含碳掺氨燃料的研究进展

doi:10.16085/j.issn.1000-6613.2022-2005

化工进展 ›› 2023, Vol. 42 ›› Issue (9): 4603-4615.DOI: 10.16085/j.issn.1000-6613.2022-2005

含碳掺氨燃料的研究进展

赖诗妮¹^,²(), 江丽霞³, 李军¹^,²^,⁴^,⁵(), 黄宏宇¹^,²^,⁵, 小林敬幸⁶

^1.中国科学院广州能源研究所，广东广州 510640
^2.中国科学技术大学能源科学与技术学院，广东广州 510640
^3.中国科学院重大科技任务局，北京 100864
^4.江西省碳中和研究中心，江西南昌 330096
^5.南方海洋科学与工程广东省实验室（广州），广东广州 511458
^6.名古屋大学化学系统工程系，日本名古屋 464-8603

收稿日期:2022-10-27 修回日期:2022-11-29 出版日期:2023-09-15 发布日期:2023-09-28
通讯作者: 李军
作者简介:赖诗妮（1999—），女，硕士研究生，研究方向为氨基燃料燃烧。E-mail：sa21178008@mail.ustc.edu.cn。
基金资助:
南方海洋科学与工程广东省实验室（广州）人才团队引进重大专项(GML2019ZD0108);广东省重点领域研发计划(2020B0202010004)

Research progress of ammonia blended fossil fuel

LAI Shini¹^,²(), JIANG Lixia³, LI Jun¹^,²^,⁴^,⁵(), HUANG Hongyu¹^,²^,⁵, KOBAYASHI Noriyuki⁶

^1.Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^2.School of Energy Science and Engineering, University of Science and Technology of China, Guangzhou 510640, Guangdong, China
^3.Bureau of Major R&D Programs, Chinese Academy of Sciences, Beijing 100864, China
^4.Jiangxi Carbon Neutralization Research Center, Nanchang 330096, Jiangxi, China
^5.Southern Marine Science and Engineering Guangdong Laboratory (Guangzhou), Guangzhou 511458, Guangdong, China
^6.Department of Chemical Systems Engineering, Nagoya University, Nagoya 464-8603, Japan

Received:2022-10-27 Revised:2022-11-29 Online:2023-09-15 Published:2023-09-28
Contact: LI Jun

摘要/Abstract

摘要：

随着经济和社会的发展，国家对能源的需求量越来越大，这与化石能源短缺、环境污染、温室效应等问题相矛盾，因此寻找高效清洁的替代燃料势在必行。氨的体积能量密度较高、成本低且完全燃烧时产物的污染性小，具有成为新时代绿色能源的潜力。但它的燃烧性能较差，通常需要掺混煤、CH₄和合成气等燃料来改善。本文主要介绍了含碳掺氨的煤掺氨和甲烷掺氨混合燃料在基础燃烧特性和燃烧应用优化方面的研究进展。总结了不同燃烧策略及燃烧器设计中掺混氨燃料的燃烧特性和排放规律，为未来工业化应用研究提供一定的参考。但在实际应用氨燃料过程中仍存在不少挑战，未来可进一步对优化分级燃烧的策略、改善相关燃烧设备的结构、调整含氨燃料的喷射方式等方面进行研究，以实现高效低污染氨燃料的应用目标。

关键词: 燃料, 氨, 甲烷, 煤燃烧, 氮氧化物

Abstract:

Fossil fuels meet most of the world’s energy demand today. But too much use of conventional fossil fuels is causing many severe problems, such as environmental pollution, global warming and energy crisis. Therefore, looking for environmentally friendly fuels is very necessary. Ammonia has attracted more and more attention because it is a carbon free carrier with advantages of high energy density and low cost. However, ammonia usually need to co-fire with some fuels such as coal, CH₄ and syngas to improve the combustion characteristics of pure ammonia. This article introduces a detailed development of ammonia/coal and ammonia/methane as fuels for main applications such as boiler and gas turbine. It summarizes the fundamental combustion characteristics and the application research progress of ammonia blends. What’s more, the current understanding of combustion characteristics and the emission characteristics are also summarized. However, using ammonia blends as alternative fuels still has many challenges. In future, the improvement of combustion strategies, equipment and injection strategies is very urgent in order to apply ammonia as a practical fuel with high efficiency and low emission.

Key words: fuel, ammonia, methane, coal combustion, nitrogen oxides

中图分类号:

TQ51

赖诗妮, 江丽霞, 李军, 黄宏宇, 小林敬幸. 含碳掺氨燃料的研究进展[J]. 化工进展, 2023, 42(9): 4603-4615.

LAI Shini, JIANG Lixia, LI Jun, HUANG Hongyu, KOBAYASHI Noriyuki. Research progress of ammonia blended fossil fuel[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4603-4615.

图/表 14

表1 2015—2020年的能源消费情况[2]

年份	传统能源占能源消费总量的比重/%
年份	煤炭	石油	天然气
2020年	56.8	18.9	8.4
2019年	57.7	19.0	8.0
2018年	59.0	18.9	7.6
2017年	60.6	18.9	6.9
2016年	62.2	18.7	6.1

图1 清洁能源系统中氨的合成、储存及运输概念[7]

表2 氨与其他燃料的性能对比[21]

性能	数值
性能	氨	氢	甲烷	甲醇
含氢质量分数/%	17.8	100	25.0	12.5
密度/kg·m^-3	0.8	0.09	0.7	786.0 (液态)
低位质量热值/MJ·kg^-1	18.8	120.0	50.1	19.7
低位体积热值/MJ·m^-3	14.3	10.8	35.9	—
常压液化压力/MPa	0.8	70.0	25.0	0.1
自燃点/℃	651	500~557	586	470
辛烷值	130	＞130	120	109

图2 大气压条件下不同当量比的层流燃烧速度对比[27]

图3 氨/煤颗粒混合燃烧的火焰对比[39]

图4 煤掺氨燃烧过程中与NO x 形成的相关反应路径[41]

表3 煤掺氨过程主要反应及部分动力学参数

反应式	A/s^-1	β	E_a/J·kmol^-1	参考文献
C _m H _n +(m/2)O₂ $→$ mCO+(n/2)H₂	4.4×10¹¹	0	1.26×10⁸	[47]
C _m H _n +mH₂O $→$ mCO+(n/2+m)H₂	3.0×10⁸	0	1.26×10⁸	[47]
Tar(C _x H _y O₂)+0.5(z-x)O₂ $→$ xCO+(y/2)H₂	6.57×10⁵	1	8.02×10⁷	[48]
Char(C₄₁₂N₅)+208.5O₂ $→$ 412CO+5NO	3.45×10¹¹	0	1.25×10⁸	[49]
Char(C₄₁₂N₅)+NO $→$ Char(C₄₁₂N₅)+0.5N₂+0.5O₂	2.36×10⁷	0	1.12×10⁸	[49]
Soot(C₁₆₆)+NO $→$ 0.9940Soot(C₁₆₆)+0.5N₂+CO	2.41×10¹²	0.5	1.25×10⁸	[49]
H₂+0.5O₂ $⇌$ H₂O	5.69×10¹¹	0	1.47×10⁸	[47]
CO+H₂O $⇌$ CO₂+H₂	2.75×10⁹	0	8.36×10⁷	[47]
CO+0.5O₂ $⇌$ CO₂	1.93×10¹³	-2	1.26×10⁸	[50]
NH₃+O₂ $→$ NO+H₂O+0.5H₂	3.5×10²	7.65	5.24×10⁸	[51]
NH₃+NO $→$ N₂+H₂O+0.5H₂	4.24×10⁵	5.3	3.5×10⁸	[51]
NH₃ $→$ 0.5N₂+1.5H₂	0.185	1.25	6.9×10⁷	[52]

表3 煤掺氨过程主要反应及部分动力学参数

反应式	A/s^-1	β	E_a/J·kmol^-1	参考文献
C _m H _n +(m/2)O₂ $→$ mCO+(n/2)H₂	4.4×10¹¹	0	1.26×10⁸	[47]
C _m H _n +mH₂O $→$ mCO+(n/2+m)H₂	3.0×10⁸	0	1.26×10⁸	[47]
Tar(C _x H _y O₂)+0.5(z-x)O₂ $→$ xCO+(y/2)H₂	6.57×10⁵	1	8.02×10⁷	[48]
Char(C₄₁₂N₅)+208.5O₂ $→$ 412CO+5NO	3.45×10¹¹	0	1.25×10⁸	[49]
Char(C₄₁₂N₅)+NO $→$ Char(C₄₁₂N₅)+0.5N₂+0.5O₂	2.36×10⁷	0	1.12×10⁸	[49]
Soot(C₁₆₆)+NO $→$ 0.9940Soot(C₁₆₆)+0.5N₂+CO	2.41×10¹²	0.5	1.25×10⁸	[49]
H₂+0.5O₂ $⇌$ H₂O	5.69×10¹¹	0	1.47×10⁸	[47]
CO+H₂O $⇌$ CO₂+H₂	2.75×10⁹	0	8.36×10⁷	[47]
CO+0.5O₂ $⇌$ CO₂	1.93×10¹³	-2	1.26×10⁸	[50]
NH₃+O₂ $→$ NO+H₂O+0.5H₂	3.5×10²	7.65	5.24×10⁸	[51]
NH₃+NO $→$ N₂+H₂O+0.5H₂	4.24×10⁵	5.3	3.5×10⁸	[51]
NH₃ $→$ 0.5N₂+1.5H₂	0.185	1.25	6.9×10⁷	[52]

图5 三种用于煤掺氨燃烧的氨燃料喷嘴结构设计[37]

图6 锅炉和发电厂的改造示意图[58]

图7 不同当量比条件下的排放特性 [70]

表4 甲烷掺氨部分反应机理及适用情况

模型	燃料类型	组分/反应的数目	模拟结果	参考文献
GRI 3.0	天然气	53/325	可用于高压燃烧条件的模拟；不包括涉及N₂H₂和N₂H₃中间产物的所有反应，模拟的层流火焰速度比实验值低；贫燃条件下NO _x 模拟值偏高	[72-75]
San Diego	天然气	20/41	可用于高压燃烧条件的模拟；能准确预测旋流火焰中的NO _x 和NH₃排放	[72-73, 76-77]
Konnov	NH₃/CH₄	129/1231	能较好地模拟甲烷含量高时燃料的层流火焰速度；高压条件下的点火延迟时间和NO、CO排放模拟结果良好	[78-80]
Tian	NH₃/CH₄	84/703	适用于低压燃烧条件的模拟^[73]；贫燃和低甲烷含量时，层流火焰速度的模拟结果较准确^[78]；实际燃气轮机运行条件下燃料的点火延迟时间和NO排放预测均较准确^[79]	[62, 73, 78-79]
Okafor	NH₃/CH₄	59/356	适用于低压的燃烧条件^[73]；能准确模拟层流燃烧速度^[78]	[73-74, 78]

图8 适用于液氨/甲烷混合燃料的旋流燃烧器[84]

表5 甲烷掺氨的旋流燃烧器设计方案

燃烧器结构	燃烧方式	运行条件	旋流数	参考文献
同轴双旋流+钝体	预混燃烧	外侧旋流燃烧器：贫预混的CH₄/空气混合物；当量比为0.6~0.7 内侧旋流燃烧器：掺氨比为0%~100%的CH₄/NH₃燃料；当量比为0.2~1.4	外侧叶片：0.84 内侧叶片：0.72	[86]
单旋流+同轴环状燃料入口	预混燃烧+非预混燃烧	掺氨比为0%~30%的CH₄/NH₃燃料；当量比为0.8~1.1	0.88	[81]
单旋流+钝体	预混燃烧	掺氨比为0%~60%的CH₄/NH₃燃料；当量比为0.56~0.74	0.42、0.73和1.27	[87-88]
切向涡流燃烧器	预混燃烧	61% NH₃/39% CH₄；当量比为0.8~1.42	1.33	[70]
单旋流+同轴双燃料入口（中间入口喷入液氨）	非预混燃烧	掺氨比为70%~100%的液氨/气态CH₄；当量比为0.66~1.37	2.34	[84-85]

图9 转速为80000r/min时NH3/CH4为燃料的微型燃气轮机发电系统效率 [90]

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含碳掺氨燃料的研究进展

Research progress of ammonia blended fossil fuel

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