Co3O4 with ordered pore structure derived from wood vessels for efficient Hg0 oxidation

doi:10.1016/j.cjche.2022.06.018

Chinese Journal of Chemical Engineering ›› 2022, Vol. 50 ›› Issue (10): 215-221.DOI: 10.1016/j.cjche.2022.06.018

• Catalysis, Kinetics and Reaction Engineering • Previous Articles Next Articles

Co₃O₄ with ordered pore structure derived from wood vessels for efficient Hg⁰ oxidation

Xiaopeng Zhang, Cheng Gao, Ziwei Wang, Ximiao Wang, Jie Cheng, Xinxin Song, Xiangkai Han, Ning Zhang, Junjiang Bao, Gaohong He

State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, China;School of Chemical Engineering, Dalian University of Technology, Panjin 124221, China

Received:2022-03-17 Revised:2022-06-02 Online:2023-01-04 Published:2022-10-28
Contact: Gaohong He,E-mail:hgaohong@dlut.edu.cn
Supported by:
We gratefully acknowledge the financial supports from the National Natural Science Foundation of China (51978124), Science Fund for Creative Research Groups of the National Natural Science Foundation of China (22021005), and the Cheung Kong Scholars Programme of China (T2012049).

Co₃O₄ with ordered pore structure derived from wood vessels for efficient Hg⁰ oxidation

Xiaopeng Zhang, Cheng Gao, Ziwei Wang, Ximiao Wang, Jie Cheng, Xinxin Song, Xiangkai Han, Ning Zhang, Junjiang Bao, Gaohong He

State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, China;School of Chemical Engineering, Dalian University of Technology, Panjin 124221, China

通讯作者: Gaohong He,E-mail:hgaohong@dlut.edu.cn
基金资助:
We gratefully acknowledge the financial supports from the National Natural Science Foundation of China (51978124), Science Fund for Creative Research Groups of the National Natural Science Foundation of China (22021005), and the Cheung Kong Scholars Programme of China (T2012049).

Abstract

Abstract: Catalytic oxidation of Hg⁰ to HgO is an efficient way to remove Hg⁰ from coal-fired flue gas. The catalyst with ordered pore structure can lower mass transfer resistance resulting in higher Hg⁰ oxidation efficiency. Therefore, in the present work, wood vessels were used as sacrificial template to obtain Co₃O₄ with ordered pore structure. SEM and BET results show that, when the mass concentrations of Co(NO₃)₂·6H₂O was 20%, the obtained catalyst (Co₃O₄ [20%Co(NO₃)₂]) possesses better pore structure and higher surface area. It will expose more available surface active sites and lower the mass transfer resistance. Furthermore, XPS results prove that Co₃O₄ [20%Co(NO₃)₂] has the highest ratio of chemisorbed oxygen which plays an important role in Hg⁰ oxidation process. These results lead to a better Hg⁰ oxidation efficiency of Co₃O₄ [20%Co(NO₃)₂], which is about 90% in the temperature range of 200 to 350 ℃. Furthermore, Co₃O₄ [20%Co(NO₃)₂] has a stable catalytic activity, and its Hg⁰ oxidation efficiency maintains above 90% at 250 ℃ even after 90 h test. A probable reaction mechanism is deduced by the XPS results of the fresh, used and regenerated catalyst of Co₃O₄ [20%Co(NO₃)₂]. Chemisorbed oxygen can react with Hg⁰ forming HgO with the reduction of Co³⁺ to Co²⁺. And lattice oxygen and gaseous oxygen can supplement the consumption of chemisorbed oxygen to oxidize Co²⁺ to Co³⁺.

Key words: Wood vessel, Elemental mercury, Ce₃O₄, Ordered pore structure

摘要： Catalytic oxidation of Hg⁰ to HgO is an efficient way to remove Hg⁰ from coal-fired flue gas. The catalyst with ordered pore structure can lower mass transfer resistance resulting in higher Hg⁰ oxidation efficiency. Therefore, in the present work, wood vessels were used as sacrificial template to obtain Co₃O₄ with ordered pore structure. SEM and BET results show that, when the mass concentrations of Co(NO₃)₂·6H₂O was 20%, the obtained catalyst (Co₃O₄ [20%Co(NO₃)₂]) possesses better pore structure and higher surface area. It will expose more available surface active sites and lower the mass transfer resistance. Furthermore, XPS results prove that Co₃O₄ [20%Co(NO₃)₂] has the highest ratio of chemisorbed oxygen which plays an important role in Hg⁰ oxidation process. These results lead to a better Hg⁰ oxidation efficiency of Co₃O₄ [20%Co(NO₃)₂], which is about 90% in the temperature range of 200 to 350 ℃. Furthermore, Co₃O₄ [20%Co(NO₃)₂] has a stable catalytic activity, and its Hg⁰ oxidation efficiency maintains above 90% at 250 ℃ even after 90 h test. A probable reaction mechanism is deduced by the XPS results of the fresh, used and regenerated catalyst of Co₃O₄ [20%Co(NO₃)₂]. Chemisorbed oxygen can react with Hg⁰ forming HgO with the reduction of Co³⁺ to Co²⁺. And lattice oxygen and gaseous oxygen can supplement the consumption of chemisorbed oxygen to oxidize Co²⁺ to Co³⁺.

关键词: Wood vessel, Elemental mercury, Ce₃O₄, Ordered pore structure

Xiaopeng Zhang, Cheng Gao, Ziwei Wang, Ximiao Wang, Jie Cheng, Xinxin Song, Xiangkai Han, Ning Zhang, Junjiang Bao, Gaohong He. Co₃O₄ with ordered pore structure derived from wood vessels for efficient Hg⁰ oxidation[J]. Chinese Journal of Chemical Engineering, 2022, 50(10): 215-221.

References

[1] R.K. Verma, M.S. Sankhla, K. Parihar, R. Kumar, M.K. Verma, The study of assessing the impact on environment by the noxious airborne chemicals:A review, Biointerface Res. Appl. Chem., 11 (3) (2021) 10844-10863
[2] X.Q. Wang, X.M. Liu, H. Wu, M. Tian, R.H. Li, Z.C. Sheng, Interpretations of Hg anomalous sources in drainage sediments and soils in China, J. Geochem. Explor. 224 (2021) 106711
[3] H.Z. Wang, L.M. Cai, Q.S. Wang, G.C. Hu, L.G. Chen, A comprehensive exploration of risk assessment and source quantification of potentially toxic elements in road dust:A case study from a large Cu smelter in central China, CATENA 196 (2021) 104930
[4] N. Singh, I. Srivastava, J. Dwivedi, N. Sankararamakrishnan, Ultrafast removal of ppb levels of Hg(II) and volatile Hg(0) using post modified metal organic framework, Chemosphere 270 (2021) 129490
[5] S. Sjostrom, M. Durham, C.J. Bustard, C. Martin, Activated carbon injection for mercury control:Overview, Fuel 89 (6) (2010) 1320-1322
[6] L.K. Zhao, C.T. Li, X.N. Zhang, G.M. Zeng, J. Zhang, Y.E. Xie, A review on oxidation of elemental mercury from coal-fired flue gas with selective catalytic reduction catalysts, Catal. Sci. Technol. 5 (7) (2015) 3459-3472
[7] W.H. Hou, J.S. Zhou, P. Qi, X. Gao, Z.Y. Luo, Effect of H₂S/HCl on the removal of elemental mercury in syngas over CeO₂-TiO₂, Chem. Eng. J. 241 (2014) 131-137
[8] J.P. Yang, Y.C. Zhao, J.Y. Zhang, C.G. Zheng, Removal of elemental mercury from flue gas by recyclable CuCl₂ modified magnetospheres catalyst from fly ash. Part 1. Catalyst characterization and performance evaluation, Fuel 164 (2016) 419-428
[9] X.P. Zhang, H. Zhang, X.X. Song, X.K. Han, J.J. Bao, N. Zhang, G.H. He, CCo₃O₄-based catalysts derived from natural wood with hierarchical structure for elemental mercury oxidation, J. Energy Inst. 94 (2021) 285-293
[10] Z. Wang, J. Liu, Y.J. Yang, F. Liu, Y.N. Yu, X.C. Yan, Molecular mechanistic nature of elemental mercury oxidation by surface oxygens over the CCo₃O₄ catalyst, J. Phys. Chem. C 124 (8) (2020) 4605-4612
[11] Z. Wang, J. Liu, Y.J. Yang, F.H. Shen, Y.N. Yu, X.C. Yan, Elucidating the mechanism of Hg⁰ oxidation by chlorine species over CCo₃O₄ catalyst at molecular level, Appl. Surf. Sci. 513 (2020) 145885
[12] J. Wu, J.X. Wu, Y.J. Huang, Q.Z. Liu, P. He, M. Zhou, Z-scheme heterojunction of flower microsphere Bi₇O₉I₃ surface loaded with gray TiO₂ particles for photocatalytic oxidation of gas-phase Hg⁰, Appl. Surf. Sci. 547 (2021) 149240
[13] W.Q. Xu, H.R. Wang, X. Zhou, T.Y. Zhu, CuO/TiO₂ catalysts for gas-phase Hg⁰ catalytic oxidation, Chem. Eng. J. 243 (2014) 380-385
[14] P. Zhang, W.G. Pan, R.T. Guo, X.B. Zhu, J. Liu, L. Qin, X.L. She, The Mo modified Ce/TiO₂ catalyst for simultaneous Hg⁰ oxidation and NO reduction, J. Energy Inst. 92 (5) (2019) 1313-1328
[15] L.Q. Li, Y. Deng, J. Ai, L.F. Li, G.Y. Liao, S.W. Xu, D.S. Wang, W.J. Zhang, Fe/Mn loaded sludge-based carbon materials catalyzed oxidation for antibiotic degradation:Persulfate vs H₂O₂ as oxidant, Sep. Purif. Technol. 263 (2021) 118409
[16] Y. Zhao, Y.H. Han, T.X. Guo, T.Z. Ma, Simultaneous removal of SO₂, NO and Hg⁰ from flue gas by ferrate (VI) solution, Energy 67 (2014) 652-658
[17] D. Jampaiah, A. Chalkidis, Y.M. Sabri, E.L.H. Mayes, B.M. Reddy, S.K. Bhargava, Low-temperature elemental mercury removal over TiO₂ nanorods-supported MnOx-FeOx-CrOx, Catal. Today 324 (2019) 174-182
[18] X. Zhang, L.Y. Dai, Y.X. Liu, J.G. Deng, L. Jing, Z.W. Wang, W.B. Pei, X.H. Yu, J. Wang, H.X. Dai, Effect of support nature on catalytic activity of the bimetallic RuCo nanoparticles for the oxidative removal of 1, 2-dichloroethane, Appl. Catal. B Environ. 285 (2021) 119804
[19] H. Zhu, X. Song, X. Han, X. Zhang, J. Bao, N. Zhang, G. He, CCo₃O₄ nanosheets preferentially growing (220) facet with a large amount of surface chemisorbed oxygen for efficient oxidation of elemental mercury from flue gas, Environ. Sci. Technol., 54 (14) (2020) 8601-8611
[20] X.P. Zhang, J.X. Wang, B.J. Tan, Z.F. Li, Y.Z. Cui, G.H. He, Ce-Co catalyst with high surface area and uniform mesoporous channels prepared by template method for Hg⁰ oxidation, Catal. Commun. 98 (2017) 5-8
[21] Y. Zhao, M. Qi, R.L. Hao, J.J. Jiang, B. Yuan, A novel catalytic oxidation process for removing elemental mercury by using diperiodatoargentate(III) in the catalysis of trace ruthenium(III), J. Hazard. Mater. 381 (2020) 120964
[22] C. He, B.X. Shen, F.K. Li, Effects of flue gas components on removal of elemental mercury over Ce-MnOx/Ti-PILCs, J. Hazard. Mater. 304 (2016) 10-17
[23] W. Yang, Y.X. Liu, Q. Wang, J.F. Pan, Removal of elemental mercury from flue gas using wheat straw chars modified by Mn-Ce mixed oxides with ultrasonic-assisted impregnation, Chem. Eng. J. 326 (2017) 169-181
[24] X.P. Zhang, Y.Z. Cui, B.J. Tan, J.X. Wang, Z.F. Li, G.H. He, The adsorption and catalytic oxidation of the element mercury over cobalt modified Ce-ZrO₂ catalyst, RSC Adv. 6 (91) (2016) 88332-88339
[25] X.P. Zhang, J.X. Wang, B.J. Tan, N. Zhang, J.J. Bao, G.H. He, Ce-Co interaction effects on the catalytic performance of uniform mesoporous Cex-Coy catalysts in Hg⁰ oxidation process, Fuel 226 (2018) 18-26
[26] X.P. Zhang, X.X. Song, X.X. Wang, Y.Y. Wei, X.K. Han, J.J. Bao, N. Zhang, G.H. He, In-situ grown CCo₃O₄ nanoparticles on wood-derived carbon with natural ordered pore structure for efficient removal of Hg⁰ from flue gas, J. Energy Inst. 98 (2021) 206-215
[27] T. Wang, J. Liu, Y.S. Zhang, H.C. Zhang, W.Y. Chen, P. Norris, W.P. Pan, Use of a non-thermal plasma technique to increase the number of chlorine active sites on biochar for improved mercury removal, Chem. Eng. J. 331 (2018) 536-544
[28] Z.M. Zhao, Y. Long, S. Luo, Y.T. Luo, M. Chen, J.T. Ma, Metal-Free C₃N₄ with plentiful nitrogen vacancy and increased specific surface area for electrocatalytic nitrogen reduction, J. Energy Chem. 60 (2021) 546-555
[29] P. Tan, B. Chen, H.R. Xu, W.Z. Cai, W. He, M. Ni, In-situ growth of CCo₃O₄ nanowire-assembled clusters on nickel foam for aqueous rechargeable Zn-Co₃O₄ and Zn-air batteries, Appl. Catal. B Environ. 241 (2019) 104-112
[30] A.C. Zhang, W.W. Zheng, J. Song, S. Hu, Z.C. Liu, J. Xiang, Cobalt manganese oxides modified titania catalysts for oxidation of elemental mercury at low flue gas temperature, Chem. Eng. J. 236 (2014) 29-38
[31] L. Gao, C.T. Li, J. Zhang, X.Y. Du, S.H. Li, J.W. Zeng, Y.Y. Yi, G.M. Zeng, Simultaneous removal of NO and Hg⁰ from simulated flue gas over CoOx-CeO₂ loaded biomass activated carbon derived from maize straw at low temperatures, Chem. Eng. J. 342 (2018) 339-349
[32] Y. Xu, G.Q. Luo, Q.C. Pang, S.W. He, F.F. Deng, Y.Q. Xu, H. Yao, Adsorption and catalytic oxidation of elemental mercury over regenerable magnetic FeCe mixed oxides modified by non-thermal plasma treatment, Chem. Eng. J. 358 (2019) 1454-1463
[33] H.M. Xu, Z. Qu, C.X. Zong, F.Q. Quan, J. Mei, N.Q. Yan, Catalytic oxidation and adsorption of Hg⁰ over low-temperature NH₃-SCR LaMnO₃ perovskite oxide from flue gas, Appl. Catal. B Environ. 186 (2016) 30-40

Co₃O₄ with ordered pore structure derived from wood vessels for efficient Hg⁰ oxidation

Co₃O₄ with ordered pore structure derived from wood vessels for efficient Hg⁰ oxidation

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 2

Recommended Articles

Metrics

Comments

[1]	Zengqiang Tan, Guoping Niu, Xiaowen Chen. Removal of elemental mercury by modified bamboo carbon [J]. Chin.J.Chem.Eng., 2015, 23(11): 1875-1880.
[2]	WU Chengli, CAO Yan, DONG Zhongbing, PAN Weiping. Impacting Factors of Elemental Mercury Re-emission across a Lab-scale Simulated Scrubber [J]. , 2010, 18(3): 523-528.