CN102353233B - 煤制气甲烷化后气体深冷分离液化的工艺方法和装置 - Google Patents

煤制气甲烷化后气体深冷分离液化的工艺方法和装置 Download PDF

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CN102353233B
CN102353233B CN201110220788.3A CN201110220788A CN102353233B CN 102353233 B CN102353233 B CN 102353233B CN 201110220788 A CN201110220788 A CN 201110220788A CN 102353233 B CN102353233 B CN 102353233B
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nitrogen
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heat exchanger
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周勇
阴红兵
黄顺泰
王磊
彭正春
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Chengdu Shuyuan Coal & Basic Energy Technology Co Ltd
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Abstract

本发明提供了煤制气甲烷化后的气体处理的方法和装置。煤制气甲烷化后的气体经净化处理后的组分主要为：H2、CH4及少量的N2、Ar、CO等杂质。本发明根据其中H2含量的多少来选择不同的工艺流程：如果其中H2含量较小，采用本发明在洗涤塔内将CH4提取和液化成LNG，而主要成分为H2和N2的气体作为驰放气。如果H2含量较多，采用该工艺可以为后续工艺提供合格的氢气，或者为合成氨工艺提供H2:N2比3:1的合成气。

Description

煤制气甲烷化后气体深冷分离液化的工艺方法和装置
技术领域
本申请涉及煤制气的深冷分离领域，具体的说，属于煤制气经初步处理后进一步深冷分离的领域。 
背景技术
 天然气与煤炭、石油并称目前世界一次能源的三大支柱。随着国民经济的发展对天然气的需求量急剧增长，目前国内天然气大量依赖进口；而我国是多煤少气的国家，为了弥补天然气的缺口，最近许多的煤化工企业采用煤制气甲烷化的方法制取主要成分为H2、CH4的气体，对于没有管输条件的企业就需将该部分气体中的CH4深冷分离液化成LNG以及后续工艺系统需要的合成气。 
发明内容
 煤制气甲烷化后的气体经净化处理后的组分主要为：H2、CH4及少量的N2、Ar、CO等杂质。如果其中H2含量较小，采用本发明在洗涤塔内将CH4提取和液化成LNG，而主要成分为H2和N2的气体作为驰放气。如果H2含量较多，采用该工艺可以为后续工艺提供合格的氢气，或者为合成氨工艺提供H2:N2比3:1的合成气。
 本发明为了提高后续合成氨的合成率和避免CH4、Ar在合成回路的循环累积；并且减少后续工艺的驰放气排放量和减少合成气压缩机的功耗，达到既环保又节能的目的，同时还可以生产LNG。为了达到此目的，本发明采用如下技术方案：
一种煤制气甲烷化后气体深冷分离液化的方法，其包括以下步骤：
A、        将BOG气体经换热器加热后送往BOG压缩机压缩，所得到的气体与经净化后的原料气混合后形成混合气体；
B、         上述混合气体经上述换热器冷却后形成气液混合物；
C、        上述气液混合物被送往气液分离器中进行气液分离，分离出的气相物流送往氮洗塔I下部，分离出第一LNG产品；
D、        上述送往氮洗塔I中的气相物流在氮洗塔I中洗涤后于塔底引出第二LNG产品，第二LNG产品与上述第一LNG产品混合，经换热器过冷后输出。
该方法还包括：
E、在氮洗塔I顶部引出H2/N2混合气，该H2/N2混合气被送入氮洗塔II下部；
F、氮洗塔II顶部的回流液为经过冷的液氮，通过调整进塔的液氮量，使氮洗塔II塔顶输出的H2/N2混合气满足合成氨的要求；
G、上述H2/N2混合气经上述换热器加热后输出；
H、在上述氮洗塔II底部引出的液氮经上述换热器加热后输出。
进一步包括：
I：氮洗塔I顶部的回流液为经过冷的液氮，通过调整进塔的液氮量，保证塔顶的回流比范围为0.06-0.1，使上述氮洗塔I顶部引出的H2/N2混合气中CH4的含量小于0.5%（体积百分比），塔底引出的第二LNG产品含氮量低于1%（质量百分比）。
进一步包括：
J：在上述C步骤进行之前，上述气液混合物被送入J-T阀中节流；
K：氮洗塔I顶部的回流液为经过冷的液氮；在氮洗塔I顶部引出的H2/N2混合气经上述换热器复热后输出。
另一种煤制气甲烷化后气体深冷分离液化的方法，包括步骤：
A、将BOG气体经换热器加热后送往BOG压缩机压缩，所得到的气体与经净化后的原料气混合后形成混合气体；
B、上述混合气体经上述换热器冷却后形成第一气液混合物；
C、上述第一气液混合物被送往第一气液分离器中进行气液分离，分离出的气相物流送往CH4精馏塔下部，分离出第一LNG产品；
D、上述送往CH4精馏塔中的气相物流在CH4精馏塔中洗涤后于塔底引出第二LNG产品，第二LNG产品与上述第一LNG产品混合，经换热器过冷后输出。
上述方法还包括：
E、在上述CH4精馏塔上部引出CH4 / H2混合气，上述CH4 / H2混合气与经过冷后的液氮热交换后形成第二气液混合物，第二气液混合物输入第二气液分离器，分离出的液体作为回流液输入CH4精馏塔顶部，分离出的氢气经上述换热器加热后输出；
F、氮洗塔顶部的回流液为经过冷的液氮，通过调整进塔的液氮量，保证塔顶的回流比小于0.4，使上述氮洗塔I顶部引出的H2/N2混合气中CH4的含量小于0.5%（体积百分比），塔底的LNG产品含氮量小于1%（质量百分比）；
G、在上述C步骤进行之前，上述气液混合物被送入J-T阀中节流到氮洗塔的工作压力。
在上述两种方法的步骤B中，经换热器冷却后的气液混合物温度为-155℃至-163℃。
另外，为了达到上述目的，本发明还提供了一种煤制气甲烷化后气体深冷分离液化装置，包括换热器、第一气液分离器、第一氮洗塔，第一J-T阀，其特征在于：
换热器包括多个流体通道；
第一气液分离器入口连接上述换热器，其上部出口连接第一氮洗塔底部，下部出口连通上述换热器；
第一氮洗塔下部出口连接上述换热器；
第一J-T阀入口连接上述换热器，出口连接第一氮洗塔上部。
上述装置还包括第二氮洗塔；上述第一氮洗塔的上部出口连接第二氮洗塔。
还提供了另外一种煤制气甲烷化后气体深冷分离液化装置，包括换热器，第一气液分离器、第二气液分离器、CH4精馏塔，其特征在于：
换热器包括多个流体通道；
第一气液分离器入口连接上述换热器，其上部出口连接CH4精馏塔底部，下部出口连通上述换热器；
CH4精馏塔上部入口通过一个J-T阀连接上述换热器，其下部出口连通上述换热器，CH4精馏塔中部出口连通设置于顶部的冷凝器入口，上述冷凝器出口连通第二气液分离器；
第二气液分离器上部出口连通上述换热器，下部出口连通上述CH4精馏塔中部。
在本发明中，由于进入氮洗塔Ⅰ的原料气先经汽液分离器分离后气相进氮洗塔Ⅰ，这样可以降低氮洗塔的设计、制造难度和塔的高度 。
而通过调节进塔的液氮量可控制氮洗塔Ⅰ顶部的H 2 /N 2 混合气中CH 4 含量＜0.5%（体积百分比），这是利用H 2 和CH 4 的沸点相差较大的原理，绝大部分CH 4 就溶解到液相中成LNG产品，少部分CH 4 随氮洗塔Ⅰ塔顶粗合成气进入氮洗塔Ⅱ，从而可以保证CH 4 的收率和减少驰放气的排量。
氮洗塔Ⅱ也是利用H 2 和CH 4 、CO、Ar的沸点相差较大的原理，通过调节进塔的液氮量,将CH 4 、CO、Ar从气相中溶解到液氮中，从而控制氮洗塔Ⅱ的顶部的H 2 /N 2 混合气中CH 4 、CO、AR杂质含量满足合成氨工艺的要求。
在换热系统内可以根据需要设置回收储罐BOG气体冷量的通道。复热后的BOG气体通过BOG压缩机增压后并入原料气进冷箱管道，这样能提高系统的CH 4 收率和减少系统的排放量，达到环保节能的目的。
氮气压缩机的出口压力需保证＞3.4MPa，并且大于原料气进冷箱的压力，这样换热器温差拟合好，能耗低。
附图说明
附图1  为本发明实施例一的流程图
附图2 为本发明实施例二的流程图
附图3 为本发明实施例三的流程图
E601：换热器             T601: 氮洗塔Ⅰ          MRC701:混合冷剂压缩机             
V601/2：汽液分离器         T602: 氮洗塔Ⅱ          WE701/2:压缩机末级冷却器
NC601:循环氮压机           P701：混合冷剂泵     
V701:汽液分离罐            C602: BOG压缩机
具体实施方式
煤制气甲烷化后的气体经净化处理后的组分主要为H2、CH4，以及少量的N2、Ar、CO等杂质。根据原料气中的H2含量的不同，以及后续工艺目的的不同，本发明采用了以下三个不同的实施例。
实施例一（当原料气中含H 2 量高，后续工艺为合成氨时）
如附图1所示，从上游净化系统来的原料气1与冷箱内复热出来的BOG气体（BOIL OF GAS 蒸发气体）25经BOG压缩机压缩后形成的气体2（冷箱内设置有BOG通道）混合后形成气体物流3进入冷箱内的换热器E601，在其中冷却到一定温度出换热器形成气液混合物4，经过汽液分离器V601分离后气相物流6进入氮洗塔Ⅰ T601下部，气液分离器底部分离出的LNG液体5与氮洗塔Ⅰ T601底部引出的LNG液体8混合后作为LNG产品9，LNG产品9可以经过J-T阀V-1B节流后进换热器E601，在换热器中过冷后出冷箱去LNG储罐，也可以不经换热器E601过冷而通过J-T阀V1-A送出冷箱去LNG储罐。氮洗塔Ⅰ T601顶的回流液10来自经换热系统E601冷却、液化、过冷的液氮；氮洗塔Ⅰ利用H 2 和CH 4 的沸点相差较大的原理，绝大部分CH 4 就溶解到液相中成LNG产品，少部分CH 4 随氮洗塔Ⅰ T601塔顶引出的粗合成气7带出（主要含量为H 2 、N 2 ，还含有少量CH 4 、CO、Ar等杂质,不符合合成氨工艺的要求），其回流比需控制在0.06-0.1。粗合成气7引入氮洗塔Ⅱ T602下部，利用H 2 和CH 4 、CO、Ar的沸点相差较大的原理，通过调节进塔的液氮量,将CH 4 、CO、Ar从气相中溶解到液氮中，从而控制氮洗塔Ⅱ T602的顶部输出的H 2 /N 2 混合气11中CH 4 、CO、AR杂质含量满足合成氨工艺的要求，为了控制H2/N2混合气的质量（含CO+O 2 ＜5PPm,CH 4 +Ar＜20PPm），塔顶的回流比需大于0.1。氮洗塔Ⅱ T602的顶部的H 2 /N 2 混合气11经换热器E601复热后形成气体15，气体15再与空分氮压机来的压力氮气22汇合后配置成H 2 :N 2 比例合格的合成气16，合成气氢氮比调节可通过调节压力氮气22的流量来最终实现；氮洗塔Ⅱ T602底部的液体13（主要为N 2 ）经J-T阀节流后再经换热器E601复热形成废氮气14后输出冷箱供用户使用。
产品9可以经过V-1B进换热器E601过冷后23出冷箱去LNG储罐，也可以不在换热器E601内过冷经V1-A 23出冷箱去LNG储罐。
从储罐来的BOG气体24经换热器E601复热后形成物流25进入BOG压缩机压缩，压缩后的气体2汇入原料气进冷箱管线。
空分的低压高纯氮气经氮气压缩机NC601压缩到压力＞3.4MPa（大于原料气进冷箱的压力）形成氮气物流17，经压缩机末级冷却器WE702水冷后形成氮气18进入换热器E601,在其中冷却、液化、过冷后的液氮19分两路，其中一路20经J-T阀节流后形成物流10作为氮洗塔Ⅰ T601的回流液，将上升气中的大部分CH4洗涤溶解到液相中；另一路21经J-T阀节流后形成的物流12作为氮洗塔Ⅱ T601的回流液，将杂质N 2 、Ar、CO等溶解到液氮中。液氮同时起到J-T效应制冷的作用及配入部分氮气的作用。
本实施例由于采用2级氮洗塔，因此既能保证LNG产品的质量（含Ar+ N 2 ＜1%）,又能保证合成气产品的质量（含CO+O 2 ＜5PPm,CH 4 +Ar＜20PPm）,同时也保证H2 、CH 4 吸收率＞99%。
 实施例二（原料气中含H 2 量低、只产LNG）
如附图2所示，从上游净化系统来的原料气201与冷箱内复热出来的BOG气体217经BOG压缩机压缩后形成的气体202（冷箱内设置有BOG通道）混合后形成气体203，气体203进入冷箱内的换热系统E601冷却到一定温度出换热器形成气液混合物204，该气液混合物经J-T阀节流到氮洗塔I的工作压力，再经过汽液分离器V601分离后气相206进入氮洗塔I T601下部，分离器底部LNG液体205与氮洗塔ⅠT601底部的LNG液体208混合后作为LNG产品209。氮洗塔I T601顶的回流液210来自经换热系统E601冷却、液化、过冷的液氮，其回流比小于0.4，氮洗塔利用H 2 和CH 4 的沸点相差较大的原理，绝大部分CH 4 就溶解到液相中成LNG产品，少部分CH 4 随氮洗塔I T601塔顶引出的气体207带出（主要是H 2 、N 2 ）。氮洗塔I T601的顶部的H 2 /N 2 混合气207中，CH4含量小于0.5%（体积百分比），经J-T阀节流后通过换热器E601复热后214出冷箱供用户使用。在工作过程中，氮洗塔I塔内的工作压力控制在1MPa左右，尤其是0.95-1.05MPa。
 LNG产品209可以经过J-T阀V-1B节流后进换热器E601，在换热器中过冷后出冷箱去LNG储罐，也可以不经换热器E601过冷而通过J-T阀V1-A送出冷箱去LNG储罐。
从储罐来的BOG气体216经换热器E601复热后气体217进入BOG压缩机压缩后的气体202）汇入原料气进冷箱管线。
空分的低压高纯氮气经氮气压缩机NC601压缩到的氮气212的压力＞3.4MPa（并且大于原料气进冷箱的压力）并经水冷却器冷却后以氮气213进入换热器E601,在其中冷却、液化、过冷后的液氮211经J-T阀节流后210作为氮洗塔I T601的回流液，将上升气中的大部分CH4洗涤溶解到LNG液体中。
    本实施例由于在进汽液分离器前设置J-T阀控制阀后压力；既可以控制LNG产品中的Ar+ N 2 ＜1%（质量百分比），保证LNG产品的质量，又保证氮洗塔需要的液氮量最小，减少氮气压缩的功耗。
实施例三（原料气中含H 2 量高、后续工艺需要较高纯度H 2 ）
如图3所示，从上游净化系统来的原料气301与冷箱内复热出来的BOG气体319经BOG压缩机压缩后的气体302（冷箱内设置有BOG通道）混合后形成气体303，气体303进入冷箱内的换热系统E601冷却到一定温度出换热器形成气液混合物304，经过汽液分离器V601分离后气相306进入CH 4 精馏塔I T601下部，分离器底部LNG液体305与氮洗塔ⅠT601底部的LNG液体308混合后作为LNG产品309。LNG产品309可以经过J-T阀V-1B节流后进换热器E601，在换热器中过冷后出冷箱去LNG储罐，也可以不经换热器E601过冷而通过J-T阀V1-A送出冷箱去LNG储罐。
送入CH 4 精馏塔I T601的物流306（主要组分CH 4 和H 2 ）,在CH 4 精馏塔I T601内进行传热传质；在塔底获得合格的LNG液体产品308；在塔顶部分气体经冷凝器K601冷凝后并经气液分离器V603分离出的液体作为CH 4 精馏塔的回流液，未冷凝的气体307（主要组分H 2 ）经换热器复热后形成氢气317去用户使用。
冷凝器K601的冷源采用独立氮循环的液氮作为冷凝器的冷源，蒸发后的氮气复热后并入循环氮气压缩机入口。补充氮气从空分系统来经氮气压缩机NC601压缩后形成氮气310，其压力＞3.4MPa（并且大于原料气进冷箱的压力），氮气310经冷却器冷却后形成氮气311，进换热系统E601冷却、液化、过冷后液氮312经J-T阀节流后形成液氮313并为冷凝器K601提供冷量，液氮313在冷凝器中蒸发成气氮314，并经换热器复热后形成气氮315并入循环氮压机NC601的入口。
从储罐来的BOG气体318经换热器E601复热后形成的气体319进入BOG压缩机压缩后形成的气体302汇入原料气进冷箱管线。
 上述三个实施例中的氮洗塔Ⅰ T601、氮洗塔Ⅱ T602和CH 4 精馏塔可以采用填料塔或筛板塔；冷箱的换热器E601由一台或多台铝制板式换热器组成
上述三个实施例的冷量大部分由下面的系统获得：
1）氮气膨胀制冷和系统等温节流效应；
2) 氮气膨胀制冷和闭式混合冷剂制冷循环组合的方式；
3)闭式混合冷剂制冷循环和氮气制冷循环组合的方式；
4)外部引入液氮冷源。
 需要申明的是，本发明的说明书中的内容是为了更好的解释权利要求而非限制权利要求的保护范围，本发明所要求保护的范围以权利要求书为准，此外本领域技术人员在参考了说明书内容的基础上所做出的不必付出创造性劳动的改动也应落入本发明所要求保护的范围。

Claims (6)

1.一种煤制气甲烷化后气体深冷分离液化的方法，其包括以下步骤：
A、将BOG气体经换热器加热后送往BOG压缩机压缩，所得到的气体与经净化后的原料气混合后形成混合气体；
B、上述混合气体经上述换热器冷却后形成气液混合物；
C、上述气液混合物被送往气液分离器中进行气液分离，分离出的气相物流送往氮洗塔I下部，分离出第一LNG产品；
D、上述送往氮洗塔I中的气相物流在氮洗塔I中洗涤后于塔底引出第二LNG产品，第二LNG产品与上述第一LNG产品混合，经换热器过冷后输出。
2.如权利要求1所述的煤制气甲烷化后气体深冷分离液化的方法，其还包括：
E、在氮洗塔I顶部引出H2/N2混合气，该H2/N2混合气被送入氮洗塔II下部；
F、氮洗塔II顶部的回流液为经过冷的液氮，通过调整进塔的液氮量，使氮洗塔II塔顶输出的H2/N2混合气满足合成氨的要求；
G、上述H2/N2混合气经上述换热器加热后输出；
H、在上述氮洗塔II底部引出的液氮经上述换热器加热后输出。
3.如权利要求1所述的煤制气甲烷化后气体深冷分离液化的方法，其还包括：
I：氮洗塔I顶部的回流液为经过冷的液氮，通过调整进塔的液氮量，保证塔顶的回流比范围为0.06-0.1，使上述氮洗塔I顶部引出的H2/N2混合气中CH4的含量小于0.5%（体积百分比），塔底引出的第二LNG产品含氮量低于1%（质量百分比）。
4.如权利要求1所述的煤制气甲烷化后气体深冷分离液化的方法，其还包括：
J：在上述C步骤进行之前，上述气液混合物被送入J-T阀中节流；
K：氮洗塔I顶部的回流液为经过冷的液氮；在氮洗塔I顶部引出的H2/N2混合气经上述换热器复热后输出。
5.一种煤制气甲烷化后气体深冷分离液化的方法，包括步骤：
A、将BOG气体经换热器加热后送往BOG压缩机压缩，所得到的气体与经净化后的原料气混合后形成混合气体；
B、上述混合气体经上述换热器冷却后形成第一气液混合物；
C、上述第一气液混合物被送往第一气液分离器中进行气液分离，分离出的气相物流送往CH4精馏塔下部，分离出第一LNG产品；
D、上述送往CH4精馏塔中的气相物流在CH4精馏塔中洗涤后于塔底引出第二LNG产品，第二LNG产品与上述第一LNG产品混合，经换热器过冷后输出。
6.如权利要求1-5之一所述的煤制气甲烷化后气体深冷分离液化的方法，其还包括：在步骤B中，经换热器冷却后的气液混合物温度为-155℃至-163℃。
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