CN105431698A - 通过低温蒸馏分离空气的方法 - Google Patents

通过低温蒸馏分离空气的方法 Download PDF

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Publication number
CN105431698A
CN105431698A CN201380051043.6A CN201380051043A CN105431698A CN 105431698 A CN105431698 A CN 105431698A CN 201380051043 A CN201380051043 A CN 201380051043A CN 105431698 A CN105431698 A CN 105431698A
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China
Prior art keywords
tower
nitrogen
stage
heat exchanger
rich gas
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CN201380051043.6A
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English (en)
Inventor
B·达维迪安
R·杜贝蒂尔-格勒尼耶
J-M·佩龙
B·索尼耶
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Publication of CN105431698A publication Critical patent/CN105431698A/zh
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • 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
    • F25J3/02—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
    • 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
    • F25J3/0406—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 nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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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
    • F25J3/02—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
    • 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
    • F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
    • F25J3/04163—Hot end purification of the feed air
    • F25J3/04169—Hot end purification of the feed air by adsorption of the impurities
    • F25J3/04175—Hot end purification of the feed air by adsorption of the impurities at a pressure of substantially more than the highest pressure column
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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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
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    • 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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    • F25J1/0201—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using only internal refrigeration means, i.e. without external refrigeration
    • F25J1/0202—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using only internal refrigeration means, i.e. without external refrigeration in a quasi-closed internal refrigeration loop
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    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • 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
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    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F25J1/0234—Integration with a cryogenic air separation unit
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    • F25J3/04084—Providing pressurised feed air or process streams within or from the air fractionation unit providing pressurized products by liquid compression and vaporisation with cold recovery, i.e. so-called internal compression of nitrogen
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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
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/20—Processes or apparatus using separation by rectification in an elevated pressure multiple column system wherein the lowest pressure column is at a pressure well above the minimum pressure needed to overcome pressure drop to reject the products to atmosphere
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/04—Internal refrigeration with work-producing gas expansion loop
    • F25J2270/06—Internal refrigeration with work-producing gas expansion loop with multiple gas expansion loops
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • 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
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Abstract

通过低温蒸馏分离空气的方法或者以大于2.5的产物比运行，在该情况下，富氮液体从贮槽(27)送入至塔系统，来自塔系统的富氮气体(29)在进口温度小于-50℃的第一压缩机(33)中被压缩，并且然后在热交换器中被加热，或者以小于2.5的产物比运行，在该情况下，从塔系统中移除的第二富氮气体在入口温度低于周围环境温度的涡轮(73)中膨胀或者在液化器中液化，富氮液体(57)从涡轮出口和/或从塔系统和/或从液化器输送至贮罐。

Description

通过低温蒸馏分离空气的方法
技术领域
本发明涉及通过低温蒸馏分离空气的方法。
背景技术
通常选择整体煤气化联合循环IGCC(IntegratedGasifiedCombinedCycle)从煤中制取清洁能源。该清洁能源生产技术尤其适用于高效工作和对于环境最小限度污染的新的煤基发电项目。
为了IGCC而气化煤炭，使用非纯高压氧气。另外，在燃气轮机合成气的燃烧中通常需要相对纯净状态的极高压氮气来稀释合成气或者在气化过程中产生的氢气，以降低氮的氧化物(NOX)的排放水平。
为了IGCC电站生产氧气，在上下文中使用的三种已知技术为：
–在独立ASU(空气分离单元)中生产氧气；
–从燃气轮机压缩机中提取用于ASU的空气；
–从燃气轮机压缩机中提取用于ASU的部分空气，并且使用专用压缩机来生产其余的空气。
气化或燃气轮机的类型确定在IGCC联合体中使用的氮气的数量。从该特征可以看出用于IGCC的空气分离单元ASU是制氧机和制氮机的组合体。
常用于这种类型应用的空气分离方法为加压方法。尽管使用这种概念的空气分离单元具有良好的能源效率和降低了的电力消耗，并不能经常使用这种类型的ASU，因为氮气/氧气的比率通常固定在与其在空气中相接近的值，也即是接近3.6。如果所需要的比率低于该值，例如大约2.5。
US-A-2008/115531描述了根据权利要求1的前序部分的方法。
发明内容
本发明的目的为提供具有减低能源消耗但是能够制造氮气/氧气比率小于3.6，优选大于4的氮气和氧气的空气分离单元。
根据本发明的一个目的，提供了通过低温蒸馏分离空气的方法，其中空气被净化，在热交换器中冷却，在至少包括有第一塔和第二塔的塔系统中分离，第一塔在比第二塔高的压力下运行，并且第一塔的顶部与第二塔的底部通过第一重沸器-冷凝器热联接，富氧液体从第一塔中移除并被送至第二塔或者源自富氧液体的液体被送至第二塔，富氮液体从第一塔中移除并被送入至第二塔，富氧液体从第二塔中移除，加压并在热交换器中蒸发以形成富氧气体，富氮流体从塔系统中移除并在热交换器中加热以形成第一富氮气体，其中
i)在第一阶段，产物比——其为产生的富氮气体的量和产生的富氧气态的量之间的比率——大于2.5，富氮液体从贮罐输送到塔系统，并且来自塔系统的第一富氮气体在进口温度小于-50℃的第一压缩机中被压缩，然后被送入至热交换器中，和
ii)在第二阶段，产物比小于2.5并且从塔系统中移除的第二富氮气体在进口温度低于环境温度的涡轮中膨胀，或者在液化器中液化，并且富氮液体从涡轮的出口和/或从塔系统和/或从液化器输入至贮罐，
其特征在于，第一富氮气体在于第一压缩机中被压缩前从第二塔中移除，并且在于第一压缩机中被压缩后在热交换器中被加热并作为产物移出，在涡轮中膨胀的第二富氮气体是从第二塔中移除的，第二塔在至少2barabs的压力下工作。
根据其他可选的特征：
–在第一阶段产物比大于3。
–在第二阶段产物比小于2。
–在第一阶段，富氮气体从第二塔中移除，未经加热地在第一压缩机中被压缩，并被送入至热交换器。
–在第二阶段，从塔系统移除的富氮气体在热交换器中被加热，在涡轮中膨胀，然后在热交换器中被加热。
–涡轮的入口温度最高为-50℃，优选最高为-100℃。
–在第二阶段，涡轮的出口压力与第二塔的压力基本相等。
–在第一阶段无富氮气体被送入到涡轮中。
–在第二阶段无气体被送入到第一压缩机。
–第二阶段的耗电量低于第一阶段。
–在第二阶段第一压缩机不工作。
–在第一阶段无富氮液体输入到贮槽中。
–在第二阶段至少一股低温流体作为最终产物从过程中提取出，并且优选为在第一阶段相同的低温流体不作为最终产物从过程中提取出。
–第一压缩机压缩来自塔系统、优选为来自第二塔的富氮气体，并且第二压缩机压缩来自塔系统的处于热交换器下游的第一富氮气体，第一和第二压缩机的出口压力基本相等。
–塔系统包括在中压下工作的第三塔。
–第二塔具有在其中间位置的第二重沸器-冷凝器。
–富氧气体被送入至IGCC系统的气化器。
–第一富氮气体用于稀释送入至IGCC系统的燃汽轮机的合成气或者氢气。
–第一阶段对应于当IGCC系统的发电量高于给定水平的阶段，第二阶段对应于发电量低于给定水平的阶段。
附图说明
参照表示出根据本发明的方法的附图1-3对本发明进行更详细的描述。
具体实施方式
图1示出了使用标准双塔的低温空气分离方法，标准双塔具有第一塔11和第二塔15，第一塔在比第二塔高的压力下工作并且位于第二塔的下方。第二塔15在至少2巴绝对压力(barabs)下工作。第一塔11的顶部与第二塔15的底部通过放置于第二塔15底部的蒸发器-冷凝器13热连接。对于第二塔也可以使用中间蒸发器-冷凝器(未示出)。
该方法还使用具有底部重沸器65和顶部冷凝器的中压塔17。塔17的出现不是必须的。
当方法运行时，压缩至第一塔11工作压力的空气流11被分为两部分。一部分3在热交换器9中冷却并且以气体形式送入至第一塔11。另一部分5通过增压压缩机7被增压至更高的压力并且送入至热交换器7。增压的空气5在热交换器9中冷却并且在膨胀后以液体或者部分冷凝的形式被送入至第一塔11。
当方法工作时，来自第一塔11底部的富氧液体19被送入至过冷器25并且然后膨胀至塔17。来自塔17底部的液体67作为流64被送入至顶部冷凝器，在顶部冷凝器液体67部分蒸发，形成的液体和气体流被送入至第二塔15。液体的一部分71从塔17的底部被送入至第二塔15。液体流21从第一塔的中间区域移除并且经膨胀后进入第二塔15。可替代的，流5的至少一部分可以直接送入至第二塔15。第一富氮液体流作为流23在第一塔顶部下方的数个塔板处被提取出，从第一塔被传送至第二塔。富氮气体流61从第一塔的顶部被提取出，在底部冷凝器65冷凝并且作为流63与流23混合。
液体流55从塔17的顶部送入至塔15的顶部。
塔系统通过从第二塔15的底部移除液态氧49、通过泵51加压并且在热交换器9中蒸发泵送的液体来产生高压气态氧流53。
塔系统通过从第一塔11的顶部移除液态氮43、通过泵45加压并且在热交换器9中蒸发泵送的液体来产生高压气态氮流47。
这些加压流可以送入至汽化器。
为了给本方法提供冷却，气态氮29、37从第二塔15的顶部移出，在过冷却器25中加热，在热交换器9中部分加热并且作为流75送入至入口温度为热交换器9的中间温度的涡轮73。膨胀氮气被送入至热交换器的冷端并且直到热端被加热。氮气75形成废物流。
氮气37的另一部分在热交换器中直到热端被加热，在压缩机39中压缩，作为流41通过管道输送至燃气涡轮。
所有的前述步骤在方法运行时随时进行。
为了增加产生的气态氮的相对数量，本方法在两个阶段使用尤为特殊的操作。
在第一阶段，产生的富氮气体41的数量和产生的富氧气体53的数量之间的比率(称为“产物比”)大于2.5。富氮液体57A从贮槽27输送至塔系统11、15，并且来自第二塔15的富氮气体29、31在具有低于-50℃的入口温度的压缩机33中被压缩，然后被送入至热交换器9的冷端。优选地，压缩机33仅仅在富氮液体57A被送入至塔中时工作。气体31然后在热交换器中被加热并且和来自压缩机39的气体混合来形成流41。或者没有氮气被送至涡轮73或者一些氮气可以被送至涡轮73。
在第二阶段，产物比小于2.5，并且从塔系统移除的富氮气体在入口温度低于周围环境温度的涡轮73中膨胀，富氮液体57从塔系统送入至贮槽。没有氮气被送入至压缩机33并且所有的流29作为流37被移出。
图2示出了图1的一个变形，其中冷涡轮73被液化器取代。在这个情况下，在第一阶段，生产的富氮气体41的数量和产生的富氧气体53的数量之间的比率(名为“产物比”)大于2.5。富氮液体57A从贮槽27中流入至塔系统11、15，来自塔系统的第二塔15的富氮气体29、31在入口温度低于-50℃的压缩机33中被压缩，然后被送入至热交换器9的冷端。优选地，压缩机33仅仅在富氮液体57A被送至塔时工作。气体31然后在热交换器中被加热并且与来自压缩机39的气体混合以形成流41。
在第二阶段，产物比小于2.5，从塔系统37移出的富氮气体被加热直至热交换器9的热端。然后部分气体被送入至压缩机39，其余部分75在压缩机101中被压缩并且一分为二。一部分79在交换器109中冷却和液化以形成部分冷凝的流。该流在相分离器中分离并且所形成的液体用作最终产物83。气体85被送回至热交换器，加热并被排入大气中。来自压缩机101的气体的另一部分进一步在增压器103、105中被压缩，在交换器109中冷却，在入口温度低于周围环境温度的涡轮73中膨胀。膨胀气体在交换器109中被加热至中间温度并且一分为二。一部分81在涡轮73在该中间温度下膨胀并且在送入至大气前在交换器中被重新加热。其余部分79在压缩机101的上游被加热和循环。
没有氮气被送入至压缩机33，并且所有的流29作为流37被移除。
图3的方法与图2中的方法的不同之处在于，用于液化器的氮气75在压缩机39的下游提取，因此不再需要压缩机101。来自涡轮73的气体的一部分79循环至位于压缩机39上游的一点。

Claims (12)

1.一种通过低温蒸馏分离空气的方法，其中空气被净化，在热交换器(9)中冷却，在至少包括第一塔(11)和第二塔的塔系统(11,15,17)中分离，第一塔在比第二塔高的压力下运行，并且第一塔的顶部与第二塔的底部通过第一重沸器-冷凝器(13)热联接，富氧液体(19)从第一塔中提取出并被送至第二塔或者源自该富氧液体的液体(67)被送至第二塔，富氮液体(23,61)从第一塔中提取出并被送入至第二塔，富氧液体(49)从第二塔中提取出，加压并在热交换器中蒸发以形成富氧气体，富氮流体(43)从塔系统中提取出并在热交换器中加热以形成第一富氮气体，其中
i)在第一阶段，产物比、即产生的富氮气体的量和产生的富氧气体的量之间的比率大于2.5，富氮液体从贮罐(27)输送到塔系统，并且来自塔系统的第一富氮气体(29)在进口温度小于-50℃的第一压缩机(33)中被压缩，然后被送入至热交换器中，和
ii)在第二阶段，产物比小于2.5并且从塔系统中提取出的第二富氮气体在进口温度低于环境温度的涡轮(73)中膨胀，或者在液化器中液化，并且富氮液体(57)从涡轮出口和/或从塔系统和/或从液化器输入至贮罐，
其特征在于，第一富氮气体在于第一压缩机中被压缩之前从第二塔中提取出，并且在于第一压缩机中被压缩之后在热交换器中被加热并作为产物移出，在涡轮中膨胀的第二富氮气体是从第二塔中提取出的，第二塔在至少为2barabs的压力下工作。
2.根据权利要求1所述的方法，其中，在第一阶段产物比大于3。
3.根据权利要求1所述的方法，其中，在第二阶段产物比小于2。
4.根据前述任一项权利要求所述的方法，其中，在第一阶段，富氮气体被从第二塔(15)中提取出，未经加热地在第一压缩机(33)中压缩，并被送入至热交换器(9)。
5.根据前述任一项权利要求所述的方法，其中，在第二阶段，从塔系统提取出的富氮气体在热交换器(9)中被加热，在涡轮(73)中膨胀，然后在热交换器中被加热。
6.根据前述任一项权利要求所述的方法，其中，涡轮(73)的入口温度最高为-50℃，优选最高为-100℃。
7.根据前述任一项权利要求所述的方法，其中，在第二阶段，涡轮(73)的出口压力与第二塔(15)的压力基本相等。
8.根据前述任一项权利要求所述的方法，其中，在第一阶段没有富氮气体被送入到涡轮(73)中。
9.根据前述任一项权利要求所述的方法，其中，在第二阶段没有气体被送入到第一压缩机(33)。
10.根据前述任一项权利要求所述的方法，其中，第二阶段的耗电量低于第一阶段。
11.根据前述任一项权利要求所述的方法，其中，在第一阶段没有富氮液体被输入到贮槽(27)中。
12.根据前述任一项权利要求所述的方法，其中，在第二阶段至少一种低温液体(83)作为最终产物被从工艺过程中提取出，并且优选地在第一阶段相同的低温液体不作为最产物从工艺过程中提取出。
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CN109387033A (zh) * 2017-08-03 2019-02-26 乔治洛德方法研究和开发液化空气有限公司 用于通过低温蒸馏来分离空气的方法和装置
CN111433545A (zh) * 2017-12-28 2020-07-17 乔治洛德方法研究和开发液化空气有限公司 在包括裂芯式主热交换器的空气分离单元中产生的富氮流的利用
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