CN116753675A - 一种适用于地下煤制气分级提纯与液化的方法 - Google Patents

一种适用于地下煤制气分级提纯与液化的方法 Download PDF

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Publication number
CN116753675A
CN116753675A CN202310358339.8A CN202310358339A CN116753675A CN 116753675 A CN116753675 A CN 116753675A CN 202310358339 A CN202310358339 A CN 202310358339A CN 116753675 A CN116753675 A CN 116753675A
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underground coal
coal gas
hydrogen
helium
refrigeration system
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CN202310358339.8A
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Inventor
刘恩斌
鲁绪栋
郝天舒
李茜
周廉乐
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Southwest Petroleum University
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Southwest Petroleum University
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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
    • F25J3/0204—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 characterised by the feed stream
    • F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • 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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0005—Light or noble gases
    • F25J1/001—Hydrogen
    • 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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/0035—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work
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    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/005—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by expansion of a gaseous refrigerant stream with extraction of work
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    • F25J1/02—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
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    • F25J1/0239—Purification or treatment step being integrated between two refrigeration cycles of a refrigeration cascade, i.e. first cycle providing feed gas cooling and second cycle providing overhead gas cooling
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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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    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0281—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc. characterised by the type of prime driver, e.g. hot gas expander
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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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
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    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/902—Details about the refrigeration cycle used, e.g. composition of refrigerant, arrangement of compressors or cascade, make up sources, use of reflux exchangers etc.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
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Abstract

本发明公开了一种地下煤制气分级提纯与液化的方法，将地下煤制气的气体分离与液化集成，提出了一种从地下煤制气中制取液氢和压缩液化天然气的方法，该方法包括以下步骤：(1)将地下煤制气预冷后，送入一级氦循环膨胀制冷系统，经进一步降温后送入精馏塔中；(2)由精馏塔底部排出的甲烷直接作为压缩液化天然气进行储存。由精馏塔顶部排出的氢气和一氧化碳，送入二级氦循环膨胀制冷系统，经进一步降温后送入两相分离器中。(3)由两相分离器底部排出的一氧化碳对地下煤制气进行预冷。由两相分离器顶部排出的氢气，经三级氦循环膨胀制冷系统降温和正仲态转化后，送入液氢储罐中储存。本发明有效提高了地下煤制气的利用效率和经济效益。

Description

一种适用于地下煤制气分级提纯与液化的方法
技术领域
本发明属于地下煤制气综合利用技术领域，涉及一种利用氦气膨胀制冷分离与液化地下煤制气的方法。
背景技术
传统的煤炭开采方法，投资高、效率低、安全性差和污染大。因此，“煤炭地下气化”这一技术近年来吸引了广泛的关注。
煤炭地下气化是指将处于地下的煤炭进行有控制的燃烧，形成甲烷(CH4)、氢气(H2)和一氧化碳(CO)等可燃气体的过程。该技术的成熟对我国能源利用有着众多优势。煤炭地下气化技术不仅可以回收矿井遗弃的煤炭资源，而且还可以用于开采井工难以开采或开采经济性、安全性较差的薄煤层、深部煤层、“三下”压煤和高硫、高灰、高瓦斯煤层。煤地下气化技术在地下作业，可有效避免煤矿开采带来的生态环境问题，提高资源利用效率。传统的开采方式仅能采出煤炭储量的15％左右，且伴随着地表沉降、工作环境危险、机械耗能高、透水、瓦斯气等不利因素，相反，煤地下气化能使闲置地下煤炭资源充分利用且安全性得到了提高。
煤炭地下气化产生的气体称为地下煤制气，地下煤气中一般含有H2、CO2、CO、CH4，另外还有少量C2H6、苯、甲苯以及对二甲苯等，含有的组分复杂，且有较多无用气体。目前地下煤制气主要是用于发电，这种利用方式效率低，经济效益差。地下煤制气也可以化工产品的原料气，用于制甲烷、制甲醇和制油等。但是化工产品的原料气一般对氢碳比有一定的要求，例如：制甲烷的原料气中氢碳比需控制在2.97～3.06之间。而煤炭地下气化不能很好的控制地下煤制气中的氢碳比，所以将地下煤制气作为化工产品的原料气不一定可行。因此为了有效利用地下煤制气，提高地下煤制气的利用效率和经济价值，可以对地下煤制气进行分级提纯，以得到纯组分进行利用。未来中深层煤炭地下富氧气化/富氧-水蒸气气化是发展重点，它产生的地下煤制气以甲烷和氢气为主。因此，煤炭地下气化技术的成熟可以实现中国天然气和氢气产量的跨越式增长，具有较好的经济效益和环境效益。
地下煤制气从井口出来以后，通常要经过预处理、水洗和脱酸气等单元，这些单元可以有效脱除地下煤制气中的杂质。经过处理的地下煤制气通常只含有CH4、H2和CO等三种气体。利用氦膨胀制冷系统、精馏塔和两相分离器等可以将三种气体进行分离，得到液氢(LH2)、压缩液化天然气(PLNG)，这样便于储存和运输。而分离出来的CO可以作为燃料气。利用地下煤制气制取氢气具有能耗优势，同时得到的CH4和H2都是中国目前大力发展的清洁能源。
发明内容
针对现有的地下煤制气利用方式存在效率低，经济效益差，同时地下煤制气中的氢碳比难以控制等问题。本发明提供了一种利用氦气膨胀制冷分离和液化地下煤制气的方法，开发了一种从地下煤制气中分离氢气和甲烷并将它们液化的工艺流程。该流程适用于经过净化处理的，只含有氢气、甲烷和一氧化碳三种组成的地下煤制气。该流程涉及一种带有精馏模块和两相分离模块的低温气体分离与液化的技术，用于对地下煤制气进行气体分离和液化，通过利用氦气作为低温工质，建立三级氦膨胀制冷低温循环为地下煤制气的液化提供冷量，其中每级氦膨胀制冷低温循环相对独立，系统中的精馏塔可以将甲烷从地下煤制气中有效分离，系统中的两相分离器可以将氢气和一氧化碳有效分离。地下煤制气经过预冷后进入到一级氦循环膨胀制冷系统降温后，进入精馏塔，从精馏塔底部可分别得到纯度在99.6％以上的加压液化天然气产品。此外一级氦循环膨胀制冷系统为精馏塔中的冷凝器提供冷量，为精馏塔中的再沸器提供热量。氢气和一氧化碳经过二级氦循环膨胀制冷系统冷却后，进入到两相分离器。分离器顶部可以得到纯度在99.99％以上的氢气产品。三级氦循环膨胀制冷系统为第一正仲态转化和第二正仲态转化提供冷能。制冷工质氦为闭式循环。整个系统实现了良好的能量整合，所有的膨胀功均被相应的循环膨胀制冷系统中的压缩机回收利用，精馏塔中的冷凝器和再沸器传递的能量均被系统整合。本发明首次实现了从地下煤制气中得到两种高纯度的液态产品，是地下煤制气利用方面工艺发展的突破。
本发明的目的可以通过以下技术方案实现：
一种适用于地下煤制气分级提纯与液化的方法，该方法包括以下步骤：
1)将地下煤制气预冷后，送入一级氦循环膨胀制冷系统，经过进一步降温后进入到精馏塔中；
2)由精馏塔底部排出的液态甲烷，直接送入到储罐中，作为加压液化天然气(PLNG)进行储存。由精馏塔顶部排出的氢气和一氧化碳进入到二级氦循环膨胀制冷系统，经过进一步降温以后送入到两相分离器中。
3)由两相分离器底部排出的液态CO，对步骤1)中的地下煤制气进行预冷。由两相分离器顶部排出的氢气首先进入膨胀机进行降压降温，然后依次进行第一正仲态转化、第二正仲态转化后，送入液氢储罐进行储存。
步骤3)中，所述的第一正仲态转化和第二仲态转化都由三级氦膨胀制冷系统提供冷量。
步骤1)中，所述的地下煤制气由甲烷、氢气及一氧化碳组成。地下煤制气预先经过净化至只含有甲烷、氢气及一氧化碳。地下煤制气经过预冷后，经过进一步降温至-120℃后，送入精馏塔中。
步骤2)中，所述的加压液化天然气压力为2000kPa。
步骤2)中，所述的氢气和一氧化碳经过进一步降温至-228.8℃后，送入到两相分离器中。
步骤3)中，所述的氢气经过膨胀机降压至500kPa后，送入到三级氦循环膨胀制冷系统。氢气经过三级氦循环膨胀制冷系统降温液化后，进行第一正仲态转化。第一正仲态转化完成后，氢气再次进入三级氦循环膨胀制冷系统。氢气再次经过三级氦循环膨胀制冷系统降温液化后，进行第二正仲态转化。
步骤3)中，所述的第一正仲态转化过程及第二正仲态转化过程均在催化转化器中进行。
所述的一级氦循环膨胀制冷系统、二级氦循环膨胀制冷系统及三级氦循环膨胀制冷系统中的制冷剂均为氦气。本发明中为了生产液氢产品，需要提供极低的冷量，而传统的氮膨胀液化流程无法提供氢气所需的低温，因此采用氦气作为低温工质。三级制冷系统均采用氦气作为制冷剂，可以大大降低系统复杂程度。
所述的一级氦循环膨胀制冷系统、二级氦循环膨胀制冷系统及三级氦循环膨胀制冷系统相互独立，它们之间不会相互影响。
与现有技术相比，本发明的有益之处在于：
(1)本发明充分利用了地下煤制气中富含氢气和甲烷的特点，利用氦气膨胀制冷系统可以从地下煤制气中制取液氢(LH2)和加压液化天然气(PLNG)。通过利用Aspen HYSYS软件模拟计算，证实本发明可实现甲烷和氢气的回收率分别高达99.6％和98.3％。产生的液氢(LH2)和加压液化天然气(PLNG)的纯度分别高达99.99％和99.6％。
(2)本发明将地下煤制气分级提纯与甲烷和氢气液化工艺集成，简化了工艺流程，大幅减少了工艺设备投资。
(3)氢气和甲烷的产品纯度和回收率高，流程适应性强。
(4)分离出的甲烷直接作为加压液化天然气(PLNG)进行储存，加压液化天然气(PLNG)降低了液化和再气化的成本，同时也降低了运输成本。
(5)现有的地下煤制气利用方式以作为燃料气用于发电为主，这种方式的利用效率低。而本发明通过氦循环膨胀制冷系统，低温精馏塔以及两相分离器将地下煤制气中的氢气和甲烷分离出来，得到纯组分进行销售，有效的提高了地下煤制气的利用效率和经济效益。
附图说明
图1为本发明的工艺流程示意图。
其中，E-101-预冷器；E-101、E-102、E-103、E-104-多流股换热器；T-100-精馏塔；V-100-两相分离器；K-100、K-102、K-103、K-105、K-107、K-108-压缩机；K-101、K-104、K-106、K-109-膨胀机；CSTR-101、CSTR-102-催化转化装置；V-101-PLNG储罐；V-102-LH2储罐；AC-100、AC-101、AC-102、AC-103、AC-104、AC-105-水冷器；E-105、E-106、E-107-换热器；VLV-100-节流阀。
图2为原位煤制气进精馏塔的温度与甲烷纯度的关系。
图3为原位煤制气进精馏塔的温度与甲烷回收率的关系。
图4为原位煤制气进精馏塔的温度与一级氦循环膨胀制冷系统能耗的关系。
图5为精馏塔的塔压与甲烷纯度和甲烷回收率的关系。
图6为H2和CO混合气体进两相分离器的温度与两相分离器顶部流出的气相中H2摩尔分率的关系。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。本实施例以本发明技术方案为前提进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1：含甲烷高的地下煤制气分级提纯制取加压液化天然气(PLNG)和液氢(LH2)实例
经过预处理、水洗和脱酸气的地下煤制气气质组成及工况条件：
地下煤制气处理规模：19560Nm3/h；
地下煤制气压力：3800kPa；
地下煤制气温度：-51.72℃；
地下煤制气组成见表1。
表1、地下煤制气组成
地下煤制气组分 CH4 H2 CO
mol％ 62.78 28.13 9.09
本发明提供的地下煤制气分级提纯制取加压液化天然气(PLNG)和液氢(LH2)实例1工艺流程如图1所示，其流程简述如下：
1)将净化后的地下煤制气与分离出来的一氧化碳在换热器E-107进行换热，温度降低至-75℃，随后气体进入到一级氦循环膨胀制冷系统中，温度降至-120℃。该温度是根据图2～4确定的，从图2和图3中可以看出随着温度的降低，甲烷的回收率和纯度在增加。当温度从-110℃降低-120℃时，甲烷的纯度和回收率增加幅度较大，而从-120℃降低-160℃时，甲烷纯度和回收率增加较为平缓。甲烷的纯度和回收率并不是越高越好。因为从图4中可以看出随着温度降低，能耗也在增加。因此，应该在满足产品要求的同时，尽量升高入塔温度。在-120℃时，甲烷纯度和回收率增加幅度开始变平缓，因此选-120℃作为入塔温度。此时混合气体气化率为0.5765，一级氦膨胀低温循环工质压缩终压为1350kPa。
2)将通过步骤1)降温后的地下煤制气引入精馏塔T-100，塔压的确定如图5所示，随着塔压增加产品纯度和回收率在减低，因此确定塔压为2000kPa。从精馏塔底部得到纯度在99.6％以上的甲烷产品，其流量为519.4kmol/h，温度为-108℃，压力为2000kPa，气化率为0。从精馏塔顶部得到氢气与一氧化碳的混合气体，其流量为307.9kmol/h，温度为-175.2℃，压力为2000kPa，气化率为1。
3)将通过步骤2)得到的氢气与一氧化碳混合气体引入二级氦循环膨胀制冷系统，温度降至-228.8℃。该温度是根据图6确定出来的，从图中可以看出，随着温度的降低，气相中氢气的摩尔分率在逐渐增加，直到变成1。氢气的摩尔分率并不是越高越好，因为摩尔分率越高，氢气的损失量也越大。因此，当氢气产品的纯度为99.99％时，气相中氢气的摩尔分率为0.9999即可，此时的温度为-228.8℃。此时混合气体气化率为0.7433，二级氦膨胀低温循环工质压缩终压为800kPa，此过程能耗为4115kW。
4)将通过步骤3)降温得到的氢气与一氧化碳混合气体引入两相分离器V-100中，从分离器底部得到的一氧化碳产品，其流量为79.02kmol/h，温度为-228.8℃，压力为2000kPa。从分离器顶部得到纯度为99.99％的氢气产品，其流量为228.9kmol/h，温度为-228.8℃，压力为2000kPa，气化率为1。
5)将通过步骤4)分离出的氢气引入膨胀机K-106中，降压至500kPa。此时氢气的温度为-238.6℃。
6)将通过步骤5)降压后的氢气引入三级氦循环膨胀制冷系统中，温度降至-240℃，此时氢气的气化率为0.9999。
7)将通过步骤6)降温后的氢气引入催化转化装置CSTR-101进行正仲态转化。
8)将通过步骤7)进行第一次正仲态转化后的氢气再次引入三级氦循环膨胀制冷系统降温液化，温度降至-250℃，此时氢气的气化率为0。
9)将通过步骤8)液化的氢气引入催化转化装置CSTR-102进行第二次正仲态转化。
10)将通过步骤9)转化完成的氢气引入节流阀VLV-100，降压到储存压力300kPa。
11)将通过步骤2)和步骤10)液化后的加压液化天然气和液氢产品引入储罐储存即可。
其中，步骤1)、步骤3)、步骤6)、步骤8)中所述的一级氦循环膨胀制冷系统、二级氦循环膨胀制冷系统及三级氦循环膨胀制冷系统为三个独立的氦膨胀低温制冷循环系统。制冷剂氦为闭式循环，均为带有回热循环的膨胀制冷系统，其中膨胀机的输出功均被其所在的低温循环的压缩机回收利用。三级氦膨胀循环流量分别为4000kmol/h、4050kmol/h、4700kmol/h。
经过模拟计算得出，该利用地下煤制气制取加压液化天然气和液氢工艺流程中，甲烷和氢气回收率分别高达99.65％和98.34％，甲烷和氢气的纯度分别高达99.64％和99.99％。总能耗为17145kWh，相较于利用传统工艺分别制取两种产品，获得相同产量所需能耗约为35000kWh(氢气制取：50kWh/kg，氢气液化：12.5-15kWh/kg，天然气液化：0.7kWh/kg)，能耗降低了51％。
实施例2：含氢气高的地下煤制气分级提纯制取加压液化天然气(PLNG)和液氢(LH2)实例
经过预处理、水洗和脱酸气的地下煤制气气质组成及工况条件：
地下煤制气处理规模：19560Nm3/h；
地下煤制气压力：3800kPa；
地下煤制气温度：-51.72℃；
地下煤制气组成见表2。
表2、地下煤制气组成
地下煤制气组分 CH4 H2 CO
mol％ 30 60 10
本发明提供的地下煤制气分级提纯制取加压液化天然气(PLNG)和液氢(LH2)实例1工艺流程如图1所示，其流程简述如下：
1)将净化后的地下煤制气与分离出来的一氧化碳在换热器E-107进行换热，温度降低至-85℃，随后气体进入到一级氦循环膨胀制冷系统中，温度降至-120℃，此时混合气体气化率为1，一级氦膨胀低温循环工质压缩终压为1350kPa。
2)将通过步骤1)降温后的地下煤制气引入精馏塔T-100，从精馏塔底部得到纯度在99.99％以上的甲烷产品，其流量为248.2kmol/h，温度为-107.6℃，压力为2000kPa，气化率为0。从塔顶得到氢气与一氧化碳的混合气体，其流量为579.1kmol/h，温度为-183.6℃，压力为2000kPa，气化率为1。
3)将通过步骤2)得到的氢气与一氧化碳混合气体引入二级氦循环膨胀制冷系统，温度降至-228.8℃，此时混合气体气化率为0.8499，二级氦膨胀低温循环工质压缩终压为800kPa，此过程能耗为5892kW。
4)将通过步骤3)降温得到的氢气与一氧化碳混合气体引入两相分离器V-100中，从分离器底部得到的一氧化碳产品，其流量为86.91kmol/h，温度为-228.8℃，压力为2000kPa。从分离器顶部得到纯度为99.99％的氢气产品，其流量为228.9kmol/h，温度为-228.8℃，压力为2000kPa，气化率为1。
5)将通过步骤4)分离出的氢气引入膨胀机K-106中，降压至500kPa。此时氢气的温度为-238.6℃。
6)将通过步骤5)降压后的氢气引入三级氦循环膨胀制冷系统中，温度降至-240℃，此时氢气的气化率为0.9999。
7)将通过步骤6)降温后的氢气引入催化转化装置CSTR-101进行正仲态转化。
8)将通过步骤7)进行第一次正仲态转化后的氢气再次引入三级氦循环膨胀制冷系统降温液化，温度降至-250℃，此时氢气的气化率为0。
9)将通过步骤8)液化的氢气引入催化转化装置CSTR-102进行第二次正仲态转化。
10)将通过步骤9)转化完成的氢气引入节流阀VLV-100，降压到储存压力300kPa。
11)将通过步骤2)和步骤10)液化后的加压液化天然气和液氢产品引入储罐储存即可。
其中，步骤1)、步骤3)、步骤6)、步骤8)中所述的一级氦循环膨胀制冷系统、二级氦循环膨胀制冷系统及三级氦循环膨胀制冷系统为三个独立的氦膨胀低温制冷循环系统。制冷剂氦为闭式循环，均为带有回热循环的膨胀制冷系统，其中膨胀机的输出功均被其所在的低温循环的压缩机回收利用。三级氦膨胀循环流量分别为4300kmol/h、5800kmol/h、5500kmol/h。
经过模拟计算得出，该利用地下煤制气制取加压液化天然气和液氢工艺流程中，甲烷和氢气回收率分别高达99.99％和99.15％，甲烷和氢气的纯度分别高达99.99％和99.99％。总能耗为29197kWh，相较于利用传统工艺分别制取两种产品，获得相同产量所需能耗约为65350kWh(氢气制取：50kWh/kg，氢气液化：12.5-15kWh/kg，天然气液化：0.7kWh/kg)，能耗降低了55.3％。

Claims (10)

1.一种适用于地下煤制气分级提纯与液化的方法，其特征在于，该方法包括以下步骤：
1)将地下煤制气预冷后，送入一级氦循环膨胀制冷系统，经进一步降温后送入精馏塔中；
2)由精馏塔底部排出的液态甲烷，直接作为加压液化天然气(PLNG)进行储存。而精馏塔顶部排出的氢气和一氧化碳，进入到二级氦循环膨胀制冷系统，经进一步降温后送入到两相分离器中；
3)两相分离器底部排出的液态一氧化碳对步骤1)中的地下煤制气进行预冷。两相分离器顶部排出的氢气进入膨胀机进行降温降压，随后依次进行第一正仲态转化、第二正仲态转化后，送入液氢储罐中储存；
步骤3)中，所述的第一正仲态转化和第二正仲态转化由三级氦循环膨胀制冷系统提供冷量；
所述的一级氦循环膨胀制冷系统、二级氦循环膨胀制冷系统及三级氦循环膨胀制冷系统之间相互独立。
2.根据权利要求1所述的一种适用于地下煤制气分级提纯与液化的方法，其特征在于，步骤1)中，所述的地下煤制气经过净化预处理，不含有二氧化碳和水，主要由甲烷、氢气和一氧化碳组成。
3.根据权利要求1所述的一种适用于地下煤制气分级提纯与液化的方法，其特征在于，步骤1)中，所述的地下煤制气经进一步降温至-120℃以下后，送入精馏塔中。
4.根据权利要求1所述的一种适用于地下煤制气分级提纯与液化的方法，其特征在于，步骤2)中，所述的甲烷经精馏塔出来以后，压力为2000kPa，直接作为加压液化天然气(PLNG)进行储存。
5.根据权利要求1所述的一种适用于地下煤制气分级提纯与液化的方法，其特征在于，步骤3)中，氢气经膨胀机降温降压后，进入到三级氦循环膨胀制冷系统进行进一步降温，降温完成后进行第一正仲态转化，第一正仲态转化转化完成后，再次进入到三级氦循环膨胀制冷系统进行液化，液化完成后进行第二正仲态转化。
6.根据权利要求1所述的一种适用于地下煤制气分级提纯与液化的方法，其特征在于，步骤2)中，氢气和一氧化碳经进一步降温至-228.8℃后，送入到两相分离器中。
7.根据权利要求1所述的一种适用于地下煤制气分级提纯与液化的方法，其特征在于，步骤3)中，氢气经膨胀机降压至500kPa后，进行第一正仲态转化。
8.根据权利要求1所述的一种适用于地下煤制气分级提纯与液化的方法，其特征在于，步骤1)中，一级氦循环膨胀制冷系统为精馏塔中的冷凝器提供冷量，为精馏塔中的再沸器提供热量，它的特点在于氦气经压缩机压缩后，变成高温高压气体，用于给精馏塔的再沸器提供热量，氦气经膨胀机降压后，变成低温低压气体，先给精馏塔的冷凝器提供冷量，然后在对地下煤制气进行降温。
9.根据权利要求1所述的一种适用于地下煤制气分级提纯与液化的方法，其特征在于，所述的一级氦循环膨胀制冷系统、二级氦循环膨胀制冷系统及三级氦循环膨胀制冷系统中的制冷剂均为氦气。
10.根据权利要求1所述的一种适用于地下煤制气分级提纯与液化的方法，其特征在于，步骤1)中，所述的地下煤制气是经过预处理、水洗和脱酸气的，其温度为-51.72℃，压力为3800kPa。
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