Study on catalytic performance and reaction mechanism of catalytic denitrification
YUN Yu-pan1,2, MIAO Zhi-jia1, WANG Xiao-lei3, WANG Wei-yan3, YU Hai-tao2
1. Hebei Province Collaborative Innovation Center for Sustainable Utilization of Water Resources and Optimization of Industrial Structure, Hebei GEO University, Shijiazhuang 0500312, China; 2. Hebei Key Laboratory of Organic Functional Molecules, College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang 0500312, China; 3. Wastewater Treatment and Resource Reusing Technology Innovation Center of Hebei Province, Hebei Yuehai Water Group Co., Ltd., Shijiazhuang 050031, China
Abstract：In order to resolve nitrate pollution in water body, the novel catalytic denitrification by synergistic effect of zero-valent iron (Fe0) and Pd-Cu catalyst was proposed. The optimization of operational conditions, reaction mechanism, and kinetic study were further investigated. Results found that using response surface methodology for experimental design and data analyses, 74.6% of N2 conversion was obtained under the following optimal conditions:5.0pH, 135min reaction time, 3.1mass ration (Pd:Cu), and 3.1g/L Fe0. In the catalytic process, Fe0primarily serves as the electron donor. Pd and Cu coated on the carrier play critical roles in catalytic denitrification. Physical-chemical characteristics of carrier (such as porous structure, specific surface area, adsorption ability etc.) dramatically influence the catalytic performance. It's also found that N2conversion could be greatly improved by controlling solution pH, acid wash of carrier, and replacement of catalyst's active ingredient. Catalytic reduction of nitrate was better demonstrated by first-order equation of Langmuir-Hinshelwood modeling. Catalytic denitrification has been regarded as the typical multiphase and multistage reaction process. Acid and alkaline wash by certain concentration of HCl or NaOH solution may partially regenerate the catalyst and improve its catalytic performance.
Zhang N, He Y C, Yi X, et al. Rapid start-up of autotrophic shortcut nitrifification system in SBR and microbial community analysis[J]. Environmental Technology, 2022,43(25):4363-4375.
[2]
Rahimi S, Modin O, Mijakovic I. Technologies for biological removal and recovery of nitrogen from wastewater[J]. Biotech. Adv., 2020,43:107570.
[3]
Rong C, Luo Z B, Wang T J, Guo Y, Kong Z, Wu J. Chemical oxygen demand and nitrogen transformation in a large pilot-scale plant with a combined submerged anaerobic membrane bioreactor and one-stage partial nitritation-anammox for treating mainstream wastewater at 25◦C[J]. Bioresource Technology, 2021,341:125840.
[4]
于妍,刘宁,廖祖刚,等.铁型反硝化脱氮技术研究进展[J]. 中国环境科学, 2022,42(1):83-91. Yu Y, Liu N, Liao Z G, et al. Research progress of iron-type denitrification removal technology[J]. China Environmental Science, 2022,42(1):83-91.
[5]
杜睿,彭永臻.城市污水生物脱氮技术变革:厌氧氨氧化的研究与实践新进展[J]. 中国科学:技术科学, 2021,51:1-14. Du R, Peng Y Z. Technical revolution of biological nitrogen removal from municipal wastewater:Recent advances in Anammox research and application[J]. Sci. Sin. Tech., 2022,52:389-402.
[6]
沈耀良.城市污水处理工艺:生命周期评价[J]. 苏州科技大学学报(工程技术版), 2019,32(1):1-9. Shen Y L. Municipal wastewater treatment processes:Life cycle assessment (LCA)[J]. Journal of Suzhou University of Science and Technology (Engineering and Technology), 2019,32(1):1-9.
[7]
Zhang Y, Xie Z, Lu C. Study on the electron transfer capability of porphyrin ring and the mechanisms in the catalytic denitrification[J]. Biochemical Engineering Journal, 2021,175:108010.
[8]
Mendow G, Sanchez A, Grosso C, et al. A novel process for nitrate reduction in water using bimetallic Pd-Cu catalysts supported on ion exchange resin[J]. J. Environ. Chem. Eng, 2017,5(2):1404-1414.
[9]
Kim M, Chung S, Yoo C, et al. Catalytic reduction of nitrate in water over Pd-Cu/TiO2 catalyst:Effect of the strong metal-support interaction (SMSI) on the catalytic activity[J]. Applied Catalysis B:Environmental, 2013,142:354-361
[10]
Marco D, Pinna F, Strukul G. Nitrate and nitrite hydrogenation with Pd and Pt/SnO2catalysts:the effect of the support porosity and the role of carbon dioxide in the control of selectivity[J]. Applied Catalysis B:Environmental, 2004,(53):161-168.
[11]
Garron A, Epron F. Use of formic acid as reducing agent for application in catalytic reduction of nitrate in water[J]. Water Research, 2005,39(13):3073-3081.
[12]
朱艳芳,金朝晖,方悦,等.催化还原脱除地下水中硝酸盐的研究[J]. 环境科学学报, 2006,26(4):567-571. Zhu Y F, Jin C H, Fang Y, et al. Catalytic reduction of itrate in groundwater[J]. Acta Science Circumstantiae, 2006,26(4):567-571.
[13]
Haddar W, Elksib I, Meksi N, et al. Valorization of the leaves of fennel (Foeniculum vulgare) as natural dyes fixed on modified cotton:A dyeing process optimization based on a response surface methodology[J]. Ind. Crop. Prod, 2014,52:588-596.
[14]
Imran M A, Awais H T. Modelling the properties of one-step pigment-dyed and finished polyester/cotton fabrics using response surface methodology[J]. Coloration Technology, 2016,132(5):414-420.
[15]
Gasemloo S, Khosravi M, Sohrabi M R, et al. Response surface methodology (RSM) modeling to improve removal of Cr (VI) ions from tannery wastewater using sulfated carboxymethyl cellulose nanofilter[J]. J. Clean. Prod., 2019,208:736-742.
[16]
Gasemloo S, Khosravim M, Sohrabi M R, et al. Response surface methodology (RSM) modeling to improve removal of Cr (VI) ions from tannery wastewater using sulfated carboxymethyl cellulose nanofilter[J]. J. Clean. Prod., 2019,208:736-742.
[17]
Abdullah N, Saidur R, Zainoodin A M, et al. Optimization of electrocatalyst performance of platinumeruthenium induced with MXene by response surface methodology for clean energy application[J]. J. Clean. Prod., 2020,277:123395.
[18]
Kim M, Ba S. Immobilization and characterization of Fe(0) catalyst on NaOH-treated coal fly ash for catalytic reduction of p-nitrophenol[J]. Chemosphere, 2018,212:1020-1029.
[19]
Li P J, Lin K R, Fang Z Q, et al. Enhanced nitrate removal by novel bimetallic Fe/Ni nanoparticles supported on biochar[J]. J. Clean. Prod., 2017,151:21-33.
[20]
Hao S, Zhang H, High Catalytic performance of nitrate reduction by synergistic effect of zero-valent iron (Fe0) and bimetallic composite carrier catalyst[J]. J. Clean Prod., 2017,167:192-200.
[21]
Yun Y P, Wen X Y, Liang Z, et al. Study on reaction mechanism and Langmuir-Hinshelwood kinetic model of catalytic denitrification by Fe0and bimetallic catalyst[J]. Journal of Environmental Science and Health, Part A, 2021,56(5):501-507.
[22]
Lubphoo Y, Chyan J M, Grisdanurak N, et al. Influence of Pd-Cu on nanoscale zero-valent iron supported for selective reduction of nitrate[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016,59:285-294.
[23]
Jiao Z, Zhou Y, Miao Z J, et al. Research on catalytic denitrification by zerovalent iron (Fe0) and Pd-Ag catalyst[J]. Plos One, 2022,17(4):e0266057.
[24]
贺泓,李俊华,何洪,等.环境催化-原理及应用[M]. 北京:科学出版社, 2008. He H, Li J H, He H, et al. Environmental Catalysis-Principles and Applications[M]. Beijing:Science Press, 2008.
[25]
Yun Y P, Li Z F, Chen Y H, et al. Elimination of nitrate in secondary effluent of wastewater treatment plants by Fe0and Pd-Cu/diatomite[J]. Journal of Water Reuse and Desalination, 2018,1(8):29-37.
