生物质对赤泥碱性的调控及其催化过一硫酸盐降解碘帕醇的性能及机理

王桂珍; 魏红; 黄雪桐; 高美娟; 张泽慧; 滕锐杰; 宋俊其; 潘峰

PDF(3517 KB)

中国环境科学 ›› 2025, Vol. 45 ›› Issue (8) : 4434-4447.

固体废物

生物质对赤泥碱性的调控及其催化过一硫酸盐降解碘帕醇的性能及机理

王桂珍¹, 魏红¹, 黄雪桐¹, 高美娟^1,2, 张泽慧¹, 滕锐杰¹, 宋俊其¹, 潘峰¹

作者信息 +

Regulation of red mud alkalinity by biomass and its catalytic performance and mechanism in activating peroxymonosulfate for iopamidol degradation

WANG Gui-zhen¹, WEI Hong¹, HUANG Xue-tong¹, GAO mei-juan^1,2, ZHANG Ze-hui¹, TENG Rui-jie¹, SONG jun-qi¹, PAN Feng¹

Author information +

文章历史 +

摘要

选择赤泥(RM)作为Fe源,橙皮(OP,pH:3.0~4.9)作为RM脱碱的碳源,经浸渍、共热解制备RM@OPB催化材料,考察橙皮对赤泥碱性调节及影响因素.并探讨其催化过一硫酸盐(PMS)降解碘帕醇(IPM)的性能.通过活性物种淬灭实验和RM@OPB反应前后的X射线衍射(XRD)、X射线光电子能谱(XPS)等表征,探究其降解IPM的中间产物、降解途径及降解机理,并预测其生态毒性变化.结果表明,浸渍过程中,浸渍时间及橙皮/赤泥的质量比对赤泥碱性的降低均有影响,浸渍时间24h,m_RM:m_OP=1:2.5时,原始赤泥pH值由11.0降至7.27.热解过程中,生物质产生的还原性气体促进赤泥中Fe₂O₃向Fe₃O₄和Fe⁰的转化.其中,RM@OPB-800因Fe⁰的存在而表现出优异的催化性能. RM@OPB-800投加量0.5g/L, PMS浓度1.0mmol/L,初始pH=6.7,8mg/L的IPM在60min降解96.5%(k_obs=0.065min^-1).活性物种淬灭实验结果表明RM@OPB-800/PMS体系降解IPM的主要活性物种是¹O₂.IPM的降解主要包括侧链酰胺水解及氧化、脱氢、脱碘和羟基加成,共生成12种中间产物.研究结果表明橙皮改性RM可有效提高RM的资源化利用.

Abstract

Red mud (RM) was selected as the Fe source and orange peel (OP, pH=3.0~4.9) as the carbon source, RM@OPB composite was prepared through impregnation-pyrolysis method. The regulation of red mud alkalinity by orange peel and the influencing factors were analyzed. The catalytic performance of RM@OPB in activating PMS for IPM degradation was investigated as well. The mechanism of IPM degradation in the RM@OPB/PMS system was further explored through the combination of HPLC/MS analysis, active species quenching experiments, fluorescence spectroscopy, electron paramagnetic resonance (EPR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) of the pre-post-reaction of RM@OPB.Finally, the ecological toxicity of IPM and its intermediates was predicted using the Ecological Structure Activity Relationships (ECOSAR) software. The results demonstrated that orange peel co-impregnation effectively regulated the alkalinity of red mud, with the leachate pH decreasing from 11.0 to 7.27, at impregnation time and m_RM: m_OP of 24h and 1:2.5, respectively. During the pyrolysis, reductive gases generated from orange peel facilitated the transformation of Fe₂O₃ in RM into Fe₃O₄ and Fe⁰, magnetic RM@OPB materials was manufactured. Notably, RM@OPB-800exhibited effective catalytic performance for IPM degradation, with the degradation of 8mg/L IPM achieving 96.5% in 60min (k=0.065min⁻¹), under the experimental conditions of 0.5g/L RM@OPB-800, 1.0mmol/L PMS, and initial pH=6.7, respectively. Singlet oxygen (¹O₂) was identified as the dominant reactive species in the RM@OPB-800/PMS system. IPM degraded mainly through side-chain amide hydrolysis and oxidation, dehydrogenation, deiodination, and hydroxyl addition, with 12intermediates generated. ECOSAR analysis confirmed no highly toxic intermediates were formed. The findings can provide some critical insights into the resource utilization of red mud.

导出引用

王桂珍, 魏红, 黄雪桐, 高美娟, 张泽慧, 滕锐杰, 宋俊其, 潘峰. 生物质对赤泥碱性的调控及其催化过一硫酸盐降解碘帕醇的性能及机理[J]. 中国环境科学. 2025, 45(8): 4434-4447

WANG Gui-zhen, WEI Hong, HUANG Xue-tong, GAO mei-juan, ZHANG Ze-hui, TENG Rui-jie, SONG jun-qi, PAN Feng. Regulation of red mud alkalinity by biomass and its catalytic performance and mechanism in activating peroxymonosulfate for iopamidol degradation[J]. China Environmental Science. 2025, 45(8): 4434-4447

中图分类号： X705

参考文献

[1] Yoon K, Cho D W, Tsang Y F, et al. Synthesis of functionalised biochar using red mud, lignin, and carbon dioxide as raw materials [J]. Chemical Engineering Journal, 2019,361:1597-1604.
[2] Khairul M A, Zanganeh J, Moghtaderi B. The composition, recycling and utilisation of bayer red mud [J]. Resources, Conservation and Recycling, 2019,141:483-498.
[3] Loebsack G, Kang K, Klinghoffer N B, et al. Adsorption mechanisms and optimal production of magnetic biochar composites from red mud and soft wood biomass [J]. Journal of Analytical and Applied Pyrolysis, 2024,177:106340.
[4] Li H, Shi B, Fu X, et al. Preparation and application of red mud-based zero-valent iron heterogeneous fenton catalyst: a new idea for red mud recycling [J]. Journal of Environmental Chemical Engineering, 2023, 11(3):109998.
[5] Cheng N, Wang B, Wu P, et al. Adsorption of emerging contaminants from water and wastewater by modified biochar: a review [J]. Environmental Pollution, 2021,273:116448.
[6] Cho D W, Yoon K, Ahn Y, et al. Fabrication and environmental applications of multifunctional mixed metal-biochar composites (MMBC) from red mud and lignin wastes [J]. Journal of Hazardous Materials, 2019,374:412-419.
[7] Wu C, Huang L, Xue S G, et al. Arsenic sorption by red mud-modified biochar produced from rice straw [J]. Environmental Science and Pollution Research, 2017,24(22):18168-18178.
[8] Wang J, Shen M, Wang H, et al. Red mud modified sludge biochar for the activation of peroxymonosulfate: singlet oxygen dominated mechanism and toxicity prediction [J]. Science of the Total Environment, 2020,740:140388.
[9] Liang W, Couperthwaite S J, Kaur G, et al. Effect of strong acids on red mud structural and fluoride adsorption properties [J]. Journal of Colloid and Interface Science, 2014,423:158-165.
[10] Cai T, Yang M, Pan R. Study on the effect of sodium removal from citric acid pretreated red mud on the physical properties of red mud [J]. Environmental Science and Pollution Research, 2024,31(31):44191- 44204.
[11] Siles J A, Vargas F, Gutiérrez M C, et al. Integral valorisation of waste orange peel using combustion, biomethanisation and co-composting technologies [J]. Bioresource Technology, 2016,211:173-182.
[12] Wang J, Shen J, Ye D, et al. Disinfection technology of hospital wastes and wastewater: suggestions for disinfection strategy during coronavirus disease 2019(COVID-19) pandemic in China [J]. Environmental Pollution, 2020,262:114665.
[13] 魏红,滕锐杰,郑佳欣,等.Cu(Ⅱ)催化NaOCl氧化碘帕醇的效果和过程解析[J].中国环境科学, 2024,44(6):3167-3178. Wei H, Teng R J, Zheng J X, et al. The performance and process analysis of copper ion activated chlorine system in the removal of Iopamidol [J]. China Environmental Science, 2024,44(6):3167-3178.
[14] Luo J, Bo S, Qin Y, et al. Transforming goat manure into surface- loaded cobalt/biochar as PMS activator for highly efficient ciprofloxacin degradation [J]. Chemical Engineering Journal, 2020, 395:125063.
[15] Wang Y, Yan P, Dou X, et al. Degradation of benzophenone-4by peroxymonosulfate activated with microwave synthesized well- distributed CuBi₂O₄ microspheres: theoretical calculation of degradation mechanism [J]. Applied Catalysis B: Environmental, 2021, 290:120048.
[16] Wu L, Guo P, Wang X, et al. The synergy of sulfur vacancies and heterostructure on CoS@FeS nanosheets for boosting the peroxymonosulfate activation [J]. Chemical Engineering Journal, 2022,446:136759.
[17] Wang C, Zhang X, Sun R, et al. Neutralization of red mud using bio-acid generated by hydrothermal carbonization of waste biomass for potential soil application [J]. Journal of Cleaner Production, 2020, 271:122525.
[18] Xu K, Lin Q, Fan X, et al. Enhanced degradation of sulfamethoxazole by activation of peroxodisulfate with red mud modified biochar: synergistic effect between adsorption and nonradical activation [J]. Chemical Engineering Journal, 2023,460:141578.
[19] Fu H, Zhao P, Xu S, et al. Fabrication of Fe₃O₄and graphitized porous biochar composites for activating peroxymonosulfate to degrade p-hydroxybenzoic acid: insights on the mechanism [J]. Chemical Engineering Journal, 2019,375:121980.
[20] Zou C, Ma C, Zhao J, et al. Characterization and non-isothermal kinetics of shenmu bituminous coal devolatilization by TG-MS [J]. Journal of Analytical and Applied Pyrolysis, 2017,127:309-320.
[21] Ma J, Zhou B, Zhang H, et al. Fe/S modified sludge-based biochar for tetracycline removal from water [J]. Powder Technology, 2020,364: 889-900.
[22] Zhang H, Yue X, Li F, et al. Preparation of rice straw-derived biochar for efficient cadmium removal by modification of oxygen-containing functional groups [J]. Science of the Total Environment, 2018,631- 632:795-802.
[23] Yu J, Tang L, Pang Y, et al. Magnetic nitrogen-doped sludge-derived biochar catalysts for persulfate activation: internal electron transfer mechanism [J]. Chemical Engineering Journal, 2019,364:146-159.
[24] Du L, Xu W, Liu S, et al. Activation of persulfate by graphitized biochar for sulfamethoxazole removal: the roles of graphitic carbon structure and carbonyl group [J]. Journal of Colloid and Interface Science, 2020,577:419-430.
[25] Wang S, Zhao M, Zhou M, et al. Biochar-supported nZVI (nZVI/BC) for contaminant removal from soil and water: a critical review [J]. Journal of Hazardous Materials, 2019,373:820-834.
[26] Xiao P, Jiang D, Ju L, et al. Construction of RGO/CdIn₂S₄ /g-C₃N₄ternary hybrid with enhanced photocatalytic activity for the degradation of tetracycline hydrochloride [J]. Applied Surface Science, 2018,433:388-397.
[27] Hu J, Zhang P, An W, et al. In-situ Fe-doped g-C₃N₄heterogeneous catalyst via photocatalysis-fenton reaction with enriched photocatalytic performance for removal of complex wastewater [J]. Applied Catalysis B: Environmental, 2019,245:130-142.
[28] Zhang Q, He D, Li X, et al. Mechanism and performance of singlet oxygen dominated peroxymonosulfate activation on CoOOH nanoparticles for 2,4-dichlorophenol degradation in water [J]. Journal of Hazardous Materials, 2020,384:121350.
[29] Sonawane S, Rayaroth M P, Landge V K, et al. Thermally activated persulfate-based advanced oxidation processes — recent progress and challenges in mineralization of persistent organic chemicals: a review [J]. Current Opinion in Chemical Engineering, 2022,37:100839.
[30] Qin Y, Li X, Wang L, et al. Valuable cobalt/biochar with enriched surface oxygen-containing groups prepared from bio-waste shrimp shell for efficient peroxymonosulfate activation [J]. Separation and Purification Technology, 2022,281:119901.
[31] 李瑞华,刘璐.赤泥基ZnFe₂O₄光催化降解抗生素四环素的研究[J].化学工程师, 2022,36(11):42-46. Li Rui hua, Liu Lu.Study on photocatalytic degradation of tetracycline by red mud based ZnFe₂O₄ [J]. Chemical Engineer, 2022,36(11):42- 46.
[32] Feng Y, Wu D, Liao C, et al. Red mud powders as low-cost and efficient catalysts for persulfate activation: pathways and reusability of mineralizing sulfadiazine [J]. Separation and Purification Technology, 2016,167:136-145.
[33] Xiao J, Zhang L, Gu J, et al. Enhanced degradation of high concentration lomefloxacin hydrochloride by three-dimensional electrocatalytic system with novel red mud-based CuFeS₂/FeS₂ particle electrode [J]. Separation and Purification Technology, 2024: 131214.
[34] Dong H, Hou K, Qiao W, et al. Insights into enhanced removal of TCE utilizing sulfide-modified nanoscale zero-valent iron activated persulfate [J]. Chemical Engineering Journal, 2019,359:1046-1055.
[35] Gao P, Tian X, Fu W, et al. Copper in LaMnO₃ to promote peroxymonosulfate activation by regulating the reactive oxygen species in sulfamethoxazole degradation [J]. Journal of Hazardous Materials, 2021,411:125163.
[36] Liu F, Cao J, Yang Z, et al. Heterogeneous activation of peroxymonosulfate by cobalt-doped MIL-53(al) for efficient tetracycline degradation in water: coexistence of radical and non- radical reactions [J]. Journal of Colloid and Interface Science, 2021, 581:195-204.
[37] Appiani E, Ossola R, Latch D E, et al. Aqueous singlet oxygen reaction kinetics of furfuryl alcohol: effect of temperature, pH, and salt content [J]. Environmental Science: Processes & Impacts, 2017, 19(4):507-516.
[38] Ouyang D, Chen Y, Yan J, et al. Activation mechanism of peroxymonosulfate by biochar for catalytic degradation of 1,4-dioxane: important role of biochar defect structures [J]. Chemical Engineering Journal, 2019,370:614-624.
[39] 宋俊其,魏红,潘峰,等.钴、硫共掺杂荞麦皮生物炭活化PMS高效降解碘帕醇[J].环境科学学报, 2024,44(7):69-82. Song Jun qi, Wei Hong, Pan Feng, et al. Efficient activation of peroxymonosulfate by Co,S co-doped buckwheat husk biochar for Iopamidol degradation [J]. Acta Scientiae Circumstantiae, 2024,44(7): 69-82.
[40] Chen X, Oh W D, Lim T T. Graphene- and CNTs-based carbocatalysts in persulfates activation: material design and catalytic mechanisms [J]. Chemical Engineering Journal, 2018,354:941-976.
[41] Lan S, Chen Y, Zeng L, et al. Piezo-activation of peroxymonosulfate for benzothiazole removal in water [J]. Journal of Hazardous Materials, 2020,393:122448.
[42] Rode U, Müller R. Transformation of the ionic X-ray contrast agent diatrizoate and related triiodinated benzoates by trametes versicolor [J]. Applied and Environmental Microbiology, 1998,64(8):3114-3117.
[43] Hu J, Dong H, Qu J, et al. Enhanced degradation of iopamidol by peroxymonosulfate catalyzed by two pipe corrosion products (CuO and δ-MnO₂) [J]. Water Research, 2017,112:1-8.
[44] Kong X, Jiang J, Ma J, et al. Comparative investigation of X-ray contrast medium degradation by UV/chlorine and UV/H₂O₂ [J]. Chemosphere, 2018,193:655-663.
[45] Jeong J, Jung J, Cooper W J, et al. Degradation mechanisms and kinetic studies for the treatment of X-ray contrast media compounds by advanced oxidation/reduction processes [J]. Water Research, 2010,44(15):4391-4398.
[46] 邱琪,郑瑞彬,周伟伟,等.磁性生物炭催化高铁酸盐降解新污染物探究[J].中国环境科学, 2025,45(1):302-309. Qiu Q, Zheng R B, Zhou W W, et al. Degradation of emerging pollutants via ferrate catalyzed by magnetic biochar: efficiency and mechanism [J]. China Environmental Science, 2025,45(1):302-309.
[47] Zhao Y, Zhao Y, Zhou R, et al. Insights into the degradation of 2,4-dichlorophenol in aqueous solution by α-MnO₂ nanowire activated persulfate: catalytic performance and kinetic modeling [J]. RSC Advances, 2016,6(42):35441-35448.
[48] Yang W, Hong P, Yang D, et al. Enhanced fenton-like degradation of sulfadiazine by single atom iron materials fixed on nitrogen-doped porous carbon [J]. Journal of Colloid and Interface Science, 2021, 597:56-65.
[49] Zhao Y S, Sun C, Sun J Q, et al. Kinetic modeling and efficiency of sulfate radical-based oxidation to remove p-nitroaniline from wastewater by persulfate/Fe₃O₄ nanoparticles process [J]. Separation and Purification Technology, 2015,142:182-188.
[50] Yang T, Yu D, Wang D, et al. Accelerating Fe(Ⅲ)/Fe(Ⅱ) cycle via Fe(Ⅱ) substitution for enhancing fenton-like performance of fe-MOFs [J]. Applied Catalysis B: Environmental, 2021,286:119859.
[51] Rani S K, Easwaramoorthy D, Bilal I M, et al. Studies on mn(II)-catalyzed oxidation of α-amino acids by peroxomonosulphate in alkaline medium-deamination and decarboxylation: a kinetic approach [J]. Applied Catalysis A: General, 2009,369(1/2):1-7.
[52] Gao M, Wei H, Cai Q, et al. Performance and mechanism of the biochar-supported Ni⁰/Co⁰/MnO composite catalyst for peroxymonosulfate activation to degrade iopamidol [J]. Journal of Environmental Chemical Engineering, 2024,12(6):114811.