面向钢铁烧结烟气NO<sub><i>x</i></sub>吸附净化的吸附剂特性

刘应书; 吴晓永; 李子宜; 杨雄; 刘文海; 侯环宇; 邢奕; 李金娟

doi:10.13374/j.issn2095-9389.2021.11.01.001

面向钢铁烧结烟气NO_x吸附净化的吸附剂特性

doi: 10.13374/j.issn2095-9389.2021.11.01.001

1.
北京科技大学能源与环境工程学院，北京 100083
2.
河钢集团钢研总院，石家庄 050023
3.
贵州大学资源与环境工程学院，喀斯特地质资源与环境教育部重点实验室，贵阳 550025

基金项目: 国家自然科学基金资助项目（21808012）；“十三五”国家重点研发专项资助项目（2017YFC0210302）；贵州省科技支撑计划资助项目（黔科合支撑[2021]一般 497）

详细信息

通讯作者:
E-mail: ziyili@ustb.edu.cn

中图分类号: X701.7;TF09
计量
- 文章访问数: 70
- HTML全文浏览量: 29
- PDF下载量: 23
- 被引次数: 0
出版历程
- 收稿日期: 2021-11-01
- 网络出版日期: 2022-02-22

Adsorbents for the adsorption purification of NO_x in the ore-sintering flue gas

1.
School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China
2.
HBIS Technology Research InstituteInstitute, Shijiazhuang 050023, China
3.
College of Resources and Environmental Engineering, Key Laboratory of Karst Georesources and Environment (Ministry of Education), Guizhou University, Guiyang 550025, China

More Information

Corresponding author: E-mail: ziyili@ustb.edu.cn

摘要

摘要: 吸附法是有望同时实现烟气NO_x超低排放深度净化与资源化的关键技术，高效NO_x吸附剂是其核心关键，然而目前针对满足应用需求的NO_x吸附剂仍缺乏系统认识。本文基于烟气NO_x净化效率及材料热稳定性实际需求，分析挑选了沸石、金属氧化物、硅铝胶等代表性吸附剂，研究了NO_x在各吸附剂上的吸附穿透、吸附量、程序升温脱附等关键特性，结合吸附剂孔道特性对比发现，中低硅H-ZSM-5沸石兼具较高NO_x净化深度、NO_x吸附量、较低脱附温度且可获得更易于资源化的NO_x解吸气，因而可作为优选NO_x吸附剂。进一步地，随着吸附温度升高，硅铝比(w(SiO₂)/w(Al₂O₃) )为25、38的H-ZSM-5的NO_x吸附量均降低，其中低硅H-ZSM-5的NO_x吸附量较高，但吸附传质系数较低。本文可为烟气NO_x吸附净化的效益环保技术提供指导。
- 烟气净化 /
- 氮氧化物 /
- 吸附剂 /
- 吸附 /
- 资源化回收
Abstract: Nitrogen oxides (NO_x) are major air pollutants produced by fuel combustion that cause adverse effects on the environment and human health. The deep purification of NO_x from ﬂue gases has become a worldwide issue. In China, a rigorous ultra-low emission standard (ULES) of NO_x≤ 50 mg·m^–3 has been implemented in the power and steel industries in recent years. NO₂ is a valuable chemical feedstock that is worthy of being recycled from flue gas. Adsorption is a promising technology that can achieve deep purification and resource recovery of NO_x from industrial flue gas, in which a high-performance NO_x adsorbent plays a key role. However, a systematic understanding of NO_x adsorbents for practical applications is still lacking. This study compares and analyzes the NO_x adsorption and desorption performances of typical practical adsorbents including zeolites, metal oxides, and silica-alumina gels based on the practical need for both NO_x purification efficacy and material thermal stability. NO_x adsorption capacities, breakthrough curves, uptake curves, and temperature-programmed desorption (TPD) curves were also measured. Results show that compared to Fe–Mn–Ce and 13X as competitive adsorbents, H-ZSM-5_25 showed NO_x deep purification (purification efficiency close to 100% before adsorption breakthrough), great NO_x adsorption capacity (0.206 mmol·g^–1), and high NO₂ concentration ratio in desorption, which are likely due to its high NO catalytic oxidation rate and comparable NO₂ physical adsorption rate. Regarding the desorption characteristics, H-ZSM-5_25 showed a bimodal TPD desorption peak with a lower desorption temperature (400–470 K) in the low-temperature region. Meanwhile, NO₂ is the primary NO_x component in the desorbed gas (adsorption-desorption enrichment ratio of NO₂ being up to 57), which can easily be recovered using the liquefaction method. Furthermore, by comparing the adsorption performances on the H-ZSM-5 with different silica-to-alumina ratios, the NO_x adsorption was found to decrease (from 0.706 to 0.206 mmol·g^–1 for H-ZSM-5_25 and from 0.454 to 0.127 mmol·g^–1 for H-ZSM-5_38) with increasing temperature (298–398 K). The dependence of the NO₂ adsorption on the temperature was more significant for H-ZSM-5_25 compared to H-ZSM-5_38. Compared to H-ZSM-5_38, H-ZSM-5_25 with a lower silica-to-alumina ratio (consequently, more cation sites) rendered greater NO oxidation performance, a potentially higher NO₂ adsorption capacity, and a greater decreasing trend of the adsorption capacity with increasing temperature. Results of adsorption kinetic experiments showed that the NO_x mass transfer parameters on H-ZSM-5_25 were lower than those on H-ZSM-5_38 with a smaller primary micro pore channel. Results of the current work can provide technical references for economic flue gas denitrification.
- flue gas purification /
- nitrogen oxide /
- adsorbent /
- adsorption /
- recovery

HTML全文

图 1 NO_x吸附实验系统

Figure 1. NO_x adsorption experimental system

下载: 全尺寸图片幻灯片

图 2 孔径分布及87 K下Ar的吸附等温线

Figure 2. Pore size distributions and adsorption isotherms of Ar at 87 K

下载: 全尺寸图片幻灯片

图 3 各吸附剂的NO_x穿透曲线（398 K）

Figure 3. NO_x breakthrough curves on adsorbents (398 K)

下载: 全尺寸图片幻灯片

图 4 H-ZSM-5_25在有氧和无氧条件下的NO_x穿透曲线（298 K）

Figure 4. NO_x breakthrough curves of H-ZSM-5_25 with and without oxygen (298 K)

下载: 全尺寸图片幻灯片

图 5 NO_x在各吸附剂的程序性升温脱附（TPD）曲线（a）和NO与NO₂含量图（b）

Figure 5. Temperature-programmed desorption curves of NO_x (a) and amounts of NO and NO₂ (b) in the desorbed gas on each adsorbent

下载: 全尺寸图片幻灯片

图 6 不同硅铝比的H-ZSM-5在不同温度下的穿透曲线

Figure 6. Breakthrough curves of H-ZSM-5 at different temperatures for different Si–Al ratios

下载: 全尺寸图片幻灯片

图 7 H-ZSM-5_25、H-ZSM-5_38的NO_x吸附量随温度的变化曲线

Figure 7. Variation curves of the NO_x absorption capacity with temperature for H-ZSM-5_25 and H-ZSM-5_38

下载: 全尺寸图片幻灯片

图 8 H-ZSM-5_25、H-ZSM-5_38的吸附速率曲线（298 K）及LDF模型拟合曲线

Figure 8. Adsorption uptake curves (298 K) of H-ZSM-5_25 and H-ZSM-5_38 along with linear driving force model fitting curves

下载: 全尺寸图片幻灯片

表 1 吸附剂的物理参数及NO_x吸附量

Table 1. Physical parameters and NO_x adsorption capacity of adsorbents

Adsorbents	Brunauer–Emmett–Teller surface area/(m²·g^–1)	Pore volume/ (cm³·g^–1)	Primary micropore channel/nm	NO_x adsorption capacity/(mmol·g^–1)
H-ZSM-5_25	353	0.32	0.68	0.206
H-ZSM-5_38	337	0.30	0.72	0.127
H-ZSM-5_198	397	0.43	0.72	0.013
13X	393	0.48	1.00	0.181
NaY	537	0.38	1.15	0.027
Si–Al gel	463	0.43	1.17	0.016
Fe–Mn–Ce	99	0.09	4.58	0.200

下载: 导出CSV

表 2 LDF模型拟合参数

Table 2. Linear driving force model fitting parameters

Adsorbents	R²	–k_i	C
H-ZSM-5_25	0.998	–1.14 × 10^–4± 3.79 × 10^–8	0.08 ± 5.83 × 10^–4
H-ZSM-5_38	0.995	–2.19 × 10^–4 ± 1.32 × 10^–7	0.05 ± 0.01

下载: 导出CSV

参考文献(42)

[1]	Shelef M. Selective catalytic reduction of NO_x with N-free reductants. Chem Rev, 1995, 95(1): 209 doi: 10.1021/cr00033a008
[2]	Pârvulescu V I, Grange P, Delmon B. Catalytic removal of NO. Catal Today, 1998, 46(4): 233 doi: 10.1016/S0920-5861(98)00399-X
[3]	Ministry of Ecology and Environment of the People's Republic of China. Opinions on promoting the implementation of ultra-low emissions in the steel industry [EB/OL]. Government Information Disclosure (2019-04-28) [2021-11-01].https://www.mee.gov.cn/xxgk2018/xxgk/xxgk03/201904/t20190429_701463.html 中华人民共和国生态环境部. 关于推进实施钢铁行业超低排放的意见[EB/OL]. 政府信息公开 (2019-04-28) [2021-11-01].https://www.mee.gov.cn/xxgk2018/xxgk/xxgk03/201904/t20190429_701463.html
[4]	Ministry of Ecology and Environment of the People's Republic of China. HJ 2053—2018 Technical Specifications for Flue Gas Ultra-low Emission Engineering of Coal-fired Power Plant. Beijing: China Environmental Press, 2018 中华人民共和国生态环境部. HJ 2053—2018燃煤电厂超低排放烟气治理工程技术规范. 北京: 中国环境科学出版社, 2018
[5]	Meng Z H, Wang C Y, Wang X R, et al. Simultaneous removal of SO₂ and NO_x from flue gas using (NH₄)₂S₂O₃/steel slag slurry combined with ozone oxidation. Fuel, 2019, 255: 115760 doi: 10.1016/j.fuel.2019.115760
[6]	Paulauskas, Jõgi, Striūgas, et al. Application of non-thermal plasma for NO_x reduction in the flue gases. Energies, 2019, 12(20): 3955 doi: 10.3390/en12203955
[7]	Zhang Q, He S L, Zhang Z, et al. Low-temperature selective catalytic reduction of NO_z and anti-toxicity of MnO_x–FeO_y/TiO₂–ZrO₂–CeO₂. Chin J Eng, 2020, 42(3): 321 张晴, 贺拴玲, 张铮, 等. MnO_x–FeO_y/TiO₂–ZrO₂–CeO₂低温选择性催化还原NO_z和抗毒性研究. 工程科学学报, 2020, 42(3):321
[8]	Ding L, Qian L X, Yang T, et al. Influence of Zn in the iron ore sintering flue gas on the removal of NO_x and dioxins by V₂O₅–WO₃/TiO₂ catalyst. Chin J Eng, 2021, 43(8): 1125 丁龙, 钱立新, 杨涛, 等. 烧结烟气中Zn对V₂O₅–WO₃/TiO₂催化剂脱除NO_x和二噁英性能的影响. 工程科学学报, 2021, 43(8):1125
[9]	Xing Y, Zhang W B, Su W, et al. Research of ultra-low emission technologies of the iron and steel industry in China. Chin J Eng, 2021, 43(1): 1 邢奕, 张文伯, 苏伟, 等. 中国钢铁行业超低排放之路. 工程科学学报, 2021, 43(1):1
[10]	Yang R T. Gas Separation by Adsorption Processes. London: World Scientific, 1997
[11]	Ren F P, Tian X Z, Ren Y L, et al. Nitrogen dioxide-catalyzed aerobic oxidation of benzyl alcohols under cocatalyst and acid-free conditions. Catal Commun, 2017, 101: 98 doi: 10.1016/j.catcom.2017.08.003
[12]	Kong Y, Cha C Y. NO_x adsorption on char in presence of oxygen and moisture. Carbon, 1996, 34(8): 1027 doi: 10.1016/0008-6223(96)00050-4
[13]	Hu M M, Zhang Z Q, Atkinson J D, et al. Porous materials for steady-state NO conversion: Comparisons of activated carbon fiber cloths, zeolites and metal-organic frameworks. Chem Eng J, 2019, 360: 89 doi: 10.1016/j.cej.2018.11.102
[14]	Machida M, Yoshii A, Kijima T. Temperature swing adsorption of NO_x over ZrO₂-based oxides. Int J Inorg Mater, 2000, 2(5): 413 doi: 10.1016/S1466-6049(00)00062-3
[15]	Xing N, Wang X P, Yu Q, et al. Adsorption performance of zeolites for NO and NO₂. Chin J Catal, 2007, 28(3): 205 doi: 10.3321/j.issn:0253-9837.2007.03.006 邢娜, 王新平, 于青, 等. 分子筛对NO和NO₂的吸附性能. 催化学报, 2007, 28(3):205 doi: 10.3321/j.issn:0253-9837.2007.03.006
[16]	An J L, Wang Y S, Li X, et al. Analysis of the relationship between NO, NO₂ and O₃ concentrations in Beijing. Environ Sci, 2007, 28(4): 4706 安俊琳, 王跃思, 李昕, 等. 北京大气中NO、NO₂和O₃浓度变化的相关性分析. 环境科学, 2007, 28(4):4706
[17]	Brown C E, Hall P G. Physical adsorption of nitric oxide on graphite and silica and adsorption of gases on nitric oxide preadsorbed on carbon. J Colloid Interface Sci, 1973, 42(2): 334 doi: 10.1016/0021-9797(73)90297-X
[18]	Brown C E, Hall P G. Physical adsorption of nitric oxide on metal oxides. Surf Sci, 1973, 36(2): 569 doi: 10.1016/0039-6028(73)90403-2
[19]	Deng H, Yi H H, Tang X L, et al. Adsorption equilibrium for sulfur dioxide, nitric oxide, carbon dioxide, nitrogen on 13X and 5A zeolites. Chem Eng J, 2012, 188: 77 doi: 10.1016/j.cej.2012.02.026
[20]	Penkova A, Hadjiivanov K, Mihaylov M, et al. FTIR spectroscopic study of low temperature NO adsorption and NO + O₂ coadsorption on H-ZSM-5. Langmuir, 2004, 20(13): 5425 doi: 10.1021/la0496643
[21]	Szanyi J, Hun Kwak J, Moline R A, et al. The adsorption of NO₂ and the NO+O₂ reaction on Na–Y, FAU: An in situ FTIR investigation. Phys Chem Chem Phys, 2003, 5(18): 4045 doi: 10.1039/B306585E
[22]	Liu Y S, Sun N Q, Li Z Y, et al. Recovery of high-purity NO₂ and SO₂ products from iron-ore sintering flue gas by distillation: Process design, optimization and analysis. Sep Purif Technol, 2021, 264: 118308 doi: 10.1016/j.seppur.2021.118308
[23]	Ghouma I, Jeguirim M, Dorge S, et al. Activated carbon prepared by physical activation of olive stones for the removal of NO₂ at ambient temperature. Comptes Rendus Chimie, 2015, 18(1): 63 doi: 10.1016/j.crci.2014.05.006
[24]	Liu H R. Variation of spontaneous combustion point of activated carbon with different oxidation degree. Fire Sci Technol, 2013, 32(4): 367 doi: 10.3969/j.issn.1009-0029.2013.04.006 刘函如. 不同氧化程度的活性炭自燃点变化规律研究. 消防科学与技术, 2013, 32(4):367 doi: 10.3969/j.issn.1009-0029.2013.04.006
[25]	Silas K, Wan Azlina Wan Ab Karim Ghani, Choong T S Y, et al. Carbonaceous materials modified catalysts for simultaneous SO₂/NO_x removal from flue gas: A review. Catal Rev, 2019, 61(1): 134 doi: 10.1080/01614940.2018.1482641
[26]	Jiang H X, Wang Q Y, Wang H Q, et al. MOF-74 as an efficient catalyst for the low-temperature selective catalytic reduction of NO_x with NH₃. ACS Appl Mater Interfaces, 2016, 8(40): 26817 doi: 10.1021/acsami.6b08851
[27]	Bauer S, Serre C, Devic T, et al. High-throughput assisted rationalization of the formation of metal organic frameworks in the iron(III) aminoterephthalate solvothermal system. Inorg Chem, 2008, 47(17): 7568 doi: 10.1021/ic800538r
[28]	Zhang Z Q, Atkinson J D, Jiang B Q, et al. NO oxidation by microporous zeolites: Isolating the impact of pore structure to predict NO conversion. Appl Catal B Environ, 2015, 163: 573 doi: 10.1016/j.apcatb.2014.06.044
[29]	Liu Y S, You Y, Li Z Y, et al. NO_x removal with efficient recycling of NO₂ from iron-ore sintering flue gas: A novel cyclic adsorption process. J Hazard Mater, 2021, 407: 124380 doi: 10.1016/j.jhazmat.2020.124380
[30]	You Y, Liu Y S, Yang X, et al. A new adsorption process for flue gas NO_x purification and recovery. CIESC J, 2021, 72(4): 2132 游洋, 刘应书, 杨雄, 等. 面向烟气NO_x净化与回收的新型吸附工艺. 化工学报, 2021, 72(4):2132
[31]	Huang H Y, Yang R T. Removal of NO by reversible adsorption on Fe−Mn based transition metal oxides. Langmuir, 2001, 17(16): 4997 doi: 10.1021/la0102657
[32]	Yang X, Liu Y S, Li Z Y, et al. Vacuum exhaust process in pilot-scale vacuum pressure swing adsorption for coal mine ventilation air methane enrichment. Energies, 2018, 11(5): 1030 doi: 10.3390/en11051030
[33]	Li Z Y, Liu Y S, Yang X, et al. Desorption kinetics of naphthalene and acenaphthene over two activated carbons via thermogravimetric analysis. Energy Fuels, 2015, 29(8): 5303 doi: 10.1021/acs.energyfuels.5b01159
[34]	Li G, Xiao P, Zhang J, et al. The role of water on postcombustion CO₂ capture by vacuum swing adsorption: Bed layering and purge to feed ratio. Aiche J, 2014, 60(2): 673 doi: 10.1002/aic.14281
[35]	Li Z Y, Liu Y S, Wang H H, et al. A numerical modelling study of SO₂ adsorption on activated carbons with new rate equations. Chem Eng J, 2018, 353: 858 doi: 10.1016/j.cej.2018.07.119
[36]	Zhu X Q, Liu Y S, Yang X, et al. Study of a novel rapid vacuum pressure swing adsorption process with intermediate gas pressurization for producing oxygen. Adsorption, 2017, 23(1): 175 doi: 10.1007/s10450-016-9843-4
[37]	Mendes A M M, Costa C A V, Rodrigues A E. Linear driving force approximation for isothermal non-isobaric diffusion/convection with binary Langmuir adsorption. Gas Sep Purif, 1995, 9(4): 259 doi: 10.1016/0950-4214(95)00008-Y
[38]	Zhang B W, Tang X L, Yi H H, et al. Study on NO adsorptive removal on modified activated carbon. New Chem Mater, 2015, 43(7): 111 张波文, 唐晓龙, 易红宏, 等. 改性活性炭吸附去除NO实验研究. 化工新型材料, 2015, 43(7):111
[39]	Zhang J Q, Liu Y Y, Fan W B, et al. Adsorption and temperature programmed desorption of NO, NO+O₂, NO₂ and NO + NO₂ over CoH-ZSM-5. Fuel, 2007, 86(10-11): 1577 doi: 10.1016/j.fuel.2006.11.011
[40]	Loiland J A, Lobo R F. Low temperature catalytic NO oxidation over microporous materials. J Catal, 2014, 311: 412 doi: 10.1016/j.jcat.2013.12.013
[41]	Li R, Wu B, Chen Y Q, et al. Influence of polyethylene glycol on the catalytic activity of MnFeO_x for NO oxidation at low-temperature. Catal Lett, 2019, 149(7): 1864 doi: 10.1007/s10562-019-02793-9
[42]	Wang Z, Guo M, Mu X Y, et al. Highly sensitive capacitive gas sensing at ionic liquid-electrode interfaces. Anal Chem, 2016, 88(3): 1959 doi: 10.1021/acs.analchem.5b04677