REMOVAL PERFORMANCE OVER MnCeOx/P84 CATALYTIC FILTER WITH SPHERICAL CATALYTIC INTERFACE
-
摘要: 催化滤布可同时去除烟气中的粉尘颗粒和NOx,满足水泥等行业NOx脱除的迫切需求。而催化滤布中催化界面的形貌会显著影响其脱硝性能。制备了具有球形催化界面的MnCeOx/P84催化滤布(α-MnCeOx/P84),并考察其NOx脱除性能。结果表明:当MnCeOx负载量为60 g/m2时,α-MnCeOx/P84在130 ℃时NOx脱除率为86.9%,160~190 ℃时NOx脱除率>97%。同时,α-MnCeOx/P84具有较好的抗SO2性能和稳定性,通入体积分数为0.003%的SO2后,在190 ℃下,其NOx脱除率达到83%左右;停止通入SO2后,α-MnCeOx/P84的NOx脱除率上升并稳定在93%左右。且经过200 h的脱硝反应测试后,α-MnCeOx/P84的脱硝活性与催化剂负载量未下降。表征分析结果表明,α-MnCeOx/P84中球形MnCeOx活性组分以弱结晶形式存在,紧密地包裹在滤料纤维表面,且分散均匀;中孔是MnCeOx催化剂的主要孔结构,能够为催化反应的进行提供通道。H2-TPR与Insitu DRIFTS分析进一步表明,α-MnCeOx/P84在100~200 ℃有良好的氧化还原能力,且具有丰富的Lewis和Brnsted酸位,为其优越的低温NH3-SCR脱硝性能提供了重要保障。具有球形催化界面的MnCeOx/P84催化滤布具有低负载量、高稳定性的特点,为滤料除尘脱硝技术的推广应用提供参考。Abstract: Catalytic filters are low-cost and high-efficiency for synergistic removal of NOx and particulates, which have become the development direction of air pollution control technology in the cement and steel industries. The morphology of the catalytic interface in the catalytic filter has a significant influence on its denitration performance. MnCeOx/P84 catalytic filter with a spherical catalytic interface (α-MnCeOx/P84) was prepared, and its NOx removal performance was investigated. The results showed that the NOx removal efficiency of α-MnCeOx/P84 was 86.9% at 130 ℃ and 97% above at 160 ℃ to 190 ℃ when the MnCeOx loading was 60 g/m2. At the same time, α-MnceOx/P84 had good SO2 resistance and stability, and the NOx removal rate of α-MnceOx/P84 could reach 83% at 190 ℃ after introducing SO2 with a volume fraction of 0.003%. When the injection of SO2 was stopped, NOx removal rate of α-MnceOx/P84 increased and stabilized at about 93%. After 200 hours denitrification reaction test, the denitrification efficiency and catalyst loading of α-MnCeOx/P84 did not decrease significantly. The characterization results showed that the spherical MnCeOx active component in α-MnCeOx/P84 was present in weak crystalline form, tightly wrapped around the surface of the filter fiber, uniformly dispersed, and the mesopore was the main pore structure of the MnCeOx catalyst, which could provide a channel for the catalytic reaction to proceed. Further analysis of H2-TPR and In-situ DRIFTS showed that α-MnCeOx/P84 had good redox ability at 100 ℃ to 200 ℃ and had abundant Lewis acid sites and Brnsted acid sites, which provided an important guarantee for its superior low-temperature NH3-SCR denitrification performance. MnCeOx/P84 catalyst filter with a spherical catalytic interface had the characteristics of low load and high stability, which laid a foundation for the promotion and application of dust and NOx removal over catalytic filters.
-
Key words:
- catalytic filter cloth /
- NOx> /
- denitrification /
- catalytic interface
-
[1] HUANG R J, ZHANG Y L, BOZZETTI C, et al. High secondary aerosol contribution to particulate pollution during haze events in China[J]. Nature, 2014, 514(7521):218-222. [2] BONINGARI T, SMIRNIOTIS P G. Impact of nitrogen oxides on the environment and human health:Mn-based materials for the NOx abatement[J]. Current Opinion in Chemical Engineering, 2016,(13):133-141. [3] 毕谆,周红刚.PM2.5引起的肺部疾病及其作用机制的研究进展[J].环境工程,2016,34(增刊1):496-499. [4] XU J Q, CHEN G R, GUO F, et al. Development of wide-temperature vanadium-based catalysts for selective catalytic reducing of NOx with ammonia:review[J]. Chemical Engineering Journal, 2018,353:507-518. [5] 廖玉云,王梦瑜,曹宗平, 等.水泥窑SCR烟气脱硝催化剂的选型与应用[J].中国水泥,2016(5):82-86. [6] YANG B, HUANG Q, CHEN M D, et al. Mn-Ce-Nb-Ox/P84 catalytic filters prepared by a novel method for simultaneous removal of particulates and NO[J]. Journal of Rare Earths, 2019, 37(3):273-281. [7] 国务院关于印发打赢蓝天保卫战三年行动计划的通知[J]. 中华人民共和国国务院公报, 2018(20):40-52. [8] 环境保护部, 国家质量监督检验检疫总局. 水泥工业大气污染物排放标准:GB 4915-2013[S].北京:中国环境科学出版社,2013. [9] ZHENG Y Y, ZHANG Y B, WANG X, et al. MnO2 catalysts uniformly decorated on polyphenylene sulfide filter felt by a polypyrrole-assisted method for use in the selective catalytic reduction of NO with NH3[J]. RSC Adv, 2014, 4(103):59242-59247. [10] YANG B, ZHENG D H, SHEN Y S, et al. Influencing factors on low-temperature deNOx performance of Mn-La-Ce-Ni-Ox/PPS catalytic filters applied for cement kiln[J]. Journal of Industrial and Engineering Chemistry, 2015, 24:148-152. [11] 杨波, 沈岳松, 邱云顺, 等. Mn-La-Ce-Ni-Ox/P84一体化滤布的低温脱硝影响因素[J]. 环境工程学报, 2016, 10(11):6583-6587. [12] YANG B, SHEN Y S, SU Y, et al. Removal characteristics of nitrogen oxides and particulates of a novel Mn-Ce-Nb-Ox/P84 catalytic filter applied for cement kiln[J]. Journal of Industrial and Engineering Chemistry, 2017,50:133-141. [13] 付彬彬, 郑玉婴, 陈健, 等. 氧化还原沉淀法制备Mn-Ce-Co-Ox/PPS滤料及其低温SCR活性[J]. 燃料化学学报, 2017, 45(6):731-739. [14] LIU M C, JING D W, ZHOU Z H, et al. Twin-induced one-dimensional homojunctions yield high quantum efficiency for solar hydrogen generation[J]. Nat Commun, 2013, 4(1):2278-2286. [15] PAN L, WANG S B, ZOU J J, et al. Ti3+-defected and V-doped TiO2 quantum dots loaded on MCM-41[J]. Chem Commun (Camb), 2014, 50(8):988-990. [16] GAO F Y, TANG X L, YI H H, et al. In-situ DRIFTS for the mechanistic studies of NO oxidation over α-MnO2, β-MnO2 and γ-MnO2 catalysts[J]. Chemical Engineering Journal, 2017,322:525-537. [17] LI Y, LI Y P, WAN Y, et al. Structure-performance relationships of MnO2 nanocatalyst for the low-temperature SCR removal of NOx under ammonia[J]. RSC Advances, 2016, 6(60):54926-54937. [18] LIU C, DING R Y, XIE F C. Facile synthesis of manganese dioxide nanoparticles for efficient removal of aqueous As(Ⅲ)[J]. Journal of Chemical & Engineering Data, 2020, 65(8):3988-3997. [19] 梅超强,杨波,戴毅, 等.Co改性α-MnO2催化剂用于低温同时催化脱除烟气中的NO和C6H5Cl[J/OL].南京工业大学学报(自然科学版):1-7[2022-04-26].http://kns.cnki.net/kcms/detail/32.1670.N.20220412.1036.010.html. [20] LI Y R, GUO Y Y, XIONG J, et al. The roles of sulfur-containing species in the selective catalytic reduction of NO with NH3 over activated carbon[J]. Industrial & Engineering Chemistry Research, 2016, 55(48):12341-12349. [21] 陈健, 郑玉婴, 张延兵, 等. 氧化还原沉淀法制备MnO2/MWCNTs催化剂及其低温SCR活性[J]. 无机材料学报,2016,31(12):1347-1354. [22] KANG M, PARK E, KIM J, et al. Manganese oxide catalysts for NOx reduction with NH3 at low temperatures[J]. Applied Catalysis A:General, 2007, 327(2):261-269. [23] QI G S, YANG R T. Performance and kinetics study for low-temperature SCR of NO with NH3 over MnOx-CeO2 catalyst[J]. Journal of Catalysis, 2003, 217(2):434-441. [24] LIU L J, SU S, XU K, et al. Insights into the highly efficient Co modified MnSm/Ti catalyst for selective catalytic reduction of NOx with NH3 at low temperature[J]. Fuel, 2019, 255:115798. [25] DENG S C, MENG T T, XU B L, et al. Advanced MnOx/TiO2 catalyst with preferentially exposed anatase {001} facet for low-temperature SCR of NO[J]. Acs Catalysis, 2016, 6(9):5807-5815. [26] TANG X L, HAO J M, XU W G, et al. Low temperature selective catalytic reduction of NOx with NH3 over amorphous MnOx catalysts prepared by three methods[J]. Catalysis Communications, 2007, 8(3):329-334. [27] CHAO Z X, WANG Y F, JAKOBSEN J P, et al. Numerical investigation of the sorption enhanced steam methane reforming in a fluidized bed reactor[J]. Energy Procedia, 2012, 26:15-21. [28] LIU X L, GUO J X, CHU Y H, et al. Desulfurization performance of iron supported on activated carbon[J]. Fuel, 2014, 123:93-100. [29] 唐晓龙. 低温选择性催化还原NOx技术及反应机理[M]. 北京:冶金工业出版社, 2007. [30] ZHANG D S, ZHANG L, FANG C, et al. MnOx-CeOx/CNTs pyridine-thermally prepared via a novel in situ deposition strategy for selective catalytic reduction of NO with NH3[J]. Rsc Advances, 2013, 3(23):8811-8819. [31] CHENG F, ZHANG D S, SHI L Y, et al. Highly dispersed CeO2 on carbon nanotubes for selective catalytic reduction of NO with NH3[J]. Catalysis Science & Technology, 2013, 3(3):803-811. [32] 樊荣, 杨波, 黄琼, 等. Nb改性对MnCe0.2Ox低温SCR抗硫和水热稳定性能的影响[J]. 南京工业大学学报(自然科学版), 2020,42(6):751-759. [33] ZHA K W, CAI S X, HANG H, et al. In situ DRIFTs investigation of promotional effects of Tungsten on MnOx-CeO2/meso-TiO2 catalysts for NOx reduction[J]. The Journal of Physical Chemistry C, 2017, 121(45):25243-25254. [34] FANG N J, GUO J X, SHU S, et al. Enhancement of low-temperature activity and sulfur resistance of Fe0.3Mn0.5Zr0.2 catalyst for NO removal by NH3-SCR[J]. The Chemical Engineering Journal, 2017, 325:114-123. [35] LI G, WANG B D, WANG Z C, et al. Reaction mechanism of low-temperature selective catalytic reduction of NOx over Fe-Mn oxides supported on fly-ash-derived SBA-15 molecular sieves:structure-activity relationships and in situ DRIFT analysis[J]. The Journal of Physical Chemistry, C Nanomaterials and Interfaces, 2018, 122(35):20210-20231. [36] ZHA K W, KANG L, FENG G,et al. Improved NOx reduction in the presence of alkali metals by using hollandite Mn-Ti oxide promoted Cu-SAPO-34 catalysts[J]. Environmental Science Nano, 2018(5):1408-1419. [37] PENG Y, WANG C Z, LI J H. Structure-activity relationship of VOx/CeO2 nanorod for NO removal with ammonia[J]. Applied Catalysis B Environmental, 2014, 144:538-546. [38] ZHU J, GAO F, DONG L H, et al. Studies on surface structure of MxOy/MoO3/CeO2 system (M=Ni, Cu, Fe) and its influence on SCR of NO by NH3[J]. Applied Catalysis B:Environmental, 2010, 95(1/2):144-152. [39] QUAN X, YANG W J, CUI S T, et al. Sulfur resistance of Ce-Mn/TiO2 catalysts for low-temperature NH3-SCR[J]. Royal Society Open Science, 2018, 5(3):171846-171855. [40] 张茹杰,王夫美,白鹏飞, 等.球磨制备低钒基催化剂的NH3-SCR脱硝性能[J].环境工程,2021,39(3):103-110. [41] 沈伯雄, 刘亭. 低温NH3-SCR催化剂MnOx-CeOx/ACF的SO2中毒机理[J]. 物理化学学报, 2010,26(11):3009-3016.
点击查看大图
计量
- 文章访问数: 97
- HTML全文浏览量: 18
- PDF下载量: 6
- 被引次数: 0