CN1597496A - 从合成气中除去氮、甲烷和氩用低△p净化器 - Google Patents
从合成气中除去氮、甲烷和氩用低△p净化器 Download PDFInfo
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- CN1597496A CN1597496A CNA2004100712290A CN200410071229A CN1597496A CN 1597496 A CN1597496 A CN 1597496A CN A2004100712290 A CNA2004100712290 A CN A2004100712290A CN 200410071229 A CN200410071229 A CN 200410071229A CN 1597496 A CN1597496 A CN 1597496A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 title description 10
- 229910052786 argon Inorganic materials 0.000 title description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000000034 method Methods 0.000 claims abstract description 70
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 57
- 239000012530 fluid Substances 0.000 claims abstract description 56
- 239000002699 waste material Substances 0.000 claims abstract description 48
- 238000004821 distillation Methods 0.000 claims abstract description 39
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000002407 reforming Methods 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims description 117
- 230000015572 biosynthetic process Effects 0.000 claims description 58
- 239000007788 liquid Substances 0.000 claims description 56
- 238000003786 synthesis reaction Methods 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000009833 condensation Methods 0.000 claims description 22
- 230000005494 condensation Effects 0.000 claims description 22
- 238000000746 purification Methods 0.000 claims description 20
- 239000011261 inert gas Substances 0.000 claims description 19
- 241000282326 Felis catus Species 0.000 claims description 18
- 230000006872 improvement Effects 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- 238000011144 upstream manufacturing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000005057 refrigeration Methods 0.000 abstract 1
- 238000007710 freezing Methods 0.000 description 13
- 230000008014 freezing Effects 0.000 description 13
- 230000006835 compression Effects 0.000 description 12
- 238000007906 compression Methods 0.000 description 12
- 230000009471 action Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001833 catalytic reforming Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 235000019628 coolness Nutrition 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
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- 239000002912 waste gas Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000005514 two-phase flow Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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Abstract
公开了一种由合成气制备氨的方法,该方法用过量空气进行重整,并且除氮时压力损失小。通过来自蒸馏塔的贫氢液流的膨胀提供使合成气冷却的自冷冻以低温富氢。
Description
技术领域
本发明涉及改进制氨用合成气的制备的方法和装置。本发明降低洗氮净化器装置中的压力损失。
背景技术
由烃和空气通过氢/氮合成气体(合成气)制备氨的方法众所周知。典型地,外来合成气组分包括来自空气中的惰性气体和/或烃进料如氩和甲烷。当在合成气制备中使用过量的空气时,存在的氮也超过化学计量比,从而必须从原始(makeup)合成气流中除去氮或从氨合成回路中清除氮以保持所需的氨合成反应器进料的组成。
Grotz的美国专利US 3,422,613公开了一种使用过量空气的合成气制备方法和低温合成气净化方法,其依赖在净化上游的合成气的压降来冷冻。随后,在压缩机中弥补该压降,所述压缩机将合成气的压力升高至氨合成回路的压力。在合成气净化中,由于在上游从组成合成气中除去了惰性气体如氩和甲烷,所以该方法还降低了循环速率或来自氨反应器回路的吹扫气流的流动(flow)。
Mandelik等人的美国专利US 4,568,530提供了一种在氨合成反应器中使用高活性催化剂来合成氨的方法。通过在循环至合成回路压缩机的合成气侧流进行的氢富集过程来去除吹扫气体。总的循环流量(flow)约为组成合成气体积流量的3倍。
Pinto的美国专利US 4,681,745推荐使用空气分离来提供富氧空气,这样重整产生了烃的减少(slip)比其它制氨系统中高的合成气。在回收氨产物后,通过从残留的合成气流中清除来使氨合成中的非反应气体的浓度维持较高。此方法依靠空气分离而除去了前端气体重整反应器,但表面上看来在氨合成之后使更小的吹扫气流的处理成为可能。
Lee等人的美国专利US 5,180,570描述了一种用于合成甲醇和氨的整体处理系统。氨合成部分使用通过低温分馏(fractionation)进行的氮洗涤来净化氨合成气,同时由外部提供冷冻且在该过程中不提供膨胀功率的回收。
Gosnell等人,″New Kellogg Brown & Root AmmoniaProcess,″1999年7月,存在于AIChE Ammonia SafetySymposium,1999年9月,描述了一种氨合成方法,该方法在合成中使用与优化的、用于产生合成气体的设备前端(plant frontend)一体化的低温合成气净化方法与高活性氨催化剂。
发明内容
本发明提供一种净化合成气,例如在制氨过程中出现的合成气的方法。该方法使用低温蒸馏来净化合成气,并使用液体膨胀机由废流体膨胀获得用于蒸馏的冷冻从而从该废流体中回收机械功。此方法降低了合成气流中的压力损失,并且同时,相对于相似的利用除去氮和惰性气体的现有技术氨合成方法,降低了压缩费用和能量。
本发明的方法特别适用于基础设备设计(grassroots plantdesign),优选地,也可以用于改进现有合成气系统从而改善方法性能和经济状况。例如,在改进中,本发明的较低压降可以允许用过量空气重整和从组成合成气中除去氮而对方法进行改进,而不用对合成回路和/或组成气体压缩机进行昂贵的改进或更换。
在一个实施方案中,本发明提供一种净化合成气的方法,包括:(a)将含过量氮的原始合成气流引入到蒸馏塔的进料区中; (b)用具有功输出(work output)的液体膨胀机(liquid expander)使来自该蒸馏塔的液态塔底流出物流膨胀从而形成冷却的废流体物流;(c)精馏来自该蒸馏塔中进料区的蒸气从而形成氮和惰性气体含量降低的塔顶蒸气流;(d)用冷却的废流体物流以间接热交换的方式来冷却该塔顶蒸气流从而形成部分冷凝的塔顶流出物流和相对热的废流体物流;(e)将部分冷凝的塔顶流出物流分成冷凝物流与氮和惰性气体含量降低的净化的合成气蒸气流;和(f)用该冷凝物流回流蒸馏塔。该方法还可以包括以下步骤:在引入到进料区之前,通过穿过Joule-Thompson(J-T)阀的膨胀来冷却原始合成气流。另外,该方法可以包括以下步骤,用热的废流体物流和净化的合成气蒸气流以交叉换热(cross-exchange)的方式来冷却原始合成气流。在此实施方案中,通过调整进行膨胀的液态塔底流出物流的流量来控制蒸馏塔中的液位。
该方法还可以包括通过重整烃来制备原始合成气,其中重整包括自热重整或用过量空气的二级重整。并且,通过此方法,可以向用于制氨的氨合成回路提供净化的合成气蒸气流。
在另一个实施方案中,本发明提供一种氨合成方法,包括:(a)重整烃以形成合成气从而形成用于氨合成的、含过量氮的原始合成气流,其中重整包括自热重整或用过量空气的二级重整;(b)在交叉换热器(cross-exchanger)中冷却该原始合成气流;(c)使来自该交叉换热器的冷却的原始合成气流膨胀;(d)将该膨胀的原始合成气流引入到蒸馏塔的进料区中;(e)通过液体膨胀机使来自蒸馏塔的液态塔底流出物流膨胀从而形成冷却的废流体物流;(f)精馏来自该蒸馏塔中进料区的蒸气从而形成氮和惰性气体含量降低的塔顶蒸气流;(g)用该冷却的废流体物流以间接热交换的方式来冷却该塔顶蒸气流从而形成部分冷凝的塔顶流出物流和部分变热的废流体物流;(h)将部分冷凝的塔顶流出物流分离成冷凝物流与氮和惰性气体含量降低的净化的合成气蒸气流;(i)用该冷凝物流回流蒸馏塔;(j)加热交叉换热器中的净化的合成气蒸气流;(k)加热交叉换热器中的部分变热的废流体物流;(l)将净化的合成气蒸气流从交叉换热器供应至氨合成回路。
在另一个实施方案中,本发明可以用于改善包括以下步骤的氨合成方法:用过量空气重整烃从而形成原始合成气流;通过蒸馏从该原始合成气流中除去氮和惰性气体,其中由通过膨胀发生机形成的过程流体膨胀(process fluid expansion)来提供冷却,并且其中通过使来自蒸馏塔的底部液体膨胀而冷却的废流体将塔顶流出物流部分冷凝,并向氨合成回路供应经蒸馏的、氮和惰性气体含量降低的合成气。在此实施方案中,对氨合成方法的改进包括:(a)任选地,使穿过蒸馏塔的Joule-Thompson阀上游的原始合成气流膨胀;和(b)通过具有功输出的液体膨胀机使底部液体膨胀。
在另一个实施方案中,本发明提供一种用于净化含过量氮的原始合成气流的净化装置,包括:用于将原始合成气流引入蒸馏塔中进料区的装置;用于使来自蒸馏塔的液态塔底流出物流膨胀从而形成冷却废流体物流的设备;用于精馏来自该蒸馏塔中进料区的蒸气从而形成氮和惰性气体含量降低的塔顶蒸气流的设备;用于通过用冷却的废流体物流以间接热交换的方式来冷却该塔顶蒸气流从而形成部分冷凝的塔顶流出物流和相对热的废流体物流的设备;用于将部分冷凝的塔顶流出物流分成冷凝物流与氮和惰性气体含量降低的净化的合成气蒸气流的设备;和用于用冷凝物流回流蒸馏塔的设备。
在另一个实施方案中,本发明提供一种氨合成方法装置,包括:(a)用于重整烃从而形成合成气的设备,其中该重整设备包括自热或二级重整装置以及用于向该自热或二级重整装置供应过量空气的设备,从而形成用于氨合成的、含过量氮的原始合成气流;(b)用于冷却该原始合成气流的交叉换热器设备;(c)用于使来自该交叉换热器的冷却的原始合成气流膨胀的设备;(d)用于将该膨胀的原始合成气流引入到蒸馏塔的进料区中的设备;(e)用于通过液体膨胀机使来自蒸馏塔的液态塔底流出物流膨胀从而形成冷却的废流体物流的设备;(f)用于精馏来自该蒸馏塔中进料区的蒸气从而形成氮和惰性气体含量降低的塔顶蒸气流的设备;(g)用于用该冷却的废流体物流以间接热交换的方式来冷却该塔顶蒸气流从而形成部分冷凝的塔顶流出物流和部分变热的废流体物流的设备;(h)用于将部分冷凝的塔顶流出物流分成冷凝物流与氮和惰性气体含量降低的净化的合成气蒸气流的设备;(i)用于用该冷凝物流回流蒸馏塔的设备;(j)用于加热交叉换热器中净化的合成气蒸气流的设备;(k)用于加热交叉换热器中部分变热的废流体物流的设备;和(l)用于将净化的合成气蒸气流从交叉换热器供应至氨合成回路的设备。
附图说明
图1是说明现有技术合成气净化方法的流程示意图,该方法采用上游合成气进料来驱动膨胀机并以功的形式抽出合成气能量以实现自冷冻。
图2是本发明一个实施方案方法的流程示意图,该方法使用富氮废流体物流的膨胀在该过程中产生自冷冻。
图3是说明本发明另一个实施方案方法的流程示意图,其中可以使合成气进料或液化的废气通过液体膨胀机膨胀来冷冻。
图4是本发明一个实施方案的方块流程图,该实施方案说明与氨合成方法中用过量空气的二级重整和热交换重整一体化的低压降除氮。
图5是本发明一个实施方案的方块流程图,该实施方案说明与氨合成方法中常规初级蒸气重整和用过量空气的二级重整一体化的低压降除氮。
具体实施方式
参考图1-3,其中相似的流体和元件编号相似,图1描述了现有技术的合成气净化方法PA。合成气进料流10驱动膨胀机12,以功14的形式抽出合成气能量而实现自冷冻。在交叉换热器16、18中,通过与来自蒸馏塔20中的冷产物流进行间接热传递而冷冻原料流10。在交叉换热器16、18之间,原始合成气10在涡轮膨胀机(turboexpander)12中膨胀,冷却该原始合成气10并回收功14。例如,在启动的过程中,可以绕过膨胀机12或通过使用Joule-Thompson(J-T)阀22来弥补。来自交叉换热器18的部分液化原始合成气13进入蒸馏塔20而被进一步冷却,部分冷凝并精馏,产生氮和惰性气体含量降低的净化的合成气流24和贫氢废气流26。如上所述,净化的合成气流24和废气流26流过交叉换热器16、18以冷冻原始合成气进料流10。
废气流26作为塔底流出物流28从蒸馏塔20排出,迅速经过液位控制阀30,并用作与蒸馏塔20一体化的热交换器32中的冷却剂。热交换器32冷却并部分冷凝来自塔20的塔顶蒸气从而获得合成气液体以回流塔20。为了提高于较高压下运转的氨合成反应器(未示出)中的转化率,压缩组成合成气流24。这样,在净化方法PA中,由原始合成气10引起的压降必须通过消耗额外的压缩功率而在下游被弥补。
图2描述了根据本发明的合成气净化方法34的一个实施方案,该实施方案使用液体塔底流出物流28的机械膨胀而在净化方法34中产生自冷冻的主要部分。在图1交叉换热器16、18的位置上使用单个交叉换热器36,尽管交叉换热器36可以包括许多物理阶段(physicalstages)。原始合成气流10通过蒸馏塔20的阀站38上游。阀站38可以包括初级的、用于在正常运转的过程中控制流量的线尺寸阀(line-size valve)和用于调整和/或启动自冷冻的J-T二级阀。然后,原始合成气流10优选以合成气蒸气和液体混合物的形式进入塔20的入口区40。在入口区40中,合成气液体分离并被收集在液体滞留区42中。液体作为塔底流出物流28通过下出口44离开塔20。通过液体膨胀机46使塔底流出物流28膨胀从而使塔底流出物流28自冷冻并回收功48,而功48可用于驱动泵、压缩机、发电机等。当在本文中使用时,″膨胀机”是一种功输出设备,该设备接收液态供应物并生成液态或蒸气流出物,优选蒸气-液体混合流出物。在该流出物流体是液体的情况下,液体膨胀机46可以是水力涡轮机。
旁路J-T阀用于例如在启动时的气相流动或两相流动。优选地,在操作中,塔底流出物流2 8的膨胀是本发明合成气净化方法34中的自冷冻的主要来源,而穿过阀站38处的旁路J-T阀的膨胀是相对次要的来源。然而,该旁路J-T阀可以是启动过程中的重要冷冻来源。
冷冻的废流体物流28从液体膨胀机46进入与塔20一体化的间接热交换区32的冷却剂入口52中。基于合成气分析仪56的反馈,液体膨胀机46的流速控制滞留区42中的液位,还部分调整塔20中的状态。塔20中的状态决定净化的合成气流24的组成,即较多的冷冻降低氮含量,而较少的冷冻增加氮含量。冷冻的废流体物流28通过热交换区32,由冷却剂出口56从塔20排出。在通过热交换区32的过程中,塔底流出物流28冷却并将来自塔20的塔顶蒸气部分冷凝。
合成气蒸气从入口区40向上流经接触区58,与向下流经接触区58的流体接触从而吸收氮并增加蒸气中的氢含量。在接触区58的上端,该蒸气进入直蒸气管(vapor riser)60并流向位于热交换区32上端的蒸气入口区62。该蒸气经过热交换区32的管侧以用废流体物流28部分冷凝,这进一步富集了该蒸气中的低沸点组分。蒸气和冷凝物离开热交换区32,并在分离(knockout)区64中被分离。蒸气作为净化的合成气流24离开塔20,通过合成气出口66排放。冷凝物收集在分离区64下面的并与接触区58连接的液封池68(liquid seal well)中。如上所述,冷凝物从液封池68中溢出而向下流经接触区58至液体滞留区42。
图3描述了合成气净化方法70的另一个实施方案,其中可以根据本发明对图1的方法PA进行改进或更新。增加了一个底部液体膨胀机以通过例如作为能48来回收功从而使塔底流出物流28自冷冻。与图2中一样,也安装旁路J-T阀。得到的改进净化方法70可与图2中本发明的实施方案相比,但如果需要,也可以按原始配置操作。对于低压降操作,绕过原始合成气涡轮膨胀机12,并将阀22设置为全开或任选地绕过(未示出)。
在本发明的一个优选实施方案中,吹扫气体的液态副产物流即塔底流出物流28的膨胀产生净化方法所需的自冷冻的主要部分。这避免了在图1的现有技术配置中引起的合成气的主要压力损失。典型地,在现有技术方法PA中,从合成气进料流10的引入到净化的合成气流24的离开出现约3.1巴的压降。此压降大部分发生在穿过膨胀机12处,其使原始合成气压力降低约1.8-2.0巴。在图2中所示的本发明的实施方案中,可以通过来自塔底流出物流28而非来自原始合成气进料流10的膨胀获得所需自冷冻的主要部分,从而将从合成气原料流10的引入到净化的合成气流24的离开出现的压降限制在约0.75-1.3巴。
参考图4,氨制备方法的实施方案可以包括在商业名称为KRES的已知类型的反应器/换热器(exchemger)104中催化重整含烃100和蒸气102的进料。在二级重整装置108中可以实现使用过量空气106作为氧化剂额外重整含烃100和蒸气102的进料。该方法还可以包括高和/或低温转换(shift conversion)和去除二氧化碳110、甲烷化和干燥112、根据图2或3描述的合成气净化114、压缩116和氨合成118。例如,为了甲烷化和干燥112,将吹扫气流120从氨合成118循环至合成气净化114的上游。循环液流120的质量流速比原始合成气流10的可以相对较小(见图2),例如,为原始合成气流10的约5-25重量%,优选为原始合成气流10的10-20重量%。废气流26可以作为燃料气体排出。
参考图5,制氨方法的另一个实施方案包括在常规的初级重整装置122中催化重整含烃100和蒸气102的进料,随后在常规的二级催化重整装置124中用过量空气106进行额外的重整。转换(shiftconversion)和去除二氧化碳110、甲烷化和干燥112、合成气净化114、压缩116、氨合成118和吹扫气流120循环参考图4的描述。废气流26可以作为初级重整装置122中的燃料燃烧和/或与图4中一样作为燃料气体排出。
图2的净化方法可以在改进能量消耗和基建费用节约的新型装置中使用,或可以用于改进如图1的现有净化方法以减少操作成本和/或增加生产能力。图2的方法还可以用于改进不使用净化和/或过量空气的现有装置。通过将一些重整功能转移给二级重整装置并降低初级重整装置的工作温度,用过量空气对重整进行改进可以提高现有装置的生产能力并提高现有重整装置中管子和/或其它内部构件的寿命。增加除氮步骤也可以使重整操作更灵活(例如,更高的甲烷减少量(methane slip)),并且由于通过除氮降低了惰性气体,从而导致来自氨合成回路中的吹扫或循环较少。使用本发明低ΔP净化方法所带来的氮净化/过量空气改进可以提高通过降低或消除对组成合成气压缩机改进的程度带来的改进,对于较大数量的现有氨装置,这可以使改进在经济上合算。
实施例:将图2中本发明实施方案的净化方法与图1中现有技术的净化方法相比。图1和2的方法都处理原始合成气进料流10以制备净化的合成气流24和废气流26,并且入口和出口物流组成在两种情况下是相同的,如下面的表1所示。
表1-净化合成气规格
物流组成,摩尔%
气体组分 原始合成气 净化的合成气 废气(26)
(10) (24)
氢气 65.8 74.7 6.6
氮气 31.4 24.9 74.2
甲烷 2.2 0.006 16.7
氩气 0.6 0.4 2.5
总计 100.0 100.0 100.0
图2的低ΔP方法用2200吨/天的氨加工装置模拟操作以将其操作温度、压力和流速与作为基本情况的、图1现有技术方法的相比较。结果示于下面的表2中。
表2-净化操作条件
基础:2200MTPD氨
处理物流,位置 基本情况(图1) 实施例(图2)
原始合成气(10),交叉换热器(20)的入口
温度,℃ 4.0 4.0
压力,kPa 3,479.0 3,479.0
质量流量,千克/小时 142,124 142,124
原始合成气(10),塔(20)的入口
温度,℃ -172.6 -172.0
压力,kPa 3,240.0 3,454.0
质量流量,千克/小时 142,124 142,124
合成气(24),来自塔(20)的出口
温度,℃ -178.6 -178.2
压力,kPa 3,215.0 3,429.0
质量流量,千克/小时 99,607 99,529
合成气(24),来自交叉换热器
(16、20)的出口
温度,℃ 1.3 2.1
压力,kPa 3,165.0 3,404.0
质量流量,千克/小时 99,607 99,52 9
底部流体(28),来自塔(20)的出口
温度,℃ -172.8 -172.2
压力,kPa 3,240.0 3,454.0
质量流量,千克/小时 42,517 42,596
废流体(26),换热器(32)的入口
温度,℃ -186.0 -187.6
压力,kPa 319.0 302.1
质量流量,千克/小时 42,517 42,596
废流体(26),来自交叉换热器
(16、36)的出口
温度,℃ 1.3 2.1
压力,kPa 256.4 253.3
质量流量,千克/小时 42,517 42,596
表2中的数据表明,在与图1基本情况相比的图2实施例中,流量和温度相似,但在净化处理入口与出口间合成气的压降显著降低。这通常需要为氨合成回路压力提供更少的组成气体压缩。对于图1基本情况和图2实施例,还确定了用于组成合成气压缩、流体膨胀功率输出以及净压缩和膨胀所需的功率。结果示于下面的表3中。
表3-功率平衡
基础:2200MTPD氨
压缩/膨胀 基本情况(图1) 实施例(图2)
组成合成气压缩,千瓦 8,310.66 7,453.49
原始合成气膨胀,千瓦 -203.39 --
废流体膨胀,千瓦 -- -120.40
净压缩/膨胀功率,千瓦 8,107.27 7,333.09
正如上面给出的数据所示,图2的净化方法的特征在于合成气压降比图1现有技术方法的低。虽然在图2的实施例中,从废流体的膨胀中回收的功率少于在图1基本情况下合成气进料膨胀的功率,但组成压缩功率的下降更显著。这样,不但合成气压降降低,而且总的功率需求也更少,这可能节约新的氨装置中的投资和生产费用。在现有的无净化器的氨装置的改进中,图2实施例中下降的压降可以使生产能力增加和/或对组成合成气压缩机的改进较小或不对其进行改进。
以上参考只是为了进行说明而提供的非限制实施例描述了本发明。各种改进和变化对本领域普通技术人员来说显而易见,即所有这些变化和改进都在附加的权利要求书的范围和精神内,并应该包括在本发明内。
Claims (19)
1.一种净化合成气的方法,包括:
将含过量氮的原始合成气流引入到蒸馏塔的进料区中;
用具有功输出的液体膨胀机使来自该蒸馏塔的液态塔底流出物流膨胀从而形成冷却的废流体物流;
精馏来自该蒸馏塔中进料区的蒸气从而形成氮和惰性气体含量降低的塔顶蒸气流;
用冷却的废流体物流以间接热交换的方式来冷却该塔顶蒸气流从而形成部分冷凝的塔顶流出物流和相对热的废流体物流;
将部分冷凝的塔顶流出物流分成冷凝物流与氮和惰性气体含量降低的净化的合成气蒸气流;和
用该冷凝物流回流蒸馏塔。
2.权利要求1的方法,还包括在引入到进料区之前,使穿过Joule-Thompson阀的原始合成气流冷却并膨胀。
3.权利要求2的方法,其中该原始合成气流的冷却包括与热的废流体物流和净化的合成气蒸气流交叉换热。
4.权利要求1的方法,其中通过调整液态塔底流出物流膨胀的流量来控制蒸馏塔中的液位。
5.权利要求1的方法,其中来自液体膨胀机的废流体包括混合的蒸气和液体。
6.权利要求5的方法,其中来自冷却塔顶蒸气的热废流体由气相组成。
7.权利要求1的方法,其中该液体膨胀机包括水力涡轮机。
8.权利要求1的方法,还包括通过重整烃来制备原始合成气,其中所述重整包括自热重整或用过量空气的二级重整。
9.权利要求1的方法,还包括向氨合成回路供应净化的合成气蒸气流以形成氨。
10.一种氨合成方法,包括:
重整烃以形成合成气,从而形成用于氨合成的、含过量氮的原始合成气流,其中所述重整包括自热重整或用过量空气的二级重整;
在交叉换热器(cross-exchanger)中冷却该原始合成气流;
使来自该交叉换热器的冷却的原始合成气流膨胀;
将该膨胀的原始合成气流引入到蒸馏塔的进料区中;
通过液体膨胀机使来自蒸馏塔的液态塔底流出物流膨胀从而形成冷却的废流体物流;
精馏来自该蒸馏塔中进料区的蒸气从而形成氮和惰性气体含量降低的塔顶蒸气流;
用该冷却的废流体物流以间接热交换的方式来冷却该塔顶蒸气流从而形成部分冷凝的塔顶流出物流和部分变热的废流体物流;
将部分冷凝的塔顶流出物流分成冷凝物流与氮和惰性气体含量降低的净化合成气蒸气流;
用该冷凝物流回流蒸馏塔;
加热交叉换热器中的净化的合成气蒸气流;
加热交叉换热器中的部分变热的废流体物流;
将净化的合成气蒸气流从交叉换热器供应至氨合成回路。
11.权利要求10的方法,其中来自液体膨胀机的废流体包括混合的蒸气和液体。
12.权利要求11的方法,其中来自冷却塔顶蒸气的热废流体由气相组成。
13.权利要求10的方法,其中该液体膨胀机包括水力涡轮机。
14.一种改进,在包括用过量空气重整烃以形成原始合成气流步骤的氨合成方法中,通过蒸馏从原始合成气流中除去氮气和惰性气体,其中由通过膨胀发生机的过程流体膨胀来提供冷却,并且其中塔顶流出物流用通过膨胀来自蒸馏塔的底部液体而冷却的废流体物流来部分冷凝,并将氮和惰性气体含量降低的合成气从蒸馏塔供应至氨合成回路,改进之处在于使底部液体通过具有功输出的液体膨胀机而膨胀。
15.权利要求14的改进,其中来自液体膨胀机的废流体包括混合的蒸气和液体。
16.权利要求14的改进,其中该液体膨胀机包括水力涡轮机。
17.权利要求14的改进,还包括使原始合成气穿过蒸馏塔的Joule-Thompson阀上游而膨胀。
18.一种用于净化含过量氮的原始合成气流的装置,包括:
用于将原始合成气流引入蒸馏塔中进料区的设备;
用于使来自蒸馏塔的液态塔底流出物流通过液体膨胀机膨胀从而形成冷却废流体物流的设备;
用于精馏来自该蒸馏塔中进料区的蒸气从而形成氮和惰性气体含量降低的塔顶蒸气流的设备;
用于通过用冷却的废流体物流以间接热交换的方式来冷却该塔顶蒸气流从而形成部分冷凝的塔顶流出物流和相对热的废流体物流的设备;
用于将部分冷凝的塔顶流出物流分成冷凝物流与氮和惰性气体含量降低的净化的合成气蒸气流的设备;和
用于用冷凝物流回流蒸馏塔的设备。
19.一种氨加工装置,包括:
用于重整烃而形成合成气的设备,其中该重整设备包括自热或二级重整装置以及用于向该自热或二级重整装置供应过量空气的设备,从而形成用于氨合成的、含过量氮的原始合成气流;
用于冷却该原始合成气流的交叉换热器设备;
用于使来自该交叉换热器的冷却的原始合成气流膨胀的设备;
用于将该膨胀的原始合成气流引入到蒸馏塔的进料区中的设备;
用于通过液体膨胀机使来自蒸馏塔的液态塔底流出物流膨胀从而形成冷却的废流体物流的设备;
用于精馏来自该蒸馏塔中进料区的蒸气从而形成氮和惰性气体含量降低的塔顶蒸气流的设备;
用于用该冷却的废流体物流以间接热交换的方式来冷却该塔顶蒸气流从而形成部分冷凝的塔顶流出物流和部分变热的废流体物流的设备;
用于将部分冷凝的塔顶流出物流分成冷凝物流与氮和惰性气体含量降低的净化的合成气蒸气流的设备;
用于用该冷凝物流回流蒸馏塔的设备;
用于加热交叉换热器中净化的合成气蒸气流的设备;
用于加热交叉换热器中部分变热的废流体物流的设备;
用于将净化的合成气蒸气流从交叉换热器供应至氨合成回路的设备。
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-
2003
- 2003-07-17 US US10/604,404 patent/US7090816B2/en not_active Expired - Lifetime
-
2004
- 2004-07-07 CA CA2473045A patent/CA2473045C/en not_active Expired - Lifetime
- 2004-07-15 DE DE602004016796T patent/DE602004016796D1/de not_active Expired - Lifetime
- 2004-07-15 EP EP04016768A patent/EP1503160B1/en not_active Expired - Lifetime
- 2004-07-16 RU RU2004121999/15A patent/RU2331575C2/ru active
- 2004-07-16 CN CNB2004100712290A patent/CN100519406C/zh not_active Expired - Lifetime
- 2004-07-16 MX MXPA04006957A patent/MXPA04006957A/es active IP Right Grant
-
2006
- 2006-06-22 US US11/472,590 patent/US20060239871A1/en not_active Abandoned
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102498058A (zh) * | 2009-09-02 | 2012-06-13 | 阿梅尼亚·卡萨莱股份有限公司 | 利用深冷净化制取氨补充合成气 |
CN102498058B (zh) * | 2009-09-02 | 2016-01-20 | 卡萨尔公司 | 利用深冷净化制取氨补充合成气 |
CN105358476A (zh) * | 2013-06-26 | 2016-02-24 | 卡萨尔公司 | 一种净化包含氢气和杂质的合成气的方法 |
Also Published As
Publication number | Publication date |
---|---|
US20050013768A1 (en) | 2005-01-20 |
CA2473045A1 (en) | 2005-01-17 |
EP1503160B1 (en) | 2008-10-01 |
US20060239871A1 (en) | 2006-10-26 |
CN100519406C (zh) | 2009-07-29 |
US7090816B2 (en) | 2006-08-15 |
DE602004016796D1 (de) | 2008-11-13 |
RU2331575C2 (ru) | 2008-08-20 |
MXPA04006957A (es) | 2005-06-17 |
EP1503160A1 (en) | 2005-02-02 |
RU2004121999A (ru) | 2006-01-20 |
CA2473045C (en) | 2011-09-27 |
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