面向烟气NOx净化与回收的新型吸附工艺

doi:10.11949/0438-1157.20200899

摘要/Abstract

摘要：

合理高效的吸附工艺是决定吸附法净化和回收烟气中NO_x工业可行性的关键工艺环节。提出一种通过外部补充气体实现固定床循环体空间内多次循环解吸NO_x的新型吸附工艺（GVTSA）。基于该工艺，采用Na-ZSM-5分子筛作为吸附剂，以某钢厂烧结机脱硫后烟气为原料（组分）进行了NO_x吸附回收实验研究。结果表明，GVTSA工艺相较传统吸附工艺（TSA工艺、VSA工艺）可获取更高的NO_x回收量，在优选条件下（220℃，-50 kPa），NO_x回收率达到90%，解吸气中NO₂浓度由原料气的36 mg·m^-3提升到2%以上，NO_x循环吸附量可达0.10 mmol·g^-1，16次吸脱附循环稳定。研究结果可为烟气NO_x治理与资源化工业应用提供参考。

关键词: 烟气净化, 氮氧化物, 吸附（作用）, 回收, 再生

Abstract:

Reasonable and efficient adsorption process is the key process link that determines the industrial feasibility of the adsorption method to purify and recover NO_x in flue gas. In this paper, a novel adsorption process (GVTSA) with NO_x desorption using multiple hot gas circulations (GC) within the enclosed fixed bed through extra gas replenishment was proposed. Based on Na-ZSM-5 zeolites as sorbents, experimental studies on NO_x adsorption and recycling from desulfurized iron-ore sintering flue gas of a steel plant were conducted. The results show that the GVTSA obtained a higher NO_x recovery compared with traditional adsorption processes (e.g. TSA, VSA), reaching 90% under the optimal conditions (220℃, -50 kPa). The concentration of desorbed NO₂ was more than 2%, significantly enhanced from merely 36 mg·m^-3 in the feed gas. The NO_x cyclic adsorption capacity reached 0.10 mmol·g^-1 for up to 16 cycles. This work can provide references for industrial engineering application of flue gas ultra-low emission control and resource utilization.

Key words: flue gas purification, nitrogen oxide, adsorption, recovery, regeneration

中图分类号:

TF 09

游洋, 刘应书, 杨雄, 吴晓永, 赵春雨, 王正, 侯环宇, 李子宜. 面向烟气NO_x净化与回收的新型吸附工艺[J]. 化工学报, 2021, 72(4): 2132-2138.

YOU Yang, LIU Yingshu, YANG Xiong, WU Xiaoyong, ZHAO Chunyu, WANG Zheng, HOU Huanyu, LI Ziyi. A new adsorption process for flue gas NO_x purification and recovery[J]. CIESC Journal, 2021, 72(4): 2132-2138.

图/表 10

图1 NOx吸附分离回收现场实验设备及工艺（蓝色路线：吸附流程；红色路线：解吸流程）1—过滤器；2—阀门开启；3—阀门关闭；4—脱水塔；5—增压泵；6—脱硝塔；7—换热器；8—循环鼓风机；9—储气罐；10—冷却器；11—真空泵

Fig.1 Field test equipment and process of NOx adsorption separation and recycling (blue line: adsorption process; red line: desorption process)

表1 现场实验不同位置的烟气条件

Table 1 Information about flue gases at different locations of field experiment

位置

烟气温度/℃

RH/%

O₂/%

CO₂/%

CO/%

NO/

(mg·m^-3)

表2 大、小规模现场实验参数

Table 2 Experimental parameters of larger and smaller tower field tests

参数	小塔	大塔
脱硝塔内径/cm	3	8
脱硝塔高度/cm	26	220
填装体积V_a/L	0.184	11.1
吸附剂质量/g	70	5000
堆积密度/(kg·m^-3)	381	452
烟气流量/(L·min^-1)	1	65
烟气温度/℃	308	308
环境温度/℃	298	298
空速/h^-1	326.6	352.6
空塔流速/(m·s^-1)	0.0236	0.2156
循环流量/(L·min^-1)	0.3	20
单次循环补充气量/L	1	65
循环次数	1~3	1~3
前期吹扫气流量/(L·min^-1)	0.2	13
前期吹扫时间/min	10	10
后期吹扫气流量/(L·min^-1)	0.5	35

图2 Na-ZSM-5吸附剂的NOx吸附等温线 (25℃)

Fig.2 NOx adsorption isotherm (25℃) of Na-ZSM-5 adsorbent

图3 解吸温度对NOx二次吸附量的影响

Fig.3 Variation of NOx secondary adsorption capacity with desorption temperature

图4 解吸压力对NOx二次吸附量的影响

Fig.4 Variation of NOx secondary adsorption capacity with desorption pressure

图6 不同吸附工艺的NOx解吸量

Fig.6 qd-NOxfor different adsorption processes

图5 不同吸附工艺的NO2、NO、CO2、CO的浓度

Fig.5 Concentration of NO2, NO, CO2, CO for different adsorption processes

图7 GVTSA工艺第1~16次循环的NOx循环吸附量

Fig.7 NOx cyclic adsorption capacities for 1st—16th cycles of GVTSA process

图8 GVTSA工艺第4~16次循环的NOx、NO和NO2穿透曲线的平均值

Fig.8 NOx, NO and NO2 breakthrough curves averaged over 4th—16th cycles of GVTSA process

参考文献 35

1	Gholami F, Tomas M, Gholami Z, et al. Technologies for the nitrogen oxides reduction from flue gas: a review[J]. Sci. Total. Environ., 2020, 714: 136712.
2	Giampiccolo A, Tobaldi D M, Leonardi S G, et al. Sol gel graphene/TiO₂ nanoparticles for the photocatalytic-assisted sensing and abatement of NO₂[J]. Appl. Catal. B, 2019, 243: 183-194.
3	Resitoglu I A, Keskin A. Hydrogen applications in selective catalytic reduction of NO_x emissions from diesel engines[J]. Int. J. Hydrogen Energy, 2017, 42(36): 23389-23394.
4	Liu J, Luo X, Yao S, et al. Influence of flue gas recirculation on the performance of incinerator-waste heat boiler and NO_x emission in a 500 t/d waste-to-energy plant[J]. Waste Manage., 2020, 105: 450-456.
5	Yamamoto Y, Yamamoto H, Takada D, et al. Simultaneous removal of NO_x and SO_x from flue gas of a glass melting furnace using a combined ozone injection and semi-dry chemical process[J]. Ozone-Sci. Eng., 2016, 38(3): 211-218.
6	Ren F, Tian X, Ren Y L, et al. Nitrogen dioxide-catalyzed aerobic oxidation of benzyl alcohols under cocatalyst and acid-free conditions[J]. Catal. Commun., 2017, 101: 98-101.
7	Nesbitt H, Browne G, Odonovan K, et al. Nitric oxide up-regulates RUNX2 in LNCaP prostate tumours: implications for tumour growth in vitro and in vivo[J]. J. Cell Physiol., 2016, 231(2): 473-482.
8	Choi S, Drese J H, Jones C W, et al. Adsorbent materials for carbon dioxide capture from large anthropogenic point sources[J]. ChemSusChem, 2009, 2(9): 796-854.
9	Mohapatro S, Rajanikanth B S. Cascaded cross flow DBD-adsorbent technique for NO_xabatement in diesel engine exhaust, IEEE Trans[J]. Dielectr. Electr. Insul., 2010, 17: 1543-1550.
10	Selleri T, Gramigni F, Nova I, et al. NO oxidation on Fe- and Cu-zeolites mixed with BaO/Al₂O₃: free oxidation regime and relevance for the NH₃-SCR chemistry at low temperature[J]. Appl. Catal. B, 2018, 225: 324-331.
11	Breedon M, Spencer M, Miura N. The adsorption of NO on YSZ(111) and oxygen-enriched YSZ(111) surfaces[J]. Chem. Phys. Lett., 2014, 593: 61-68.
12	Shirahama N, Moon S H, Choi K, et al. Mechanistic study on adsorption and reduction of NO₂ over activated carbon fibers[J]. Carbon, 2002, 40(4): 2605-2611.
13	Wang X, Hanson J C, Kwak J H, et al. Cation movements during dehydration and NO₂ desorption in a Ba-Y, FAU zeolite: an in situ time-resolved X-ray diffraction study[J]. J. Phys. Chem. C, 2013, 117(8): 3915-3922.
14	Li J, Han X, Zhang X, et al. Capture of nitrogen dioxide and conversion to nitric acid in a porous metal–organic framework[J]. Nat. Chem., 2019, 11(12): 1085-1090.
15	Li Y, Liu W, Yan R, et al. Hierarchical three-dimensionally ordered macroporous Fe-V binary metal oxide catalyst for low temperature selective catalytic reduction of NO_xfrom marine diesel engine exhaust[J]. Appl. Catal. B, 2020, 268: 118455.
16	Liu H, Zhang Z, Xu Y, et al. Adsorption-oxidation reaction mechanism of NO on Na-ZSM-5 molecular sieves with a high Si/Al ratio at ambient temperature[J]. Chin. J. Catal., 2010, 31(9/10): 1233-1241.
17	Liu L, Li Z, Liu S, et al. Effect of exhaust gases of exhaust gas recirculation(EGR) coupling lean-burn gasoline engine on NO_x purification of lean NO_x trap(LNT) [J]. Mech. Syst. Signal Pr., 2017, 87: 195-213.
18	Yoshida K, Rajanikanth B S, Okubo M, et al. NO_x reduction and desorption studies under electric discharge plasma using a simulated gas mixture: a case study on the effect of corona electrodes[J]. Plasma Sci. Technol., 2019, 11(3): 327-333.
19	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[J]. C. R. Chim., 2015, 18(1): 63-74.
20	Machida M, Yoshii A, Kijima T. Temperature swing adsorption of NO_x over ZrO₂-based oxides[J]. Int. J. Inorg. Mater., 2000, 2(5): 413-417.
21	Matsuok S, Kodama T, Kumagai M, et al. Development of adsorption process for NO_x recycling in a reprocessing plant[J]. J. Nucl. Sci. Technol., 2003, 40(6): 410-416.
22	Yoshida K. The effect of NO pre-oxidizing in a temperature-swing-adsorption system for diesel NO_x after treatment—mechanisms to enhance its performance[J]. J. Taiwan Inst. Chem. Eng., 2018, 86: 141-147.
23	Saleman T L, Li G, Rufford T E, et al. Capture of low grade methane from nitrogen gas using dual-reflux pressure swing adsorption[J]. Chem. Eng. J., 2015, 281: 739-748.
24	Han Z, Wang D, Jiang P, et al. Enhanced removal and recovery of binary mixture of n-butyl acetate and p-xylene by temperature swing-vacuum pressure swing hybrid adsorption process[J]. Process Saf. Environ. Prot., 2020, 135: 273-281.
25	Zhang W, Yahiro H, Mizuno N, et al. Removal of nitrogen monoxide on copper ion-exchanged zeolites by pressure swing adsorption[J]. Langmuir, 1993, 9(9): 2337-2343.
26	Zhang Z, John D A, Jiang B, et al. NO oxidation by microporous zeolites: isolating the impact of pore structure to predict NO conversion[J]. Appl. Catal. B, 2015, 163(2): 573-583.
27	Lee Y, Park J, Jun S, et al. NO_x adsorption-temperature programmed desorption and surface molecular ions distribution by activated carbon with chemical modification[J]. Carbon, 2004, 42(1): 59-69.
28	Silas K, Ghani W, Choong T, et al. Carbonaceous materials modified catalysts for simultaneous SO₂/NO_x removal from flue gas: a review[J]. Catalysis Reviews, 2018, 61(1): 134-161.
29	Paolo D. SO₂ and NO_x adsorption properties of activated carbons obtained from a pitch containing iron derivatives[J]. Carbon, 2001, 39(14): 2173-2179.
30	Yu H, Xie Q. Discussion on reducing abrasion loss of active coke in dry-type desulfurization and denitrification technology [J]. Mining Engineering, 2018, 16(2): 37-39.
31	Szanyi J, Kwak J, Peden C. The effect of water on the adsorption of NO₂ in Na- and Ba-Y, FAU zeolites: a combined FTIR and TPD investigation[J]. J. Phys. Chem. B, 2004, 108: 3746-3753.
32	Seredych M, Bashkova S, Pietrzak R, et al. Interactions of NO₂ and NO with carbonaceous adsorbents containing silver nanoparticles[J]. Langmuir, 2010, 26(12): 9457-9464.
33	Szanyi J, Kwak J H, Moline R A, et al. The adsorption of NO₂ and the NO + O₂ reaction on Na-Y, FAU: an in situ FTIR investigation[J]. Phys. Chem. Chem. Phys., 2003, 5(18): 4045-4051.
34	Delachaux F, Vallières C, Monnier H, et al. Experimental study of NO and NO₂ adsorption on a fresh or dried NaY zeolite: influence of the gas composition by breakthrough curves measurements[J]. Adsorption, 2019, 25(1): 95-103.
35	Liu L, Jin S, Ko K, et al. Alkyl-functionalization of (3-aminopropyl) triethoxysilane-grafted zeolite beta for carbon dioxide capture in temperature swing adsorption[J]. Chem. Eng. J., 2020, 382: 122834.

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