CN115451651A - 用于低温分离和液化生物气流中包含的甲烷和二氧化碳的组合设备 - Google Patents

用于低温分离和液化生物气流中包含的甲烷和二氧化碳的组合设备 Download PDF

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CN115451651A
CN115451651A CN202210647752.1A CN202210647752A CN115451651A CN 115451651 A CN115451651 A CN 115451651A CN 202210647752 A CN202210647752 A CN 202210647752A CN 115451651 A CN115451651 A CN 115451651A
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methane
column
biogas
exchanger
mixture
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T·R·J·埃内斯托
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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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  • Separation By Low-Temperature Treatments (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明涉及用于低温分离和液化包含在生物气流中的甲烷和二氧化碳的组合设备，包括：用于将生物气与再循环气体R混合的装置M1；用于将混合物压缩至蒸馏压力的压缩机；用于冷却压缩混合物的交换器E01；被供应冷却混合物并在塔顶部生产甲烷和在塔底部生产富含CO2的液体的蒸馏塔K01；用于液化甲烷的交换器E02；用于将液化甲烷分成“回流”部分和“产品”部分的装置M2；用于膨胀和加热富含CO2的液体并用于从富含CO2的液体中回收冷量的装置M3；和用于接收富含CO2的流并用于回收顶部蒸气和液态CO2的分离器容器V01，再循环气体R对应于顶部蒸气，交换器E01和装置M3组合为一体。还涉及使用上述设备来低温分离和液化包含在生物气流中的甲烷和二氧化碳的组合方法。

Description

用于低温分离和液化生物气流中包含的甲烷和二氧化碳的组 合设备
技术领域
本发明涉及从生物气流中生产液态甲烷和液态二氧化碳的设备和方法。
背景技术
生物气/沼气是在无氧条件下有机物降解(厌氧发酵)过程(也称为甲烷化)中产生的气体。这可能是自然降解——因此在沼泽地或家庭垃圾填埋场观察到了这种现象——但生物气的产生也可能是废物在称为甲烷化器或消化器的专用反应器中甲烷化的结果。
由于其主要成分为甲烷和二氧化碳，生物气是一种强大的温室气体；与此同时，它也是一种可再生能源，在化石燃料日益稀缺的背景下，这种能源是值得重视的。
生物气主要包含甲烷(CH4)和二氧化碳(CO2)，其比例可根据其获得方式而变化，但生物气还包含较小比例的水、氮、硫化氢、氧以及痕量的其它有机化合物。
取决于已被降解的有机物和所使用的技术，组分的比例不同，但平均而言，基于干燥气体，生物气包括30％至75％的甲烷、15％至60％的CO2、0至15％的氮、0至5％的氧和痕量化合物。
在预处理这些污染物的步骤后，生物气可用于供应锅炉或热电联产装置，或者可被纯化以获得符合注入天然气网络的规格的气体(例如:最大3％的CO2)。
在欧洲和全世界的许多地区，在可发酵废物生产区附近并不总是能获得天然气网络。此外，虽然在生物气生产现场不需要热量，但取决于电力的购买价格，热电联产并不总是有足够的产出来使消化单元的主要投资获利。在这两种情况下，将生物气运输到分配或消耗点是有利的。纯化后的生物气液化将使以较低成本运输生物甲烷成为可能。根据某些地理区域的规定，禁止将CH4释放到环境中；这增加了额外的约束，并限制了对高效方法的生物气分离工艺的选择。
目前，生物气纯化工艺主要基于吸收、渗透或吸附技术。于是，这些系统需要添加补充模块，以获得液态的生物甲烷。此外，在大多数情况下，在该纯化步骤结束时，生物气中的CO2含量仍然太高，以至于不能供应给这种液化系统。
已经提出了基于可逆交换器原理的低温捕集系统。该系统基于生物气中存在的CO2在冷表面上的固化(捕集)，随后是使用热源的CO2升华或液化步骤。对于生物甲烷的连续生产，有必要用几个平行的交换器工作。他们的技术方案使得在两个独立的步骤中分离和液化甲烷和CO2成为可能，但是不可能回收用于固化CO2的冷量。
由此开始，出现的一个问题是提供一种从生物气中分离和液化甲烷和CO2的方法，该方法具有最小的甲烷损失和最少数量的操作。
发明内容
本发明的一种技术方案是一种用于低温分离和液化包含在生物气流中的甲烷和二氧化碳的组合设备，包括:
-装置M1，其用于将生物气1与再循环气体R混合；
-压缩机，其用于将混合物压缩至蒸馏压力；
-交换器E01，其用于冷却压缩后的混合物；
-蒸馏塔K01，其被供应冷却后的混合物，并使得能够在塔顶部生产甲烷，并且在塔底部生产富含CO2的液体；
-交换器E02，其用于液化在塔顶部生产的甲烷；
-装置M2，其用于将液化的甲烷分成以下两个部分：“回流”部分3和“产品”部分2；
-装置M3，其用于膨胀和加热在塔底部回收的富含CO2的液体并用于从富含CO2的液体中回收冷量；和
-分离器容器V01，其用于接收来自装置M3的富含CO2的流，并用于回收顶部蒸气和液态CO2 4，
其中
-所述装置M1使得再循环气体R对应于在所述分离器容器V01的出口处回收的顶部蒸气，并且
-所述交换器E01和所述装置M3是组合为一体的。
根据情况，根据本发明的设备可具有以下特征中的一者或多者：
-该设备在装置M1的上游包括用于对生物气进行干燥和脱硫的装置；
-该设备在装置M1的上游包括用于将生物气压缩至再循环气体R的压力的装置C01；
-该设备在装置M1的上游包括用于将生物气冷却至环境温度的装置C01E和/或装置C02E；
-交换器E02位于闭环的制冷回路中；
-制冷回路使用甲烷作为制冷剂流体；
-蒸馏塔K01包括在塔底部的加热装置。
本发明还涉及一种使用前述设备来低温分离和液化包含在生物气流中的甲烷和二氧化碳的组合方法，包括:
a)将生物气1与再循环气体R混合的步骤；
b)将混合物压缩至蒸馏压力的步骤；
c)在交换器E01中冷却压缩后的混合物的步骤；
d)在蒸馏塔K01中对冷却后的混合物进行蒸馏以在塔顶部生产甲烷并在塔底部生产富含CO2的液体的步骤；
e)在交换器E02中使在塔顶部生产的甲烷液化的步骤；
f)用于将液化的甲烷分成以下两个部分的分流步骤:“回流”部分3和“产品”部分2；
g)在交换器E01中膨胀和加热在塔底部回收的富含CO2的液体，并从富含CO2的液体中回收冷量的步骤；和
h)在分离器容器V01中将来自交换器E01的富含CO2的流分离成液态CO2 4和顶部蒸气的步骤，
其中，再循环气体R对应于在步骤h)中生产的顶部蒸气。
根据情况，根据本发明的方法可具有以下特征中的一者或多者：
-该方法在步骤a)的上游/之前包括干燥和脱硫步骤。
-该方法在步骤a)之前包括将生物气压缩至再循环气体R的压力的步骤。
-该方法在步骤a)之前包括将生物气冷却至环境温度的步骤。
-该方法在步骤h)之后包括加热液态CO2以使其气化的步骤。
-通过借助制冷剂流体冷却所生产的甲烷来进行步骤e)。塔顶部的产品是纯甲烷蒸气。这种蒸气在交换器中被液化，该交换器由与该过程热集成的闭环制冷循环冷却。一部分液态甲烷作为产品离开回路，另一部分用作塔回流物。
-在步骤b)中，混合物被压缩至7巴至46巴的压力。
根据本发明的方法使得能够在单个的组合的蒸馏/液化操作中分离和液化生物气的产品。已经计算了塔的入口和出口处以及再循环部分中的产品的操作条件，以防止固体CO2的形成。
分离部分的流和制冷循环的流之间的热集成能够回收在CO2液化和液体甲烷循环中使用的冷量。如果不期望CO2作为产品或者当它可以以气态使用时，可以完全或部分回收在CO2液化中使用的能量。
附图说明
图1示出了根据本发明的一个实施例的用于低温分离和液化包含在生物气流中的甲烷和二氧化碳的组合设备的示意图。
具体实施方式
将通过图1对本发明进行更详细的描述。
将预处理的生物气1(通过干燥、脱硫预处理)在大气压力和温度下引入工艺中，在压缩机C01中第一次压缩至循环回路的压力(约8巴)。压缩后，在C01E中用CW(＝冷却水)或空气将其冷却至环境温度。
接下来，将其与再循环流R混合，在压缩机C02中根据下游交换器E01的要求将混合物压缩至蒸馏塔的压力(约15巴)或更高，并且在C02E中用CW或空气将混合物冷却至环境温度。
优选地，C01E和C02E是壳管式交换器(压缩机的冷却器)。
生物气和再循环流R的混合物被送至交换器E01。该交换器的主要目的是冷却混合物，以便为蒸馏做准备。然后，混合物可以膨胀或直接供应到塔中，在此，其将用作再沸器。
如果在塔的底部没有热源，则有必要将混合物注入底部，以确保蒸气从底部循环。如果塔底部有热源(再沸器)，则混合物被引入塔的更高处。
蒸馏塔K01将甲烷与二氧化碳分离。该塔的进料是生物气和再循环流R的混合物。该进料充当主再沸器；也可以使用额外的热源(例如电阻加热器、间接接触的热生物气的一部分或蒸气)。塔顶部的产物是气态的纯CH4。底部产物是富含CO2的液体，其含有大约95％-98％的CO2。
塔顶部的甲烷在交换器E02中通过来自闭环制冷回路的流体而被液化。甲烷的一个部分2作为产品离开循环，并且其另一部分3(回流部分)用作塔的循环物，并重新注入到塔顶部。
在塔底部回收的富含CO2的液体在交换器E01中与生物气和再循环流R的混合物逆流地/相逆地被膨胀和加热。
来自交换器E01的富含CO2的流被送至分离容器V01。
容器V01的顶部蒸气在交换器E01中再加热，然后与生物气混合。它对应于先前命名为“再循环流R”的流。
来自容器V01底部的液体是纯CO2 4。根据需要，这可以作为产品离开该工艺，或者在交换器E01中和在制冷回路的另一个交换器E03中被再加热，以便在离开循环之前完全气化。注意，纯CO2可以替代地在交换器E03中被再加热和气化，而不经过交换器E01。
因此，交换器E01使用以下物质作为冷源:在塔底部回收的富含CO2的液体；在交换器E01的出口处的、称为“再循环流R”的来自容器V01的顶部蒸气；以及可选的在容器V01底部回收的纯液体CO2(在期望其气化的情况下)。
该方法需要输入制冷功率以进行操作。这种冷量输入在图1中由制冷回路表示:它包括:
带有冷却器C03E的压缩机C03；
交换器E03，其使用再循环的制冷剂流体和从分离循环中回收的冷量来冷却压缩的流体；
涡轮机ET01和JT阀PV05，用于制冷剂流体的膨胀和产生冷；
分离制冷剂流体的气相和液相的分离器容器V02；
交换器E02，其使用制冷剂流体的液相来液化蒸馏塔顶部的生物甲烷。
该方案中使用的制冷剂流体是CH4，但也可以用其他流体代替，如N2、N2+H2等。
该制冷循环可由其他冷源替代(取决于待生产的液态生物甲烷的量)。
举例来说，但不排他地:
-使用液氮源；
-通过布雷登(Brayton)循环过程。

Claims (14)

1.一种用于低温分离和液化包含在生物气流中的甲烷和二氧化碳的组合设备，包括：
-装置M1，其用于将生物气(1)与再循环气体R混合；
-压缩机，其用于将混合物压缩至蒸馏压力；
-交换器E01，其用于冷却压缩后的混合物；
-蒸馏塔K01，其被供应冷却后的混合物，并使得能够在塔顶部生产甲烷，并且在塔底部生产富含CO2的液体；
-交换器E02，其用于液化在塔顶部生产的甲烷；
-装置M2，其用于将液化的甲烷分成以下两个部分：“回流”部分(3)和“产品”部分(2)；
-装置M3，其用于膨胀和加热在塔底部回收的富含CO2的液体并用于从所述富含CO2的液体中回收冷量；和
-分离器容器V01，其用于接收来自所述装置M3的富含CO2的流，并用于回收顶部蒸气和液态CO2(4)，
其中
-所述装置M1使得所述再循环气体R对应于在所述分离器容器V01的出口处回收的顶部蒸气，并且
-所述交换器E01和所述装置M3是组合为一体的。
2.根据权利要求1所述的设备，其特征在于，该设备在所述装置M1的上游包括用于对生物气进行干燥和脱硫的装置。
3.根据权利要求1或2所述的设备，其特征在于，该设备在所述装置M1的上游包括用于将生物气压缩至所述再循环气体R的压力的装置C01。
4.根据权利要求1至3中任一项所述的设备，其特征在于，该设备在所述装置M1的上游包括用于将生物气冷却至环境温度的装置C01E和/或装置C02E。
5.根据权利要求1至4中任一项所述的设备，其特征在于，所述交换器E02位于闭环的制冷回路中。
6.根据权利要求5所述的设备，其特征在于，所述制冷回路使用甲烷作为制冷剂流体。
7.根据权利要求1至6中任一项所述的设备，其特征在于,所述蒸馏塔K01包括在塔底部的加热装置。
8.一种使用根据权利要求1至7中任一项所述的设备来低温分离和液化包含在生物气流中的甲烷和二氧化碳的组合方法，该方法包括：
a)将生物气(1)与再循环气体R混合的步骤；
b)将混合物压缩至蒸馏压力的步骤；
c)在交换器E01中冷却压缩后的混合物的步骤；
d)在蒸馏塔K01中对冷却后的混合物进行蒸馏以在塔顶部生产甲烷并在塔底部生产富含CO2的液体的步骤；
e)在交换器E02中使在塔顶部生产的甲烷液化的步骤；
f)用于将液化的甲烷分成以下两个部分的分流步骤:“回流”部分(3)和“产品”部分(2)；
g)在交换器E01中膨胀和加热在塔底部回收的富含CO2的液体，并从富含CO2的液体中回收冷量的步骤；和
h)在分离器容器V01中将来自交换器E01的富含CO2的流分离成液态CO2(4)和顶部蒸气的步骤，
其中，所述再循环气体R对应于在步骤h)中生产的顶部蒸气。
9.根据权利要求8所述的方法，其特征在于，该方法在步骤a)之前包括干燥和脱硫步骤。
10.根据权利要求8或9所述的方法，其特征在于，该方法在步骤a)之前包括将生物气压缩至所述再循环气体R的压力的步骤。
11.根据权利要求8至10中任一项所述的方法，其特征在于，该方法在步骤a)之前包括将生物气冷却至环境温度的步骤。
12.根据权利要求8至11中任一项所述的方法，其特征在于，该方法在步骤h)之后包括加热所述液态CO2以使其气化的步骤。
13.根据权利要求8至12中任一项所述的方法，其特征在于，通过借助制冷剂流体冷却所生产的甲烷来执行步骤e)。
14.根据权利要求8至13中任一项所述的方法，其特征在于，在步骤b)中，混合物被压缩至7巴至46巴的压力。
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EP4101915B1 (fr) 2024-02-07
EP4101915A1 (fr) 2022-12-14
US20220397344A1 (en) 2022-12-15

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