CN110950304A - 一种利用天然气制备高纯度氢气的方法 - Google Patents

一种利用天然气制备高纯度氢气的方法 Download PDF

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CN110950304A
CN110950304A CN201911293322.9A CN201911293322A CN110950304A CN 110950304 A CN110950304 A CN 110950304A CN 201911293322 A CN201911293322 A CN 201911293322A CN 110950304 A CN110950304 A CN 110950304A
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李洪
蔡阳
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Jianyang Greenfir New Energy Equipment Co ltd
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Abstract

本发明公开了一种利用天然气制备高纯度氢气的方法，包括天然气原料中加入脱硫剂和脱氯剂净化后获得脱硫天然气；将脱硫天然气和预热的蒸汽通入转化炉管中，在高温催化剂作用下发生烃‑蒸汽转化反应，经过预转化后获得转化气；转化气经过废热锅炉换热至300℃~400℃后进入变换炉使一氧化碳和水反应变换成氢气和二氧化碳；再经过换热、冷凝、汽水分离，通过程序控制将气体依序通过装有三种特定吸附剂的吸附塔；由变压吸附PSA升压吸附氮气、一氧化碳、甲烷、二氧化碳提取产品氢气；降压解析放出杂质并使吸附剂得到再生。本发明的制氢方法能够利用天然气制备氢气，能够获得高纯度的氢气。

Description

一种利用天然气制备高纯度氢气的方法
技术领域
本发明涉及制氢技术领域，具体涉及到一种利用天然气制备高纯度氢气的方法。
背景技术
常温常压下，氢气是一种极易燃烧，无色透明、无臭无味且难溶于水的气体。氢气是世界上已知的密度最小的气体，氢气的密度只有空气的1/14，即在0℃时，一个标准大气压下，氢气的密度为0.089g/L。所以氢气可作为飞艇、氢气球的填充气体（由于氢气具有可燃性，安全性不高，飞艇现多用氦气填充）。氢气是相对分子质量最小的物质，主要用作还原剂。
工业上一般从天然气或水煤气制氢气，而不采用高耗能的电解水的方法。制得的氢气大量用于石化行业的裂化反应和生产氨气。氢气分子可以进入许多金属的晶格中，造成“氢脆”现象，使得氢气的存储罐和管道需要使用特殊材料（如蒙耐尔合金），设计也更加复杂。
天然气中主要成分为甲烷；是各类化合物中氢原子质量占比最大的化合物,储氢量为25%。同时天然气属地球三大化石能源之一,储量巨大(最近盛行的页岩气、可然冰与此也类似),因此很早就发展成为工业中最主流的氢气制备技术,在许多国家中占压倒性优势地位。由于甲烷化学结构稳定,所以工业上常采用便宜易得的水蒸气、氧气介质与甲烷反应,先生成合成气,再经化学转化与分离,制备氢气。另外针对含CO2酸性气的天然气矿源,有着CO干重整制氢的技术需求。最近,发展了天然气的直接无氧芳构化技术可以得到不含CO的氢气及大量高价值的芳烃产品。
发明内容
本发明的目的是提供一种利用天然气制备高纯度氢气的方法。
为达上述目的，本发明的一个实施例中提供了一种利用天然气制备高纯度氢气的方法，包括以下步骤：
（1）原料预处理：
天然气原料中通入氢气，加入加氢催化剂，然后升温至400℃~450℃，加入脱硫剂和脱氯剂；净化完毕后获得脱硫天然气；
（2）蒸汽预转化：
将脱硫天然气和预热的蒸汽通入转化炉管中，脱硫天然气与蒸汽按照碳水比4~5:1的比值混合，在高温催化剂作用下发生烃-蒸汽转化反应，反应温度为700℃~800℃，；转化管外用天然气和回收的尾气燃烧加热为反应提供能量；经过预转化后获得的转化气为含有氢气、一氧化碳和二氧化碳的转化气；
（3）变换反应：
转化气经过废热锅炉换热至300℃~400℃后进入变换炉使一氧化碳和水反应变换成氢气和二氧化碳；再经过换热、冷凝、汽水分离，通过程序控制将气体依序通过装有三种特定吸附剂的吸附塔；由变压吸附PSA升压吸附氮气、一氧化碳、甲烷、二氧化碳提取产品氢气；降压解析放出杂质并使吸附剂得到再生。
本发明优化的方案之一，原料预处理过程中，天然气原料中通入的氢气体积百分比为2%~6%；加氢催化剂为铁锰催化剂。
本发明优化的方案之一，天然气压缩至2MPa~3MPa后加热至400℃~450℃后进行脱硫和脱氯。
本发明优化的方案之一，脱硫剂为氧化锌；天然气脱硫至0.2ppm以下。
本发明优化的方案之一，蒸汽预转化的高温催化剂为镍类催化剂。
综上所述，本发明具有以下优点：
本发明的制氢方法能够利用天然气制备氢气，能够获得高纯度的氢气。
具体实施方式
本发明公开了一种利用天然气制备氢气的方法，包括以下步骤
（1）原料预处理：
天然气原料中通入氢气，加入加氢催化剂，然后升温至400℃~450℃，加入脱硫剂和脱氯剂；净化完毕后获得脱硫天然气；
（2）蒸汽预转化：
将脱硫天然气和预热的蒸汽通入转化炉管中，脱硫天然气与蒸汽按照碳水比4~5:1的比值混合，在高温催化剂作用下发生烃-蒸汽转化反应，反应温度为700℃~800℃，；转化管外用天然气和回收的尾气燃烧加热为反应提供能量；经过预转化后获得的转化气为含有氢气、一氧化碳和二氧化碳的转化气；
（3）变换反应：
转化气经过废热锅炉换热至300℃~400℃后进入变换炉使一氧化碳和水反应变换成氢气和二氧化碳；再经过换热、冷凝、汽水分离，通过程序控制将气体依序通过装有三种特定吸附剂的吸附塔；由变压吸附PSA升压吸附氮气、一氧化碳、甲烷、二氧化碳提取产品氢气；降压解析放出杂质并使吸附剂得到再生。
原料预处理过程中，天然气原料中通入的氢气体积百分比为2%~6%；加氢催化剂为铁锰催化剂。天然气压缩至2MPa~3MPa后加热至400℃~450℃后进行脱硫和脱氯。脱硫剂为氧化锌；天然气脱硫至0.2ppm以下。蒸汽预转化的高温催化剂为镍类催化剂。

Claims (5)

1.一种利用天然气制备高纯度氢气的方法，包括以下步骤：
（1）原料预处理：
天然气原料中通入氢气，加入加氢催化剂，然后升温至400℃~450℃，加入脱硫剂和脱氯剂；净化完毕后获得脱硫天然气；
（2）蒸汽预转化：
将脱硫天然气和预热的蒸汽通入转化炉管中，脱硫天然气与蒸汽按照碳水比4~5:1的比值混合，在高温催化剂作用下发生烃-蒸汽转化反应，反应温度为700℃~800℃，；转化管外用天然气和回收的尾气燃烧加热为反应提供能量；经过预转化后获得的转化气为含有氢气、一氧化碳和二氧化碳的转化气；
（3）变换反应：
转化气经过废热锅炉换热至300℃~400℃后进入变换炉使一氧化碳和水反应变换成氢气和二氧化碳；再经过换热、冷凝、汽水分离，通过程序控制将气体依序通过装有三种特定吸附剂的吸附塔；由变压吸附PSA升压吸附氮气、一氧化碳、甲烷、二氧化碳提取产品氢气；降压解析放出杂质并使吸附剂得到再生。
2.如权利要求1所述的方法，其特征在于：所述原料预处理过程中，天然气原料中通入的氢气体积百分比为2%~6%；所述加氢催化剂为铁锰催化剂。
3.如权利要求1所述的方法，其特征在于：所述天然气压缩至2MPa~3MPa后加热至400℃~450℃后进行脱硫和脱氯。
4.如权利要求1所述的方法，其特征在于：所述脱硫剂为氧化锌；天然气脱硫至0.2ppm以下。
5.如权利要求1所述的方法，其特征在于：所述蒸汽预转化的高温催化剂为镍类催化剂。
CN201911293322.9A 2019-12-16 2019-12-16 一种利用天然气制备高纯度氢气的方法 Pending CN110950304A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112265960A (zh) * 2020-09-16 2021-01-26 中国海洋石油集团有限公司 一种lng制备燃料电池用氢和食品级干冰的方法
CN113620244A (zh) * 2020-05-07 2021-11-09 中国石油化工股份有限公司 一种天然气水蒸汽重整制氢的系统及其方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002003201A (ja) * 2000-06-15 2002-01-09 Toyota Motor Corp 水素生成装置
CN102849680A (zh) * 2012-08-30 2013-01-02 苏州金宏气体股份有限公司 从天然气中合成及纯化氢气的方法
CN108439337A (zh) * 2018-03-16 2018-08-24 新地能源工程技术有限公司 一种天然气转化制氢的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002003201A (ja) * 2000-06-15 2002-01-09 Toyota Motor Corp 水素生成装置
CN102849680A (zh) * 2012-08-30 2013-01-02 苏州金宏气体股份有限公司 从天然气中合成及纯化氢气的方法
CN108439337A (zh) * 2018-03-16 2018-08-24 新地能源工程技术有限公司 一种天然气转化制氢的方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113620244A (zh) * 2020-05-07 2021-11-09 中国石油化工股份有限公司 一种天然气水蒸汽重整制氢的系统及其方法
WO2021223733A1 (zh) * 2020-05-07 2021-11-11 中国石油化工股份有限公司 一种天然气水蒸汽重整制氢的系统及其方法
CN112265960A (zh) * 2020-09-16 2021-01-26 中国海洋石油集团有限公司 一种lng制备燃料电池用氢和食品级干冰的方法

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