Progress in materials and technologies for deep removal of ammonia gas

doi:10.16085/j.issn.1000-6613.2020-1612

Abstract

Abstract:

Ammonia gas (NH₃), as a harmful basic gas, not only pollutes the environment but also causes irreversible damages to human beings. In electronic information, energy, and other related industries, a trace amount of NH₃ can affect product quality and reduce process performance. Therefore, deep removal of NH₃ has important industrial significance. In this review, the status of deep removal of NH₃ is reviewed, and the separation performance of various materials, including ionic liquids, deep eutectic solvents, modified activated carbon, molecular sieves, modified alumina, metal salts, metal-organic frameworks, porous organic polymers, covalent organic frameworks, graphite oxide, and Prussian blue analogs are discussed. The technological characteristics for deep removal of NH₃ as well as the performance requirements for deamination materials are summarized. The challenges in this field are briefly analyzed with suggestions put forward for future development.

Key words: ammonia gas, deep removal, absorption, adsorption, separation

摘要：

氨气（NH₃）作为一种危害性碱性有毒气体，不仅危害环境，而且会对人体造成不可逆伤害。在电子信息、能源等行业，极微量的NH₃即可影响产品品质、降低过程性能。因此，NH₃的深度脱除在工业上具有重要的意义。本文综述了近年来NH₃深度脱除的工艺现状，分析了NH₃脱除材料如离子液体、低共熔溶剂、改性活性炭、分子筛、改性氧化铝、金属盐类、金属有机框架材料、多孔有机聚合物、共价有机骨架材料、氧化石墨烯、普鲁士蓝类似物对NH₃的分离性能。总结了深度脱除NH₃的工艺特点和脱氨材料的性能，浅析了该领域发展面临的问题，并对未来的发展方向提出了建议。

关键词: 氨气, 深度脱除, 吸收, 吸附, 分离

CLC Number:

TQ028

CHEN Peikun, ZHANG Yuanbin, CUI Xili, XING Huabin. Progress in materials and technologies for deep removal of ammonia gas[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 3957-3975.

陈沛坤, 张袁斌, 崔希利, 邢华斌. 氨气深度脱除材料与技术研究进展[J]. 化工进展, 2021, 40(7): 3957-3975.

Figures/Tables 16

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吸收剂种类	吸收条件		吸收量/mmol·g^-1	文献	吸收剂种类	吸收条件		吸收量/mmol·g^-1	文献
吸收剂种类	温度/K	压力/kPa	吸收量/mmol·g^-1	文献	吸收剂种类	温度/K	压力/kPa	吸收量/mmol·g^-1	文献
［Emim］［Ac］	298.3	101.3	1.88	［32］	［Choline］［NTf₂］	293.15	100	4.82	［35］
［Emim］［SCN］	298.1	101.3	2.64	［32］	［EtOHmim［NTf₂］	313	127	2.05	［36］
［Emim］［EtOSO₃］	298.15	418	2.35	［32］	［EtOHim］［NTf₂］	313	100	7.88	［37］
［DMEA］［Ac］	298.1	163	5.50	［32］	［Bim］［NTf₂］	313	100	6.65	［38］
［Bmim］［PF₆］	298.0	174	1.84	［33］	［C_nmim］₂［Co（NCS）₄］	303	100	10.59	［39］
［Hmim］［Cl］	297.8	133	1.45	［33］	ChCl∶Res∶Gly（1∶3∶5）	313	101	7.65	［40］
［Emim］［NTf₂］	323.15	171	0.24	［33］	ChCl∶D-f∶Gly（1∶3∶5）	313	101	6.47	［40］
［Bmim］［BF₄］	313.15	101.3	1.71	［33］	Bmim∶MeSO₃（1∶1）	313.2	172.6	1.05	［41］
［C₂MIM］［BF₄］	298.15	110	0.94	［34］	ChCl∶PhOH∶EG（1∶5∶4）	313.2	101.3	6.99	［42］
［C₄MIM］［BF₄］	298.15	220	2.01	［34］	NH₄SCN：Gly（2∶3）	303	100	10.35	［43］
［C₆MIM］［BF₄］	298.15	220	2.24	［34］	ChCl∶ImZ∶EG（3∶7∶14）	313.2	101.6	4.91	［44］
［C₈MIM］［BF₄］	298.15	120	1.41	［34］	EaCl∶Gly（1∶2）	298.2	106.7	9.63	［45］

吸收剂种类	吸收条件		吸收量/mmol·g^-1	文献	吸收剂种类	吸收条件		吸收量/mmol·g^-1	文献
吸收剂种类	温度/K	压力/kPa	吸收量/mmol·g^-1	文献	吸收剂种类	温度/K	压力/kPa	吸收量/mmol·g^-1	文献
［Emim］［Ac］	298.3	101.3	1.88	［32］	［Choline］［NTf₂］	293.15	100	4.82	［35］
［Emim］［SCN］	298.1	101.3	2.64	［32］	［EtOHmim［NTf₂］	313	127	2.05	［36］
［Emim］［EtOSO₃］	298.15	418	2.35	［32］	［EtOHim］［NTf₂］	313	100	7.88	［37］
［DMEA］［Ac］	298.1	163	5.50	［32］	［Bim］［NTf₂］	313	100	6.65	［38］
［Bmim］［PF₆］	298.0	174	1.84	［33］	［C_nmim］₂［Co（NCS）₄］	303	100	10.59	［39］
［Hmim］［Cl］	297.8	133	1.45	［33］	ChCl∶Res∶Gly（1∶3∶5）	313	101	7.65	［40］
［Emim］［NTf₂］	323.15	171	0.24	［33］	ChCl∶D-f∶Gly（1∶3∶5）	313	101	6.47	［40］
［Bmim］［BF₄］	313.15	101.3	1.71	［33］	Bmim∶MeSO₃（1∶1）	313.2	172.6	1.05	［41］
［C₂MIM］［BF₄］	298.15	110	0.94	［34］	ChCl∶PhOH∶EG（1∶5∶4）	313.2	101.3	6.99	［42］
［C₄MIM］［BF₄］	298.15	220	2.01	［34］	NH₄SCN：Gly（2∶3）	303	100	10.35	［43］
［C₆MIM］［BF₄］	298.15	220	2.24	［34］	ChCl∶ImZ∶EG（3∶7∶14）	313.2	101.6	4.91	［44］
［C₈MIM］［BF₄］	298.15	120	1.41	［34］	EaCl∶Gly（1∶2）	298.2	106.7	9.63	［45］

分子筛	温度/K	低压		常压
分子筛	温度/K	NH₃分压/kPa	平衡吸附量/mmol·g^-1	NH₃分压/kPa	平衡吸附量/mmol·g^-1
4A zeolite TG242	298.15	0.0171	2.039	97.8	8.717
5A zeolite KE154	298.15	0.0058	1.864	97.6	7.674
13X zeolite WE894	298.15	0.0041	1.742	93.8	9.326
5A zeolite Lancaster	298.15	0.0126	3.206	97.7	7.815
13X zeolite Lancaster	298.15	0.058	3.786	97.4	9.326
5A zeolite Sigma	298.15	0.0085	2.460	98.7	7.430
13X zeolite Sigma	298.15	0.0115	2.489	96.7	9.030

分子筛	温度/K	低压		常压
分子筛	温度/K	NH₃分压/kPa	平衡吸附量/mmol·g^-1	NH₃分压/kPa	平衡吸附量/mmol·g^-1
4A zeolite TG242	298.15	0.0171	2.039	97.8	8.717
5A zeolite KE154	298.15	0.0058	1.864	97.6	7.674
13X zeolite WE894	298.15	0.0041	1.742	93.8	9.326
5A zeolite Lancaster	298.15	0.0126	3.206	97.7	7.815
13X zeolite Lancaster	298.15	0.058	3.786	97.4	9.326
5A zeolite Sigma	298.15	0.0085	2.460	98.7	7.430
13X zeolite Sigma	298.15	0.0115	2.489	96.7	9.030

材料	组成	298K、1bar下动态吸附容量/mmol·g^-1
PB	Na_0.05Fe［Fe（CN）₆］_0.70·5.3H₂O	3.1
CoPBA	K_0.05Co［Co（CN）₆］_0.66·4.4H₂O	1.9
FePBA（CoⅢ）	Fe［Co（CN）6］₂·3.4H₂O（estimated）	2.5
CuPBA（FeⅡ），［Fe（CN）₆］·Cu=0.66	K_0.64Cu［Fe（CN）₆］_0.66·3.2H₂O	2.6
CuPBA（FeⅡ），［Fe（CN）₆］·Cu=0.59	K_0.33Cu［Fe（CN）₆］_0.59·4.1H₂O	2.1
CuPBA（FeⅡ），［Fe（CN）₆］·Cu=0.57	K_0.19Cu［Fe（CN）₆］_0.57·4.4H₂O	2.7
CuPBA	K_0.05Cu［Fe（CN）₆］_0.46·5.0H₂O	2.1
离子交换树脂（IE）		0.38
13X 分子筛（ZL）		0.28
AC 分子筛		0.02