碳中和背景下工业副产气制氢技术研究与应用

doi:10.16085/j.issn.1000-6613.2021-2240

摘要/Abstract

摘要：

我国工业副产气排放量大，在对环境造成污染的同时，副产气中H₂、CO等有效成分随排放而浪费。氢气既是重要的化工原料，也是无碳、高效的能源，用工业副产气制备或分离提纯氢气既减少资源浪费，又可减少CO₂排放。本文介绍了我国含氢工业副产气排放情况，详述了焦炉煤气制氢、炼厂副产气制氢、氯碱尾气制氢等三种典型工业副产气制氢工艺，对煤制氢、天然气制氢、甲醇制氢及三种典型工业副产气制氢工艺的成本和CO₂排放进行了计算和整理分析。文章指出，考虑二氧化碳排放和碳交易成本等因素，与煤制氢、天然气制氢、甲醇制氢和电解水制氢相比，现阶段下工业副产气制氢的综合成本优势更加明显。在碳中和背景下，工业副产气制氢是获取低碳氢气的有效和经济的途径，研究和开发工业副产气制氢技术，将为碳减排提供一条高效路径。

关键词: 碳减排, 工业副产气, 制氢, 变压吸附, 焦炉煤气

Abstract:

China's industrial by-product gas emissions is large, which makes pollution to the environment, and meanwhile wastes the valuable resources such as H₂ and CO. Hydrogen is an important chemical raw material, and also is a carbon-free and high-efficiency energy. The separation and purification of hydrogen from industrial by-product gas could reduce resources waste and CO₂ emission. This article introduces the current emissions status of hydrogen-containing industrial by-product gas in China, three typical industrial hydrogen production processes, the calculation and analyses of their costs and CO₂ emissions. These three typical processes are hydrogen production from Coke Oven Gas, refinery gas, and chlor-alkali emission gas. Taking into account factors such as carbon dioxide emissions and carbon transaction costs, the comprehensive cost advantage of hydrogen production from industrial by-product gas is more competitive. In the context of carbon neutrality, hydrogen production from industrial by-product gas is an effective and feasible way to obtain low-carbon hydrogen energy. Further researches and development of industrial by-product gas hydrogen production technologies would provide an efficient way to reduce carbon emissions.

Key words: carbon emissions reduction, industrial by-product gas, hydrogen production, pressure swing adsorption, coke oven gas

中图分类号:

TQ02

陈健, 姬存民, 卜令兵. 碳中和背景下工业副产气制氢技术研究与应用[J]. 化工进展, 2022, 41(3): 1479-1486.

CHEN Jian, JI Cunmin, BU Lingbing. Research and application of hydrogen production technology from industrial by-product gas under the background of carbon neutrality[J]. Chemical Industry and Engineering Progress, 2022, 41(3): 1479-1486.

图/表 11

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序号	排放气类别	产量/×10⁸m³?a^-1	典型组成（体积分数）/%	氢气量/×10⁸m³?a^-1
1	焦炉煤气	约1114	H₂∶57，CH₄∶25.5，CO∶6.5，C _n H _m ∶2.5，CO₂∶2，N₂∶4	约635
2	炼厂气	约1193	H₂∶14~90，CH₄∶3~25，C₂₊∶15~30	约620
3	合成氨尾气	约124	H₂∶20~70，CH₄∶7~18，Ar∶3~8，N₂∶7~25	约86
4	甲醇驰放气	约239	H₂∶60~75，CH₄∶5~11，CO∶5~7，CO₂∶2~13，N₂∶0.5~20	约161
5	兰炭尾气	约290	H₂∶26~30，CO∶12~16，CH₄∶7~8.5，CO₂∶6~9，N₂∶35~39	约81.2
6	氯酸钠副产气	约5.7	H₂∶约95，O₂∶2.5，其他	约5
7	聚氯乙烯（PVC）尾气	约12.86	H₂∶50~70，C₂H₂∶5~15，C₂H₃Cl∶8~25，N₂∶10~15	约6
8	烧碱尾气	约99.17	H₂∶约98.5，N₂约0.5，O₂∶约1，其他	约97.7
9	丙烷脱氢（PDH）尾气	约3.8	H₂∶80~92，C₂H₆∶1~2，C₃H₈∶0.5~1，N₂∶1~2	约3.1

序号	排放气类别	产量/×10⁸m³?a^-1	典型组成（体积分数）/%	氢气量/×10⁸m³?a^-1
1	焦炉煤气	约1114	H₂∶57，CH₄∶25.5，CO∶6.5，C _n H _m ∶2.5，CO₂∶2，N₂∶4	约635
2	炼厂气	约1193	H₂∶14~90，CH₄∶3~25，C₂₊∶15~30	约620
3	合成氨尾气	约124	H₂∶20~70，CH₄∶7~18，Ar∶3~8，N₂∶7~25	约86
4	甲醇驰放气	约239	H₂∶60~75，CH₄∶5~11，CO∶5~7，CO₂∶2~13，N₂∶0.5~20	约161
5	兰炭尾气	约290	H₂∶26~30，CO∶12~16，CH₄∶7~8.5，CO₂∶6~9，N₂∶35~39	约81.2
6	氯酸钠副产气	约5.7	H₂∶约95，O₂∶2.5，其他	约5
7	聚氯乙烯（PVC）尾气	约12.86	H₂∶50~70，C₂H₂∶5~15，C₂H₃Cl∶8~25，N₂∶10~15	约6
8	烧碱尾气	约99.17	H₂∶约98.5，N₂约0.5，O₂∶约1，其他	约97.7
9	丙烷脱氢（PDH）尾气	约3.8	H₂∶80~92，C₂H₆∶1~2，C₃H₈∶0.5~1，N₂∶1~2	约3.1

尾气	组成/%
尾气	H₂	N₂	O₂	C₂H₃Cl	C₂H₂	H₂O	Cl₂
氯酸钠尾气	约92	—	5	—	—	≤1	10~30mg/m³
氯乙烯尾气	30~70	8~15	—	8~25	5~10	饱和	—

尾气	组成/%
尾气	H₂	N₂	O₂	C₂H₃Cl	C₂H₂	H₂O	Cl₂
氯酸钠尾气	约92	—	5	—	—	≤1	10~30mg/m³
氯乙烯尾气	30~70	8~15	—	8~25	5~10	饱和	—

项目	成本/CNY?m^-3
项目	原料	辅助材料	燃料动力消耗	直接工资	制造费用	财务及管理费用	合计
煤制氢	0.375	0.253	0.069	0.012	0.135	0.060	0.904
天然气制氢	0.990	0.031	0.232	0.007	0.138	0.080	1.478
甲醇制氢	1.300	0.160	0.395	0.012	0.055	0.020	1.942
电解水制氢	0.012	0.100	3.000	0.038	0.235	0.041	3.426
焦炉煤气制氢	0.600	0.006	0.216	0.007	0.078	0.028	0.935
炼厂气制氢	0.684	0.020	0.016	0.006	0.051	0.033	0.810
氯碱尾气	0.440	0.020	0.020	0.006	0.062	0.020	0.568