CN102007358A - 深冷分离氢气和一氧化碳的混合物的方法和设备 - Google Patents
深冷分离氢气和一氧化碳的混合物的方法和设备 Download PDFInfo
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- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000001257 hydrogen Substances 0.000 title claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000009833 condensation Methods 0.000 claims abstract description 13
- 230000005494 condensation Effects 0.000 claims abstract description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 70
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000007599 discharging Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000009834 vaporization Methods 0.000 description 9
- 230000008016 vaporization Effects 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 239000003245 coal Substances 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
本发明涉及一种深冷分离氢气和一氧化碳的混合物(1)的方法,所述混合物任选包含用于通过一步部分冷凝生产纯CO的少量甲烷、氩气和氮气,在交换管线(3)中将混合物冷却,部分冷凝,并将由部分冷凝得到的至少一部分液体(11)输送至汽提塔(15)的顶部,富含一氧化碳的至少第一料流和第二料流(17、19、21)从汽提塔得到,在不同温度下冷却第一和第二料流,在膨胀后将第一料流输送至分离罐(27)中,在交换管线中再加热分离罐中的气体(31)并输送至包括至少两级的一氧化碳压缩机(33、35、37)的第一级中,在交换管线中再加热第二料流并输送至第一级下游的压缩机的级中,并在不同压力下在交换管线中再加热分离罐中的气体和第二料流。
Description
本发明涉及深冷分离氢气和一氧化碳的混合物,尤其是具有氢气和一氧化碳作为主要组分的混合物的方法和设备。
生产一氧化碳和氢气的单元可以分成两部分:-合成气的产生(基本上包含H2、CO、CH4、CO2、Ar和N2的混合物)。在各种生产合成气的工业路线中,基于煤气化的路线变得越来越流行,尤其是在煤矿丰富的国家中,例如中国。包括用于煤与氧气和蒸汽气化的反应器的这种单元的设计基于所需的CO生产和所需的氢气生产。
-合成气的纯化。发现如下:
-用液体溶剂涤气的单元,目的在于除去存在于合成气中的较大部分酸性气体,
-用于在吸附床上纯化的单元,
-对于生产CO而言,用于通过深冷路线分离的单元,即“低温试验箱”。
一般而言,合成气包含高压(通常为30-60巴)混合物且十分富含CO(约50摩尔%)。煤气化方法的另一优点是在生产纯CO的低温试验箱的入口处合成气中存在的杂质(CH4、氩气和氮气)含量低。
这使得可以设计相对简化的低温试验箱流程图,其中深冷分离限于CO与氢气之间的分离。合成气中惰性物质的含量与大多数情况下客户所要求的CO纯度相容。
这种流程图不包括致力于分离的循环。
需要在高压下从CO中分离氢气以能够在PSA中或在合成甲醇的单元中或其它单元中经济地利用它。
所述低温试验箱的一部分分离能量由合成气与在低压下生产的纯CO之间的自由膨胀提供,但是在大多数情况下,这种自由膨胀不足以完成该单元的制冷平衡。需要补给液氮来保持低温试验箱的低温和完成制冷平衡。
在主要交换管线中冷却来自预处理单元(CO2和MeOH分离)的压力通常为30-60巴的合成气,并在供给一步部分冷凝分离罐之前进行部分冷凝。在交换管线中再加热后,富含氢气的蒸气在大多数情况下被输送至MeOH单元或PSA。该容器液体(vessel liquid)在膨胀后被输送至中压汽提塔(约14巴)。称作闪蒸气体的顶部蒸气在再加热后从低温试验箱排出,并作为燃料或再循环材料借助压缩机输送至该系统中。
将在容器底部以上水平处从该塔排出的料流低温冷却至某一温度水平,使其膨胀,并输送至热虹吸罐,然后在输送至CO压缩机的吸入部分之前在交换管线中使其汽化。
将来自汽提塔的容器液体在交换管线中低温冷却至不比上述膨胀前的料流冷的温度水平,在主要交换管线中将其汽化并再加热,最后输送至CO压缩机的中间级。
第三料流可以在该塔的另一水平(在容器底部以上的水平)处排出,并低温冷却至不同于前述两个温度水平的温度水平,使其膨胀,在交换管线中将其汽化和再加热。
CO压缩机使得可以将生产的CO(其为从汽提塔排出的所有液体的总和)压缩至下游单元(乙酸或其它)需要的压力。
将一氧化碳料流低温冷却至不同温度水平的优点在于降低了KS和热负荷,因此降低了主要交换管线的资本成本。将中压料流低温冷却至不比在如果它们都混合时冷的温度水平。
这样使得可以降低CO压缩机33、35、37的电能。中压水平的低温冷却消耗较少的能量。仅将各个富含CO的料流低温冷却至在膨胀后防止产生气体的某一温度水平,其使得可以避免必须安装用于主要交换管线的两相(液-气)进样罐。
这样使得可以具有富含一氧化碳的低压液体(在热虹吸罐27处的最低压力水平),其可以包含比汽提塔的容器底部更多的氢气,因此使得对于相同的压力水平可以具有低的汽化温度,因此使得可以进一步冷却合成气(对于相同的ΔT)并提高该单元的CO产量。另外,在相同的产量下,这使得可以降低压缩机的电能,因为可以增加压缩机的吸入压力。
根据本发明的一个主题,提供如权利要求1所述的方法。
任选地:
-具有不同纯度的第一和第二料流;
-具有相同纯度的第一和第二料流;
-至少一种料流在汽提塔的容器处排出;
-第一料流是一种在汽提塔容器处排出的料流,在交换管线中将其冷却至第一温度,使其膨胀,然后在交换管线中再加热,第二料流在汽提塔的中间水平处排出,冷却至比第一温度低的第二温度,使其膨胀,然后在交换管线中再加热。
-将冷却至第二温度的第二料流输送至分离罐;
-在高于或低于第二料流水平的汽提塔的中间水平处排出第三料流,冷却至低于或高于第一温度和/或低于或高于第二温度的第三温度,使其膨胀,然后在交换管线中再加热。
根据本发明的另一主题,提供一种深冷分离氢气和一氧化碳的混合物的设备,所述混合物任选包含用于通过一步部分冷凝生产纯一氧化碳的低含量甲烷、氩气和氮气,所述设备包括交换管线、汽提塔、第一和第二分离罐、包括至少两级的一氧化碳压缩机、用于将待冷却混合物输送至交换管线的装置、用于将冷却的混合物输送至第一分离罐的装置、用于将至少一部分由第一罐的部分冷凝所得液体排出的装置、用于将该液体输送至汽提塔顶部的装置、用于至少将富含一氧化碳的第一料流和富含一氧化碳的第二料流从汽提塔分流的装置、用于在交换管线中分别将第一和第二料流冷却至第一和第二温度的装置、用于在膨胀后将第一温度的第一料流或第二温度的第二料流输送至第二分离罐的装置、用于在交换管线中将来自分离罐的气体再加热的装置和用于将再加热的气体输送至一氧化碳压缩机的第一级的装置、用于在交换管线中再加热第二料流或第一料流的装置和用于将再加热的第二料流或再加热的第一料流输送至第一级下游的压缩机的级中的装置。
任选地,该设备包括:
-用于在汽提塔的相同水平处排出该至少第一和第二料流的装置;
-用于在通过汽提塔的至少一个理论级分离的水平处排出该至少第一和第二料流的装置;
-用于在汽提塔的容器处排出至少第一料流的装置;
-用于在汽提塔的容器处排出第一料流的装置和/或用于在汽提塔的第一中间水平处排出第二料流的装置;
-用于在低于或高于汽提塔的第一中间水平的水平处排出第三料流的装置;
-将在交换管线中冷却的第二料流或在交换管线中冷却的第一料流输送至分离罐的装置。
将参照附图更详细地描述本发明,所述附图为本发明方法的示意图。
在图1中,压力通常为30-60巴的合成气料流1包含氢气和一氧化碳以及任选少量的甲烷、氩气和氮气。将其冷却至交换管线3的中间水平,排出并借助交换器5用于使塔15的容器重新沸腾。随后,在交换管线3中继续冷却合成气,并将合成气输送至分离罐7中,在其中将其部分冷凝。在交换管线中将顶部蒸气9再加热以形成富含氢气的料流。在阀13中将容器液体11膨胀至14巴,并输送至汽提塔15的顶部,还在该顶部用注射液氮进行供料。在膨胀前在交换管线3中低温冷却在汽提塔15的中间水平处排出的液体19,并送至热虹吸罐27中。利用热虹吸操作在交换管线3中将来自罐27的容器液体29汽化,并将顶部气体31输送至CO压缩机的第一级33的吸入部分。
在交换管线3中将来自汽提塔15的容器液体21低温冷却至不比上述排出的液体冷的温度水平,使其膨胀,然后在交换管线3中将其汽化以在CO压缩机的中间级35处供给压缩机。
在塔的中间水平处排出不同于料流19的第三料流17(可以在高于或低于料流19的水平处排出),并低温冷却至不比料流19冷的温度水平。随后,使该料流膨胀,然后在交换管线3中将其汽化以在CO压缩机的级37处供给压缩机。
在汽化前将三种料流17、19、21膨胀至不同的压力。
在汽化和再加热后,三种混合的料流17、19、21形成一氧化碳产物39。
在图2中,压力通常为30-60巴的合成气料流1包含氢气和一氧化碳以及任选少量的甲烷、氩气和氮气。将其冷却至交换管线3的中间水平,排出并借助交换器5用于使塔15的容器重新沸腾。随后,在交换管线3中继续冷却合成气,并将合成气输送至分离罐7中,在其中将其部分冷凝。在交换管线中将顶部蒸气9再加热以形成富含氢气的料流。在阀13中将容器液体11膨胀至约14巴的压力,并输送至汽提塔15的顶部,还在该顶部用注射液氮进行供料。将来自汽提塔15的容器液体21分成三个级分41、43、45,在膨胀前将其各自在交换管线3中低温冷却至不同的温度。将第一料流45输送至热虹吸罐27中。利用热虹吸操作在交换管线3中将来自罐27的容器液体47汽化,并将顶部气体31输送至CO压缩机的第一级33的吸入部分。
将其它料流41、43膨胀至不同的压力,然后在交换管线3中将其汽化以在CO压缩机的中间级35和37处供给压缩机。
在汽化前将三种料流41、43、45膨胀至不同的压力。
三种混合的料流41、43、45形成一氧化碳产物39。
Claims (10)
1.一种深冷分离氢气和一氧化碳的混合物的方法,所述混合物任选包含用于通过一步部分冷凝生产纯CO的低含量甲烷、氩气和氮气,其中在交换管线(3)中将混合物冷却,部分冷凝,并将由部分冷凝得到的至少一部分液体输送至汽提塔(15)的顶部,至少将富含一氧化碳的第一料流和富含一氧化碳的第二料流(17、19、21)从汽提塔以液体的形式排出并输送至交换管线,在交换管线中将第一和第二料流冷却至不同的温度,在膨胀后将第一和第二料流(19、45)中的一个输送至分离罐(27)中,在交换管线中将来自分离罐的气体再加热并输送至包括至少两级(33、35、37)的一氧化碳压缩机的第一级(33)中,使其它的第一和第二料流(17、21、41、43)膨胀,然后在交换管线中再加热,并输送至第一级下游的压缩机的级中,其中在不同压力下在交换管线中再加热来自分离罐的气体和其它的第一和第二料流,第一和第二料流的膨胀用于提供低温试验箱的至少一部分分离能量。
2.如权利要求1所述的方法,其中第一和第二料流(17、19、21)具有不同的纯度。
3.如权利要求1所述的方法,其中第一和第二料流(41、43、45)具有相同的纯度。
4.如前述权利要求任一项所述的方法,其中至少一个料流(21)在汽提塔的容器处排出。
5.如权利要求4所述的方法,其中第一料流(21)是一种在汽提塔容器处排出的料流,在交换管线(3)中将其冷却至第一温度,使其膨胀,然后在交换管线中再加热,第二料流(19)在汽提塔的中间水平处排出,冷却至比第一温度低的第二温度,使其膨胀,然后在交换管线中再加热。
6.如权利要求5所述的方法,其中将冷却至第二温度的第二料流输送至分离罐(27)中。
7.一种深冷分离氢气和一氧化碳的混合物的设备,所述混合物任选包含用于通过一步部分冷凝生产纯CO的低含量甲烷、氩气和氮气,所述设备包括交换管线(3)、汽提塔(15)、第一和第二分离罐(7、27)、包括至少两级的一氧化碳压缩机(33、35、37)、用于将待冷却混合物输送至交换管线的装置、用于将冷却的混合物输送至第一分离罐的装置、用于将由第一罐的部分冷凝得到的至少一部分液体排出的装置、用于将该液体输送至汽提塔顶部的装置、用于至少将液体形式的富含一氧化碳的第一料流和富含一氧化碳的第二料流从汽提塔分流的装置、用于在交换管线中分别将第一和第二料流冷却至第一和第二温度的装置、用于在膨胀后将第一温度的第一料流或不同于第一温度的第二温度的第二料流输送至第二分离罐的装置、用于在交换管线中将来自分离罐的气体再加热的装置和用于将再加热的气体输送至一氧化碳压缩机的第一级的装置、用于膨胀和在交换管线中再加热第二料流或第一料流的装置和用于将再加热的第二料流或再加热的第一料流输送至第一级下游的压缩机的级中的装置。
8.如权利要求7所述的设备,其包括用于在汽提塔的相同水平处排出至少第一和第二料流(41、43、45)的装置。
9.如权利要求7所述的设备,其包括用于在通过汽提塔的至少一个理论级分离的水平处排出至少第一和第二料流(17、19、21)的装置。
10.如权利要求7、8或9所述的设备,其包括用于在汽提塔的容器处排出至少第一料流(21)的装置。
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PCT/FR2009/050484 WO2009144423A2 (fr) | 2008-04-18 | 2009-03-20 | Procédé et appareil de séparation cryogénique d'un mélange d'hydrogène et de monoxyde de carbone |
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WO2009144423A4 (fr) | 2010-11-18 |
WO2009144423A2 (fr) | 2009-12-03 |
HUE037714T2 (hu) | 2018-09-28 |
EP2268989A2 (fr) | 2011-01-05 |
CN102007358B (zh) | 2013-09-18 |
US8869553B2 (en) | 2014-10-28 |
ZA201007329B (en) | 2011-06-29 |
FR2930332A1 (fr) | 2009-10-23 |
EP2268989B1 (fr) | 2018-05-02 |
WO2009144423A3 (fr) | 2010-09-30 |
PL2268989T3 (pl) | 2018-08-31 |
US20110056239A1 (en) | 2011-03-10 |
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