DTAB修饰不同模式两性膨润土的热力学和表征
|
摘要
为了探究阳离子型修饰剂修饰不同模式两性膨润土的热力学和表面特征,采用十二烷基三甲基溴化铵(DTAB,简写为DT)对不同十二烷基二甲基甜菜碱(BS-12,简写为BS)修饰模式膨润土进行复配修饰,研究其吸附热力学和温度效应,并分析BS和BS+DT修饰土样总有机碳(TOC)含量和比表面积(S_(BET))、X射线衍射(XRD)、红外光谱(FTIR)、热重(TG)和扫描电镜(SEM)的特征。结果表明:DTAB吸附量、温度效应比(S_(40)/S_(20))的转折点均随膨润土表面BS疏水修饰的增强而减小。20~40℃范围内,CK(膨润土)对DTAB的吸附为增温正效应,不同模式BS膨润土对DTAB的吸附呈增温负效应。CK和不同模式BS膨润土对DTAB的吸附均属于自发反应。随BS疏水修饰的增强,反应自发性增强,且由吸热、熵增(CK)转为放热、熵减过程。随着BS和DT疏水修饰的增强,土样TOC含量、晶层间距(d_(001))均增大,而S_(BET)减小。TG、FTIR和SEM特征均证实了DTAB在BS膨润土表面的修饰。
Three different BS-12 modified amphiprotic bentonites were chosen to explore the impact of dodecyl trimethyl ammonium bro-mide(DTAB or DT)re-modification on thermodynamics and surface characteristics of BS-12 bentonites. Their adsorption thermodynamic properties and temperature effects were studied. In addition, TOC(total organic carbon), XRD(x-ray diffraction), S_(BET)(specific surfacearea), FTIR(fourier transform infrared spectroscopy), TG(thermogravimetry) and SEM(scanning electron microscope) characteristics of different modified bentonites were analyzed. Results showed that:adsorption amount of DTAB and turning point of temperature effect(S_(40)/S_(20))decreased with increasing hydrophobic property of BS bentonite. CK(bentonite)presented positive temperature effect on DTAB adsorption from 20 ℃ to 40 ℃, while BS bentonites showed negative temperature effect; DTAB adsorption on CK and different BS bentonites were a spontaneous process. With enhanced hydrophobic property of BS-12 bentonite, the adsorption spontaneity was promoted and the reaction changed from endothermic and entropy increase process to exothermic and entropy decrease process; TOC content and interlayer spacing increased, but S_(BET) decreased in different BS+DT modified bentonites with enhanced hydrophobic modification by BS+DT. FTIR,TG and SEM results all proved the modification effects of DTAB on BS bentonites.
Three different BS-12 modified amphiprotic bentonites were chosen to explore the impact of dodecyl trimethyl ammonium bro-mide(DTAB or DT)re-modification on thermodynamics and surface characteristics of BS-12 bentonites. Their adsorption thermodynamic properties and temperature effects were studied. In addition, TOC(total organic carbon), XRD(x-ray diffraction), S_(BET)(specific surfacearea), FTIR(fourier transform infrared spectroscopy), TG(thermogravimetry) and SEM(scanning electron microscope) characteristics of different modified bentonites were analyzed. Results showed that:adsorption amount of DTAB and turning point of temperature effect(S_(40)/S_(20))decreased with increasing hydrophobic property of BS bentonite. CK(bentonite)presented positive temperature effect on DTAB adsorption from 20 ℃ to 40 ℃, while BS bentonites showed negative temperature effect; DTAB adsorption on CK and different BS bentonites were a spontaneous process. With enhanced hydrophobic property of BS-12 bentonite, the adsorption spontaneity was promoted and the reaction changed from endothermic and entropy increase process to exothermic and entropy decrease process; TOC content and interlayer spacing increased, but S_(BET) decreased in different BS+DT modified bentonites with enhanced hydrophobic modification by BS+DT. FTIR,TG and SEM results all proved the modification effects of DTAB on BS bentonites.
引文
[1]Bergaya F,Lagaly G.Surface modification of clay minerals[J].Applied Clay Science,2001,19(1):1-3.
[2]Wang T,Zhu J,Zhu R,et al.Enhancing the sorption capacity of CTMAbentonite by simultaneous intercalation of cationic polyacrylamide[J].Journal of Hazardous Materials,2010,178(1):1078-1084.
[3]孟昭福,李荣华,张一平,等.有机修饰塿土对苯胺的吸附[J].土壤通报,2008,39(1):143-149.MENG Zhao-fu,LI Rong-hua,ZHANG Yi-ping,et al.Adsorption of aniline on an organic modified Lou soil[J].Chinese Journal of Soil Science,2008,39(1):143-149.
[4]Mc Bride M B.Environmental chemistry of soils[M].New York:Oxford University Press,1994:363.
[5]Li Z H,Bowman R S.Sorption of perchloroethylene by surfactant-modified zeolite as controlled by surfactant loading[J].Environmental Science&Technology,1998,32(15):2278-2282.
[6]Xu S H,Boyd S A.Cationic surfactant sorption to a vermiculitic subsoils via hydrophobic bonding[J].Environmental Science&Technology,1995,29(2):312-320.
[7]孟昭福,龚宁,李荣华,等.有机修饰剂对塿土的离子交换修饰研究[J].环境科学,2008,29(5):1412-1417.MENG Zhao-fu,GONG Ning,LI Rong-hua,et al.Ionic exchange modification mechanism between organic modifier and Lou soil[J].Environmental Science,2008,29(5),1412-1417.
[8]Lee S M,Tiwari D.Organo and inorgano-organo-modified clays in the remediation of aqueous solutions:An overview[J].Applied Clay Science,2012,59/60:84-102.
[9]戴荣玲,章钢娅,古小治,等.有机黏土矿物修复有机污染研究进展[J].土壤,2007,39(5):718-725.DAI Rong-ling,ZHANG Gang-ya,GU Xiao-zhi,et al.Advancement in the study on organoclay minerals in remediation of organic contaminated soils[J].Soils,2007,39(5):718-725.
[10]甘莉,杨晓燕,刘欣萍,等.改性低品质膨润土处理柴油废水[J].环境科学与技术,2012,35(7):117-121.GAN Li,YANG Xiao-yan,LIU Xin-ping,et al.Treatment of diesel oil wastewater using modified low quality bentonite[J].Environmental Science&Technology,2012,35(7):117-121.
[11]朱利中,陈宝梁,沈韩艳,等.双阳离子有机膨润土吸附处理水中有机物的性能[J].中国环境科学,1999,19(4):38-42.ZHU Li-zhong,CHEN Bao-liang,SHEN Han-yan,et al.Property of dual-cation organobentonites to remove organic compounds from water[J].China Environmental Science,1999,19(4):38-42.
[12]杨维,杨军锋,王立东,等.阴/阳离子有机膨润土制备及其对苯酚吸附性能的实验研究[J].环境污染与防治,2007,29(10):725-730.YANG Wei,YANG Jun-feng,WANG Li-dong,et al.Preparation of anion-cation organic bentonite and its adsorption of phenol[J].Environmental Pollution&Control,2007,29(10):725-730.
[13]朱利中,杨坤,董舒.阳-非离子混合表面活性剂对沉积物吸附硝基苯的影响[J].环境科学,2004,25(3):164-167.ZHU Li-zhong,YANG Kun,DONG Shu.Adsorption of cation-nonionic mixed surfactants onto sediment and their effects on adsorption of nitrobenzene from water[J].Environmental Science,2004,25(3):164-167.
[14]Meng Z F,Zhang Y P,Zhang Z Q.Simultaneous adsorption of phenol and cadmium on amphoteric modified soil[J].Journal of Hazardous Materials,2008,159(2/3):492-498.
[15]崔晓波,孟昭福,杨亚莉,等.苯酚在BS-Tw80复配修饰膨润土和高岭土上吸附的比较[J].农业环境科学学报,2015,34(10):1905-1913.CUI Xiao-bo,MENG Zhao-fu,YANG Ya-li,et al.Comparison of phenol adsorption on bentonite and kaolinite co-modified by BS-12 and Tween-80[J].Journal of Agro-Environment Science,2015,34(10):1905-1913.
[16]李婷,孟昭福,张斌.两性修饰膨润土对苯酚的吸附及热力学特征[J].环境科学,2012,33(5):1632-1638.LI Ting,MENG Zhao-fu,ZHANG Bin.Adsorption of amphoteric modified bentonites to phenol and its thermodynamics[J].Environmental Science,2012,33(5):1632-1638.
[17]李彬,孟昭福,王建涛,等.BS-CTMAB复配修饰膨润土对苯酚的吸附[J].农业环境科学学报,2014,33(6):1131-1138.LI Bin,MENG Zhao-fu,WANG Jian-tao,et al.Adsorption of phenol on amphoteric-cationic modified bentonites[J].Journal of Agro-Environment Science,2014,33(6):1131-1138.
[18]王建涛.BS-SDS复配修饰膨润土对Cd(Ⅱ)、苯酚和Cr(Ⅵ)的吸附特征[D].杨凌:西北农林科技大学,2014:37-40.WANG Jian-tao.Adsorption characteristics of Cd(Ⅱ),Cr(Ⅵ)and phenol on complex modified bentonites with BS-12 and SDS[D].Yangling:Northwest A&F University of China,2014:37-40.
[19]Zhang Z Z,Sparks D L,Scrivner N C.Sorption and desorption of quaternary amine cations on clays[J].Environmental Science&Technology,1993,27(8):1625-1631.
[20]Alkaram U F,Mukhlis A A,Al-Dujaili A H.The removal of phenol from aqueous solutions by adsorption using surfactant-modified bentonite and kaolinite[J].Journal of Hazardous Materials,2009,169(1):324-332.
[21]Carvalho M N,Motta M D,Benachour M,et al.Evaluation of BTEX and phenol removal from aqueous solution by multi-solute adsorption onto smectite organoclay[J].Journal of Hazardous Materials,2012,239/240:95-101.
[22]Ikhtiyarova G A,魻zcan A S,G觟k魻,et al.Characterization of naturaland organo-bentonite by XRD,SEM,FT-IR and thermal analysis techniques and its adsorption behaviour in aqueous solutions[J].Clay Minerals,2012,47(1),31-44.
[23]路来福,高芒来,杨森锋,等.两性表面修饰剂改性膨润土的制备及其对环丙沙星的吸附性能[J].材料研究学报,2013,27(6):577-582.LU Lai-fu,GAO Mang-lai,YANG Sen-feng,et al.Preparation and adsorption for ciprofloxacin of bentonite modified by zwitterionic surfactant[J].Chinese Journal of Materials Research,2013,27(6):577-582.
[24]杨亚莉.BS-12与OTMA复配修饰膨润土和高岭土的性能表征及其对Cd2+、苯酚的吸附[D].杨凌:西北农林科技大学,2015:10-20.YANG Ya-li.Characterization of bentonites and kaolinite complex modified with BS-12 and OTMA and its adsorption of Cd2+and phenol[D].Yangling:Northwest A&F University of China,2015:10-20.
[25]李彬.BS-12和CTMAB复配修饰膨润土对苯酚、Cd2+和Cr O2-4平衡吸附的研究[D].杨凌:西北农林科技大学,2014:39-45.LI Bin.Studies on the equilibrium adsorption of amphoteric-cationic modified bentonites to Cd2+,Cr O2-4and phenol[D].Yangling:Northwest A&F University of China,2014:39-45.
[26]李文斌,杨淑英,孟昭福,等.DTAB对两性膨润土的复配修饰机制和吸附菲的影响[J].农业环境科学学报,2015,34(9):1722-1729.LI Wen-bin,YANG Shu-ying,MENG Zhao-fu,et al.Secondary Modification Mechanism of BS-12 Modified Bentonite with DTAB and Phenanthrene Adsorption by Combinedly Modified Bentonite[J].Journal of Agro-Environment Science,2015,34(9):1722-1729.
[27]王泽民,周凤岐,马小凡,等.膨润土的提纯及应用研究[J].非金属矿,1999,22(3):19-20.WANG Ze-min,ZHOU Feng-qi,MA Xiao-fan,et al.The purification and application of bentonite[J].Non-Metallic Mines,1999,22(3):19-20.
[2]Wang T,Zhu J,Zhu R,et al.Enhancing the sorption capacity of CTMAbentonite by simultaneous intercalation of cationic polyacrylamide[J].Journal of Hazardous Materials,2010,178(1):1078-1084.
[3]孟昭福,李荣华,张一平,等.有机修饰塿土对苯胺的吸附[J].土壤通报,2008,39(1):143-149.MENG Zhao-fu,LI Rong-hua,ZHANG Yi-ping,et al.Adsorption of aniline on an organic modified Lou soil[J].Chinese Journal of Soil Science,2008,39(1):143-149.
[4]Mc Bride M B.Environmental chemistry of soils[M].New York:Oxford University Press,1994:363.
[5]Li Z H,Bowman R S.Sorption of perchloroethylene by surfactant-modified zeolite as controlled by surfactant loading[J].Environmental Science&Technology,1998,32(15):2278-2282.
[6]Xu S H,Boyd S A.Cationic surfactant sorption to a vermiculitic subsoils via hydrophobic bonding[J].Environmental Science&Technology,1995,29(2):312-320.
[7]孟昭福,龚宁,李荣华,等.有机修饰剂对塿土的离子交换修饰研究[J].环境科学,2008,29(5):1412-1417.MENG Zhao-fu,GONG Ning,LI Rong-hua,et al.Ionic exchange modification mechanism between organic modifier and Lou soil[J].Environmental Science,2008,29(5),1412-1417.
[8]Lee S M,Tiwari D.Organo and inorgano-organo-modified clays in the remediation of aqueous solutions:An overview[J].Applied Clay Science,2012,59/60:84-102.
[9]戴荣玲,章钢娅,古小治,等.有机黏土矿物修复有机污染研究进展[J].土壤,2007,39(5):718-725.DAI Rong-ling,ZHANG Gang-ya,GU Xiao-zhi,et al.Advancement in the study on organoclay minerals in remediation of organic contaminated soils[J].Soils,2007,39(5):718-725.
[10]甘莉,杨晓燕,刘欣萍,等.改性低品质膨润土处理柴油废水[J].环境科学与技术,2012,35(7):117-121.GAN Li,YANG Xiao-yan,LIU Xin-ping,et al.Treatment of diesel oil wastewater using modified low quality bentonite[J].Environmental Science&Technology,2012,35(7):117-121.
[11]朱利中,陈宝梁,沈韩艳,等.双阳离子有机膨润土吸附处理水中有机物的性能[J].中国环境科学,1999,19(4):38-42.ZHU Li-zhong,CHEN Bao-liang,SHEN Han-yan,et al.Property of dual-cation organobentonites to remove organic compounds from water[J].China Environmental Science,1999,19(4):38-42.
[12]杨维,杨军锋,王立东,等.阴/阳离子有机膨润土制备及其对苯酚吸附性能的实验研究[J].环境污染与防治,2007,29(10):725-730.YANG Wei,YANG Jun-feng,WANG Li-dong,et al.Preparation of anion-cation organic bentonite and its adsorption of phenol[J].Environmental Pollution&Control,2007,29(10):725-730.
[13]朱利中,杨坤,董舒.阳-非离子混合表面活性剂对沉积物吸附硝基苯的影响[J].环境科学,2004,25(3):164-167.ZHU Li-zhong,YANG Kun,DONG Shu.Adsorption of cation-nonionic mixed surfactants onto sediment and their effects on adsorption of nitrobenzene from water[J].Environmental Science,2004,25(3):164-167.
[14]Meng Z F,Zhang Y P,Zhang Z Q.Simultaneous adsorption of phenol and cadmium on amphoteric modified soil[J].Journal of Hazardous Materials,2008,159(2/3):492-498.
[15]崔晓波,孟昭福,杨亚莉,等.苯酚在BS-Tw80复配修饰膨润土和高岭土上吸附的比较[J].农业环境科学学报,2015,34(10):1905-1913.CUI Xiao-bo,MENG Zhao-fu,YANG Ya-li,et al.Comparison of phenol adsorption on bentonite and kaolinite co-modified by BS-12 and Tween-80[J].Journal of Agro-Environment Science,2015,34(10):1905-1913.
[16]李婷,孟昭福,张斌.两性修饰膨润土对苯酚的吸附及热力学特征[J].环境科学,2012,33(5):1632-1638.LI Ting,MENG Zhao-fu,ZHANG Bin.Adsorption of amphoteric modified bentonites to phenol and its thermodynamics[J].Environmental Science,2012,33(5):1632-1638.
[17]李彬,孟昭福,王建涛,等.BS-CTMAB复配修饰膨润土对苯酚的吸附[J].农业环境科学学报,2014,33(6):1131-1138.LI Bin,MENG Zhao-fu,WANG Jian-tao,et al.Adsorption of phenol on amphoteric-cationic modified bentonites[J].Journal of Agro-Environment Science,2014,33(6):1131-1138.
[18]王建涛.BS-SDS复配修饰膨润土对Cd(Ⅱ)、苯酚和Cr(Ⅵ)的吸附特征[D].杨凌:西北农林科技大学,2014:37-40.WANG Jian-tao.Adsorption characteristics of Cd(Ⅱ),Cr(Ⅵ)and phenol on complex modified bentonites with BS-12 and SDS[D].Yangling:Northwest A&F University of China,2014:37-40.
[19]Zhang Z Z,Sparks D L,Scrivner N C.Sorption and desorption of quaternary amine cations on clays[J].Environmental Science&Technology,1993,27(8):1625-1631.
[20]Alkaram U F,Mukhlis A A,Al-Dujaili A H.The removal of phenol from aqueous solutions by adsorption using surfactant-modified bentonite and kaolinite[J].Journal of Hazardous Materials,2009,169(1):324-332.
[21]Carvalho M N,Motta M D,Benachour M,et al.Evaluation of BTEX and phenol removal from aqueous solution by multi-solute adsorption onto smectite organoclay[J].Journal of Hazardous Materials,2012,239/240:95-101.
[22]Ikhtiyarova G A,魻zcan A S,G觟k魻,et al.Characterization of naturaland organo-bentonite by XRD,SEM,FT-IR and thermal analysis techniques and its adsorption behaviour in aqueous solutions[J].Clay Minerals,2012,47(1),31-44.
[23]路来福,高芒来,杨森锋,等.两性表面修饰剂改性膨润土的制备及其对环丙沙星的吸附性能[J].材料研究学报,2013,27(6):577-582.LU Lai-fu,GAO Mang-lai,YANG Sen-feng,et al.Preparation and adsorption for ciprofloxacin of bentonite modified by zwitterionic surfactant[J].Chinese Journal of Materials Research,2013,27(6):577-582.
[24]杨亚莉.BS-12与OTMA复配修饰膨润土和高岭土的性能表征及其对Cd2+、苯酚的吸附[D].杨凌:西北农林科技大学,2015:10-20.YANG Ya-li.Characterization of bentonites and kaolinite complex modified with BS-12 and OTMA and its adsorption of Cd2+and phenol[D].Yangling:Northwest A&F University of China,2015:10-20.
[25]李彬.BS-12和CTMAB复配修饰膨润土对苯酚、Cd2+和Cr O2-4平衡吸附的研究[D].杨凌:西北农林科技大学,2014:39-45.LI Bin.Studies on the equilibrium adsorption of amphoteric-cationic modified bentonites to Cd2+,Cr O2-4and phenol[D].Yangling:Northwest A&F University of China,2014:39-45.
[26]李文斌,杨淑英,孟昭福,等.DTAB对两性膨润土的复配修饰机制和吸附菲的影响[J].农业环境科学学报,2015,34(9):1722-1729.LI Wen-bin,YANG Shu-ying,MENG Zhao-fu,et al.Secondary Modification Mechanism of BS-12 Modified Bentonite with DTAB and Phenanthrene Adsorption by Combinedly Modified Bentonite[J].Journal of Agro-Environment Science,2015,34(9):1722-1729.
[27]王泽民,周凤岐,马小凡,等.膨润土的提纯及应用研究[J].非金属矿,1999,22(3):19-20.WANG Ze-min,ZHOU Feng-qi,MA Xiao-fan,et al.The purification and application of bentonite[J].Non-Metallic Mines,1999,22(3):19-20.