CN103561844B - 用于从生物气中分离和纯化甲烷的方法和系统 - Google Patents
用于从生物气中分离和纯化甲烷的方法和系统 Download PDFInfo
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Abstract
用于从生物气中分离和纯化甲烷的方法和系统,包括收集一个粗生物气气流(2),该粗生物气气流(2)具有甲烷、二氧化碳、水、硫化合物和非甲烷有机化合物(NMOC)组分。将生物气流(2)进料到一个液体硫洗涤器或一个硫吸附器单元(3)的进气中,其中将该生物气分离成一个在该系统中被传送至下游的主气流(16)以及一个从该系统中被去除的硫化合物流(4)。然后将主气流(16)通过一个NMOC吸收器(7)进行处理并且进一步在下游通过一个NMOC吸附器(12)进行处理。将由两个NMOC过程产生的NMOC液化、从该系统中去除并且储存。自这些NMOC过程上游,将该主气流通过至少一个CO2、N2、O2气体分离单元(16)进行处理,该气体分离单元产生一个富含甲烷气体的可用产物流(17)、以及一个废气流(19),一个VPSAU(20)处理废气流用于排放和再循环。
Description
技术领域
本发明涉及一个混合流中气体和蒸汽化合物的分离,并且具体地涉及一种用于从生物气中分离和纯化甲烷的方法和系统。
背景技术
从生物气产生来源(如厌氧消化池和填埋场)中取得、分离和纯化甲烷允许该纯化的甲烷作为一种天然气的代用品而使用。一种用于从生物气中分离和回收纯甲烷气体的常规方法要求使这些收集的非甲烷有机化合物(NMOC)在发动机、燃烧室、燃烧塔(flare)或热氧化器中进行热破坏。该生物气的非甲烷有机化合物(NMOC)的热破坏导致二氧化碳(一种温室气体)的产生,这进一步增加全球变暖。
诸位发明人还不知道有方法能够从生物气气体中分离和纯化甲烷而不从该生物气的纯化方法的不可避免的热破坏相中产生二氧化碳。因而,存在对一种分离生物气气体(特别非甲烷有机化合物(NMOC))的方法和系统的需要,而不产生二氧化碳气流,以便提供一种与天然气可互换的实质上纯化的甲烷流。
因此,一种解决这些上述问题的用于从生物气中分离和纯化甲烷的方法和系统是所希望的。
发明内容
用于从生物气中分离和纯化甲烷的方法和系统分离了生物气、纯化了可用的甲烷、并且收集了非甲烷有机化合物(NMOC),从而避免了非甲烷有机化合物的热破坏以及随后温室气体释放到大气中。该方法收集了一个包含甲烷、二氧化碳、水、硫化合物和NMOC气体/蒸汽的粗生物气气流。将该生物气流进料到一个液体硫洗涤器或一个硫吸附器单元的进气中,其中将该生物气分离成一个在该系统中被传送至下游的主气流以及一个从该系统中被去除的硫化合物流。然后将该主气流通过一个NMOC吸收器进行处理,并且进一步在游通过一个NMOC吸附器进行处理。将由两个NMOC过程回收的NMOC液化、从该系统去除并且储存。
自这些NMOC过程下游,该主气流通过至少一个CO2、N2、O2气体分离单元进行处理,该单元产生了一个富含甲烷气体的可用产物流、以及一个废气流,在其中一个排气变压吸附单元(VPSAU)处理该废气用于排放和再循环。
根据以下说明书和附图的进一步综述,本发明的这些和其他特征将很容易变得清楚。
附图说明
该唯一附图是示出了根据本发明的用于从生物气中分离和纯化甲烷的示例性系统的框图。
贯穿所附的附图,类似的参考符号一致地表示相对应的特征。
具体实施方式
用于从生物气中分离和纯化甲烷的方法和系统分离了生物气、纯化了可用的甲烷、并且收集了非甲烷有机化合物(NMOC),从而避免了该NMOC的热破坏以及所产生的温室气体排放到大气中。该方法可以收集一个包含至少甲烷、二氧化碳、水、硫化合物和NMOC气体/蒸汽的粗生物气气流。如在该附图中所示的,该方法将该粗生物气气流分离成至少一个硫化合物流和一个主气流。本领域的普通技术人员应该理解,可以通过贯穿系统100布置的压缩机和/或泵单元协助在此讨论的气体和液体流的流动。对于在此描述的系统110的每个处理步骤,此类处理步骤可以在一个具有合适设计的压力容器中发生以有助于这些所述的过程。此外,可以通过使用贯穿系统100的热交换器协助所要求的热的和冷凝操作。
在消化池或填埋场5中的废物上的厌氧菌作用产生生物气,将该生物气进料到一个导管2内以引导一个粗生物气流,该粗生物气流包含甲烷、二氧化碳、水和非甲烷有机化合物(NMOC)气体/蒸汽。空气也可以找到其进入消化池/填埋场5或粗生物气气流2导管内的方式,这增加了另外的气体分离要求。在产生该生物气流2的导管系统内,粗生物气流2具有每立方英尺气体约500英制热量单位(BTU)的热值,并且粗生物气流2还具有在该系统内任何点上最高的硫化合物、二氧化碳、氧气、氮气、非甲烷有机化合物(NMOC)。
将粗生物气流2进料到将无机硫化合物硫化氢(H2S)氧化为元素硫或硫酸盐(一种更安全和易管理的化合物)的一个液体硫洗涤器或一个硫吸附器单元3中。
该H2S分离单元3可以是使用嗜氧菌作用以将该无机硫化合物硫化氢(H2S)氧化为元素硫或硫酸盐的一个气液硫洗涤器。在另一个方面,如果该H2S分离单元3是一个吸附器,一种固体吸附材料用于捕获H2S。两种单元类型将H2S转化为更安全和更易管理的化合物,并且将硫化合物流4收集并在H2S去除点50上去除。
该主气流流动穿过一个向NMOC吸收单元7进料的硫去除单元主气体流出管道6。该NMOC吸收器是一个气液洗涤器,该气液洗涤器通过使用NMOC选择性吸收到一种布置在NMOC吸收单元7中的海绵溶液中来产生一个第一非甲烷有机化合物(NMOC)流9。气液洗涤器NMOC吸收单元7以连续和或分批模式吸收NMOC,使用NMOC蒸汽压、温度和选择性吸收以吸收和收集在压力和/或温度控制的海绵溶液中呈液体的NMOC。含有该吸收的NMOC的海绵溶液通过压力和/或温度进行再生,并且将所得到的NMOC液流9从该体系中去除并且作为一种低级燃料在一个NMOC去除点10上储存。
该主气流经由NMOC吸收单元主气体流出管道11继续其下游流动穿过系统100,NMOC吸收单元主气体流出管道11向一个NMOC吸附单元12进料。NMOC吸附单元12是一个捕获在该固体吸附材料的表面上和多个孔内的NMOC的固体吸附床。使用温度和或压力通过基于NMOC脱附特性的吸附材料的再生将该NMOC从该吸附材料的表面和孔中去除,以便从而产生一个第二非甲烷有机化合物(NMOC)流14,将该第二非甲烷有机化合物(NMOC)流收集并且从该体系中去除并且作为一种低级燃料在NMOC去除点10储存。
该主气流经由NMOC吸附单元主气体流出管道15继续从NMOC吸附单元12向下游流动,NMOC吸附单元主气体流出管道15向至少一个CO2、N2、O2气体分离单元16进料。自气体分离单元16所得到的产物气流17相对于流动穿过NMOC吸附单元流出管道15并且进入气体分离单元16的主气流,富含甲烷并且贫二氧化碳、氧气、氮气、和NMOC。气体分离单元16还可以产生一个再循环流160,将再循环流160向下游进料回到一个较早的分离步骤。还可以将一个氧气和氮气气体分离步骤包括在气体分离单元16中,以便产生一个富含甲烷并且贫二氧化碳、氧气、氮气、和NMOC的产物气流17。优选地,产物气流17具有大于每立方英尺950英制热量单位(BTU)的热值,并且具有足够的品质以允许产物气17被管道输送到至一个天然气网18。气体分离单元16还提供一个被管道输送到一个排气变压吸附单元(VPSAU)20的废气流19。
废气气流19相对于单元16的进气是贫甲烷并且富含二氧化碳、氧气、和氮气的。废气气流19还可以含有少量的甲烷和NMOC。排气变压吸附单元(VPSAU)20收集废气流19中的少量甲烷和NMOC并且形成一个VPSAU再循环流170,将VPSAU再循环流170传送回去并且与在该方法的一个较早步骤中的主气流进行混合。VPSAU再循环流170相对于废气流19是贫二氧化碳、氧气、和氮气的,但富含甲烷和NMOC。VPSAU20还产生一个排出气流21,排出气流21是贫甲烷和NMOC的,但富含被排放到大气22中的厌氧产生的二氧化碳、氧气、和氮气。一个排出气流21气体品质的测试显示相对于在进气导管2的粗生物气气体输入流,存在大于98重量百分比的总非甲烷有机化合物(NMOC)的排放减少。
实例
该实例显示了在宾夕法尼亚州,南方公园(SouthPark)中的废物管理南山填埋场(WasteManagementSouthHillslandfillsite)完成的工作。该实例证明了由系统100处理的粗生物气气流可以成功地进行功能上测试和用文件证明。该测试使用阿美特克(Ametek)Proline型质谱仪作为初级测试仪器以确认气体品质和测试结果。具有粗生物气的废物管理的填埋场,ARC技术公司的现有气体纯化系统由以下各项组成:一个H2S洗涤器、一个收集并液化该NMOC的非甲烷有机化合物(NMOC)吸收单元、一个收集并液化该NMOC的非甲烷有机化合物(NMOC)吸附床单元、一个将甲烷和NMOC收集/返回至该气体纯化系统的入口的新增的试验排气变压吸附单元(VPSAU)、以及压缩和所有相关联的管道/控制装置。该排气变压吸附单元(VPSAU)也允许将厌氧产生的二氧化碳和空气从该生物气气体纯化方法和系统中排放。
根据这些测试,将一个粗生物气气流经由一个气体收集系统从生物气来源(填埋场)中进行回收。该粗生物气气流是大约54摩尔百分比甲烷、38摩尔百分比二氧化碳、4摩尔百分比氮气、0.4摩尔百分比氧气、约4000ppmv的非甲烷有机化合物(NMOC)、60ppm的硫化合物,并且被水蒸汽饱和。该粗生物气气流的流量是大约每天800,000立方英尺。该测试使用在这些质量数内的质谱仪质量数72至92,以及84峰值点,以便总结给出5.446488545E-11安培的总粗气体NMOC实例的峰电流值。
在通过系统100处理该粗生物气气流后,将该NMOC液流收集,从该场所去除,并且被宾夕法尼亚州批准用作一种低级加热燃料。来自该NMOC洗涤器的离开气体具有NMOC上的减少,这由在24小时的时间段内从该吸收单元中去除3.8加仑量的液体证明。
来自该NMOC洗涤器的离开气体具有NMOC上的减少,这由从该NMOC吸附床(对于20天的时间段是活性的)的一次再生循环中去除55加仑量的液体证明。
使用在这些质量数内的质谱仪质量数72至92以及同样的84峰值点测试VPSAU20上的排出气体并且总结给出9.16398E-13安培的总排出气体NMOC实例的峰电流值。9.16398E-13(排出气体NMOC)/5.446488545E-11(粗气体NMOC)=该粗气体NMOC的1.68E-02或1.68百分比安培,这相对于进气导管2上的粗生物气气流是98.3百分比的总非甲烷有机化合物(NMCC)的减少。从可商购的单独部件形成系统100,这些单独部件,当如上所述的进行组合时,将会将填埋场气体转化为一种可以被进料到一个天然气网中的可用的天然气。可以将该系统建造在一个填埋场、废气场、或诸如此类。
应该理解,本发明不限于以上所述的这些实施例,而包括在以下权利要求书的范围内的任何和所有实施例。
Claims (19)
1.一种用于从生物气中分离和纯化甲烷的方法,包括以下步骤:
收集一个粗生物气流,该粗生物气流包括至少甲烷、二氧化碳、水、硫化氢、以及非甲烷有机化合物(NMOC);
进行一个粗生物气流分离程序,在其中将该粗生物气流分离成一个硫化合物流和一个主气流,将该硫化合物流从进一步处理中去除,将该主气流从该硫化氢中纯化;
从该主气流中吸收一个非甲烷有机化合物(NMOC)液流,将该NMOC液流从进一步处理中去除,将该主气流从这些非甲烷有机化合物中实质性地纯化;
从该主气流中吸附一个非甲烷有机化合物(NMOC)液流,将该NMOC液流从进一步处理中去除,将该主气流从这些非甲烷有机化合物中实质性地纯化;
进行一个主气流分离程序,在其中将该主气流分离成一个实质上由二氧化碳、氮气和氧气组成的废气流、以及一个实质上由纯化的甲烷气体组成的产物流;
进行一个废气流吸附程序,从而形成一个排出气流和一个再循环流;
将该排出气流排放到大气中,相对于粗生物气气体输入流,存在大于98重量百分比的总非甲烷有机化合物(NMOC)的排放减少;并且
在进行一个粗生物气流分离程序的步骤之后并且在吸收一个第一非甲烷有机化合物(NMOC)液流的步骤之前,将该再循环流与该主气流进行混合。
2.根据权利要求1所述的一种用于从生物气中分离和纯化甲烷的方法,其中,所述进行一个主气流分离程序的步骤进一步包括在进行一个粗生物气流分离程序的步骤之后并且在吸收一个第一非甲烷有机化合物(NMOC)液流的步骤之前,产生一个再循环流和将该再循环流进料到该主气流中的步骤。
3.根据权利要求1所述的用于从生物气中分离和纯化甲烷的方法,进一步包括在所述进行一个主气流分离程序的步骤之前,从该主气流中吸收一个非甲烷有机化合物(NMOC)液流的步骤,将该NMOC液流从进一步处理中去除,通过去除这些吸收的非甲烷有机化合物使该主气流部分地纯化。
4.根据权利要求3所述的用于从生物气中分离和纯化甲烷的方法,其中,所述NMOC吸收步骤进一步包括以下步骤:
利用一种海绵溶液来吸收该NMOC;并且
使随该NMOC流和该海绵溶液的蒸汽点压力而变的海绵溶液热力学上再生。
5.根据权利要求1所述的用于从生物气中分离和纯化甲烷的方法,其中,所述进行一个废气流吸附程序的步骤进一步包括迫使所述废气流与纳米孔的和或微孔的吸附性材料相接触的步骤,这些吸附性材料对于甲烷和非甲烷有机化合物(NMOC)具有选择性并且对于二氧化碳、氧气和氮气不具有选择性。
6.根据权利要求1所述的用于从生物气中分离和纯化甲烷的方法,其中,所述粗生物气流分离程序进一步包括使用一种固体吸附材料来捕获该硫化氢(H2S)以从该粗生物气流中去除的步骤。
7.根据权利要求1所述的用于从生物气中分离和纯化甲烷的方法,其中,所述粗生物气流分离程序进一步包括使用嗜氧菌作用将包括硫化氢(H2S)的无机硫化合物氧化成元素硫或硫酸盐类以从该粗生物气流中去除的步骤。
8.根据权利要求1所述的用于从生物气中分离和纯化甲烷的方法,其中,所述吸附一个非甲烷有机化合物(NMOC)液流的步骤进一步包括使用这些NMOC的分子对选择性吸附性材料的表面和孔的粘附性的步骤。
9.根据权利要求8所述的用于从生物气中分离和纯化甲烷的方法,进一步包括通过使所述选择性吸附性材料暴露于一种具有温度和压力控制的载体气体而使所述选择性吸附性材料再生,以便使这些NMOC分子对所述选择性吸附性材料的粘附性反向,从而产生一个混合的NMOC气体载体流的步骤。
10.根据权利要求9所述的用于从生物气中分离和纯化甲烷的方法,进一步包括将该NMOC从该混合的NMOC气体载体流中冷凝出来,以便形成一个NMOC液流的步骤。
11.一个用于从生物气流中分离和纯化甲烷的系统,包括:
用于收集一个粗生物气流的装置,该粗生物气流包括甲烷、二氧化碳、水、硫化氢、以及非甲烷有机化合物(NMOC);
用于处理该粗生物气流以将其一部分作为一个主气流传送到下游用于进一步处理的装置;
用于将该非甲烷有机化合物(NMOC)从该主气流中分离的装置;
至少一个CO2、N2、O2气体分离单元,接收来自用于分离这些非甲烷有机化合物的装置下游的主气流,该至少一个CO2、N2、O2气体分离单元产生一个富含甲烷的产物流以及一个富含CO2、N2、O2气体的废气流;
一个排气变压吸附单元(VPSAU),接收该富含CO2、N2、O2气体的废气流,该VPSAU产生一个排出气流和一个VPSAU再循环流;
将该排出气流排放到大气中,相对于粗生物气气体输入流,存在大于98重量百分比的总非甲烷有机化合物(NMOC)的排放减少;以及
用于将该VPSAU上游的VPSAU再循环流进行再循环的装置。
12.根据权利要求11所述的用于甲烷分离和纯化的系统,进一步包括一个布置在所述粗生物气流与所述主气流之间的液体硫洗涤器。
13.根据权利要求11所述的用于甲烷分离和纯化的系统,进一步包括一个布置在该粗生物气流与该主气流之间的嗜氧菌硫氧化器。
14.根据权利要求11所述的用于甲烷分离和纯化的系统,其中,所述用于从所述主气流中分离所述非甲烷有机化合物(NMOC)的装置进一步包括:
用于利用一种海绵溶液来吸收该NMOC的装置;以及
用于使所述随该NMOC流和该海绵溶液的蒸汽点压力而变的海绵溶液热力学上再生的装置。
15.根据权利要求11所述的用于甲烷分离和纯化的系统,其中,所述排气变压吸附单元(VPSAU)进一步包括对甲烷和非甲烷有机化合物(NMOC)具有选择性并且对二氧化碳、氧气、和氮气不具有选择性的吸附性材料。
16.根据权利要求11所述的用于甲烷分离和纯化的系统,其中,所述将该非甲烷有机化合物(NMOC)从该主气流中分离的装置进一步包括用于使用该NMOC的分子对选择性吸附性材料的表面和孔的粘附性来吸附该NMOC的装置。
17.根据权利要求16所述的用于甲烷分离和纯化的系统,其中,所述用于吸附该NMOC的装置进一步包括用于通过将所述选择性吸附性材料暴露于一个具有温度和压力控制的载体气体而使所述选择性吸附性材料再生,从而使该NMOC的粘附性反向,以便形成一个混合的NMOC气体载体流的装置。
18.根据权利要求17所述的用于甲烷分离和纯化的系统,其中,所述用于吸附该NMOC的装置进一步包括用于将该NMOC从该混合的NMOC气体载体流中冷凝出来的装置。
19.根据权利要求11所述的用于甲烷分离和纯化的系统,其中,所述至少一个CO2、N2、O2气体分离单元进一步包括用于产生一个再循环流并且用于将该再循环流进料回至所述一个CO2、N2、O2气体分离单元上游的装置。
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US8568512B2 (en) | 2013-10-29 |
PT2701824T (pt) | 2020-10-19 |
EP2701824B1 (en) | 2020-07-15 |
AU2011366910B2 (en) | 2015-12-24 |
RU2558881C2 (ru) | 2015-08-10 |
US20120276616A1 (en) | 2012-11-01 |
KR20140044807A (ko) | 2014-04-15 |
WO2012148431A1 (en) | 2012-11-01 |
BR112013027793A2 (pt) | 2017-01-10 |
AU2011366910A2 (en) | 2013-11-14 |
AU2011366910A1 (en) | 2013-11-07 |
CA2834700C (en) | 2018-02-13 |
EP2701824A4 (en) | 2014-11-05 |
CN103561844A (zh) | 2014-02-05 |
EP2701824A1 (en) | 2014-03-05 |
ES2823573T3 (es) | 2021-05-07 |
BR112013027793B1 (pt) | 2021-02-09 |
KR101886900B1 (ko) | 2018-09-10 |
RU2013148908A (ru) | 2015-06-10 |
CA2834700A1 (en) | 2012-11-01 |
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