1. School of Resource and Geosciences, China University of Mining and Technology, Xuzhou 221116, China; 2. State Key Laboratory of CokingCoal Resources Green Exploitation, China University of Mining and Technology, Xuzhou 221116, China; 3. National EngineeringResearch Center of Coal Preparation and Purification, China University of Mining and Technology, Xuzhou 221116, China
Abstract：Coke powder (CP), a coking byproduct, was employed as an adsorbent to investigate the adsorption performance and mechanisms toward polycyclic aromatic hydrocarbons (PAHs) substituted with different functional groups—naphthalene, naphthol, and naphthoic acid. The potential of CP for removing PAHs from wastewater was further evaluated through systematic analyses. Adsorption performance tests demonstrated removal efficiencies of 97.4%, 86.6%, and 76.8% for naphthalene, naphthol, and naphthoic acid, respectively, within 120 min, with pseudo-second-order kinetic rate constants of 0.680, 0.532, and 0.183g/(mg?min). The maximum adsorption capacities followed the order: naphthalene (23.8mg/g) > naphthol (8.04mg/g) > naphthoic acid (3.94 mg/g). While pH exhibited minimal effects on the adsorption of naphthalene and naphthol, naphthoic acid adsorption was significantly enhanced under acidic conditions compared to neutral or alkaline environments. Results of FTIR, XPS, DRUV-Vis spectroscopy, and DFT calculation revealed that the adsorption of naphthalene on CP was multilayered, primarily driven by hydrophobic interactions, van der Waals forces, and π-π electron donor-acceptor (EDA) interactions. In contrast, the adsorption of naphthol and naphthoic acid involved monolayer chemisorption, attributed to strong π donors and the π-π EDA interactions with the polarized electron-depleted regions on the CP surface. The hydrophilic nature of the hydroxyl group in naphthol reduced the saturation adsorption capacity. While electrostatic repulsion between naphthoic acid and CP weakened the π-π EDA interaction, resulting in a slightly lower adsorption capacity.
[1] 冯建祥,陈攀攀,石朝益,等.Ni/焦粉催化CO2 重整焦炉煤气的研究[J]. 天然气化工(C1化学与化工), 2017,42(1):52-57. Feng J X, Chen P P, Shi Z Y, et al. CO2-COG reforming over Ni/coke powder catalyst [J]. Natural Gas Chemical Industry, 2017,42(1):52-57. [2] 罗道成,刘俊峰.无烟煤配入瘦煤和焦粉制备优质型焦[J]. 煤炭科学技术, 2006,34(8):61-63. Luo D C, Liu J F. Anthracite coal blended with lean coal and coking coal powder to prepare excellent quality coke [J]. Coal Science and Technology, 2006,34(8):61-63. [3] Gao Q Y, Wang L, Li Z P, et al. Adsorptive removal of pyridine in simulation wastewater using coke powder [J]. Processes, 2019,7(7): 459. [4] Li X F, Chen W Y, Ma L M, et al. Characteristics and mechanisms of catalytic ozonation with Fe-shaving-based catalyst in industrial wastewater advanced treatment [J]. Journal of Cleaner Production, 2019,222:174-181. [5] 孟祥帅,陈鸿汉,郑从奇,等.焦化厂不同污染源作用下土壤PAHs污染特征[J]. 中国环境科学, 2020,40(11):4857-4864. Meng X S, Chen H H, Zheng C Q, et al. Pollution characteristics of PAHs in soil at an abandoned coking plant affected by different sources [J]. China Environmental Science, 2020,40(11):4857-4864. [6] Wang L, Yang Y Y, Ou Y, et al. Enhancement of coal tar pitch carbonization with biochar: A metallurgical formed biocoke product produced by waste coke breeze and bamboo powder [J]. Fuel, 2024, 358:130238. [7] Zhang C, Li J F, Cheng F Q. Recycling of powder coke to cost effective adsorbent material and its application for tertiary treatment of coking wastewater [J]. Journal of Cleaner Production, 2020,261: 121114. [8] Zhang C, Chen Z L, LI J F, et al. Removal of recalcitrant organic pollutants from bio-treated coking wastewater using coal-based carbonaceous materials [J]. Desalination and Water Treatment, 2017, 88:75-84. [9] Chen X J, Guo Y X, Cui J L, et al. Activated carbon preparation with the addition of coke-making by-product—coke powder: Texture evolution and mechanism [J]. Journal of Cleaner Production, 2019,237: 117812. [10] Chen X J, Zhang H R, Guo Y X, et al. Activation mechanisms on potassium hydroxide enhanced microstructures development of coke powder [J]. Chinese Journal of Chemical Engineering, 2020,28(1): 299-306. [11] Wang H, Wang W C, Zhang G T, et al. Research on the performance of modified blue coke in adsorbing hexavalent chromium [J]. Scientific Reports, 2023,13(1):7223. [12] Gao Q Y, Jin P R, Wang L, et al. Removal of organic pollutants in coking wastewater based on coal-based adsorbents: A pilot-scale study of static adsorption and flotation [J]. Journal of Environmental Chemical Engineering, 2021,9(6):106844. [13] Gai H j, Jiang Y B, Qian Y, et al. Conceptual design and retrofitting of the coal-gasification wastewater treatment process [J]. Chemical Engineering Journal, 2008,138(1-3):84-94. [14] 张娟,吴建芝,刘燕.北京市绿地土壤多环芳烃分布及健康风险评价[J]. 中国环境科学, 2017,37(3):1146-1153. Zhang J, Wu J Z, Liu Y. Polycyclic aromatic hydrocarbons in urban green space of Beijing: distribution and potential risk [J]. China Environmental Science, 2017,37(3):1146-1153. [15] Liu Y, Wu Z Y, Peng P, et al. A pilot-scale three-dimensional electrochemical reactor combined with anaerobic-anoxic-oxic system for advanced treatment of coking wastewater [J]. Journal of Environmental Management, 2020,258:110021. [16] Fajin J L C, Gomes J R B, Cordeiro M N D S. DFT study of the adsorption of D-(L-)Cysteine on flat and chiral stepped gold surfaces [J]. Langmuir, 2013,29(28):8856-8864. [17] Hoeffling B, Ortmann F, Hannewald K, et al. Single cysteine adsorption on Au(110): A first-principles study [J]. Physical Review B—Condensed Matter and Materials Physics, 2010,81(4):045407. [18] Delley B. Hardness conserving semilocal pseudopotentials [J]. Physical Review B, 2002,66(15):155125. [19] Preethi G, Jeyanthi J. Biosorption of heavy metals using Gracilaria edulis seaweed - batch adsorption, kinetics and thermodynamic studies [J]. Global Nest Journal, 2023,25(10):33-46. [20] 崔鹤,陈云嫩,刘晨,等.胺基改性沸石同步净化水中的硝酸盐和总磷[J]. 中国环境科学, 2023,43(11):5765-5776. Cui H, Chen Y N, Liu C, et al. Amine-modified zeolite synchronously cleans nitrate and total phosphorus from water [J]. China Environmental Science, 2023,43(11):5765-5776. [21] Foo K Y, Hameed B H. Insights into the modeling of adsorption isotherm systems [J]. Chemical Engineering Journal, 2010,156(1):2- 10. [22] Li N, Cheng W Y, Pan Y Z. Adsorption of naphthalene on modified zeolite from aqueous solution [J]. Journal of Environmental Protection, 2017,8(4):416-425. [23] Ge X, Tian F, Wu Z, et al. Adsorption of naphthalene from aqueous solution on coal-based activated carbon modified by microwave induction: Microwave power effects [J]. Chemical engineering and processing: Process intensification, 2015,91:67-77. [24] Zhu M, Tian W, Chai H, et al. Acid-hydrolyzed agricultural residue: A potential adsorbent for the decontamination of naphthalene from water bodies [J]. Korean Journal of Chemical Engineering, 2017,34:1073- 1080. [25] Chen B L, Chen Z M. Sorption of naphthalene and 1-naphthol by biochars of orange peels with different pyrolytic temperatures [J]. Chemosphere, 2009,76(1):127-133. [26] Hanna K, Lassabatere L, Bechet B. Transport of two naphthoic acids and salicylic acid in soil: experimental study and empirical modeling [J]. Water research, 2012,46(14):4457-4467. [27] Wu L, Li B, Liu M. Influence of aromatic structure and substitution of carboxyl groups of aromatic acids on their sorption to biochars [J]. Chemosphere, 2018,210:239-246. [28] Liu J J, Wang X C, Fan B. Characteristics of PAHs adsorption on inorganic particles and activated sludge in domestic wastewater treatment [J]. Bioresource technology, 2011,102(9):5305-5311. [29] Zheng X, Xu T, Kang X, et al. Structural dependent persulfate activation by coke powder for aniline degradation [J]. Chemical Engineering Journal, 2022,431:134088. [30] Zhang Y J, Zhou G Y, Yue J P, et al. Enhanced removal of polyethylene terephthalate microplastics through polyaluminum chloride coagulation with three typical coagulant aids [J]. Science of the Total Environment, 2021,800:149589. [31] Pathak S, Sakhiya A K, Anand A, et al. A state-of-the-art review of various adsorption media employed for the removal of toxic Polycyclic aromatic hydrocarbons (PAHs): An approach towards a cleaner environment [J]. Journal of Water Process Engineering, 2022, 47:102674. [32] Yuliani G, Garnier G, Chaffee A L. Utilization of raw and dried Victorian brown coal in the adsorption of model dyes from solution [J]. Journal of Water Process Engineering, 2017,15:43-48. [33] Zhang X N, Lin X Y, He Y, et al. Phenolic hydroxyl derived copper alginate microspheres as superior adsorbent for effective adsorption of tetracycline [J]. International journal of biological macromolecules, 2019,136:445-459. [34] Pereira D S J C, Bruno M C E, Mangrich A S, et al. Optical (DRUV-Vis) and magnetic (EPR) behavior of synthetic melanins [J]. Materials Research-Ibero-American Journal of Materials, 2012,15(2): 209-212. [35] Fagan S B, Souza A G, Lima J O G, et al. 1,2-dichlorobenzene interacting with carbon nanotubes [J]. Nano Letters, 2004,4(7):1285- 1288. [36] Chen X J, Guo Y X, Zhang H R, et al. Coke powder improving the performance of desulfurized activated carbon from the cyclic thermal regeneration [J]. Chemical Engineering Journal, 2022,448:137459. [37] ZUO L Z, Guo Y, Li X, et al. Enhanced adsorption of hydroxyl- and amino-substituted aromatic chemicals to nitrogen-doped multiwall carbon nanotubes: A combined batch and theoretical calculation study [J]. Environmental Science & Technology, 2016,50(2):899-905. [38] 徐天缘,郑茜,王连娟,等.焦粉高效活化过硫酸盐对苯胺的降解性能[J]. 化工进展, 2022,41(6):3314-3323. Xu T Y, Zheng X, Wang L J, et al. Persulfate activation by coke powder for aniline degradation [J]. Chemical Industry and Engineering Progress, 2022,41(6):3314-3323. [39] Chen W, Duan L, Wang L L, et al. Adsorption of hydroxyl- and amino-substituted aromatics to carbon manotubes [J]. Environmental Science and Technology, 2008,42(18):6862-6868. [40] Huang Z W, Sun H, Zhang H Y, et al. π–π interaction of quinacridone derivatives [J]. Journal of Computational Chemistry, 2011,32(10): 2055-2063. [41] Tan Z Y, Deng H Y, Ou H L, et al. Interfacial quantum chemical characterization of aromatic organic matter adsorption on oxidized microplastic surfaces [J]. Chemosphere, 2024,350:141132.
