HIGH EFFICIENCY ADSORPTION OF Hg2+ BY SULFUR-MODIFIED COW MANURE BIOCHAR AND ITS MECHANISM
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摘要: 以牛粪为原料在400,500,600 ℃条件下限氧热解制备牛粪生物炭(BC),然后以不同质量比将升华硫和BC混合共热解制备硫改性牛粪生物炭(BCS)。使用元素分析仪、SEM、FTIR、XPS和BET对制得的BC和BCS进行了表征,并研究了各BC和BCS对Hg2+的吸附特性。结果表明:热解过程使BC和BCS变得粗糙多孔,Hg2+被吸附到生物炭表面和孔道内;BC和BCS的吸附过程符合准二级动力学模型,BCS对Hg2+的吸附平衡时间仅为30 min,且吸附过程不受pH影响;Langmuir模型可较好地描述BC吸附过程,吸附量随热解温度的升高而降低,BCS吸附过程符合Freundlich模型,吸附能力较BC显著提升,最大拟合吸附量达到407.81 mg/g;BCS的吸附稳定性较高,在各解吸剂中的解吸率均低于5%;BC主要吸附机理为官能团络合,BCS主要吸附机理为HgS沉淀。因此BCS是一种高效稳定的Hg2+吸附材料。Abstract: Cow manure biochar (BC) were prepared by low-limit oxygen pyrolysis of cow manure at 400 ℃, 500 ℃ and 600 ℃, and then sulfur-modified cow manure biochar (BCS) were prepared by co-pyrolysis of sublimated sulfur and BC at different mass ratios. The BC and BCS were characterized by elemental analyzer, SEM, FTIR, XPS and BET, and the adsorption characteristics of each BC and BCS sample for Hg2+ were studied. The results showed that with the increase of pyrolysis temperature, BC and BCS became coarse and porous, and Hg2+ was adsorbed on the surface and pore of biochar. Kinetic experiments showed that the adsorption process of BC and BCS could be better described by the pseudo-second-order model than the pseudo-first-order model. The equilibrium time of BCS for Hg2+ adsorption was only 30 min, and the adsorption process was not affected by pH. The results of isothermal experiments showed that Langmuir model could better describe the adsorption process of BC, and the adsorption capacity decreased when increasing pyrolysis temperature. The isothermal adsorption of BCS to Hg2+ conformed to the Freundlich equation, the adsorption capacity of BCS was significantly higher than BC, and the maximum adsorption capacity was 407.81 mg/g. The desorption experiments showed that the adsorption stability of BCS was higher than BC, and the desorption rate was lower than 5% in each desorption agent. The results of FTIR and XPS showed that the main adsorption mechanisms of BC and BCS were functional group complexation and HgS precipitation, respectively. Therefore, BCS is a highly efficient and stable mercury adsorption material.
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Key words:
- cow manure biochar /
- sulfur modified /
- mercury /
- adsorption /
- mechanism
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[1] CABRITA M T, DUARTE B, CESÁRIO R, et al. Mercury mobility and effects in the salt-marsh plant Halimione portulacoides:uptake, transport, and toxicity and tolerance mechanisms[J]. Science of the Total Environment, 2019,650:111-120. [2] YU C H, XU Y P, YAN Y Y, et al. Mercury and methylmercury in China's lake sediments and first estimation of mercury burial fluxes[J]. Science of the Total Environment, 2021,770:145338. [3] KOPEC A D, KIDD K A, FISHER N S, et al. Spatial and temporal trends of mercury in the aquatic food web of the lower Penobscot River, Maine, USA, affected by a chlor-alkali plant[J]. Science of the Total Environment, 2019,649:770-791. [4] 朱先芳,唐磊,季宏兵,等.北京北部水系沉积物中重金属的研究[J].环境科学学报, 2010,30(12):2553-2562. [5] LANDIS M S, KEELER G J, AL-WALI K I, et al. Divalent inorganic reactive gaseous mercury emissions from a mercury cell chlor-alkali plant and its impact on near-field atmospheric dry deposition[J]. Atmospheric Environment, 2004,38(4):613-622. [6] HADAVIFAR M, BAHRAMIFAR N, YOUNESI H, et al. Adsorption of mercury ions from synthetic and real wastewater aqueous solution by functionalized multi-walled carbon nanotube with both amino and thiolated groups[J]. Chemical Engineering Journal, 2014,237:217-228. [7] 贾威,陈金全,常军军.汞污染生物修复研究进展[J].环境工程, 2020,38(5):171-178. [8] 刘支强,康钦利,侯志成,等.含汞气田水硫化物的沉淀脱汞[J].油气田地面工程, 2012,31(4):41-42. [9] AHMAD M, RAJAPAKSHA A U, LIM J E, et al. Biochar as a sorbent for contaminant management in soil and water:a review[J]. Chemosphere, 2014,99:19-33. [10] 周俊,李燕,管益东,等.杨木生物炭对水溶液中3种磺胺类抗生素的混合吸附[J].环境工程, 2021,39(3):1-6. [11] 陈林,平巍,闫彬,等.不同制备温度下污泥生物炭对Cr (Ⅵ)的吸附特性[J].环境工程, 2020,38(8):119-124. [12] ZHAO J W, GAO F, SUN Y, et al. New use for biochar derived from bovine manure for tetracycline removal[J]. Journal of Environmental Chemical Engineering, 2021,9(4):105585. [13] VAUGHN S F, KENAR J A, THOMPSON A R, et al. Comparison of biochars derived from wood pellets and pelletized wheat straw as replacements for peat in potting substrates[J]. Industrial Crops and Products, 2013,51:437-443. [14] HIGASHIKAWA F S, CONZ R F, COLZATO M, et al. Effects of feedstock type and slow pyrolysis temperature in the production of biochars on the removal of cadmium and nickel from water[J]. Journal of Cleaner Production, 2016,137:965-972. [15] 谢婧如,陈本寿,张进忠,等.巯基改性海泡石吸附水中的Hg (Ⅱ)[J].环境科学, 2016,37(6):2187-2194. [16] LYU H H, XIA S Y, TANG J C, et al. Thiol-modified biochar synthesized by a facile ball-milling method for enhanced sorption of inorganic Hg2+ and organic CH3Hg+[J]. Journal of Hazardous Materials, 2020,384:121357. [17] O'CONNOR D, PENG T, LI G, et al. Sulfur-modified rice husk biochar:a green method for the remediation of mercury contaminated soil[J]. Science of the Total Environment, 2018,621:819-826. [18] 彭华,张洪宇,张晶.畜禽粪污治理利用主要进展及问题对策[J].中国猪业, 2018,13(9):53-57. [19] 陈佼,黄雯,陆一新,等.羊粪生物炭对SBR系统污水处理性能的影响[J].水处理技术, 2021,47(10):108-112. [20] JEFFREY M, NOVAK I L B, XING J W G C, K. C. Das M A D, et al. Characterization of designer biochar produced at different temperatures and their effects on a loamy sand[J]. Annals of Environmental Science, 2009,3:195-206. [21] SAHOO S S, VIJAY V K, CHANDRA R, et al. Production and characterization of biochar produced from slow pyrolysis of pigeon pea stalk and bamboo[J]. Cleaner Engineering and Technology, 2021,3:100101. [22] PARK J, WANG J J, KIM S, et al. Cadmium adsorption characteristics of biochars derived using various pine tree residues and pyrolysis temperatures[J]. Journal of Colloid and Interface Science, 2019,553:298-307. [23] HUANG F, ZHANG S M, WU R R, et al. Magnetic biochars have lower adsorption but higher separation effectiveness for Cd2+ from aqueous solution compared to nonmagnetic biochars[J]. Environmental Pollution, 2021,275:116485. [24] AHMAD Z, GAO B, MOSA A, et al. Removal of Cu (Ⅱ), Cd (Ⅱ) and Pb (Ⅱ) ions from aqueous solutions by biochars derived from potassium-rich biomass[J]. Journal of Cleaner Production, 2018,180:437-449. [25] WEBER W J, MORRIS J C. Kinetics of adsorption on carbon from solution[J]. Journal of the Sanitary Engineering Division, 1963,2(89):31-60. [26] 张艳素,豆小敏,于新,等.锆铁复合氧化物颗粒对As (Ⅴ)的去除研究[J].环境化学, 2011,30(8):1396-1404. [27] KUN-Yi A L, YU-Ting L, SHEN-Yi C. Adsorption of fluoride to UiO-66-NH2 in water:stability, kinetic, isotherm and thermodynamic studies[J]. Journal of Colloid and Interface Science, 2016,461:79-87. [28] YAO Y J, BING H, XU F F, et al. Equilibrium and kinetic studies of methyl orange adsorption on multiwalled carbon nanotubes[J]. Chemical Engineering Journal, 2011,170(1):82-89. [29] 曹健华,刘凌沁,黄亚继,等.原料种类和热解温度对生物炭吸附Cd2+的影响[J].化工进展, 2019,38(9):4183-4190. [30] LI R H, ZHANG Y C, DENG H X, et al. Removing tetracycline and Hg (Ⅱ) with ball-milled magnetic nanobiochar and its potential on polluted irrigation water reclamation[J]. Journal of Hazardous Materials, 2020,384:121095. [31] WALY S M, EL-WAKIL A M, EL-MAATY W M A, et al. Efficient removal of Pb (Ⅱ) and Hg (Ⅱ) ions from aqueous solution by amine and thiol modified activated carbon[J]. Journal of Saudi Chemical Society, 2021,25(8):101296. [32] SITKO R, MUSIELAK M, SERDA M, et al. Thiosemicarbazide-grafted graphene oxide as superior adsorbent for highly efficient and selective removal of mercury ions from water[J]. Separation and Purification Technology, 2021,254:117606. [33] XU X Y, CAO X D, ZHAO L. Comparison of rice husk-and dairy manure-derived biochars for simultaneously removing heavy metals from aqueous solutions:role of mineral components in biochars[J]. Chemosphere, 2013,92(8):955-961. [34] XU X Y, CAO X D, ZHAO L, et al. Removal of Cu, Zn, and Cd from aqueous solutions by the dairy manure-derived biochar[J]. Environmental Science and Pollution Research, 2013,20(1):358-368. [35] HUANG Y, TANG J C, GAI L, et al. Different approaches for preparing a novel thiol-functionalized graphene oxide/Fe-Mn and its application for aqueous methylmercury removal[J]. Chemical Engineering Journal, 2017,319:229-239. [36] CHEN D, WANG X B, WANG X L, et al. The mechanism of cadmium sorption by sulphur-modified wheat straw biochar and its application cadmium-contaminated soil[J]. Science of the Total Environment, 2020,714:136550. [37] COATES J. Interpretation of infrared spectra, a practical approach[M]. John Wiley&Sons, Ltd., 2006. [38] RAO C N R, VENKATARAGHAVAN R. The CS stretching frequency and the"-N-CS bands"in the infrared[J]. Spectrochimica Acta Part A:Molecular Spectroscopy, 1989,45:299-305. [39] DONG X, MA L Q, ZHU Y, et al. Mechanistic investigation of mercury sorption by brazilian pepper biochars of different pyrolytic temperatures based on X-ray photoelectron spectroscopy and flow calorimetry[J]. Environmental Science&Technology, 2013,47(21):12156-12164. [40] TANG H J, YOU W Q, WANG Z W, et al. Detrimental effects of SO2 on gaseous mercury (Ⅱ) adsorption and retention by CaO-based sorbent traps:competition and heterogeneous reduction[J]. Journal of Hazardous Materials, 2020,387:121679. [41] STROYUK O, RAEVSKAYA A, SPRANGER F, et al. Mercury-indium-sulfide nanocrystals:a new member of the family of ternary in based chalcogenides[J]. The Journal of Chemical Physics, 2019,151(14):144701. [42] ZYLBERAJCH-ANTOINE C, BARRAUD A, ROULET H, et al. XPS characterization of inserted mercury sulfide single layers in a Langmuir-Blodgett matrix[J]. Applied Surface Science, 1991,52(4):323-327.
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