A Cu-modified active carbon fiber significantly promoted H₂S and PH₃ simultaneous removal at a low reaction temperature

Highlights

• Cu_0.15-ACF performs the best for H₂S and PH₃ simultaneous removal.

• 550°C and 90°C are separately calcination and reaction temperatures.

• The reason why Cu_0.15/ACF shows better performance was found.

• The accumulation of H₂PO₄⁻ and SO₄²⁻(H₂O)₆ is the deactivation cause of Cu_0.15/ACF.

Abstract

Poisonous gases, such as H₂S and PH₃, produced by industrial production harm humans and damage the environment. In this study, H₂S and PH₃ were simultaneously removed at low temperature by modified activated carbon fiber (ACF) catalysts. We have considered the active metal type, content, precursor, calcination, and reaction temperature. Experimental results exhibited that ACF could best perform by loading 15% Cu from nitrate. The optimized calcination temperature and reaction temperature separately were 550°C and 90°C. Under these conditions, the most removal capacity could reach 69.7 mg/g and 132.1 mg/g, respectively. Characterization results showed that moderate calcination temperature (550°C) is suitable for the formation of the copper element on the surface of ACF, lower or higher temperature will generate more cuprous oxide. Although both can exhibit catalytic activity, the role of the copper element is significantly greater. Due to the exceptional dispersibility of copper (oxide), the ACF can still maintain the advantages of larger specific surface area and pore volume after loading copper, which is the main reason for better performance of related catalysts. Finally, increasing the copper loading amount can significantly increase the crystallinity and particle size of copper (oxide) on the ACF, thereby improving its catalytic performance. In situ IR found that the reason for the deactivation of the catalyst should be the accumulation of generated H₂PO₄⁻ and SO₄²⁻(H₂O)₆ which could poison the catalyst.

Graphical abstract

Keywords

ACF / H₂S / PH₃ / Cu / Low temperature / Simultaneous removal

References

[1] Abdolghaffari A H, Baghaei A, Solgi R, Gooshe M, Baeeri M, Navaei-Nigjeh M, Hassani S, Jafari A, Rezayat S M, Dehpour A R, Mehr S E, Abdollahi M (2015). Molecular and biochemical evidences on the protective effects of triiodothyronine against phosphine-induced cardiac and mitochondrial toxicity. Life Sciences, 139: 30–39

[2] Bai B C, Lee C W, Lee Y S, Im J S (2017). Modification of textural properties of CuO-supported activated carbon fibers for SO₂ adsorption based on electrical investigation. Materials Chemistry and Physics, 200: 361–367

[3] Basova Y V, Edie D D, Badheka P Y, Bellam H C (2005). The effect of precursor chemistry and preparation conditions on the formation of pore structure in metal-containing carbon fibers. Carbon, 43(7): 1533–1545

[4] de Falco G, Montagnaro F, Balsamo M, Erto A, Deorsola F A, Lisi L, Cimino S (2018). Synergic effect of Zn and Cu oxides dispersed on activated carbon during reactive adsorption of H₂S at room temperature. Microporous and Mesoporous Materials, 257: 135–146

[5] Deng J, Chen L, Wei W (2013). The study on removal the PH₃ in CO by Dephosphorization bacteria. Advanced Materials Research, 781: 861–868

[6] Du J (2012). Growth of single-crystalline Cu₂O (111) film on ultrathin MgO modified α-Al₂O₃ (0001) substrate by molecular beam epitaxy. Journal of Crystal Growth, 353(1): 63–67

[7] Fuku X, Kaviyarasu K, Matinise N, Maaza M. (2016). Punicalagin green functionalized Cu/Cu₂O/ZnO/CuO nanocomposite for potential electrochemical transducer and catalyst. Nanoscale Research Letters, 11(1): 386

[8] Gao F, Zhao D L, Li Y, Li X G, Solids C O (2010). Preparation and hydrogen storage of activated rayon-based carbon fibers with high specific surface area. Journal of Physics, 71(4): 444–447

[9] Gu T, Gao F, Tang X, Yi H, Zhao S, Zaharaddeen S, Zhang R, Zhuang R, Ma Y J E S (2019). Fe-modified Ce-MnO_x/ACF N catalysts for selective catalytic reduction of NO_x by NH₃ at low-middle temperature. Environmental Science and Pollution Research International, 26(27): 27940–27952

[10] Hou Y, Li Y, Li Q, Liu Y, Huang Z (2019). Insight into the role of TiO₂ modified activated carbon fibers for the enhanced performance in low-temperature NH₃-SCR. Fuel, 245: 554–562

[11] Kim J, Lee B K (2018). Enhanced photocatalytic decomposition of VOCs by visible-driven photocatalyst combined Cu-TiO₂ and activated carbon fiber. Process Safety and Environmental Protection, 119: 164–171

[12] Klähn M, Mathias G, Kötting C, Nonella M, Schlitter J, Gerwert K, Tavan P (2004). IR spectra of phosphate ions in aqueous solution: predictions of a DFT/MM approach compared with observations. The Journal of Physical Chemistry A, 108(29): 6186–6194

[13] Lan H, Wang A, Liu R, Liu H, Qu J (2015). Heterogeneous photo-Fenton degradation of acid red B over Fe₂O₃ supported on activated carbon fiber. Journal of Hazardous Materials, 285: 167–172

[14] Lee T, Ooi C H, Othman R, Yeoh F Y (2014). Activated carbon fiber-the hybrid of carbon fiber and activated carbon. Reviews on Advanced Materials Science, 36(2): 118–136

[15] Li S, Li K, Hao J, Ning P, Tang L, Sun X (2016). Acid modified mesoporous Cu/SBA-15 for simultaneous adsorption/oxidation of hydrogen sulfide and phosphine. Chemical Engineering Journal, 302: 69–76

[16] Liu D, Li B, Wu J, Liu Y (2020). A review on sorbents for hydrogen sulfide capture from biogas at low temperature. Environmental Chemistry Letters, 18: 113–128

[17] Ma L, Ning P, Zhang Y, Wang X (2008). Experimental and modeling of fixed-bed reactor for yellow phosphorous tail gas purification over impregnated activated carbon. Chemical Engineering Journal, 137(3): 471–479

[18] Naito S, Aida S, Kasahara T, Miyao T (2006). Infrared spectroscopic study on the reaction mechanism of CO hydrogenation over Pd/CeO₂. Research on Chemical Intermediates, 32(3‒4): 279–290

[19] Ma Y, Wang X, Ning P, Cheng C, Wang F, Wang L, Lin Y, Yu Y, Fuels (2016). Simultaneous removal of PH₃, H₂S, and dust by corona discharge. Energy, 30(11): 9580–9588

[20] Pathak A, Maity D (2009). Distinctive IR signature of CO₃⁻ and CO₃²⁻ hydrated clusters: A theoretical study. The Journal of Physical Chemistry A, 113(48): 13443–13447

[21] Stita S, Galera Martínez M, Pham Xuan H, Pham Minh D, Nzihou A, Sharrock P (2015). Metal-doped apatitic calcium phosphates: Preparation, characterization, and reactivity in the removal of hydrogen sulfide from gas phase. Composite Interfaces, 22(6): 503–515

[22] Sun L, Song X, Li K, Wang C, Sun X, Ning P, Huang H (2020). Preparation of modified manganese slag slurry for removal of hydrogen sulphide and phosphine. Canadian Journal of Chemical Engineering, 98(7): 1534–1542

[23] Sun X, Ruan H, Song X, Sun L, Li K, Ning P, Wang C (2018). Research into the reaction process and the effect of reaction conditions on the simultaneous removal of H₂S, COS and CS₂ at low temperature. RSC Advances, 8(13): 6996–7004

[24] Wang F (2016). Effect of annealing process on the heterostructure CuO/Cu₂O as a highly efficient photocathode for photoelectrochemical water reduction. Journal of Physics and Chemistry of Solids, 104: 139–144

[25] Wang Y, Lin Q, Ning P, Wang C, Sun X, Li K (2018). Preparation of Ce_0.6-Cu₆₀/Al₄₀-[O] catalyst and role of CeO₂/CuO in simultaneous removal of H₂S and PH₃. Journal of the Taiwan Institute of Chemical Engineers, 87: 44–53

[26] Xu W, Chen B, Jiang X, Xu F, Chen X, Chen L, Wu J, Fu M, Ye D (2020). Effect of calcium addition in plasma catalysis for toluene removal by Ni/ZSM-5: Acidity/basicity, catalytic activity and reaction mechanism. Journal of Hazardous Materials, 387: 122004

[27] Xu X, Huang G, Qi S (2017). Properties of AC and 13X zeolite modified with CuCl₂ and Cu(NO₃)₂ in phosphine removal and the adsorptive mechanisms. Chemical Engineering Journal, 316: 563–572

[28] Zhang X, Tang Y, Qu S, Da J, Hao Z (2015). H₂S-selective catalytic oxidation: Catalysts and processes. ACS Catalysis, 5(2): 1053–1067

[29] Zhao B, Yi H, Tang X, Li Q, Liu D, Gao F (2016). Copper modified activated coke for mercury removal from coal-fired flue gas. Chemical Engineering Journal, 286: 585–593

[30] Zhou J, Santambrogio G, Brümmer M, Moore D T, Wöste L, Meijer G, Neumark D M, Asmis K R (2006). Infrared spectroscopy of hydrated sulfate dianions. The Journal of Chemical Physics, 125: 111102

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Nos. 51968034, 41807373 and 22006058), the National Key R&D Program of China (No. 2018YFC0213400), and the Science and Technology Program of Yunnan Province (No. 2019FB069).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11783-021-1425-3 and is accessible for authorized users.

RIGHTS & PERMISSIONS

2021 Higher Education Press