CN110938480A - 包含杂质凝固的由生物气料流生产生物甲烷的方法 - Google Patents

包含杂质凝固的由生物气料流生产生物甲烷的方法 Download PDF

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CN110938480A
CN110938480A CN201910910323.7A CN201910910323A CN110938480A CN 110938480 A CN110938480 A CN 110938480A CN 201910910323 A CN201910910323 A CN 201910910323A CN 110938480 A CN110938480 A CN 110938480A
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stream
biogas
impurities
process according
substep
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G·卡东
A·特鲁巴
S·瓦伦汀
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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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Abstract

由包含甲烷、二氧化碳和选自氨、挥发性有机化合物、水、基于硫的杂质(H2S)和硅氧烷的至少一种杂质的生物气料流生产生物甲烷的方法，其包含：‑干燥生物气料流的第一步骤，‑通过杂质的凝固和脱除而至少部分脱除干燥生物气料流中包含的所述杂质的第二步骤；和‑分离获自第二步骤的生物气中包含的甲烷和二氧化碳以产生生物甲烷料流和CO2料流的第三步骤。

Description

包含杂质凝固的由生物气料流生产生物甲烷的方法
本发明涉及由包含甲烷、二氧化碳和选自氨、挥发性有机化合物、水、基于硫的杂质(H2S)和硅氧烷的至少一种杂质的生物气料流生产生物甲烷的方法。
本发明特别涉及生物气的净化，目的是生产符合注入天然气网络的规格的生物甲烷。
生物气是在有机物的无氧降解(厌气发酵)，也称为甲烷化的过程中产生的气体。这可以是自然降解-因此在沼泽地或在生活垃圾填埋场观察到-但生物气的产生也可来自在被称为甲烷化装置(methanizer)或消化器的专用反应器中的废物甲烷化。
由于其主要成分–甲烷和二氧化碳–生物气是强力温室气体；同时，其也构成在化石燃料日益短缺的背景下值得关注的可再生能量来源。
生物气主要含有甲烷(CH4)和二氧化碳(CO2)，比例可随其获得方式而变，但也含有较小比例的水、氮气、硫化氢、氧气和痕量的其它有机化合物。
根据已降解的有机物和根据所用技术，组分的比例不同，尽管平均而言，生物气包括，在干气体基础上，30至75％甲烷、15至60％CO2、0至15％氮气、0至5％氧气和痕量化合物。
生物气以各种方式投入有利可图的使用。其可在光照处理后在生产现场附近投入有利可图的使用，以供应热、电或两者的混合物(热电联产)；高二氧化碳含量降低其热值，提高压缩和运输的成本并限制由此在附近投入有利可图的使用的经济效益。
净化生物气至更大程度赋予其更广泛的用途；特别地，生物气的充分净化产生已净化到天然气规格并可替代天然气的生物气；由此净化的生物气被称为“生物甲烷”。生物甲烷因此用区域内生产的可再生比例(renewable proportion)补充天然气资源；其可投入与化石来源的天然气完全相同的用途。其可供入天然气网络、车辆加气站(vehiclefilling station)；其也可液化从而以液化天然气(LNG)的形式储存，等等。
有利可图地利用生物甲烷的方式取决于当地情况：当地能源需求、其有利可图地用作生物甲烷燃料的可能性，以及特别地，附近是否有天然气运输或分配网络。通过在给定区域中运营的各种团体(农户、制造商、市政当局)之间建立协同作用，生物甲烷的生产有助于该区域获得更大的能源自主性。
在收集生物气与获得生物甲烷(可压缩或液化的最终产品)之间需要完成许多步骤。
特别地，在旨在分离出二氧化碳以产生纯化甲烷料流的处理之前需要几个步骤。
本发明意在提供改进的生产生物甲烷的方法。
本发明的一个解决方案是一种由包含甲烷、二氧化碳和选自氨、挥发性有机化合物、水、基于硫的杂质(H2S)和硅氧烷的至少一种杂质的生物气料流生产生物甲烷的方法，其包含：
-干燥生物气料流的第一步骤，
-通过杂质的凝固和脱除而至少部分脱除干燥生物气料流中包含的所述杂质的第二步骤；和
-分离获自第二步骤的生物气中包含的甲烷和二氧化碳以产生生物甲烷料流和CO2料流的第三步骤。
图1图解这三个步骤。
视情况而定，根据本发明的方法可具有一个或多个下列特征：
-至少部分脱除所述杂质的第二步骤包含将干燥生物气料流压缩到高于5巴，优选10巴的压力的第一子步骤；通过将压缩的生物气料流冷却到低于-70℃的温度而凝固所述杂质的第二子步骤；以及沉积和脱除所述杂质的第三子步骤。优选地，这样的第二步骤循环以使所述方法保持连续运行；
-在第二子步骤中，用优选在第三步骤的过程中产生的冷却料流，优选CO2料流冷却所述生物气料流。
-在第三子步骤中，通过所述杂质的升华和用气态冲洗料流冲洗而脱除所述杂质。
-在高于升华温度的温度和低于2巴的压力下进行所述升华。
-在第二子步骤中，用冷却料流冷却所述生物气料流，并且在第三子步骤中，使用获自第二子步骤的冷却料流作为气态冲洗料流。
-优选地，第二子步骤和第三子步骤在同一子步骤中同时进行；
-所述气态冲洗料流是CO2或氮气料流。
-所述气态冲洗料流获自储存容量(storage capacity)。
-所述气态冲洗料流是在分离生物气中包含的甲烷和二氧化碳的第三步骤的过程中产生的再循环CO2料流。
-分离生物气中包含的甲烷和二氧化碳的第三步骤通过用水或用胺洗涤、吸附、二氧化碳的凝固或膜分离进行。
-干燥生物气料流的第一步骤通过冷却和凝结，接着吸附进行；
-至少部分脱除所述杂质的第二步骤使用热交换器。
-压缩生物气料流的第一子步骤使用压缩机进行。
-至少部分脱除所述杂质的第二步骤使用热交换器，在第二子步骤中，用冷却料流冷却所述生物气料流，其中所述生物气料流经过热交换器的第一通道且所述冷却料流经过热交换器的第二通道，并且在第三子步骤中，通过所述杂质的升华和用气态冲洗料流冲洗而脱除所述杂质，其中所述气态冲洗料流通过热交换器的第一通道；其中在第三子步骤的过程中所述生物气料流通过第二通道。要指出，由此再生第一通道并且第二步骤可再次循环进行。要指出，优选地，冲洗料流是CO2料流并且冷却料流也是CO2料流。在这一优选情况中，CO2料流通过一组阀门经过第二通道，然后经过第一通道。类似地，生物气料流经过一组阀门经过第一通道，然后经过第二通道。图2图解这一优选情况。
第一干燥步骤是从生物气料流中除去所有痕量水所必需的。其原因在于生物气料流中存在的水可能在压缩机中冷凝并损坏压缩机。
脱除所述杂质的第二步骤优选是在三个子步骤中运行的循环过程：
-将所述生物气料流压缩到高于5巴，优选10巴的压力
-通过冷却在热交换器中凝固生物气中所含的杂质。由此观察到热交换器中的杂质沉积。在交换器出口回收纯化生物气。
-已沉积在热交换器中的杂质的升华以再生热交换器。杂质的升华在低压下，即在低于2巴的压力下进行。优选将CO2料流注入热交换器以冲洗出进入气相的杂质。CO2同时使生物气料流-CO2料流组装件(assembly)保持冷成为可能。
CO2可源自储存容量或源自生物气本身。在后一情况下，其相当于在根据本发明的方法的第三步骤中产生的CO2料流的全部或一部分。要指出，CO2可被另一气体如氮气等替代。
在热交换器出口，可将纯化生物气减压，通过分离甲烷和二氧化碳而转化成生物甲烷，然后送回热交换器。图3图解这一送回操作。

Claims (15)

1.由包含甲烷、二氧化碳和选自氨、挥发性有机化合物、水、基于硫的杂质(H2S)和硅氧烷的至少一种杂质的生物气料流生产生物甲烷的方法，其包含：
-干燥生物气料流的第一步骤，
-通过杂质的凝固和脱除而至少部分脱除干燥生物气料流中包含的所述杂质的第二步骤；和
-分离获自第二步骤的生物气中包含的甲烷和二氧化碳以产生生物甲烷料流和CO2料流的第三步骤。
2.根据权利要求1的方法，其特征在于至少部分脱除所述杂质的第二步骤包含：
-将干燥生物气料流压缩到高于5巴，优选10巴的压力的第一子步骤，
-通过将压缩的生物气料流冷却到低于-70℃的温度而凝固所述杂质的第二子步骤；和
-沉积和脱除所述杂质的第三子步骤。
3.根据权利要求2的方法，其特征在于，在第二子步骤中，用优选在第三步骤的过程中产生的冷却料流，优选CO2料流冷却所述生物气料流。
4.根据权利要求2或3的方法，其特征在于，在第三子步骤中，通过所述杂质的升华和用气态冲洗料流冲洗而脱除所述杂质。
5.根据权利要求4的方法，其特征在于在高于升华温度的温度和低于2巴的压力下进行所述升华。
6.根据权利要求4或5的方法，其特征在于，在第二子步骤中，用冷却料流冷却所述生物气料流，并且在第三子步骤中，使用获自第二子步骤的冷却料流作为气态冲洗料流。
7.根据权利要求6的方法，其特征在于第二子步骤和第三子步骤在同一子步骤中同时进行。
8.根据权利要求4至7中任一项的方法，其特征在于所述气态冲洗料流是CO2或氮气料流。
9.根据权利要求8的方法，其特征在于所述气态冲洗料流获自储存容量。
10.根据权利要求8的方法，其特征在于所述气态冲洗料流是在分离生物气中包含的甲烷和二氧化碳的第三步骤的过程中产生的再循环CO2料流。
11.根据权利要求1至10中任一项的方法，其特征在于分离生物气中包含的甲烷和二氧化碳的第三步骤通过用水或用胺洗涤、吸附、二氧化碳的凝固或膜分离进行。
12.根据权利要求1至11中任一项的方法，其特征在于干燥生物气料流的第一步骤通过冷却和凝结，接着吸附进行。
13.根据权利要求1至12中任一项的方法，其特征在于至少部分脱除所述杂质的第二步骤使用热交换器。
14.根据权利要求2至10中任一项的方法，其特征在于压缩生物气料流的第一子步骤使用压缩机进行。
15.根据权利要求2至10中任一项的方法，其特征在于：
-至少部分脱除所述杂质的第二步骤使用热交换器，
-在第二子步骤中，用冷却料流冷却所述生物气料流，其中所述生物气料流经过热交换器的第一通道且所述冷却料流经过热交换器的第二通道，和
-在第三子步骤中，通过所述杂质的升华和用气态冲洗料流冲洗而脱除所述杂质，其中所述气态冲洗料流经过热交换器的第一通道；
其中在第三子步骤的过程中所述生物气料流经过第二通道。
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