CN115551616A - 有限甲烷损失且有限co2排放的生产生物甲烷的设备和方法 - Google Patents

有限甲烷损失且有限co2排放的生产生物甲烷的设备和方法 Download PDF

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CN115551616A
CN115551616A CN202180033856.7A CN202180033856A CN115551616A CN 115551616 A CN115551616 A CN 115551616A CN 202180033856 A CN202180033856 A CN 202180033856A CN 115551616 A CN115551616 A CN 115551616A
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gas stream
permeate
distillation column
methane
separation unit
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CN202180033856.7A
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索伦尼·瓦伦汀
F·巴洛德
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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 CN115551616A publication Critical patent/CN115551616A/zh
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    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/225—Multiple stage diffusion
    • B01D53/226—Multiple stage diffusion in serial connexion
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B01D3/145—One step being separation by permeation
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    • B01D3/148—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step in combination with at least one evaporator
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    • C12M47/00—Means for after-treatment of the produced biomass or of the fermentation or metabolic products, e.g. storage of biomass
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Abstract

披露了用于通过膜渗透处理至少包含甲烷和二氧化碳的进料气体流的设备和使用该设备的方法，该设备包含：‑能够接收该进料气体流并且供给第一渗透物和第一渗余物的第一膜分离单元，‑能够接收该第一渗余物并且供给第二渗透物和第二渗余物的第二膜分离单元，‑用于将该第一渗透物压缩至在17巴与25巴之间的压力的压缩机，‑用于将第一压缩的渗透物冷却至低于‑40℃的温度的装置，‑用于将第一冷却的渗透物分离成气体流和液体流的蒸馏塔，‑至少一个用于将离开该蒸馏塔的气体流再循环至该第一膜分离单元的入口的装置，‑用于测量离开该蒸馏塔的气体流中甲烷和/或二氧化碳浓度的装置，‑用于将通过该测量装置测得的甲烷和/或二氧化碳浓度与目标值进行比较的装置，以及‑用于根据通过该比较装置进行的比较来调节该第一渗透物的压力和/或温度的装置。

Description

有限甲烷损失且有限CO2排放的生产生物甲烷的设备和方法
本发明涉及：用于膜渗透处理至少含有甲烷和二氧化碳的气体流以产生富含甲烷的气体流的设备；以及使用这样的设备的方法。
本发明特别地涉及沼气纯化，目的是根据用于注入天然气网络内的规格产生生物甲烷。
沼气是有机物质在不存在氧气的情况下降解(厌氧发酵)(也被称为甲烷化)期间产生的气体。这可以是天然降解-因此其在沼泽地或家庭废物填埋场观察到-但沼气的产生还可以由废物在专用的反应器(称为甲烷化器或消化器)中的甲烷化产生。
由于其主要成分-甲烷和二氧化碳-沼气是强有力的温室气体；同时，在越来越缺乏化石燃料的情况下沼气还构成了相当可观的可再生能源的来源。
沼气主要含有比例可以根据其获得方式而变化的甲烷(CH4)和二氧化碳(CO2)，但是还含有较小比例的水、氮气、硫化氢、氧气，以及还有痕量的其他有机化合物。
取决于已经降解的有机物质和所使用的技术，组分的比例不同，但是平均来说，沼气基于干气体包括从30％至75％的甲烷、从15％至60％的CO2、从0％至15％的氮气、从0％至5％的氧气以及痕量的化合物。
沼气以不同方式被有利地使用。沼气可以在轻微的处理之后被有利地在生产场所附近使用以提供热量、电力或两者的混合物(热电联产)；高二氧化碳含量降低了其热值，增加了压缩和运输成本，并且限制了这种将其有利地在附近使用的方式的经济效益。
更大程度地纯化沼气允许将其更广泛地使用；特别地，沼气的广泛纯化得到了已经被纯化至天然气规格并且可以替代后者的沼气；如此纯化的沼气被称为“生物甲烷”。因此，生物甲烷对天然气资源补充了在区域内生产的可再生部分；它可以用于与化石来源的天然气完全相同的用途。它可以被进料至天然气网络或车辆加油站中；它还可以被液化以便以液化天然气(LNG)等形式储存。
有利地使用生物甲烷的方式是根据局部情况确定的：特别是局部能量要求、将其有利地作为生物甲烷燃料使用的可能性、以及是否附近存在天然气输送或分布网络。通过产生在给定区域操作的各方(农民、制造商、市政当局)之间的协同作用，生物甲烷的生产有助于这些区域获取更大的能源自主性。
在收集沼气与获得生物甲烷(能够被压缩或液化的最终产物)之间需要完成多个步骤。
特别地，在旨在将二氧化碳分离出来以便生产纯化的甲烷流的处理之前需要几个步骤。第一个步骤包括压缩已经在大气压下产生并引入的沼气，并且这种压缩可以使用压缩机(以常规方法)获得。之后的步骤旨在除去沼气的腐蚀性组分(这些组分是硫化氢和挥发性有机化合物(VOC))；使用的技术常规地为变压吸附(PSA)和活性炭捕获。接下来的步骤包括将二氧化碳分离出来，以便最终提供其后续用途所需纯度的甲烷。
二氧化碳是典型地存在于天然气中的污染物，并且通常需要将其从中除去。取决于情况，使用不同的技术来去除二氧化碳；在这些技术中，当CO2含量高时膜技术是特别有效的；并且其因此用于将存在于来源自释放气体或植物或动物废物消化器的沼气中的CO2分离出来。
用于纯化气体的膜气体分离工艺无论它们使用一个或多个膜级，均必须使得能够以低成本生产所需品质的气体，同时使需要升级的气体损失最小化。因此，在沼气纯化的情况下，进行的分离主要是CH4/CO2分离，该分离需要允许产生含有高于85％的CH4、优选地高于95％的CH4、更优先地高于97.5％的CH4的气体(取决于其用途)，同时最小化残留气体中CH4损失和纯化成本，后者很大程度上与在膜上游压缩气体的装置的电力消耗相关。
对于工厂，允许生产富含甲烷的气体流能够控制甲烷损失是优选的。
在此基础上，出现的一个问题是提供一种使得能够获得恒定浓度、而其主要组分甲烷没有任何损失的生物甲烷流的设备。
本发明的一个解决方案是一种用于膜渗透处理至少包含甲烷和二氧化碳的进料气体流的设备，所述设备包含：
-能够接收该进料气体流并且供给第一渗透物和第一渗余物的第一膜分离单元，
-能够接收该第一渗余物并且供给第二渗透物和第二渗余物的第二膜分离单元，
-用于将该第一渗透物压缩至在17巴与25巴之间的压力的压缩机，
-用于将压缩的第一渗透物冷却至低于-40℃的温度的装置，
-用于将冷却的第一渗透物分离成气体流和液体流的蒸馏塔，以及
-至少一个用于将离开该蒸馏塔的气体流再循环至该第一膜分离单元的入口的装置。
优选地，用于再循环离开蒸馏塔的气体流的装置包含一组阀门和管道。
视情况而定，根据本发明的设备可以具有以下特征中的一个或多个：
-该设备包含用于测量离开该蒸馏塔的气体流中甲烷和/或二氧化碳浓度的装置，用于将通过该测量装置测得的甲烷和/或二氧化碳浓度与目标值进行比较的装置，以及用于根据通过第一比较装置进行的比较来调节该第一渗透物的压力和/或温度的装置。
-该设备包含在该第一膜分离单元上游用于将该进料气体流压缩至在8巴与16巴之间的压力的压缩机。
-该设备包含用于蒸发离开该蒸馏塔的液体流的蒸发器。
-该设备包含用于储存离开该蒸馏塔的液体流的液体舱。
-该设备包含置于该第一膜分离单元的上游的用于纯化该进料气体流，并且用于至少部分地去除选自水、硫化氢、和挥发性有机化合物的杂质的装置。
-该用于将第一压缩的渗透物冷却至低于-40℃的温度的装置包含制冷器和热交换器组件。
本发明的主题还是一种用于膜渗透处理至少包含甲烷和二氧化碳的进料气体流的方法，所述方法使用如上所定义的设备，并且包括：
a)用该进料气体流向该第一膜分离单元进料以便产生相对于该进料气体流富含甲烷的第一渗余物和相对于该进料气体流富含二氧化碳的第一渗透物的步骤，
b)将该第一渗余物进料至该第二膜分离单元以便产生相对于该第一渗余物富含甲烷的第二渗余物和相对于该第一渗余物富含二氧化碳的第二渗透物的步骤，
c)将该第一渗透物压缩至在17巴与25巴之间的压力的步骤，
d)将该压缩的第一渗透物冷却至低于-40℃的温度的步骤，
e)在该蒸馏塔中将冷却的第一渗透物分离成气体流和液体流的步骤，以及
f)将离开该蒸馏塔的气体流再循环至该第一膜分离单元的入口的步骤。
应注意的是，该再循环使得包含在气体流中的全部CH4均能够被再循环。实际上，离开蒸馏塔的气体流将基本上包含甲烷，并且离开蒸馏塔的液体流将基本上包含二氧化碳。
进料气体流中的再循环部分将优选地为进料气体流的1/3。
视情况而定，根据本发明的方法可以具有以下特征中的一个或多个：
-该方法包括测量离开该蒸馏塔的气体流中甲烷和/或二氧化碳浓度的步骤，将通过该测量装置测得的甲烷和/或二氧化碳浓度与目标值进行比较的步骤，以及根据通过第一比较装置进行的比较来调节该第一渗透物的压力和/或温度的步骤。优选地，该三个步骤通过数据传输和数据处理装置自动进行。优选地，该目标值在10％CH4与20％CH4之间，
-该方法包括在该第一膜分离单元上游将该进料气体流压缩至在8巴与16巴之间的压力的步骤，
-该方法包括蒸发离开该蒸馏塔的液体流的步骤。
-该方法包括将离开该蒸馏塔的液体流储存在液体舱中的步骤。
-该方法包括在该第一膜分离单元的上游纯化该进料气体流以便至少部分地去除选自水、硫化氢、和挥发性有机化合物的杂质的步骤，
-该进料气体流是沼气。
本文提出的解决方案使得能够获得具有恒定浓度、而其主要组分甲烷没有损失的生物甲烷流，并且还使得能够避免二氧化碳排放。

Claims (12)

1.一种用于膜渗透处理至少包含甲烷和二氧化碳的进料气体流的设备，所述设备包含：
-能够接收该进料气体流并且供给第一渗透物和第一渗余物的第一膜分离单元，
-能够接收该第一渗余物并且供给第二渗透物和第二渗余物的第二膜分离单元，
-用于将该第一渗透物压缩至在17巴与25巴之间的压力的压缩机，
-用于将该压缩的第一渗透物冷却至低于-40℃的温度的装置，
-用于将该冷却的第一渗透物分离成气体流和液体流的蒸馏塔，
-至少一个用于将离开该蒸馏塔的气体流再循环至该第一膜分离单元的入口的装置，
-用于测量离开该蒸馏塔的气体流中甲烷和/或二氧化碳浓度的装置，
-用于将通过该测量装置测得的甲烷和/或二氧化碳浓度与目标值进行比较的装置，以及
-用于根据通过该比较装置进行的比较来调节该第一渗透物的压力和/或温度的装置。
2.如权利要求1所述的设备，其特征在于，该设备包含在该第一膜分离单元上游用于将该进料气体流压缩至在8巴与16巴之间的压力的压缩机。
3.如权利要求1和2中任一项所述的设备，其特征在于，该设备包含用于蒸发离开该蒸馏塔的液体流的蒸发器。
4.如权利要求1和2中任一项所述的设备，其特征在于，该设备包含用于储存离开该蒸馏塔的液体流的液体舱。
5.如权利要求1至4中的一项所述的设备，其特征在于，该设备包含置于该第一膜分离单元的上游的用于纯化该进料气体流，并且用于至少部分地去除选自水、硫化氢、和挥发性有机化合物的杂质的装置。
6.如权利要求1至5中的一项所述的设备，其特征在于，该用于将该压缩的第一渗透物冷却至低于-40℃的温度的装置包含制冷器和热交换器组件。
7.一种用于膜渗透处理至少包含甲烷和二氧化碳的进料气体流的方法，所述方法使用如权利要求1至6中的一项中所定义的设备，并且包括：
a)用该进料气体流向该第一膜分离单元进料以便产生相对于该进料气体流富含甲烷的第一渗余物和相对于该进料气体流富含二氧化碳的第一渗透物的步骤，
b)将该第一渗余物进料至该第二膜分离单元以便产生相对于该第一渗余物富含甲烷的第二渗余物和相对于该第一渗余物富含二氧化碳的第二渗透物的步骤，
c)将该第一渗透物压缩至在17巴与25巴之间的压力的步骤，
d)将该压缩的第一渗透物冷却至低于-40℃的温度的步骤，
e)在该蒸馏塔中将该冷却的第一渗透物分离成气体流和液体流的步骤，
f)将离开该蒸馏塔的气体流再循环至该第一膜分离单元的入口的步骤，
g)测量离开该蒸馏塔的气体流中甲烷和/或二氧化碳浓度的步骤，
h)将通过该测量装置测得的甲烷和/或二氧化碳浓度与目标值进行比较的步骤，以及
i)根据通过该比较装置进行的比较来调节该第一渗透物的压力和/或温度的步骤。
8.如权利要求7所述的方法，其特征在于，该方法包括在该第一膜分离单元上游将该进料气体流压缩至在8巴与16巴之间的压力的步骤。
9.如权利要求7和8中任一项所述的方法，其特征在于，该方法包括蒸发离开该蒸馏塔的液体流的步骤。
10.如权利要求7至9中的一项所述的方法，其特征在于，该方法包括将离开该蒸馏塔的液体流储存在液体舱中的步骤。
11.如权利要求7至10中的一项所述的方法，其特征在于，该方法包括在该第一膜分离单元的上游纯化该进料气体流以便至少部分地去除选自水、硫化氢、和挥发性有机化合物的杂质的步骤。
12.如权利要求7至11中的一项所述的方法，其特征在于，该进料气体流是沼气。
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