面向鋼鐵燒結煙氣NO<sub><i>x</i></sub>吸附凈化的吸附劑特性

劉應書; 吳曉永; 李子宜; 楊雄; 劉文海; 侯環宇; 邢奕; 李金娟

doi:10.13374/j.issn2095-9389.2021.11.01.001

面向鋼鐵燒結煙氣NO_x吸附凈化的吸附劑特性

doi: 10.13374/j.issn2095-9389.2021.11.01.001

1.
北京科技大學能源與環境工程學院，北京 100083
2.
河鋼集團鋼研總院，石家莊 050023
3.
貴州大學資源與環境工程學院，喀斯特地質資源與環境教育部重點實驗室，貴陽 550025

基金項目: 國家自然科學基金資助項目（21808012）；“十三五”國家重點研發專項資助項目（2017YFC0210302）；貴州省科技支撐計劃資助項目（黔科合支撐[2021]一般 497）

詳細信息

通訊作者:
E-mail: ziyili@ustb.edu.cn

中圖分類號: X701.7;TF09
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出版歷程
- 收稿日期: 2021-11-01
- 網絡出版日期: 2022-02-22
- 刊出日期: 2022-11-01

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: 吸附法是有望同時實現煙氣NO_x超低排放深度凈化與資源化的關鍵技術，高效NO_x吸附劑是其核心關鍵，然而目前針對滿足應用需求的NO_x吸附劑仍缺乏系統認識。本文基于煙氣NO_x凈化效率及材料熱穩定性實際需求，分析挑選了沸石、金屬氧化物、硅鋁膠等代表性吸附劑，研究了NO_x在各吸附劑上的吸附穿透、吸附量、程序升溫脫附等關鍵特性，結合吸附劑孔道特性對比發現，中低硅H-ZSM-5沸石兼具較高NO_x凈化深度、NO_x吸附量、較低脫附溫度且可獲得更易于資源化的NO_x解吸氣，因而可作為優選NO_x吸附劑。進一步地，隨著吸附溫度升高，硅鋁比(w(SiO₂)/w(Al₂O₃) )為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吸附量較高，但吸附傳質系數較低。本文可為煙氣NO_x吸附凈化的效益環保技術提供指導。
- 煙氣凈化 /
- 氮氧化物 /
- 吸附劑 /
- 吸附 /
- 資源化回收
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 ?ue 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

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圖 1 NO_x吸附實驗系統

Figure 1. NO_x adsorption experimental system

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圖 2 孔徑分布及87 K下Ar的吸附等溫線

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

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圖 3 各吸附劑的NO_x穿透曲線（398 K）

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

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圖 4 H-ZSM-5_25在有氧和無氧條件下的NO_x穿透曲線（298 K）

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

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圖 5 NO_x在各吸附劑的程序性升溫脫附（TPD）曲線（a）和NO與NO₂含量圖（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

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圖 6 不同硅鋁比的H-ZSM-5在不同溫度下的穿透曲線

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

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圖 7 H-ZSM-5_25、H-ZSM-5_38的NO_x吸附量隨溫度的變化曲線

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

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圖 8 H-ZSM-5_25、H-ZSM-5_38的吸附速率曲線（298 K）及LDF模型擬合曲線

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

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表 1 吸附劑的物理參數及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

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表 2 LDF模型擬合參數

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

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