CN113701451A - 通过低温蒸馏分离空气的方法和装置 - Google Patents
通过低温蒸馏分离空气的方法和装置 Download PDFInfo
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- CN113701451A CN113701451A CN202110543898.7A CN202110543898A CN113701451A CN 113701451 A CN113701451 A CN 113701451A CN 202110543898 A CN202110543898 A CN 202110543898A CN 113701451 A CN113701451 A CN 113701451A
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
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- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04006—Providing pressurised feed air or process streams within or from the air fractionation unit
- F25J3/04048—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) streams
- F25J3/04054—Providing pressurised feed air or process streams within or from the air fractionation unit by compression of cold gaseous streams, e.g. intermediate or oxygen enriched (waste) streams of air
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Abstract
在使用由在第一压力下运行的第一塔(101)和在第二压力下运行的第二塔(102)组成的塔***通过低温蒸馏分离空气的方法中,将压缩到高于第一压力的第三压力的构成送往所述塔***的空气的75%至98%的第一空气流(1)送往第一塔,将构成送往所述塔***的空气的5%至25%的第二空气流(33)压缩到高于第二压力但低于第三压力的第四压力,送往第二塔,第三塔(103)分离富氩料流,且送往第二塔的空气(20)构成送往所述塔***的总空气的10%至25%。
Description
本发明涉及通过低温蒸馏分离空气的方法和装置。
关于杂质的所有百分比是摩尔百分比。
已知的是,在由在第一压力下运行的第一塔和在低于第一压力的第二压力下运行的第二塔组成的塔***中分离空气。来自第一塔的塔顶气体用于加热第二塔的底部。第二塔可为两段并可连向氩气分离塔。
通常,将所有空气压缩到高于第一压力的压力,通过与水直接接触冷却,在这一压力下纯化并一分为二。将一部分送往第一塔,另一部分在增压泵中增压并通过与塔***的液体产物的热交换液化,该液体产物被汽化,并送往第一塔和任选送往第二塔。在这种配置中,只有单个吸附单元用于纯化以除去水和二氧化碳和其它次要杂质。
通过将气态或液态空气送往第一塔的涡轮机和/或通过将空气送往第二塔的涡轮机使该装置保持冷。
US4964901描述了一种方法,其中单个空气压缩机产生在两种不同压力下的空气,其在这些不同压力下纯化并送往塔***。
该方法产生相对较低纯度的氧气并且没有产生氩气。
EP1357342 A1描述了一种三塔法,其具有氩气塔,向其供给在两种不同压力下的纯化空气,所用压力明显高于根据本发明使用的压力。
根据本发明,通过使用氩气分离塔和生产纯(>99%,优选>99.5%)氧,令本领域技术人员惊讶的是,已经发现,空气分离装置仍可具有低压空气直接进入塔***的低压塔的高注入,所述塔***包括一个在比另一个塔低的压力下运行的塔。
根据本发明的一个主题,提供一种使用塔***通过低温蒸馏分离空气的方法,所述塔***由在第一压力下运行的第一塔和在低于第一压力的第二压力下运行的第二塔组成,第一塔的顶部热耦合到第二塔的底部,其中:i)将构成送往所述塔***的空气的75%至98%的第一空气流压缩到在5至6bar abs之间并高于第一压力的第三压力、冷却并在第三压力下送往第一吸附单元以纯化除去水和二氧化碳,并将纯化的第一料流送往第一塔和任选送往第二塔;
ii)将构成送往所述塔***的空气的2%至25%或甚至5%至25%的第二空气流压缩到在1.2至2bar abs之间并高于第二压力但低于第三压力的第四压力,优选在空气冷却塔中通过直接接触冷却、在第四压力下送往第二吸附单元以纯化除去水和二氧化碳,并将纯化的第二料流送往第二塔;
iii)在第一塔中分离空气以形成富氧液体(liquid)和富氮气体(gas)
iv)将富氧液体和富氮液体从第一塔送往第二塔;
v)从所述塔***取出具有大于99%,优选99.5%氧纯度的液体、压缩、然后通过与至少一部分第一空气流的热交换汽化;
vi)将富氩气体从第二塔送往第三塔并从第三塔的顶部取出富氩流体(fluid);
vii)送往第二塔的空气构成送往所述塔***的总空气的10%至25%;和
viii)富氩流体含有第一和第二空气流中所含的氩气的20%至80%。
根据其它任选方面:
·富氩流体含有第一和第二空气流中所含的氩气的45%至75%;
·所述装置的氧气产率大于95%;
·第一空气流通过在第一冷却塔中与第一水流直接接触冷却,且第二空气流通过在第二冷却塔中与第二水流直接接触冷却,将源自所述塔***的氮气送往水冷却塔并将水冷却塔中的冷却水送往第一和第二空气冷却塔;
·冷却水在水冷却塔和第二空气冷却塔之间冷却,以使送往第二空气冷却塔的水比送往第一空气冷却塔的水冷;
·空气在第一空气冷却塔中冷却到比空气在第二空气冷却塔中冷却到的温度高至少5℃,优选至少8℃的温度;
·空气在第一冷却塔中冷却到比空气在第二冷却塔中冷却到的温度高最多30℃,优选最多12℃的温度;
·第一纯化流在所述塔***上游在第一热交换器中通过与源自塔***的第一氮气流的热交换冷却,且第二纯化流在所述塔***上游在第二热交换器中通过与源自塔***的第二氮气流的热交换冷却;
·第二纯化流在所述塔***上游在第二热交换器中通过仅与源自塔***的第二氮气流的热交换冷却;
·第二氮气流在其离开塔后没有经过另一热交换器的温度下引入第二热交换器;
·第一纯化流在所述塔***上游在第一热交换器中通过与源自塔***的第一氮气流以及与从塔***取出的加压液体的热交换冷却,并且所述液体在第一热交换器中汽化;
·第二空气流在第二吸附单元和第二塔之间没有膨胀或增压;
·第一空气流的至少一部分在第一吸附单元和第一塔之间没有膨胀或增压;
·第一空气流的一部分在第一吸附单元和第一塔之间增压,然后膨胀;
·第一空气流的一部分在涡轮机中膨胀,然后以气体和/或液体形式送往第一塔;
·将总空气的至少14摩尔%送往第二塔;
·在与源自第一塔的富氧液体流相同的塔位(level of column)将纯化的第二料流送往第二塔以供分离;
·在与源自第一塔并在第三塔的塔顶冷凝器中汽化的富氧液体流相同的塔位将纯化的第二料流送往第二塔以供分离;
·将全部纯化的第一料流送往第一塔和任选送往第二塔;
·将全部纯化的第二料流送往第二塔;
·将全部在第二塔的顶部取出的氮气通过与空气的热交换加热;
·所述塔***不包含在低于第二塔的压力下运行的塔;
·第三压力在5至6bars abs之间。
根据本发明的另一主题,提供一种通过低温蒸馏分离空气的装置,其使用由在第一压力下运行的第一塔和在低于第一压力的第二压力下运行的第二塔组成的塔***,第一塔的顶部热耦合到第二塔的底部;第一吸附单元;第二吸附单元;用于将压缩到高于第一压力的第三压力的构成送往所述塔***的空气的75%至98%的第一空气流送往冷却设备、然后在第三压力下送往第一吸附单元以纯化除去水和二氧化碳的设备(means)和用于将全部纯化的第一料流送往第一塔和任选送往第二塔的设备;用于将压缩到在1.2至2bar abs之间并高于第二压力但低于第三压力的第四压力的构成送往所述塔***的空气的5%至25%的第二空气流在第四压力下送往第二吸附单元以纯化除去水和二氧化碳的设备和用于将全部纯化的第二料流送往第二塔的设备,第一塔包含热和质量交换设备以分离空气以形成富氧液体和富氮气体;用于将富氧液体和富氮液体从第一塔送往第二塔的设备;用于从所述塔***取出具有大于99%,优选99.5%氧纯度的液体的设备;用于将这种液体加压的泵;用于通过与至少一部分第一空气流的热交换将加压液体汽化的设备和用于将富氩气体从第二塔送往第三塔的设备和用于从第三塔的顶部取出富氩流体的设备。
优选地,所述塔***仅包含第一和第二塔。
参考附图更详细描述本发明。
[图1]图示了根据本发明的空气分离装置。
[图2]图示了在99.5%的恒定氧纯度和99%的恒定氧气产率下,作为在x轴上的该单元的氩气产率的函数的在y轴上的可直接注入第二塔的总进料空气的百分比。
[图1]显示将构成送往塔***的总空气的75%至98%的第一空气流1从大气压压缩到略高于第一塔101的压力的压力。第一塔的压力和在压缩机2中压缩的空气3的压力之间的差值对应于由于在压缩后和在进入塔前发生的冷却和纯化的压降。可设想其它用于冷却空气35的设备,例如制冷单元。
空气3因此可在5至6bar abs之间并送往第一冷却塔4,其在顶部供应水94和在中间位供应水98。
将在塔4的顶部取出的冷却空气5送往第一吸附单元6以除去其包含的水和二氧化碳。将纯化空气7分成三部分。一个部分8以气态在第一热交换器80中冷却并以与空气32混合以形成流10的气体形式进入塔101。
另一部分12在增压泵13中增压以形成增压流14,其在第一交换器80中冷却以形成在中间温度水平从交换器中取出的冷却流15。这种流15在涡轮机16中膨胀以形成在第二塔102的压力下的气体17并送往塔102。
另一部分19在增压泵20中增压以形成流21,然后分成两部分。一个部分22在第一交换器80中冷却、在中间温度水平(通常大约-120℃,未显示)取出、在冷增压泵24中增压、再引入交换器80、在交换器80中冷却并在涡轮机27中膨胀以形成液体28(或任选两相混合物),将其送往第一塔101。
另一部分29在交换器80中冷却并在中间温度水平(未显示)取出以形成流30,其在耦合至冷增压泵24的涡轮机31中膨胀。膨胀空气32在第一塔101的压力下。
将构成送往塔***的总空气的5%至25%,优选大于10%的第二空气流33从大气压压缩到略高于第二塔102的压力的压力。第二塔的压力和在压缩机34中压缩的空气35的压力之间的差值对应于由于在压缩后和在进入塔102前发生的冷却和纯化的压降。
空气35在1.2至2bar abs之间并送往第二冷却塔36,其在顶部供应水97和在中间位(intermediate level)供应水90。将在塔36的顶部取出的冷却空气37送往第二吸附单元38以除去其包含的水和二氧化碳。可设想其它用于冷却空气35的设备,例如制冷单元。但对于在较低压力下的空气,优选使用塔以降低相关压降。纯化的空气39以气态在第一热交换器81中冷却以形成流40并以与空气17混合以形成流120的气体形式进入塔101。流120代表总空气流的3%至5%。空气流120在与膨胀塔底液48相同的塔位和在汽化的富集液72的入口上方送往第二塔102以供分离。
因此送往第二塔102的流40代表总空气的5%至25%,优选代表送往塔***的总空气的大于10%。流120总共代表送往塔***的总空气的10%至25%,其是流40和吹入空气17的混合物。
考虑到以大于99%,优选大于99.5%的纯度生产氧气,令人惊讶的是,有可能将如此高百分比的空气送往第二塔102而不显著降低该单元的氧气产率。专利US4964901没有考虑这一点。如果没有生产氩气,实际上不可能在追求以大于99%,优选大于99.5%的纯度生产氧气的同时将如此量的空气注入低压塔。同样地,如果这次在追求获得“常规”氩气产率(在现代装置中为大约85%)和良好氧气产率(99%级别)的同时生产氩气,这也不可能。尽管由第三塔优选以大约65%的产率生产氩气,但有可能同时以通常大约99%(至少大于95%)的良好氧气产率生产纯度大于99%,优选大于99.5%的氧气。图2图示了,在99.5%的恒定氧纯度和99%的恒定氧气产率下,作为在x轴上的该单元的氩气产率的函数的可直接注入第二塔102的空气的量,就送往蒸馏的总空气流的百分比而言。
氧产率被定义为氧产物中所含的可为气体和/或液体的氧气量除以引入该装置中的所有空气流中所含的氧气量。
据观察,送往第二塔的空气的最大百分比在65%氩气产率点附近。
将来自第三塔的氩气与残留氮气混合,或在经过脱氮塔后以液体或气体形式生产。
为了对抗全球变暖,必须改进用于分离空气气体的装置的能量效率。在考虑的配置中,越多空气被注入低压的第二塔,该单元消耗的能量越低。通过加入被称为氩气混合物塔的第三塔并通过在最优氩气产率下(优选在65%附近)运行而不必生产这种氩气,可使该装置的能量消耗最小化。塔***由在第一压力下运行的第一塔101和在低于第一压力的第二压力下运行的第二塔102组成。来自第一塔的塔顶气体用于加热第二塔的底部。第二塔可为两段并可连向氩气分离塔。
空气在第一塔101中通过蒸馏分离以产生富氧塔底液体41、富氮塔顶液体53和富氮中间液体49。液体53、49在送往第二塔102前在过冷器82中冷却以形成液体54、50并分别通过阀55、51膨胀。
将富氧液体分成两部分42、46。部分46在阀47中膨胀并作为流48送往第二塔102。部分42在阀43中膨胀并作为液体44送往氩气分离塔103的塔顶冷凝器45。
来自塔101顶部的氮气在第二塔102的塔底再沸器83中冷凝以加热第二塔的底部。将冷凝的氮气送回第一塔101的顶部和第二塔102的顶部。
通过从低压塔102的中间位提取的流58向氩气分离塔103供应气体。将来自塔103的塔底液体57送回塔102。从塔103的顶部取出含有至少95%或甚至至少98%氩气的富氩流体。该流体可含有大约2%氧气并在此后与来自塔***的氮气混合或通过催化纯化。或者该流体可含有小于2ppm的氧气并在经过脱氮塔(在图中未显示)后作为产品使用。
从第二塔102的底部取出含有至少99%氧,优选至少99.5%氧的液态氧59,通过泵60加压并作为加压流61送往热交换器80,在此其完全汽化以形成该装置的主要产物,在至少10bar a.的压力下的氧气62。可想到更低的压力。
来自塔102的塔顶气体63在过冷器82中加热,然后一分为二。一个部分67在第二热交换器81中加热,其余部分65在第一热交换器80中加热。加热的流65是流66并作为流68用于再生第二吸附单元38。来自塔102的塔顶气体63也有可能在引入过冷器72之前分成两部分。在这一情况下,在第二热交换器81中加热的部分67在较低温度下引入所述交换器,从而有可能将流体40冷却到较低温度,并在与流体17混合以形成流体120后,在与该塔中的注入点处存在的温度更接近的温度下引入第二塔102,从而有可能降低该方法的不可逆性。
流67、69在部分70中用于再生第一吸附单元6和在部分71中用于在水冷却塔91中冷却水。将水90送往塔的顶部并在底部冷却离开92以经由泵93送往两个空气冷却塔4、36。
因此,向两个空气冷却塔4、36供应通过源自塔***的氮气冷却的源自单个水冷却塔91的冷却水。
打算用于第二空气冷却塔36的水95在水冷却塔91和第二塔36之间通过冷器96,例如制冷单元冷却以将水冷却到比到达第一塔4顶部的水94的温度低5℃至30℃,优选比这一温度低8℃至15℃的温度。
也有可能使用两个水冷却塔,各自向各自的空气冷却塔供应所需温度的水。在这一情况下,应该向产生打算用于冷却第二空气冷却塔的冷却水的冷却塔供应源自第二热交换器81的氮气67,因为其比源自第一热交换器80的氮气62冷。
因此,第二热交换器81进行仅两个流体,空气39、40和氮气67之间的热交换。
可将第二压缩机和第二吸附单元添加到具有第一压缩机和第一吸附单元的现有装置上,以突破现有装置的生产限制。
在与源自第一塔的富氧液体流(未显示)或与源自第一塔并在第三塔的塔顶冷凝器中汽化的富氧液体流,流体72相同的塔位将纯化的第二料流120送往第二塔102以供分离
在塔103的顶部产生的富氩流体含有第一和第二空气流1、33中所含的氩气的20%至80%,优选45%至75%。
所述装置的氧气产率大于95%。
送往第二塔的空气20构成送往塔***的总空气的10%至25%或甚至14%至25%。
如果第二料流33为总流量的5%的其最低值,则打算用于第二塔的空气的其余至少5%将是第一料流1的一部分,并且总空气的至少5%在鼓风涡轮机(blowing turbine)16中膨胀以使送往第二塔的空气流为总空气的至少10%。
可以设想用两种不同的操作进行该方法。在第一种操作中,在能源不是非常昂贵的时期,空气仅在压缩机2中压缩并且不存在流33。仅通过涡轮机16向第二塔供应空气。在这种操作期间,产生至少一种液体产物,例如液氮并可储存和任选部分作为产品使用。
在第二种操作中,空气在压缩机2和34中压缩,并优选相对于在第一种操作期间的流量减少送往压缩机2的空气流。在第二种操作期间,能源较昂贵,因此通过降低压缩到最高压力的空气量来降低操作成本。部分通过输送在第一种操作期间生产的液氮来使该装置保持冷。
Claims (17)
1.使用塔***通过低温蒸馏分离空气的方法,所述塔***由在第一压力下运行的第一塔(101)和在低于第一压力的第二压力下运行的第二塔(102)组成,第一塔的顶部热耦合到第二塔的底部,其中:
i.将构成送往所述塔***的空气的75%至98%的第一空气流(1)压缩到高于第一压力的第三压力、冷却并在第三压力下送往第一吸附单元(6)以纯化除去水和二氧化碳,并将纯化的第一料流送往第一塔和任选送往第二塔;
ii.将构成送往所述塔***的空气的2%至25%的第二空气流(33)压缩到在1.2至2barabs之间并高于第二压力但低于第三压力的第四压力,优选在空气冷却塔(36)中通过直接接触冷却、在第四压力下送往第二吸附单元(38)以纯化除去水和二氧化碳,并将纯化的第二料流送往第二塔;
iii.在第一塔中分离空气以形成富氧液体(41)和富氮气体;
iv.将富氧液体(41)和富氮液体(49、53)从第一塔送往第二塔;
v.从所述塔***取出具有大于99%,优选99.5%氧纯度的液体(59)、压缩、然后通过与至少一部分第一空气流(22、29)的热交换汽化;
vi.将富氩气体(58)从第二塔送往第三塔(103)并从第三塔的顶部取出富氩流体;
vii.送往第二塔的空气(120)构成送往所述塔***的总空气的10%至25%;和
viii.富氩流体含有第一和第二空气流(1、33)中所含的氩气的20%至80%。
2.根据权利要求1的方法,其中所述富氩流体含有第一和第二空气流(1、33)中所含的氩气的45%至75%。
3.根据权利要求1或2的方法,其特征在于所述装置的氧气产率大于95%。
4.根据权利要求1、2或3的方法,其特征在于第一空气流(1)通过在第一冷却塔(4)中与第一水流直接接触冷却,且第二空气流(33)通过在第二冷却塔(36)中与第二水流直接接触冷却,将源自所述塔***的氮气(63)送往水冷却塔(91)并将水冷却塔中的冷却水(94、95)送往第一和第二空气冷却塔。
5.根据权利要求4的方法,其中冷却水在水冷却塔(91)和第二空气冷却塔(36)之间冷却,以使送往第二空气冷却塔的水比送往第一空气冷却塔的水冷。
6.根据权利要求4或5的方法,其中空气在第一空气冷却塔(4)中冷却到比空气在第二空气冷却塔(36)中冷却到的温度高至少5℃,优选至少8℃的温度。
7.根据权利要求4、5或6的方法,其中空气在第一冷却塔(4)中冷却到比空气在第二冷却塔(36)中冷却到的温度高最多30℃,优选最多12℃的温度。
8.根据前述权利要求之一的方法,其中第一纯化流在所述塔***上游在第一热交换器(80)中通过与源自塔***的第一氮气流(65)的热交换冷却,且第二纯化流在所述塔***上游在第二热交换器(81)中通过与源自塔***的第二氮气流(67)的热交换冷却。
9.根据权利要求8的方法,其中第二纯化流在所述塔***上游在第二热交换器中通过仅与源自塔***的第二氮气流的热交换冷却。
10.根据权利要求8或9的方法,其中第二氮气流(67)在其离开塔后没有经过另一热交换器的温度下引入第二热交换器(81)。
11.根据前述权利要求之一的方法,其中第二空气流(33)在第二吸附单元(36)和第二塔(102)之间没有膨胀或增压。
12.根据前述权利要求之一的方法,其中第一空气流的至少一部分在第一吸附单元(6)和第一塔(101)之间没有膨胀或增压。
13.根据前述权利要求之一的方法,其中第一空气流的一部分(12)在第一吸附单元和第一塔(101)之间增压,然后膨胀。
14.根据前述权利要求之一的方法,其中第一空气流的一部分在涡轮机中膨胀,然后以气体和/或液体形式送往第一塔(101)。
15.根据前述权利要求之一的方法,其中将总空气的至少14摩尔%送往第二塔。
16.根据前述权利要求之一的方法,其中在与源自第一塔的富氧液体流或与源自第一塔并在第三塔的塔顶冷凝器中汽化(72)的富氧液体流相同的塔位将纯化的第二料流(40)送往第二塔(102)以供分离。
17.通过低温蒸馏分离空气的装置,其使用由在第一压力下运行的第一塔(101)和在低于第一压力的第二压力下运行的第二塔(102)组成的塔***,第一塔的顶部热耦合到第二塔的底部;第一吸附单元(6);第二吸附单元(36);用于将压缩到高于第一压力的第三压力的构成送往所述塔***的空气的75%至98%的第一空气流(1)送往冷却设备、然后在第三压力下送往第一吸附单元(6)以纯化除去水和二氧化碳的设备和用于将全部纯化的第一料流送往第一塔和任选送往第二塔的设备;用于将压缩到在1.2至2bar abs之间并高于第二压力但低于第三压力的第四压力的构成送往所述塔***的空气的2%至25%的第二空气流在第四压力下送往第二吸附单元以纯化除去水和二氧化碳的设备和用于将全部纯化的第二料流送往第二塔的设备,第一塔包含热和质量交换设备以分离空气以形成富氧液体和富氮气体;用于将富氧液体和富氮液体从第一塔送往第二塔的设备;用于从所述塔***取出具有大于99%,优选99.5%氧纯度的液体(59)的设备;用于将这种液体加压的泵;用于通过与至少一部分第一空气流的热交换将加压液体汽化的设备和用于将富氩气体(58)从第二塔送往第三塔的设备和用于从第三塔的顶部取出富氩流体的设备。
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