硝酸氧化改性褐煤提升吸附镉能力研究
|
摘要
采用固液吸附系统研究了褐煤和硝化褐煤对镉离子的等温吸附、动力学吸附等特征,用卡方检验、Avrami模型筛选和验证了2种材料适宜的吸附机制模型。结果表明,不同温度下硝化褐煤和褐煤最大单层吸附量分别为35. 61～46. 84、29. 63～38. 20 mg·g~(-1),硝化褐煤比褐煤增加吸附量在20. 18%～22. 62%。基本达到平衡吸附量时,分别用了150、330 min。硝化褐煤在低温时符合Langmuir单层吸附和准二级动力学过程,褐煤适合Freundlich模型描述。Avrami模型可较好地描述2种材料的等温吸附和动力学吸附特征。不同温度的等温吸附特征和动力学结果表明,随温度升高,2种材料经历了单层吸附、多层吸附的物理-化学过程,吸附是自发的吸热过程。红外光谱分析表明,硝化褐煤拥有较多的功能团,与吸附镉有关的为含氧功能团区、未知吸附带、脂肪族羟基和芳香C—H结构。硝化褐煤中羰基碳相对含量较褐煤高,可能是结合Cd~(2+)能力提高的原因。因此,褐煤改性后的硝化褐煤对镉离子的吸附量和吸附速率最大,硝化褐煤能提高对镉的吸附性能,热力学和动力学吸附机制在不同材料和不同温度情况下不同,模型适宜性需用误差函数卡方检验辅助确定。改变褐煤基吸附材料的关键是增加有效功能团。研究首次表明,吸附过程中动力学级数发生改变,脂肪族羟基区、未知吸收带2 360. 20 cm~(-1)和2 341. 98 cm~(-1)和含氧官能团是褐煤硝酸氧化后吸附镉能力提高的关键因素。
The isothermal and kinetic adsorption characteristics of lignite and lignite modified by nitric acid oxidation for Cadmium( II) ions were investigated though the method of solid-liquid adsorption.Nonlinear chi-square analysis and Avrami model were used to verify the optimum adsorption mechanism models of the two materials. The results showed that the maximum monolayer adsorption capacities of nitric acid oxidation lignite( NAOL) and raw lignite( RL) were 35. 61 ～ 46. 84,29. 63 ～ 38. 20 mg·g-1. The adsorption amount of NAOL increased by 20. 18% ～ 22. 62% compared with the RL. The adsorption equilibriums were achieved at about 150 minutes for NAOL and 330 minutes for RL. At low temperature,NAOL obeyed Langmuir isotherm model which describe monolayer adsorption and pseudosecond-order kinetic model,but RL were better described using Freundlich equation. Overall,all these lignite-based adsorbents could be best fitted with Avrami models at all temperature. The adsorption isotherm and kinetics of the adsorbents at different temperatures demonstrated that absorption process probably went first through monolayer sorption and successively multilayer absorption of physical-chemical process. Through thermodynamic parameters,it was verified that absorption processes were spontaneous,endothermal and favourable sorption. FT-IR analysis showed that NAOL had many functional groups,and the oxygen-containing functional group region,unknown adsorption zone,aliphatic hydroxyl group as well as aromatic C—H structure were related to the adsorption of cadmium.The relative content of carbonyl carbon in NAOL was higher than that in RL,which may be the reason for the improvement of Cd~(2+) binding capacity. Therefore,the adsorption capacity and adsorption rate of Cd~(2+) could reach to the maximum value treated by the NAOL. Though the NAOL improved the adsorption performance of Cd~(2+) ,the model suitability also needed to be confirming by chi-square test of error function. That is because the thermodynamic and kinetic adsorption mechanism varied with different materials and temperatures. The key method of lignite-based adsorption materials was to increase the effective functional groups. The study indicated for the first time that the kinetic order had changed during the adsorption process. Aliphatic hydroxyl zone,unknown absorption zone 2 360. 20 cm-1 and 2 341.98 cm-1,and the oxygen-containing functional group( mainly carbonyl carbon),were the key factors for the improvement of cadmium adsorption capacity of NAOL.
The isothermal and kinetic adsorption characteristics of lignite and lignite modified by nitric acid oxidation for Cadmium( II) ions were investigated though the method of solid-liquid adsorption.Nonlinear chi-square analysis and Avrami model were used to verify the optimum adsorption mechanism models of the two materials. The results showed that the maximum monolayer adsorption capacities of nitric acid oxidation lignite( NAOL) and raw lignite( RL) were 35. 61 ～ 46. 84,29. 63 ～ 38. 20 mg·g-1. The adsorption amount of NAOL increased by 20. 18% ～ 22. 62% compared with the RL. The adsorption equilibriums were achieved at about 150 minutes for NAOL and 330 minutes for RL. At low temperature,NAOL obeyed Langmuir isotherm model which describe monolayer adsorption and pseudosecond-order kinetic model,but RL were better described using Freundlich equation. Overall,all these lignite-based adsorbents could be best fitted with Avrami models at all temperature. The adsorption isotherm and kinetics of the adsorbents at different temperatures demonstrated that absorption process probably went first through monolayer sorption and successively multilayer absorption of physical-chemical process. Through thermodynamic parameters,it was verified that absorption processes were spontaneous,endothermal and favourable sorption. FT-IR analysis showed that NAOL had many functional groups,and the oxygen-containing functional group region,unknown adsorption zone,aliphatic hydroxyl group as well as aromatic C—H structure were related to the adsorption of cadmium.The relative content of carbonyl carbon in NAOL was higher than that in RL,which may be the reason for the improvement of Cd~(2+) binding capacity. Therefore,the adsorption capacity and adsorption rate of Cd~(2+) could reach to the maximum value treated by the NAOL. Though the NAOL improved the adsorption performance of Cd~(2+) ,the model suitability also needed to be confirming by chi-square test of error function. That is because the thermodynamic and kinetic adsorption mechanism varied with different materials and temperatures. The key method of lignite-based adsorption materials was to increase the effective functional groups. The study indicated for the first time that the kinetic order had changed during the adsorption process. Aliphatic hydroxyl zone,unknown absorption zone 2 360. 20 cm-1 and 2 341.98 cm-1,and the oxygen-containing functional group( mainly carbonyl carbon),were the key factors for the improvement of cadmium adsorption capacity of NAOL.
引文
[1]韦小了,牟力,付天岭,等.不同钝化剂组合对水稻各部位吸收积累Cd及产量的影响[J/OL].土壤学报:1-11[2019-03-20]. http://kns. cnki. net/kcms/detail/32. 1119. P. 20190313. 1456. 004. html.
[2]宋乐,韩占涛,张威,等.改性生物质电厂灰钝化修复南方镉污染土壤及其长效性研究[J].中国环境科学,2019,39(1):226-234.
[3]张迪,丁爱芳.组配钝化剂对镉铅复合污染土壤修复效果研究[J].农业环境科学学报,2018,37(12):2718-2726.
[4]路国华,赵树兰,多立安.纳米铁联合氧化石墨烯对垃圾堆肥基质高羊茅生理生态的影响[J].生态学报,2019,39(7):1-7.
[5]赵敏,范琼,邓爱妮,等.酸性土壤改良对土壤镉形态改变及树仔菜镉含量的影响[J].南方农业学报,2018,49(6):1089-1094.
[6]邢维芹,历琳,KIRK G S,等.不同添加剂对铅冶炼污染石灰性土壤的修复及土壤性质的影响研究[J].环境科学学报,2014,34(6):1534-1540.
[7]刘梅堂,王天雷,程瑶,等.中国泥炭褐煤资源及发展腐植酸钾产业潜力[J].地学前缘,2014,21(5):255-266.
[8]马宏瑞,焦文娟,任健,等.腐殖酸改性吸附剂处理染料废水的效果研究[J].环境科学与技术,2009,32(7):128-131.
[9]罗道成,刘俊峰.腐殖酸树脂处理Pb2+、Cu2+、Ni2+废水的研究[J].环境污染治理技术与设备,2005,6(10):73-76.
[10]徐铭泽.功能纳米复合材料的制备及其在核废水处理中的应用研究[D].长春:吉林大学,2014.
[11]刘方春,邢尚军,刘春生,等.褐煤腐殖酸对铵的吸附特性研究[J].植物营养与肥料学报,2005,11(4):514-518.
[12]王鲁敏,邓昌亮,殷军港,等.硝化褐煤对铬离子溶液的吸附研究[J].环境化学,2001,20(1):54-58.
[13]倪献智,刘丽晨.龙口褐煤稀硝酸氧解性能的研究[J].煤炭转化,1998,21(1):68-72.
[14] SIVARAJU S,KHADHAR MMSB. Studies on the performance of ethylamine-modified chitosan carbonized rice husk composite beads for adsorption of metal ion[J]. Bioremediation Journal,2013,17(2):97-106.
[15] FOAD R,MAJID P,ALIREZA S,et al. A detailed study on adsorption isotherms of Hg(II)removal from aqueous solutions using nanostructured sorbent Zn Cl2-MCM-41[J]. Desalination and Water Treatment,2016. 57(40):18694-18709.
[16] AGARRY S E,OGUNLEYE O O,AJANI O A. Biosorptive removal of cadmium(II)ions from aqueous solution by chemically modified onion skin:Batch equilibrium,kinetic and thermodynamic studies[J]. Chemical Engineering Communications,2015,202(5):655-673.
[17] SURABHI S,BALASUBRAMANIAN K,ARORA R.Adsorption of arsenic(V)ions onto cellulosic-ferric oxide system:kinetics and isotherm studies[J]. Desalination and Water Treatment,2016,57(20):9420-9436.
[18] MAHAMADI C,NHARINGO T. Utilization of water hyacinth weed(Eichhornia crassipes)for the removal of Pb(II),Cd(II)and Zn(II)from aquatic environments:an adsorption isotherm study[J]. Environmental Technology,2010,31(11):1221-1228.
[19] AGARRY S E,OGUNLEYE O O,AWORANTI O A.Biosorption equilibrium,kinetic and thermodynamic modelling of naphthalene removal from aqueous solution onto modified spent tea leaves[J]. Environmental Technology,2013,34(7):825-839.
[20] SHARAF EL-DEEN S E A,NABLA S A,TAREK S J.Adsorption behavior of Co(II)and Ni(II)from aqueous solutions onto titanate nanotubes[J]. Fullerenes,Nanotubes and Carbon Nanostructures, 2016, 24(7):455-466.
[21] FADEL D A,EI-BAHY S M,ABDELAZIZ Y A. Heavy metals removal using iminodiacetate chelating resin by batch and column techniques[J]. Desalination and Water Treatment,2016,57(53):25718-25728.
[22] RAIS A,SHAZIYA H. Kinetic,isotherm and thermodynamic studies for the removal of Pb2+ion by a novel adsorbent Luffa acutangula(LAPR)[J]. Desalination and Water Treatment,2016,57(38):17826-17835.
[23] OLUWASOGO A D,FOLAHAN A A,EZEKIEL O O.Kinetics and equilibrium models for sorption of Cu(II)onto a novel manganese nano-adsorbent[J]. Journal of Dispersion Science and Technology, 2016, 37(1):119-133.
[24] NJOKU V O,AYUK A A,OGUZIE E E,et al. Biosorption of Cd(II)from aqueous solution by cocoa pod husk biomass:equilibrium,kinetic,and thermodynamic studies[J]. Separation Science and Technology,2012,47(5):753-761.
[25] AYBEN P,SUKRU A. Kinetic and isotherm study of cupper adsorption from aqueous solution using waste eggshell[J]. Journal of Environmental Engineering and Landscape Management,2014,22(2):132-140.
[26]李力,陆宇超,刘娅,等.玉米秸秆生物炭对Cd(Ⅱ)的吸附机理研究[J].农业环境科学学报,2012,31(11):2277-2283.
[27]韩峰,张衍国,蒙爱红,等.云南褐煤结构的FTIR分析[J].煤炭学报,2014,39(11):2293-2299.
[28]王永刚,周剑林,陈艳巨,等.13C固体核磁共振分析煤中含氧官能团的研究[J].燃料化学学报,2013,41(12):1422-1426.
[29]李昌明,王晓玥,孙波,等.基于固态13C核磁共振波谱研究植物残体分解和转化机制的进展[J].土壤,2017,49(4):658-664.
[30]赵凡,陈秀梅,张文刚,等.氨基和羧基功能化磁性微球去除水溶液中Cd(Ⅱ)和Pb(Ⅱ)[J].硅酸盐通报,2017,36(12):4302-4307.
[2]宋乐,韩占涛,张威,等.改性生物质电厂灰钝化修复南方镉污染土壤及其长效性研究[J].中国环境科学,2019,39(1):226-234.
[3]张迪,丁爱芳.组配钝化剂对镉铅复合污染土壤修复效果研究[J].农业环境科学学报,2018,37(12):2718-2726.
[4]路国华,赵树兰,多立安.纳米铁联合氧化石墨烯对垃圾堆肥基质高羊茅生理生态的影响[J].生态学报,2019,39(7):1-7.
[5]赵敏,范琼,邓爱妮,等.酸性土壤改良对土壤镉形态改变及树仔菜镉含量的影响[J].南方农业学报,2018,49(6):1089-1094.
[6]邢维芹,历琳,KIRK G S,等.不同添加剂对铅冶炼污染石灰性土壤的修复及土壤性质的影响研究[J].环境科学学报,2014,34(6):1534-1540.
[7]刘梅堂,王天雷,程瑶,等.中国泥炭褐煤资源及发展腐植酸钾产业潜力[J].地学前缘,2014,21(5):255-266.
[8]马宏瑞,焦文娟,任健,等.腐殖酸改性吸附剂处理染料废水的效果研究[J].环境科学与技术,2009,32(7):128-131.
[9]罗道成,刘俊峰.腐殖酸树脂处理Pb2+、Cu2+、Ni2+废水的研究[J].环境污染治理技术与设备,2005,6(10):73-76.
[10]徐铭泽.功能纳米复合材料的制备及其在核废水处理中的应用研究[D].长春:吉林大学,2014.
[11]刘方春,邢尚军,刘春生,等.褐煤腐殖酸对铵的吸附特性研究[J].植物营养与肥料学报,2005,11(4):514-518.
[12]王鲁敏,邓昌亮,殷军港,等.硝化褐煤对铬离子溶液的吸附研究[J].环境化学,2001,20(1):54-58.
[13]倪献智,刘丽晨.龙口褐煤稀硝酸氧解性能的研究[J].煤炭转化,1998,21(1):68-72.
[14] SIVARAJU S,KHADHAR MMSB. Studies on the performance of ethylamine-modified chitosan carbonized rice husk composite beads for adsorption of metal ion[J]. Bioremediation Journal,2013,17(2):97-106.
[15] FOAD R,MAJID P,ALIREZA S,et al. A detailed study on adsorption isotherms of Hg(II)removal from aqueous solutions using nanostructured sorbent Zn Cl2-MCM-41[J]. Desalination and Water Treatment,2016. 57(40):18694-18709.
[16] AGARRY S E,OGUNLEYE O O,AJANI O A. Biosorptive removal of cadmium(II)ions from aqueous solution by chemically modified onion skin:Batch equilibrium,kinetic and thermodynamic studies[J]. Chemical Engineering Communications,2015,202(5):655-673.
[17] SURABHI S,BALASUBRAMANIAN K,ARORA R.Adsorption of arsenic(V)ions onto cellulosic-ferric oxide system:kinetics and isotherm studies[J]. Desalination and Water Treatment,2016,57(20):9420-9436.
[18] MAHAMADI C,NHARINGO T. Utilization of water hyacinth weed(Eichhornia crassipes)for the removal of Pb(II),Cd(II)and Zn(II)from aquatic environments:an adsorption isotherm study[J]. Environmental Technology,2010,31(11):1221-1228.
[19] AGARRY S E,OGUNLEYE O O,AWORANTI O A.Biosorption equilibrium,kinetic and thermodynamic modelling of naphthalene removal from aqueous solution onto modified spent tea leaves[J]. Environmental Technology,2013,34(7):825-839.
[20] SHARAF EL-DEEN S E A,NABLA S A,TAREK S J.Adsorption behavior of Co(II)and Ni(II)from aqueous solutions onto titanate nanotubes[J]. Fullerenes,Nanotubes and Carbon Nanostructures, 2016, 24(7):455-466.
[21] FADEL D A,EI-BAHY S M,ABDELAZIZ Y A. Heavy metals removal using iminodiacetate chelating resin by batch and column techniques[J]. Desalination and Water Treatment,2016,57(53):25718-25728.
[22] RAIS A,SHAZIYA H. Kinetic,isotherm and thermodynamic studies for the removal of Pb2+ion by a novel adsorbent Luffa acutangula(LAPR)[J]. Desalination and Water Treatment,2016,57(38):17826-17835.
[23] OLUWASOGO A D,FOLAHAN A A,EZEKIEL O O.Kinetics and equilibrium models for sorption of Cu(II)onto a novel manganese nano-adsorbent[J]. Journal of Dispersion Science and Technology, 2016, 37(1):119-133.
[24] NJOKU V O,AYUK A A,OGUZIE E E,et al. Biosorption of Cd(II)from aqueous solution by cocoa pod husk biomass:equilibrium,kinetic,and thermodynamic studies[J]. Separation Science and Technology,2012,47(5):753-761.
[25] AYBEN P,SUKRU A. Kinetic and isotherm study of cupper adsorption from aqueous solution using waste eggshell[J]. Journal of Environmental Engineering and Landscape Management,2014,22(2):132-140.
[26]李力,陆宇超,刘娅,等.玉米秸秆生物炭对Cd(Ⅱ)的吸附机理研究[J].农业环境科学学报,2012,31(11):2277-2283.
[27]韩峰,张衍国,蒙爱红,等.云南褐煤结构的FTIR分析[J].煤炭学报,2014,39(11):2293-2299.
[28]王永刚,周剑林,陈艳巨,等.13C固体核磁共振分析煤中含氧官能团的研究[J].燃料化学学报,2013,41(12):1422-1426.
[29]李昌明,王晓玥,孙波,等.基于固态13C核磁共振波谱研究植物残体分解和转化机制的进展[J].土壤,2017,49(4):658-664.
[30]赵凡,陈秀梅,张文刚,等.氨基和羧基功能化磁性微球去除水溶液中Cd(Ⅱ)和Pb(Ⅱ)[J].硅酸盐通报,2017,36(12):4302-4307.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |