CN108179046A - 一种焦炉煤气制取氢气和lng的方法 - Google Patents

一种焦炉煤气制取氢气和lng的方法 Download PDF

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CN108179046A
CN108179046A CN201810042063.1A CN201810042063A CN108179046A CN 108179046 A CN108179046 A CN 108179046A CN 201810042063 A CN201810042063 A CN 201810042063A CN 108179046 A CN108179046 A CN 108179046A
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唐脯林
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Sichuan Jerry Heng Ri Natural Gas Engineering Co Ltd
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Abstract

本发明提供了一种焦炉煤气制取氢气和LNG的方法，包括以下步骤：电除焦；压缩系统给焦炉煤气增压；利用LNG的BOG气体(所述的BOG气体是指LNG被动受热气化后的气体对原料焦炉煤气进行冷却，更进一步除去焦炉煤气中的焦油、苯、萘等物质；通过TSA工序的预处理，精脱大分子杂质，例如焦油、苯、萘等；通过湿法加干法两级脱硫，脱除焦炉气中的硫化物；经过两段低变，CO与水蒸汽反应转化为CO2和氢气；压缩机加压后用MDEA溶液法脱除二氧化碳，使用膜分离方法分离氢气与甲烷，氢气和甲烷得到分离、浓缩和纯化，分离得到的高浓度甲烷通过脱水、脱汞、液化得到LNG。本发明将焦炉煤气最终转化为利用价值较高的氢气和LNG，充分利用了焦炉煤气所含有的能量，保护了环境。

Description

一种焦炉煤气制取氢气和LNG的方法
技术领域
本发明涉及焦炉煤气处理技术领域，具体地说，是涉及一种焦炉煤气制取氢气和LNG的方法。
背景技术
焦炉煤气，又称焦炉气，可燃成分多，属于高热值煤气，粗煤气或荒煤气。是炼焦用煤在炼焦炉中经过高温干馏后，产出焦炭和焦油产品的同时所产生的一种可燃性气体，是炼焦工业的副产品。其主要成分为氢气(55％～60％)和甲烷(23％～27％)，另外还含有少量的一氧化碳(5％～8％)、C2以上不饱和烃
(2％～4％)、二氧化碳(1.5％～3％)、氧气(0.3％～0.8％))、氮气(3％～7％)及硫化物等。其中氢气、甲烷、一氧化碳、C2以上不饱和烃为可燃组分，二氧化碳、氮气、氧气为不可燃组分。
目前焦炉煤气一部分用来发电，一部分用来生产甲醇和制氢，还有相当一部分直接燃烧和排放，其能量利用率约为55％，在浪费宝贵资源的同时，也对环境造成了极大的污染，所以，对焦炉煤气的处理受到人们的关注。
同时，LNG(液化天然气)是一种清洁、高效的能源。由于进口LNG有助于能源消费国实现能源供应多元化、保障能源安全，而出口LNG有助于天然气生产国有效开发天然气资源、增加外汇收入、促进国民经济发展，因而LNG贸易正成为全球能源市场的新热点。
目前焦炉煤气的应用主要为利用氢气制甲醇或合成氨，或利用甲烷化增产甲烷制LNG，两种方式要么对甲烷的经济价值利用率不高，要么对氢气的利用价值不高，因此本工艺同时产氢气和LNG，同时还将焦炉气中的CO变换增产氢气，实现焦炉煤气经济价值最大化利用。
发明内容
本发明的目的在于克服上述传统技术的不足之处，提供一种焦炉煤气制取氢气和LNG的方法，在提升经济价值的同时，更好的保护环境，减少有害物质的排放。
常规的焦炉气利用一个方面是利用氢气制甲醇或合成氨，其余的气体的作为燃料，利用率低，焦炉气中的20～30％的甲烷只是作为燃料，整个焦炉煤气的经济利用率低，另一方面是将氢气和一氧化碳及二氧化碳甲烷化，增产甲烷，甲烷化没产一标方甲烷需要消耗3～4氢气，而常规的氢气价格约为1元/标方，而甲烷价格在1.5～2.5元/标方，因此经济价值是比较低的，而本工艺同时制取氢气和LNG保证了焦炉煤气的经济价值最大化。
本发明的目的是通过以下技术措施达到的：一种焦炉煤气制取氢气和LNG的方法，其特征在于包括以下步骤：
(8)电除焦，在高压电晕电场中除去原料气中大部分的焦油、苯、萘等液态液滴及水颗粒；
(9)压缩系统给焦炉煤气增压；
(10)利用LNG的BOG气体(所述的BOG气体是指LNG被动受热气化后的气体)对原料焦炉煤气进行冷却，更进一步除去焦炉煤气中的焦油、苯、萘等物质；
(11)通过TSA工序的预处理，精脱大分子杂质，例如焦油、苯、萘等；
(12)通过湿法加干法两级脱硫，脱除焦炉气中的硫化物；
(13)经过两段低变，CO与水蒸汽反应转化为CO2和氢气；
(14)压缩机加压后用MDEA方法脱碳，使用膜分离方法分离氢气与甲烷，氢气和甲烷得到分离、浓缩和纯化，分离得到的高浓度甲烷通过脱水、脱汞、液化得到LNG。
进一步地，使用管式电除焦器进行电除焦，电压范围为40～60KV。
电除焦的效率可以达到95％以上，而且是烟煤冷煤气站中最为普遍采用的方法。相对于电除焦，水洗法在一般冷煤气净化工艺中使用，且效率低；物理吸附法在二级除焦油中采用，而机械脱焦油法目前己经逐步趋于淘汰。此处选用管式电除焦油器，所用电压选取40～60KV。
进一步地，压缩系统给原料气加压到0.5MPa后经过冷却器冷却到40℃，压缩系统使用螺杆压缩机将原料气加压到0.5MPa。
利用螺杆压缩机给焦炉煤气增压，从原料气的0.01～0.015MPa加压至0.5MPa左右，然后经过冷却器冷却至40℃左右进入下一环节。
进一步地，低温BOG气体与焦炉煤气进行换热，将焦炉煤气的温度降到10℃以下，分离焦炉煤气中的水、萘、苯等重组分。
使用LNG的低温BOG气体对原料焦炉煤气进行冷却，利用杂质的不同物理性质，可以将原料气中大部分高碳烃类、苯、萘等重组分在低温下脱除，从而大大降低了原料气预处理系统的投资和运行成本。
进一步地，TSA变温吸附过程中，吸附塔和吸收塔两个塔交替进行吸附与再生过程，利用两塔流程，对焦炉煤气中的焦油、苯、萘等大分子物质进行吸附脱除。
萘是一种能够升华的物质，当焦炉煤气的温度降到萘的露点以下时，萘就会析出，堵塞设备及管道，严重影响设备的生产能力和管道的输送能力；另外，萘还是一种贵重的化学品，所以要脱除煤气中的萘。TSA变温吸附过程，利用两塔流程，两个塔交替进行吸附与再生过程，对焦炉煤气中的焦油、苯、萘等大分子物质进行吸附脱除。
进一步地，湿法加干法两级脱硫过程中，使用先湿法后干法的顺序进行脱硫。
湿法烟气脱硫技术是指吸收剂为液体或浆液。由于是气液反应，所以反应速度快，效率高，脱硫剂利用率高；干法采用固体粉末或颗粒为吸附剂，干法脱硫后具有较高的温度(100℃)，排出后易扩散。此处采用先湿法后干法的结合方法，因为湿法脱硫不能脱去焦炉煤气中的有机硫，但是干法可以，两者结合，可以达到脱除的要求。
进一步地，完成CO转化后清洁的焦炉煤气，用往复式压缩机再次进行压缩，增压到后续过程所需的压力。
完成CO转化后清洁的焦炉煤气，用往复式压缩机再次进行压缩，增压到后续过程所需的压力。
进一步地，经膜分离方法分离出的高浓度甲烷首先利用干燥塔干燥，干燥过程使用两个塔进行交替干燥再生工作，还包括一个再生气预干燥塔，之后利用活性炭塔脱汞，最后用混合冷剂制冷液化，得到LNG。
利用膜分离技术，渗透实现氢气和甲烷的分离。膜分离技术兼有分离、浓缩、纯化和精制的功能，又有高效、节能、环保、分子级过滤及过滤过程简单、易于控制等特征，此技术产生了巨大的经济效益和社会效益。
由于采用了上述技术方案，与现有技术相比，本发明的优点是：将焦炉煤气最终转化为利用价值较高的氢气和LNG，充分利用了焦炉煤气所含有的能量，保护了环境。
下面结合附图和具体实施方式对本发明作进一步说明。
附图说明
附图1是本发明一种焦炉煤气制取氢气和LNG的方法的工艺流程示意图。
其中，1-氢气，2-LNG，3-脱水，4-脱汞，5-液化，6-MDEA溶液法脱除二氧化碳，7-TSA变温吸附，8-电除焦。
具体实施方式
实施例：如附图1所示，一种焦炉煤气制取氢气和LNG的方法，包括以下步骤：
(1)电除焦8，使用管式电除焦油器，所用电压选取40～60KV，在高压电晕电场中除去原料气中大部分的焦油、苯、萘等液态液滴及水颗粒；
(2)压缩系统给焦炉煤气增压；
(3)利用LNG的BOG气体(所述的BOG气体是指LNG被动受热气化后的气体)对原料焦炉煤气进行冷却，更进一步除去焦炉煤气中的焦油、苯、萘等物质；
(4)通过TSA工序的预处理，精脱大分子杂质，例如焦油、苯、萘等；
(5)通过湿法加干法两级脱硫，脱除焦炉气中的硫化物；
(6)经过两段低变，CO与水蒸汽反应转化为CO2和氢气1；
(7)压缩机加压后用MDEA溶液法脱除二氧化碳6，使用膜分离方法分离氢气1与甲烷，氢气1和甲烷得到分离、浓缩和纯化，分离得到的高浓度甲烷通过脱水3、脱汞4、液化5得到LNG2。
首先作为原料的焦炉煤气经过电除焦8设备，对其中的焦油进行捕捉清除。经过此设备的处理后，一般会使焦炉煤气中的焦油含量下降到20mg/m3以下。
之后利用螺杆压缩机给焦炉煤气增压，从原料气的0.01～0.015MPa加压至0.5MPa左右，然后经过冷却器冷却至40℃左右进入下一环节。
增压结束，利用低温BOG气体与焦炉煤气进行换热。将焦炉煤气的温度降到10℃以下后，焦炉煤气中的水、萘、苯等重组分就会液化分离，留在分离设备中。利用压差计对分离设备进行检测，当压差过大时，需要对分离设备进行热吹再生。
然后，通过TSA变温吸附7，进一步脱除焦炉煤气中的焦油、苯、萘等大分子的杂质，净化煤气。
将脱除了大分子杂质的焦炉煤气通入脱硫设备，通过湿法和干法的结合，脱除硫化物。湿法烟气脱硫技术是指吸收剂为液体或浆液。由于是气液反应，所以反应速度快，效率高，脱硫剂利用率高；干法采用固体粉末或颗粒为吸附剂，干法脱硫后具有较高的温度(100℃)，排出后易扩散。此处采用先湿法后干法的结合方法，因为湿法脱硫不能脱去焦炉煤气中的有机硫，但是干法可以，两者结合，可以达到脱除的要求。
此时，经过电除焦8、低温脱除杂质，TSA变温吸附7和湿法加干法两级脱硫后焦炉煤气已经比较洁净，电除焦8、低温脱除杂质，TSA变温吸附7和湿法加干法两级脱硫多重工艺结合，可以使焦炉煤气中CO转化为CO2和氢气1之前将焦炉煤气中的高碳烃类、焦油、苯、萘等杂质处理干净，得到纯度浓度较高的CO2和氢气1。通过两段填料塔设备，将煤气中的CO和水蒸气(如果煤气中不够，需要补加)转化为CO2和氢气1。
转化完成后，为了使下面的工序能够顺利进行，此处需要用往复式压缩机对煤气进行再次压缩增压，增压到后续的脱碳工艺所需要的压力。
增压完成后，煤气首先经过脱碳塔，此处选用MDEA溶液法脱除二氧化碳6工艺。脱碳后的焦炉煤气利用膜分离技术，在渗透作用下，分离得到氢气1和甲烷，氢气1输送到用户。
高浓度的甲烷首先利用干燥塔干燥，两个塔进行交替干燥再生工作，还有一再生气预干燥塔。之后利用活性炭塔脱汞4，最后用混合冷剂制冷液化5，得到LNG2。

Claims (9)

1.一种焦炉煤气制取氢气和LNG的方法，其特征在于包括以下步骤：
(1)电除焦，在高压电晕电场中除去原料气中大部分的焦油、苯、萘等液态液滴及水颗粒；
(2)压缩系统给焦炉煤气增压；
(3)利用LNG的BOG气体(所述的BOG气体是指LNG被动受热气化后的气体)对原料焦炉煤气进行冷却，更进一步除去焦炉煤气中的焦油、苯、萘等物质；
(4)通过TSA工序的预处理，精脱大分子杂质，例如焦油、苯、萘等；
(5)通过湿法加干法两级脱硫，脱除焦炉气中的硫化物；
(6)经过两段低变，CO与水蒸汽反应转化为CO2和氢气；
(7)压缩机加压后用MDEA溶液法脱除二氧化碳，使用膜分离方法分离氢气与甲烷，氢气和甲烷得到分离、浓缩和纯化，分离得到的高浓度甲烷通过脱水、脱汞、液化得到LNG。
2.根据权利要求1所述的一种焦炉煤气制取氢气和LNG的方法，其特征在于：使用管式电除焦器进行电除焦，电压范围为40～60KV。
3.根据权利要求1所述的一种焦炉煤气制取氢气和LNG的方法，其特征在于：压缩系统给原料气加压到0.5MPa后经过冷却器冷却到40℃。
4.根据权利要求3所述的一种焦炉煤气制取氢气和LNG的方法，其特征在于：压缩系统使用螺杆压缩机将原料气加压到0.5MPa。
5.根据权利要求3所述的一种焦炉煤气制取氢气和LNG的方法，其特征在于：低温BOG气体与焦炉煤气进行换热，将焦炉煤气的温度降到10℃以下，分离焦炉煤气中的水、萘、苯等重组分。
6.根据权利要求1-5任一项所述的一种焦炉煤气制取氢气和LNG的方法，其特征在于：TSA变温吸附过程中，吸附塔和吸收塔两个塔交替进行吸附与再生过程，利用两塔流程，对焦炉煤气中的焦油、苯、萘等大分子物质进行吸附脱除。
7.根据权利要求6所述的一种焦炉煤气制取氢气和LNG的方法，其特征在于：湿法加干法两级脱硫过程中，使用先湿法后干法的顺序进行脱硫。
8.根据权利要求7所述的一种焦炉煤气制取氢气和LNG的方法，其特征在于：完成CO转化后的焦炉煤气，用往复式压缩机再次进行压缩，增压到后续过程所需的压力。
9.根据权利要求8所述的一种焦炉煤气制取氢气和LNG的方法，其特征在于：经膜分离方法分离出的高浓度甲烷首先利用干燥塔干燥，干燥过程使用两个塔进行交替干燥再生工作，还包括一个再生气预干燥塔，之后利用活性炭塔脱汞，最后用混合冷剂制冷液化，得到LNG。
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Application publication date: 20180619