响应面法优化海藻基活性炭制备工艺及其吸附机理
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摘要
将海藻石莼通过预炭化得到半焦,再用KOH活化制备高附加值产品活性炭。以亚甲基蓝吸附值、碘吸附值为吸附性能指标,探究碱炭比、活化时间、活化温度等单因素对活性炭吸附性能的影响。Box-Behnken设计-响应面法优化活化工艺,亚甲基蓝吸附模型和碘吸附模型的P值均小于0.0001表现出具有极高的显著性,两个模型方程的确定性系数均大于0.99。亚甲基蓝模型的各因素交互影响P值也都小于0.0001,影响极显著;碘模型中各因素对吸附值的影响,活化温度大于碱炭比大于活化时间。通过对模型优化确定最佳工艺参数:碱炭比为2.99、活化时间为44.47 min、活化温度为809.91℃;该条件下的理论亚甲基蓝吸附值为809.91 mg/g、碘吸附值为1 843.11 mg/g。活性炭吸附废水亚甲基蓝的吸附过程符合准二级动力学模型方程。吸附等温线更符合Langmuir模型方程,略优于Freundlich模型方程,随着温度升高活性炭的吸附能力和饱和吸附量下降。
High value-added activated carbon was prepared through pyrolysis of the semi-coke of Ulva using KOH.The effects of KOH/coke, activation time, and activation temperature on the adsorption performance of activated carbon were investigated via iodine adsorption and methylene blue adsorption. The Box-Behnken design and response surface methodology were adopted to optimize the activation process condition. P values of both the methylene blue adsorption and iodine adsorption models were less than 0.0001, thus presenting high significance. The R-squared values of both models were higher than 0.99. The interaction P value of all factors in the methylene blue model was also less than 0.0001, indicating a significant impact. In the iodine model, the influence of activation temperature on the adsorption value was greater than that of the basic carbon ratio and activation time. The iodine adsorption and methylene blue adsorption values of activated carbon were 809.91 and 1843.11 mg/g, respectively,under optimal conditions; these values were obtained using the model equation of mass ratio of KOH/coke, 2.99∶1,an activated time of 45 min, and an activated temperature at 800℃. The theoretical value was consistent with the measured value. The adsorption process of activated carbon adsorption using wastewater methylene blue conformed to the pseudo-second-order kinetic equation. The adsorption isotherm was more consistent with the Langmuir equation, which was slightly better than the Freundlich equation. The adsorption and saturation adsorption capacities of activated carbon decreased with increasing temperature.
High value-added activated carbon was prepared through pyrolysis of the semi-coke of Ulva using KOH.The effects of KOH/coke, activation time, and activation temperature on the adsorption performance of activated carbon were investigated via iodine adsorption and methylene blue adsorption. The Box-Behnken design and response surface methodology were adopted to optimize the activation process condition. P values of both the methylene blue adsorption and iodine adsorption models were less than 0.0001, thus presenting high significance. The R-squared values of both models were higher than 0.99. The interaction P value of all factors in the methylene blue model was also less than 0.0001, indicating a significant impact. In the iodine model, the influence of activation temperature on the adsorption value was greater than that of the basic carbon ratio and activation time. The iodine adsorption and methylene blue adsorption values of activated carbon were 809.91 and 1843.11 mg/g, respectively,under optimal conditions; these values were obtained using the model equation of mass ratio of KOH/coke, 2.99∶1,an activated time of 45 min, and an activated temperature at 800℃. The theoretical value was consistent with the measured value. The adsorption process of activated carbon adsorption using wastewater methylene blue conformed to the pseudo-second-order kinetic equation. The adsorption isotherm was more consistent with the Langmuir equation, which was slightly better than the Freundlich equation. The adsorption and saturation adsorption capacities of activated carbon decreased with increasing temperature.
引文
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[11]Luherne E L,Reveillac E,Ponsero A,et al.Fish community responses to green tides in shallow estuarine and coastal areas[J].Estuarine Coastal&Shelf Science,2016,175:79-92.
[12]Tripathi M,Sahu J N,Ganesam P.Effect of process parameters on production of biochar from biomass waste through pyrolysis:A review[J].Renewable&Sustainable Energy Reviews,2016,55:467-481.
[13]王冠,赵立欣,孟海波,等.我国生物质热解特性及工艺研究进展[J].节能技术,2014,32(2):120-124.Wang Guan,Zhao Lixin,Meng Haibo,et al.Biomass pyrolysis characteristics and technology progress[J].Energy Conservation Technology[J].2014,32(2):120-124.
[14]徐慧敏,何国富,戴翎翎,等.低温热水解和超声联合破解污泥优化工艺的参数研究[J].中国环境科学,2016,36(4):1093-1098.Xu Huimin,He Guofu,Dai Lingling,et al.Optimizing parameters of sludge disruption by combined low temperature thermal and ultrasonic pretreatment through response surface methodology[J].China Environmental Science,2016,36(4):1093-1098.
[15]李莉,张赛,何强,等.响应面法在试验设计与优化中的应用[J].实验室研究与探索,2015,34(8):41-45.Li Li,Zhang Sai,He Qiang,et al.Application of response surface methodology in experiment design and optimization[J].Research and Exploration in Laboratory,2015,34(8):41-45.
[16]余峻峰,陈培荣,俞志敏,等.KOH活化木屑生物炭制备活性炭及其表征[J].应用化学,2013,30(9):1017-1022.Yu Junfeng,Cheng Peirong,Yu Zhimin,et al.Preparation and characteristic of activated carbon from sawdust bio-char by chemical activation with KOH[J].Chinese Journal of Applied Chemistry,2013,30(9):1017-1022.
[17]赵阳,高建民,郝新敏,等.基于KOH活化法的核桃壳基活性炭制备及其表征[J].安全与环境学报,2016,16(2):262-266.Zhao Yang,Gao Jianmin,Hao Xinmin,et al.Preparation and characterization of the carbon purified from the walnut shells activated chemically with KOH[J].Journal of Safety and Environment,2016,16(2):262-266.
[18]王磊,张子德,赵丛枝,等.响应面法优化超临界CO2萃取无花果种籽油工艺研究[J].中国食品学报,2013,13(1):37-43.Wang Lei,Zhang Zhide,Zhao Congzhi,et al.Optimization of supercritical carbon dioxide extraction of oil from fig fruit(Ficus Carica L.)Seeds using response surface methodology[J].Journal of Chinese Institute of Food Science and Technology,2013,13(1):37-43.
[19]Das S,Mishra S.Box-Behnken statistical design to optimize preparation of activated carbon from Limonia acidissima,shell with desirability approach[J].Journal of Environmental Chemical Engineering,2017,5(1):588-600.
[20]Ghani Z A,Yusoff M S,Zaman N Q,et al.Optimization of preparation conditions for activated carbon from banana pseudo-stem using response surface methodology on removal of color and COD from landfill leachate.[J].Waste Management,2017,62:177-187.
[21]李华楠,徐冰冰,齐飞,等.响应面法优化赤泥负载Co催化剂制备及活性评价[J].环境科学,2013,34(11):4376-4385.Li Hualan,Xu Bingbing,Qi Fei,et al.Preparation of red mud loaded co catalysts:Optimization using response surface methodology(RSM)and activity evaluation[J].Environmental Science,2013,34(11):4376-4385.
[22]Sohrabi M R,Moghri M,Masoumi H R F,et al.Optimization of reactive blue 21 removal by nanoscale zero-valent Iron using response surface methodology[J].Arabian Journal of Chemistry,2016,9(4):518-525.
[23]宋道君,陆小芳,徐勇军,等.响应面法优化硫酸催化甘蔗糖蜜制备乙酰丙酸[J].精细化工,2018,35(04):612-619.Song Daojun,Lu Xiaofang,Xu Yongjun,et al.Application of response surface methodology to optimize production of levulinic acid by acid catalytic of cane molasses[J].Fine Chemicals,2018,35(04):612-619.
[24]刘萍,王红斌,李桂镇,等.响应面法优化咖啡壳基高性能活性炭活化条件的研究[J].生物质化学工程,2017,51(2):43-47.Liu Ping,Wang Hongbin,Li Guizhen,et al.Optimization of activation conditions of high-performance activated carbon from coffee shell by response surface methodology[J].Biomass Chemical Engineering,2017,51(2):43-47.
[25]陈俊英,冯向应,史召霞,等.响应面法优化混合活化剂制备脱硅稻壳基活性炭[J].郑州大学学报(工学版),2015,36(2):120-124.Cheng Junying,Feng Xiangying,Shi Zhaoxia,et al.Optimization of activated carbon preparation from desilicon rice husk via compound agents by response surface methodology[J].Journal of Zhengzhou University(Engineering Science),2015,36(2):120-124.
[26]Asfaram A,Ghaedi M,Goudarzi A,et al.Response surface methodology approach for optimization of simultaneous dye and metal ion ultrasound-assisted adsorption onto Mn doped Fe3O4-NPs loaded on AC:kinetic and isothermal studies[J].Dalton Transactions,2015,44(33):14707-14723.
[27]王彤彤,马江波,曲东,等.两种木材生物炭对铜离子的吸附特性及其机制[J].环境科学,2017,38(5):2161-2171.Wang Tongtong,Ma Jiangbo,Qu Dong,et al.Characteristics and mechanism of copper adsorption from aqueous solutions on biochar produced from sawdust and apple branch[J].Environmental Science,2017,38(5):2161-2171.
[28]Nagh W S W,Hanafiah M A K M.Adsorption of copper on rubber(Hevea brasiliensis)leaf powder:Kinetic,equilibrium and thermodynamic studies[J].Biochemical Engineering Journal,2016,39(3):521-530.
[29]Verma V K,Mishra A K.Kinetic and isotherm modeling of adsorption of dyes onto rice husk carbon.[J].Global Nest Journal,2010,12(2):190-196.
[30]Fan S,Wang Y,Wang Z,et al.Removal of methylene blue from aqueous solution by sewage sludge-derived biochar:Adsorption kinetics,equilibrium,thermodynamics and mechanism[J].Journal of Environmental Chemical Engineering,2017,5(1):601-611.
[31]廖钦洪,刘庆业,蒙冕武,等.稻壳基活性炭的制备及其对亚甲基蓝吸附的研究[J].环境工程学报,2011,5(11):2447-2452.Liao Qinhong,Liu Qingye,Meng Mianwu,et al.Study on preparation of rice husk-based activated carbon and its adsorption of methylene blue[J].Techniques and Equipment for Environmental Pollution Control,2011,5(11):2447-2452.
[2]王金表,蒋剑春,孙康,等.医药缓释载体用活性炭研究进展[J].化工新型材料,2014,42(5):4-6.Wang Jinbiao,Jiang Jianchun,Sun Kang,et al.Research progress on activated carbon as carriers for sustained release of pharmaceuticals[J].New Chemical Materials,2014,42(5):4-6.
[3]Chaitra,Vinny,Sivaraman,et al.KOH activated carbon derived from biomass-banana fibers as an efficient negative electrode in high performance asymmetric supercapacitor[J].Journal of Energy Chemistry,2017,26(1):56-62.
[4]孙龙梅,张丽平,薛建华,等.活性炭制备方法及应用的研究进展[J].化学与生物工程,2016,33(3):5-8.Sun Longmei,Zhang Liping,Xue Jianhua,et al.Research progress on preparation methods and applications of activated carbon[J].Chemistry&Bioengineering,2016,33(3):5-8.
[5]Aljeboreea M,Alshirifi A N,Alkaim A F.Kinetics and equilibrium study for the adsorption of textile dyes on coconut shell activated carbon[J].Arabian Journal of Chemistry,2014,150(S2):S3381-S3393.
[6]张本镔,刘运权,叶跃元.活性炭制备及其活化机理研究进展[J].现代化工,2014,34(3):34-39.Zhang Benbin,Liu Yunquan,Ye Yueyuan.Progress in preparation of activated carbon and its activation mechanism[J].Modern Chemical Industry,2014,34(3):34-39.
[7]胡立鹃,吴峰,彭善枝,等.生物质活性炭的制备及应用进展[J].化学通报,2016,79(3):205-212.Hu Lijuan,Wu Feng,Peng Shanzhi,et al.Progress in preparation and utilization of biomass-based activated carbons[J].Chemistry,2016,79(3):205-212.
[8]Ahmada A L,Loham M,Azizb J A.Preparation and characterization of activated carbon from oil palm wood and its evaluation on Methylene blue adsorption[J].Dyes&Pigments,2007,75(2):263-272.
[9]Takr E,Deraman M,Talib I A,et al.Physical,electrochemical and supercapacitive properties of activated carbon pellets from pre-carbonized rubber wood sawdust by CO activation[J].Current Applied Physics,2010,10(4):1071-1075.
[10]马承愚,杨超,古丽戈娜,等.磷酸法制备杏核壳活性炭及对Cr(Ⅵ)的吸附[J].环境工程学报,2014,8(8):3223-3227.Ma Chengyu,Yang Chao,Gulgina,et al.Preparation of activated carbon by almond shell with phosphoric acid as activating agent and its adsorption to Cr(Ⅳ)[J].Chinese Journal of Environmental Engineering,2014,8(8):3223-3227.
[11]Luherne E L,Reveillac E,Ponsero A,et al.Fish community responses to green tides in shallow estuarine and coastal areas[J].Estuarine Coastal&Shelf Science,2016,175:79-92.
[12]Tripathi M,Sahu J N,Ganesam P.Effect of process parameters on production of biochar from biomass waste through pyrolysis:A review[J].Renewable&Sustainable Energy Reviews,2016,55:467-481.
[13]王冠,赵立欣,孟海波,等.我国生物质热解特性及工艺研究进展[J].节能技术,2014,32(2):120-124.Wang Guan,Zhao Lixin,Meng Haibo,et al.Biomass pyrolysis characteristics and technology progress[J].Energy Conservation Technology[J].2014,32(2):120-124.
[14]徐慧敏,何国富,戴翎翎,等.低温热水解和超声联合破解污泥优化工艺的参数研究[J].中国环境科学,2016,36(4):1093-1098.Xu Huimin,He Guofu,Dai Lingling,et al.Optimizing parameters of sludge disruption by combined low temperature thermal and ultrasonic pretreatment through response surface methodology[J].China Environmental Science,2016,36(4):1093-1098.
[15]李莉,张赛,何强,等.响应面法在试验设计与优化中的应用[J].实验室研究与探索,2015,34(8):41-45.Li Li,Zhang Sai,He Qiang,et al.Application of response surface methodology in experiment design and optimization[J].Research and Exploration in Laboratory,2015,34(8):41-45.
[16]余峻峰,陈培荣,俞志敏,等.KOH活化木屑生物炭制备活性炭及其表征[J].应用化学,2013,30(9):1017-1022.Yu Junfeng,Cheng Peirong,Yu Zhimin,et al.Preparation and characteristic of activated carbon from sawdust bio-char by chemical activation with KOH[J].Chinese Journal of Applied Chemistry,2013,30(9):1017-1022.
[17]赵阳,高建民,郝新敏,等.基于KOH活化法的核桃壳基活性炭制备及其表征[J].安全与环境学报,2016,16(2):262-266.Zhao Yang,Gao Jianmin,Hao Xinmin,et al.Preparation and characterization of the carbon purified from the walnut shells activated chemically with KOH[J].Journal of Safety and Environment,2016,16(2):262-266.
[18]王磊,张子德,赵丛枝,等.响应面法优化超临界CO2萃取无花果种籽油工艺研究[J].中国食品学报,2013,13(1):37-43.Wang Lei,Zhang Zhide,Zhao Congzhi,et al.Optimization of supercritical carbon dioxide extraction of oil from fig fruit(Ficus Carica L.)Seeds using response surface methodology[J].Journal of Chinese Institute of Food Science and Technology,2013,13(1):37-43.
[19]Das S,Mishra S.Box-Behnken statistical design to optimize preparation of activated carbon from Limonia acidissima,shell with desirability approach[J].Journal of Environmental Chemical Engineering,2017,5(1):588-600.
[20]Ghani Z A,Yusoff M S,Zaman N Q,et al.Optimization of preparation conditions for activated carbon from banana pseudo-stem using response surface methodology on removal of color and COD from landfill leachate.[J].Waste Management,2017,62:177-187.
[21]李华楠,徐冰冰,齐飞,等.响应面法优化赤泥负载Co催化剂制备及活性评价[J].环境科学,2013,34(11):4376-4385.Li Hualan,Xu Bingbing,Qi Fei,et al.Preparation of red mud loaded co catalysts:Optimization using response surface methodology(RSM)and activity evaluation[J].Environmental Science,2013,34(11):4376-4385.
[22]Sohrabi M R,Moghri M,Masoumi H R F,et al.Optimization of reactive blue 21 removal by nanoscale zero-valent Iron using response surface methodology[J].Arabian Journal of Chemistry,2016,9(4):518-525.
[23]宋道君,陆小芳,徐勇军,等.响应面法优化硫酸催化甘蔗糖蜜制备乙酰丙酸[J].精细化工,2018,35(04):612-619.Song Daojun,Lu Xiaofang,Xu Yongjun,et al.Application of response surface methodology to optimize production of levulinic acid by acid catalytic of cane molasses[J].Fine Chemicals,2018,35(04):612-619.
[24]刘萍,王红斌,李桂镇,等.响应面法优化咖啡壳基高性能活性炭活化条件的研究[J].生物质化学工程,2017,51(2):43-47.Liu Ping,Wang Hongbin,Li Guizhen,et al.Optimization of activation conditions of high-performance activated carbon from coffee shell by response surface methodology[J].Biomass Chemical Engineering,2017,51(2):43-47.
[25]陈俊英,冯向应,史召霞,等.响应面法优化混合活化剂制备脱硅稻壳基活性炭[J].郑州大学学报(工学版),2015,36(2):120-124.Cheng Junying,Feng Xiangying,Shi Zhaoxia,et al.Optimization of activated carbon preparation from desilicon rice husk via compound agents by response surface methodology[J].Journal of Zhengzhou University(Engineering Science),2015,36(2):120-124.
[26]Asfaram A,Ghaedi M,Goudarzi A,et al.Response surface methodology approach for optimization of simultaneous dye and metal ion ultrasound-assisted adsorption onto Mn doped Fe3O4-NPs loaded on AC:kinetic and isothermal studies[J].Dalton Transactions,2015,44(33):14707-14723.
[27]王彤彤,马江波,曲东,等.两种木材生物炭对铜离子的吸附特性及其机制[J].环境科学,2017,38(5):2161-2171.Wang Tongtong,Ma Jiangbo,Qu Dong,et al.Characteristics and mechanism of copper adsorption from aqueous solutions on biochar produced from sawdust and apple branch[J].Environmental Science,2017,38(5):2161-2171.
[28]Nagh W S W,Hanafiah M A K M.Adsorption of copper on rubber(Hevea brasiliensis)leaf powder:Kinetic,equilibrium and thermodynamic studies[J].Biochemical Engineering Journal,2016,39(3):521-530.
[29]Verma V K,Mishra A K.Kinetic and isotherm modeling of adsorption of dyes onto rice husk carbon.[J].Global Nest Journal,2010,12(2):190-196.
[30]Fan S,Wang Y,Wang Z,et al.Removal of methylene blue from aqueous solution by sewage sludge-derived biochar:Adsorption kinetics,equilibrium,thermodynamics and mechanism[J].Journal of Environmental Chemical Engineering,2017,5(1):601-611.
[31]廖钦洪,刘庆业,蒙冕武,等.稻壳基活性炭的制备及其对亚甲基蓝吸附的研究[J].环境工程学报,2011,5(11):2447-2452.Liao Qinhong,Liu Qingye,Meng Mianwu,et al.Study on preparation of rice husk-based activated carbon and its adsorption of methylene blue[J].Techniques and Equipment for Environmental Pollution Control,2011,5(11):2447-2452.