metallgesellschaft Ag | Verfahren zur Erzeugung wasserstoffhaltiger Synthesegase aus stickstoffreichem Naturgas |
US4180553A (en) * | 1978-03-20 | 1979-12-25 | Monsanto Company | Process for hydrogen recovery from ammonia purge gases |
US4549890A (en) * | 1982-12-23 | 1985-10-29 | Air Products And Chemicals, Inc. | Process and plant for removing methane and argon from crude ammonia synthesis gas |
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CN1059131A (zh) * | 1991-06-01 | 1992-03-04 | 王师祥 | 空气连续气化深冷脱氮制合成氨的方法 |
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DK1700823T3 (da) | 2011-05-30 |
US7897130B2 (en) | 2011-03-01 |
EP1700823B1 (en) | 2011-02-16 |
EP1700823A1 (en) | 2006-09-13 |
CN1827523A (zh) | 2006-09-06 |
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