7种改性水稻秸秆对溶液中Cd~(2+)的吸附
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摘要
为实现废弃水稻秸秆资源化利用及其治理水环境中Cd~(2+)的污染问题,用KMnO_4、KOH、H_2O_2、KOH+H_2O_2、酒石酸、柠檬酸、TiO_2对水稻秸秆进行改性,制成不同的水稻秸秆吸附剂来吸附溶液中的Cd~(2+),利用扫描电子显微镜(SEM)、X射线衍射(XRD)、傅里叶红外光谱仪、比表面积及孔径分析仪和Zeta电位仪对改性前后的水稻秸秆进行表征分析,吸附过程采用准一级动力学方程、修正一级动力学方程、准二级动力学方程和颗粒内扩散模型进行拟合.结果表明:在Cd~(2+)初始浓度100mg/L,pH7,水稻秸秆添加量为10g/L,25℃条件下,7种改性水稻秸秆吸附Cd~(2+)的效果不同,其中经KMnO_4改性的水稻秸秆对Cd~(2+)的吸附效果最好,吸附量达10.024mg/g,对Cd~(2+)的去除率达到99.24%,比未改性水稻秸秆提高了99.44%,其次是KOH和KOH+H_2O_2改性处理的水稻秸秆,吸附量分别达到了9.302和9.189mg/g,对Cd~(2+)的去除率分别达92.62%和90.82%,比未改性水稻秸秆分别提高了85.07%和82.83%.改性处理水稻秸秆吸附Cd~(2+)的效果顺序为:KMnO_4>KOH>KOH+H_2O_2>TiO_2>H_2O_2>柠檬酸>酒石酸.对于Cd~(2+)的吸附过程,准一级速率方程只能较好地描述吸附初始阶段,准二级动力学方程则能很好地描述吸附的整个过程.经KMnO_4,KOH和KOH+H_2O_2改性的水稻秸秆是具有潜在利用价值的废水中Cd~(2+)吸附剂.
Aiming at the reuse of discarded rice straw and its treatment of Cd~(2+) pollution in wastewater, rice straw was modified with KMnO_4, KOH, H_2O_2, KOH+H_2O_2, tartaric acid, citric acid, and TiO_2, and made as different types of rice straw sorbentsto adsorb Cd~(2+) in solution. These adsorbents were analyzed by scanning electron microscope(SEM), X-ray diffraction(XRD), FTIR spectrometer, specific surface area and aperture analyzer, and Zeta potentiometer. The adsorption kinetic data were fitted with pseudo-first-order, modified pseudo-first-order, pseudo-second-order and intra-particle diffusion models. The results showed that, under the condition of initial Cd~(2+) concentration of 100 mg/L, pH 7, adsorbent dosage of 10g/Lrice straw and adsorption temperature of 25℃, rice straw modified with KMnO_4 had thebest Cd~(2+)adsorption in the aqueous solution, and the adsorption capacity was 10.024 mg/g Cd~(2+). Its percentage of removal of Cd~(2+)reached 99.24% and had an increase of 99.44% compared with unmodified rice straw. Followed by rice straw was modified with KOH and KOH+H_2O_2, their adsorption capacity for Cd~(2+) were 9.302 mg/g and 9.189 mg/g, percentage of removal of Cd~(2+) reached 92.62% and 90.82%, respectively. Compared with unmodified rice straw treatment, Cd~(2+) removal of rice straw modified with KOH and KOH+H_2O_2 had increases of by 85.07% and 82.83%, respectively. The adsorption order of modified rice straw treatments was: KMnO_4>KOH>KOH+H_2O_2>TiO_2>H_2O_2>citric acid>tartaric acid. It was found that quasi first order rate equation only described the initial stage of Cd~(2+) adsorption suitably, however, apseudo-second order kinetic model was the proper approach for describling the whole process of adsorption. Sum up, the rice straw modified by KMnO_4, KOH and KOH+H_2O_2 could be the potentially valuable adsorbents for absorbing Cd~(2+) in the wastewater solution.
Aiming at the reuse of discarded rice straw and its treatment of Cd~(2+) pollution in wastewater, rice straw was modified with KMnO_4, KOH, H_2O_2, KOH+H_2O_2, tartaric acid, citric acid, and TiO_2, and made as different types of rice straw sorbentsto adsorb Cd~(2+) in solution. These adsorbents were analyzed by scanning electron microscope(SEM), X-ray diffraction(XRD), FTIR spectrometer, specific surface area and aperture analyzer, and Zeta potentiometer. The adsorption kinetic data were fitted with pseudo-first-order, modified pseudo-first-order, pseudo-second-order and intra-particle diffusion models. The results showed that, under the condition of initial Cd~(2+) concentration of 100 mg/L, pH 7, adsorbent dosage of 10g/Lrice straw and adsorption temperature of 25℃, rice straw modified with KMnO_4 had thebest Cd~(2+)adsorption in the aqueous solution, and the adsorption capacity was 10.024 mg/g Cd~(2+). Its percentage of removal of Cd~(2+)reached 99.24% and had an increase of 99.44% compared with unmodified rice straw. Followed by rice straw was modified with KOH and KOH+H_2O_2, their adsorption capacity for Cd~(2+) were 9.302 mg/g and 9.189 mg/g, percentage of removal of Cd~(2+) reached 92.62% and 90.82%, respectively. Compared with unmodified rice straw treatment, Cd~(2+) removal of rice straw modified with KOH and KOH+H_2O_2 had increases of by 85.07% and 82.83%, respectively. The adsorption order of modified rice straw treatments was: KMnO_4>KOH>KOH+H_2O_2>TiO_2>H_2O_2>citric acid>tartaric acid. It was found that quasi first order rate equation only described the initial stage of Cd~(2+) adsorption suitably, however, apseudo-second order kinetic model was the proper approach for describling the whole process of adsorption. Sum up, the rice straw modified by KMnO_4, KOH and KOH+H_2O_2 could be the potentially valuable adsorbents for absorbing Cd~(2+) in the wastewater solution.
引文
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[22]关连珠,赵亚平,张广才,等.玉米秸秆生物质炭对外源金霉素的吸持与解吸[J].中国农业科学,2012,45(24):5057-5064.
[23]鲍艳宇,周启星,万莹,等.3种四环素类抗生素在褐土上的吸附和解吸[J].中国环境科学,2010,30(10):1383-1388.
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[27]王宇.利用农业秸秆制备阴离子吸附剂及其性能的研究[D].山东大学,2007.
[28]Cui X,Fang S,Yao Y,et al.Potential mechanisms of cadmium removal from aqueous solution by Canna indica derived biochar.[J].Science of the Total Environment,2016,562:517-525.
[29]马锋锋,赵保卫,刁静茹.小麦秸秆生物炭对水中Cd2+的吸附特性研究[J].中国环境科学,2017,37(2):551-559.
[30]刘新,冷言冰,谷仕艳,等.油菜秸秆外壳对水溶液中六价铬的吸附作用[J].中国环境科学,2015,35(6):1740-1748.
[31]于芳.小麦秸秆对溶液中铅、镉离子吸附性能的研究[D].西北大学,2013.
[32]安增莉,侯艳伟,蔡超,等.水稻秸秆生物炭对Pb(Ⅱ)的吸附特性[J].环境化学,2011,30(11):1851-1857.
[33]黄色燕,刘云凤,曹威,等.改性稻草对Cr(Ⅵ)的吸附动力学[J].环境化学,2013,32(2):240-248.
[34]Xu X,Gao B,Wang W,et al.Adsorption of phosphate from aqueous solutions onto modified wheat residue:Characteristics,kinetic and column studies[J].Colloids&Surfaces B Biointerfaces,2009,70(1):46-52.
[2]林芳芳.改性花生壳对水中Cd2+和Pb2+的吸附特性研究[D].华南理工大学,2011.
[3]林晓燕,牟仁祥,曹赵云,等.耐镉细菌菌株的分离及其吸附镉机理研究[J].农业环境科学学报,2015,(9):1700-1706.
[4]Nriagu J O,Pacyna J M.Quantitative assessment of worldwide contamination of air,water and soils by trace metals[J].Nature,1988,333(6169):134-139.
[5]Kumar P,Sohail A,Nath C,et al.Agro and Horticultural Wastes as Low Cost Adsorbents for Removal of Heavy Metals from Wastewater:A Review[J].International Journal of Engineering Science,2013,2:2319-182118.
[6]文永林,刘攀,汤琪.农林废弃物吸附脱除废水中重金属研究进展[J].化工进展,2016,35(4):1208-1215.
[7]Johns M M,Marshall W E,Toles C A.Agricultural activated carbons for adsorbing dissolved metals and organics[J].Journal of Chemical Technology&Biotechnology,1998,71(2):131-140.
[8]Gao H,Liu Y,Zeng G,et al.Characterization of Cr(VI)removal from aqueous solutions by a surplus agricultural waste--rice straw.[J].Journal of Hazardous Materials,2008,150(2):446-452.
[9]唐剑武,郭怀成.环境承载力及其在环境规划中的初步应用[J].中国环境科学,1997,17(1):6-9.
[10]毕于运,王亚静,高春雨.我国秸秆焚烧的现状危害与禁烧管理对策[J].安徽农业科学,2009,37(27):13181-13184.
[11]朱彬,苏继锋,韩志伟,等.秸秆焚烧导致南京及周边地区一次严重空气污染过程的分析[J].中国环境科学,2010,30(5):585-592.
[12]尹聪,朱彬,曹云昌,等.秸秆焚烧影响南京空气质量的成因探讨[J].中国环境科学,2011,31(2):207-213.
[13]丁杨,张丽鑫,权跃,等.盐酸改性稻草秸秆对Cr(Ⅵ)的吸附研究[J].安徽农业科学,2014,(31):11055-11057.
[14]吴婉滢,姚广超,张晓文,等.改性稻草对钍的吸附行为[J].核技术,2015,38(4):40301-040301.
[15]Li W C,Law F Y,Chan Y H M.Biosorption studies on copper(II)and cadmium(II)using pretreated rice straw and rice husk[J].Environmental Science and Pollution Research,2017,24(10):8903.
[16]Ding Y,Jing D,Gong H,et al.Biosorption of aquatic cadmium(II)by unmodified rice straw.[J].Bioresource Technology,2012,114:20-25.
[17]黄界颍,胡宏祥,伍震威,等.水稻、油菜秸秆对水中镉的吸附特性[J].安全与环境学报,2015,15(4):244-249.
[18]Nawar N,Ebrahim M,Sami E.Removal of Heavy Metals Fe3+,Mn2+,Zn2+,Pb2+and Cd2+from Wastewater by Using Rice Straw as Low Cost Adsorbent[J].International Journal of Social Sciences&Education,2013,2:85-95.
[19]李瑞月,陈德,李恋卿,等.不同作物秸秆生物炭对溶液Pb2+、Cd2+的吸附[J].农业环境科学学报,2015,34(5):1001-1008.
[20]Kumar R,Obrai S,Sharma A.Biosorption of heavy metal ions by using modified waste tree bark material[J].International Journal of Environmental Sciences,2012.3(1):720-726.
[21]谢胜,李娟英,赵庆祥.磺胺类抗生素的活性炭吸附过程研究[J].环境工程学报,2012,06(2):483-488.
[22]关连珠,赵亚平,张广才,等.玉米秸秆生物质炭对外源金霉素的吸持与解吸[J].中国农业科学,2012,45(24):5057-5064.
[23]鲍艳宇,周启星,万莹,等.3种四环素类抗生素在褐土上的吸附和解吸[J].中国环境科学,2010,30(10):1383-1388.
[24]Venkata M S,Chandrasekhar R N,Karthikeyan J.Adsorptive removal of direct azo dye from aqueous phase onto coal based sorbents:a kinetic and mechanistic study[J].Journal of Hazardous Materials,2002,90(2):189-204.
[25]郭磊.改性稻秸对废水中铅、镉的吸附特征及其机制研究[D].沈阳农业大学,2014.
[26]Zhang Y,Banks C.A comparison of the properties of polyurethane immobilised Sphagnum,moss,seaweed,sunflower waste and maize for the biosorption of Cu,Pb,Zn and Ni in continuous flow packed columns[J].Water Research,2006,40(4):788-798.
[27]王宇.利用农业秸秆制备阴离子吸附剂及其性能的研究[D].山东大学,2007.
[28]Cui X,Fang S,Yao Y,et al.Potential mechanisms of cadmium removal from aqueous solution by Canna indica derived biochar.[J].Science of the Total Environment,2016,562:517-525.
[29]马锋锋,赵保卫,刁静茹.小麦秸秆生物炭对水中Cd2+的吸附特性研究[J].中国环境科学,2017,37(2):551-559.
[30]刘新,冷言冰,谷仕艳,等.油菜秸秆外壳对水溶液中六价铬的吸附作用[J].中国环境科学,2015,35(6):1740-1748.
[31]于芳.小麦秸秆对溶液中铅、镉离子吸附性能的研究[D].西北大学,2013.
[32]安增莉,侯艳伟,蔡超,等.水稻秸秆生物炭对Pb(Ⅱ)的吸附特性[J].环境化学,2011,30(11):1851-1857.
[33]黄色燕,刘云凤,曹威,等.改性稻草对Cr(Ⅵ)的吸附动力学[J].环境化学,2013,32(2):240-248.
[34]Xu X,Gao B,Wang W,et al.Adsorption of phosphate from aqueous solutions onto modified wheat residue:Characteristics,kinetic and column studies[J].Colloids&Surfaces B Biointerfaces,2009,70(1):46-52.