N掺杂木质素对钨的吸附

doi:10.3969/j.issn.1000-1565.2024.03.006

摘要/Abstract

摘要： 木质素经胺化和季铵化改性后制备了N掺杂木质素,并用于吸附钨,通过SEM-EDS和FTIR对吸附剂进行表征,考察pH值、钨初始质量浓度、吸附时间和吸附剂用量对吸附容量的影响,利用SEM-EDS、FTIR和XPS分析揭示吸附过程的机制.结果表明,N掺杂木质素表面疏松多孔且含有大量的酚羟基、胺基和季铵官能团,在总钨浓度为0.005 mol/L、pH<4.7时,钨的存在形态为H₂W₁₂O^6-₄₀.H₂W₁₂O^6-₄₀通过与N掺杂木质素中氢键的静电吸引、胺基的配合和氯离子的离子交换作用而被吸附.在pH=4.0、钨初始质量浓度为800 mg/L、吸附时间为960 min的条件下,1 g/L N掺杂木质素对钨的饱和吸附容量为421.68 mg/g.吸附过程遵循Langmuir模型和准二级动力学模型,表明吸附过程为单分子层均质化学吸附.

关键词: N掺杂木质素, 钨, 吸附行为, 吸附机制

Abstract: N-doped lignin used for adsorption of tungsten was synthesized by polyamination and quaternization from lignin. The adsorbent was characterized by SEM-EDS and FTIR. The effects of pH, initial mass concentration of tungsten, adsorption time and amount of adsorbent on the adsorption capacity were investigated. The adsorption mechanism was revealed by SEM-EDS and FTIR and XPS. The results showed that N-doped lignin was loose and porous and contained a large amount of phenolic hydroxyl, amine and quaternary ammonium functional groups. When the total concentration of tungsten was 0.005 mol/L and the value of pH was smaller than 4.7, the existing form of tungsten was H₂W₁₂O^6-₄₀. H₂W₁₂O^6-₄₀ was adsorbed by N-doped lignin through electrostatic attraction of hydrogen bond and coordination with amino and ion exchange with Cl^-. The saturated adsorption capacity of 1 g/L N-doped lignin for tungsten reached 421.68 mg/g at pH of 4.0, with initial tungsten mass concentration of 800 mg/L and adsorption time of 960 min. The adsorption followed Langmuir model and quasi-second-order kinetic model, indicating that the adsorption was monolayer homogeneous chemisorption.

Key words: N-doped lignin, tungsten, adsorption behavior, adsorption mechanism

中图分类号:

TF839

张保平,柯晶,方诗媛,李文灿. N掺杂木质素对钨的吸附[J]. 河北大学学报(自然科学版), 2024, 44(3): 269-280.

ZHANG Baoping, KE Jing, FANG Shiyuan, LI Wencan. Adsorption of tungsten by N-doped lignin[J]. Journal of Hebei University(Natural Science Edition), 2024, 44(3): 269-280.

参考文献

[1] HU Z P,LIU Y,CHEN S H,et al. Achieving high-performance pure tungsten by additive manufacturing:Processing,microstructural evolution and mechanical properties[J]. Int J Refract Met Hard Mater,2023,113:106211. DOI:10.1016/j.ijrmhm.2023.106211.
[2] LO S C,CHENG T M,HU C C,et al. Separation of tungsten and cobalt from cemented tungsten carbide by rapid breakdown anodization[J]. Sep Purif Technol,2023,310:123140. DOI:10.1016/j.seppur.2023.123140.
[3] PANDEY A K,SHARMA A K,MARQUES C. On the application of stacked periodic tungsten grating nanostructure in wide-range plasmonic sensing and other photonic devices[J]. Plasmonics,2021,16(1):9-17. DOI:10.1007/s11468-020-01248-x.
[4] BARIK R,YADAV A K,JHA S N,et al. Two-dimensional tungsten oxide/selenium nanocomposite fabricated for flexible supercapacitors with higher operational voltage and their charge storage mechanism[J]. ACS Appl Mater Interfaces,2021,13(7):8102-8119. DOI:10.1021/acsami.0c15818.
[5] TIMOFEEV I,KOSHELEVA N,KASIMOV N. Contamination of soils by potentially toxic elements in the impact zone of tungsten molybdenum ore mine in the Baikal region:A survey and risk assessment[J]. Sci Total Environ,2018,642:63-76. DOI:10.1016/j.scitotenv.2018.06.042.
[6] GUO W,LI J Q,MANICA R,et al. Quantifying bubble-scheelite interaction under the effect of sodium oleate[J].Miner Eng, 2023,204:108371.DOI:10.1016/j.mineng.108371.
[7] CHEN Y L,HUO G S,GUO X Y,et al. Sustainable extraction of tungsten from the acid digestion product of tungsten concentrate by leaching-solvent extraction together with raffinate recycling[J]. J Clean Prod,2022,375:133924. DOI:10.1016/j.jclepro.2022.133924.
[8] ZEILER B,BARTL A,SCHUBERT W D. Recycling of tungsten:Current share,economic limitations,technologies and future potential[J]. Int J Refract Met Hard Mater,2021,98:105546. DOI:10.1016/j.ijrmhm.2021.105546.
[9] ALI N,SHAH S,KHAN A,et al. Selective separation of tungsten from the model and industrial effluents through supported liquid membrane[J]. Chem Pap,2021,75(2): 553-563. DOI:10.1007/s11696-020-01309-9.
[10] MASRY B A,DAOUD J A. Sorption behavior of tungsten and molybdenum on TVEX-TOPO resin from nitric acid solution[J]. J Chem Tech & Biotech,2021,96(5):1399-1410. DOI:10.1002/jctb.6660.
[11] 张恒,张保平,肖煜坤,等.氨基硫脲/季铵木质素对铂的吸附[J].复合材料学报,2022,39(10):4674-4684. DOI:10.13801/j.cnki.fhclxb.20211018.004.
[12] DIAS D,DON D,JANDOSOV J,et al. Highly efficient porous carbons for the removal of W(Ⅵ)oxyanion from wastewaters[J]. J Hazard Mater,2021,412:125201. DOI:10.1016/j.jhazmat.2021.125201.
[13] WANG X,LENG W Q,NAYANATHARA R M O,et al. Recent advances in transforming agricultural biorefinery lignins into value-added products[J]. J Agric Food Res,2023,12:100545. DOI: 10.1016/j.jafr.2023.100545.
[14] CULEBRAS M,COLLINS G A,BEAUCAMP A,et al. Lignin/Si hybrid carbon nanofibers towards highly efficient sustainable Li-ion anode materials[J]. Eng Sci,2022,17:195-203. DOI:10.30919/es8d608.
[15] ZHANG B P,WANG Y,LIN G,et al. Extraction of gold from the leachate of copper anode slime by quaternary ammonium rice husk lignin[J]. Solvent Extraction and Ion Exchange,2023,41(1):1-19. DOI:10.1080/07366299.2022.2115845.
[16] YADAV R,ZABIHI O,FAKHRHOSEINI S,et al. Lignin derived carbon fiber and nanofiber:Manufacturing and applications[J]. Compos Part B:Eng,2023,255:110613. DOI: 10.1016/j.compositesb.2023.110613.
[17] DU B Y,LI W J,ZHU H W,et al. A functional lignin for heavy metal ions adsorption and wound care dressing[J]. Int J Biol Macromol,2023,239:124268. DOI:10.1016/j.ijbiomac.2023.124268.
[18] 曹才放,章行,李小文,等.氯型季铵树脂对钨酸根吸附的热力学研究[J].有色金属科学与工程,2018,9(3):1-4. DOI:10.13264/j.cnki.ysjskx.2018.03.001.
[19] LI F Y,LIANG H N,SHAN J X,et al. Lignin-grafted quaternary ammonium phosphate with temperature and pH responsive behavior for improved enzymatic hydrolysis and cellulase recovery[J]. Int J Biol Macromol,2023,234:123779. DOI:10.1016/j.ijbiomac.2023.123779.
[20] SONG C Y, GAO C, FATEHI P, et al. Influence of structure and functional group of modified kraft lignin on adsorption behavior of dye[J]. Int J Biol Macromol,2023,240:124368. DOI:10.1016/j.ijbiomac.2023.124368.
[21] WANG H,LIU P Y,CHEN X Y,et al. Efficient dissolution of tungstic acid by isopolytungstate solution based on the polymerization theory of tungsten[J]. Hydrometallurgy,2022,209:105835. DOI:10.1016/j.hydromet.2022.105835.
[22] 梁英教,车荫昌,刘晓霞.无机物热力学数据手册[M].沈阳:东北大学出版社,1993.
[23] REDKIN A F,BONDARENKO G V. Raman spectra of tungsten-bearing solutions[J]. J Solut Chem,2010,39(10):1549-1561. DOI:10.1007/s10953-010-9595-9.
[24] CRUYWAGEN J J,LZAK F J MERWE V D. Tungsten(Ⅵ)equilibria:a potentiometric and calorimetric investigation[J]. J Chem Soc,Dalton Trans,1987(7):1701-1705. DOI:10.1039/DT9870001701.
[25] 张家靓,赵中伟,陈星宇,等.W-Mo-H₂O体系钨钼分离的热力学分析[J].中国有色金属学报,2013,23(5):1463-1470. DOI:10.19476/j.ysxb.1004.0609.2013.05.040.
[26] LUO B Y,LIU X H,LI J T,et al. Kinetics of tungstate and phytate adsorption by D201 resin[J]. JOM,2021,73(5):1337-1343. DOI:10.1007/s11837-021-04626-w.
[27] 朱倩倩,熊春华,厉炯慧,等.吗啡啉螯合树脂对水中钨离子的吸附及解吸性能[J].化工学报,2017,68(8):3119-3125. DOI:10.11949/j.issn.0438-1157.20170163.
[28] WANG Y Y,HUANG K. Biosorption of tungstate onto garlic peel loaded with Fe(Ⅲ),Ce(Ⅲ),and Ti(Ⅳ)[J]. Environ Sci Pollut Res,2020,27(27):33692-33702. DOI:10.1007/s11356-020-09309-8.
[29] OGATA F,NAKAMURA T,UETA E,et al. Adsorption of tungsten ion with a novel Fe-Mg type hydrotalcite prepared at different Mg²⁺/Fe³⁺ ratios[J]. J Environ Chem Eng,2017,5(4):3083-3090. DOI:10.1016/j.jece.2017.06.017.
[30] ORDINARTSEV D P,SVIRIDOV A V,SVIRIDOV V V. Extracting vanadium,molybdenum,and tungsten from acidic solutions via adsorption on modified montmorillonite[J]. Russ J Phys Chem A,2018,92(10):2060-2064. DOI:10.1134/S0036024418100229.
[31] WANG J L,GUO X. Adsorption isotherm models:Classification,physical meaning,application and solving method[J]. Chemosphere,2020,258:127279. DOI:10.1016/j.chemosphere.2020.127279.
[32] RAMRAJ S M, KUBAIB A, IMRAN P M, et al. Utilizing sida acuta leaves for low-cost adsorption of chromium(Ⅵ)heavy metal with activated charcoal[J].Journal of Hazardous Materials Advances,2023,11:100338. DOI:10.1016/j.hazadv.2023.100338.
[33] JUNIOR A B B,PINHEIRO E F,ESPINOSA D C R,et al. Adsorption of lanthanum and cerium on chelating ion exchange resins:Kinetic and thermodynamic studies[J]. Sep Sci Technol,2022,57(1):60-69. DOI:10.1080/01496395.2021.1884720.
[34] GÜRKAN E H,I·LYAS B,TIBET Y. Adsorption performance of heavy metal ions from aqueous solutions by a waste biomass based hydrogel:comparison of isotherm and kinetic models[J]. Int J Environ Anal Chem,2023,103(6):1343-1360. DOI:10.1080/03067319.2021.1873314.
[35] PITCHAY T,JAWAD A H,JOHARI I S,et al. Kinetics studies of metallic ions adsorption by immobilised chitosan[J]. Sci Lett,2022,16(1):137-148. DOI:10.24191/sl.v16i1.15932.
[36] DENG Z E, LUO Y, BIAN M, et al. Synthesis of easily renewable and recoverable magnetic PEI-modified Fe₃O₄ nanoparticles and its application for adsorption and enrichment of tungsten from aqueous solutions[J]. Environ Pollut, 2023,330:121703. DOI:10.1016/j.envpol.2023.121703.
[37] BATUEVA T D,SHCHERBAN M G,KONDRASHOVA N B. Mesoporous silica materials and their sorption capacity for tungsten(Ⅵ)and molybdenum(Ⅵ)ions[J]. Inorg Mater,2019,55(11):1146-1150. DOI:10.1134/S0020168519110013.
[38] HONG H J, YOO H J, JEON J H,et al. Differential adsorption of vanadium(Ⅴ)and tungsten(W)on ion exchange resins: A novel approach for separation and recovery of spent catalyst leachate[J]. J Clean Prod,2023,426:139157. DOI:10.1016/j.jclepro.2023.139157. (