五种改性纳米纤维素吸附剂的制备及除磷性能比较
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摘要
含磷废水的排放是造成水体富营养化的重要原因,吸附法可以有效去除废水中的磷。开发环境友好的高效吸附剂是该法进一步推广的关键因素之一。采用TEMPO氧化+机械剪切结合的方法制备纳米纤维素(CNFs),分别用Fe(OH)_3、Al(OH)_3、Mg(OH)_2、La_2O_3和MnO_2对CNFs进行改性。将改性前后的CNFs用于吸附去除废水中磷,并比较了不同p H条件下的除磷效果。结果表明,Fe(OH)_3、Al(OH)_3、Mg(OH)_2、La_2O_3和MnO_2均能成功负载于CNFs上。经改性后的CNFs对磷的吸附去除效果有明显提高,p H越低吸附容量越高。同一p H条件下,吸附容量依次为Fe(OH)_3@CNFs>Al(OH)_3@CNFs>Mg(OH)_2@CNFs>La_2O_3@CNFs>MnO_2@CNFs。Fe(OH)_3@CNFs对磷的吸附效果最好,且受pH变化的影响不大。在磷初始浓度为10mg/L、p H为4时,Fe(OH)_3@CNFs对磷的吸附容量为7.58mg/g,为未负载CNFs的94.75倍;当p H升高至7时,其吸附容量仍可达到7.09mg/g。将其用于实际废水除磷时无需调节pH,可节约药剂,降低处理成本。
The discharge of phosphorus wastewater is considered as a dominant factor for water eutrophication. Adsorption is an effective method for phosphorus removal in the wastewater treatment. The development of environment friendly adsorbents with good adsorption capacity is one of the key factors for the further a adsorption application. The TEMPO oxidation combined physical treatments was used to prepare the cellulose nanofiber hybrid(CNFs). Then, Fe(OH)_3, Al(OH)_3,Mg(OH)_2,La_2O_3 and MnO_2 were used to modify CNFs. CNFs and modified CNFs were applied in the phosphate removal from wastewater. The performance of phosphate removal at different p H was investigated. Fe(OH)_3,Al(OH)_3,Mg(OH)_2,La_2O_3 and MnO_2 could be successfully loaded onto CNFs. While modified CNFs showed higher adsorption capacity than CNFs. The phosphate adsorption capacities of modified CNFs were as follows: Fe(OH)_3@CNFs > Al(OH)_3@CNFs > Mg(OH)_2@CNFs >La_2O_3@CNFs>MnO_2@CNFs,and they all had better phosphate adsorption performance in lower p H. It could be concluded that Fe(OH)_3@CNFs had a superior adsorption performance. When the initial concentration of phosphate is 10 mg/L,the adsorption capacity of Fe(OH)_3@CNFs was 7.58 mg/g at pH 4,which is 95.75 times that of CNFs,7.09 mg/g at pH 7 for practical applications,Fe(OH)_3@CNFs isa good adsorbent for phosphate removal,because there is no need to adjust the p H,the cost and consumption of chemicals are reduced.
The discharge of phosphorus wastewater is considered as a dominant factor for water eutrophication. Adsorption is an effective method for phosphorus removal in the wastewater treatment. The development of environment friendly adsorbents with good adsorption capacity is one of the key factors for the further a adsorption application. The TEMPO oxidation combined physical treatments was used to prepare the cellulose nanofiber hybrid(CNFs). Then, Fe(OH)_3, Al(OH)_3,Mg(OH)_2,La_2O_3 and MnO_2 were used to modify CNFs. CNFs and modified CNFs were applied in the phosphate removal from wastewater. The performance of phosphate removal at different p H was investigated. Fe(OH)_3,Al(OH)_3,Mg(OH)_2,La_2O_3 and MnO_2 could be successfully loaded onto CNFs. While modified CNFs showed higher adsorption capacity than CNFs. The phosphate adsorption capacities of modified CNFs were as follows: Fe(OH)_3@CNFs > Al(OH)_3@CNFs > Mg(OH)_2@CNFs >La_2O_3@CNFs>MnO_2@CNFs,and they all had better phosphate adsorption performance in lower p H. It could be concluded that Fe(OH)_3@CNFs had a superior adsorption performance. When the initial concentration of phosphate is 10 mg/L,the adsorption capacity of Fe(OH)_3@CNFs was 7.58 mg/g at pH 4,which is 95.75 times that of CNFs,7.09 mg/g at pH 7 for practical applications,Fe(OH)_3@CNFs isa good adsorbent for phosphate removal,because there is no need to adjust the p H,the cost and consumption of chemicals are reduced.
引文
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[11]DAI J,YANG H,YAN H,et al.Phosphate adsorption from aqueous solutions by disused adsorbents:chitosan hydrogel beads after the removal of copper(Ⅱ)[J].Chemical Engineering Journal,2011,166(3):970-977.
[12]ZHANG L,WAN L,CHANG N,et al.Removal of phosphate from water by activated carbon fiber loaded with lanthanum oxide[J].Journal of Hazardous Materials,2011,190(1):848-855.
[13]IIZUKA A,SASAKI T,HONGO T,et al.Phosphorus adsorbent derived from concrete sludge(PAde CS)and its phosphorus recovery performance[J].Industrial&Engineering Chemistry Research,2012,51(34):11266-11273.
[14]YADAV D,KAPUR M,KUMAR P,et al.Adsorptive removal of phosphate from aqueous solution using rice husk and fruit juice residue[J].Process Safety&Environmental Protection,2015,94:402-409.
[15]朱加乐,王欣泽,沈剑,等.十四烷基三甲基溴化铵改性活性炭吸附水中硝酸盐和磷酸盐[J].化工进展,2017,36(7):2676-2683.ZHU J L,WANG X Z,SHEN J,et al.Adsorption of nitrate and phosphate by MTAB-modified activated carbon[J].Chemical Industry and Engineering Progress,2017,36(7):2676-2683.
[16]陈爱燕,程翔,黄新瑞,等.Zn-Al类水滑石磷吸附剂的制备及其吸附性能[J].化工学报,2008,59(9):2270-2275.CHEN A Y,CHENG X,HUANG X R,et al.Synthesis of Zn-Al hydrotalcite-like compounds as phosphate adsorbent and its adsorption capacity[J].Journal of Chmeical Industry and Engineering(China),2008,59(9):2270-2275.
[17]韩强,杜晓丽,崔申申,等.颗粒态铁锰复合氧化物对磷的吸附特征及影响因素[J].化工进展,2017,36(6):2311-2317.HAN Q,DU X L,CUI S S,et al.Adsorptive characteristics and effect parameters of granular Fe-Mn binary oxide for phosphate[J].Chemical Industry and Engineering Progress,2017,36(6):2311-2317.
[18]ZHANG X,WANG Y,ZHAO J,et al.Mechanically strong and thermally responsive cellulose nanofibers/poly(N-isopropylacrylamide)composite aerogels[J].ACS Sustainable Chemistry&Engineering,2016,4(8):4321-4327.
[19]CUI G,LIU M,CHEN Y,et al.Synthesis of a ferric hydroxide-coated cellulose nanofiber hybrid for effective removal of phosphate from wastewater[J].Carbohydrate Polymers,2016,154:40-47.
[20]魏静.细菌纤维素/镧系氧化物纳米纤维的制备及性能研究[D].南京:南京理工大学,2015.WEI J.Synthesis and properties of the bacterial cellulose/Lanthanum metal compounds nanofibers[D].Nanjing:Nanjing University of Science&Technology,2015.
[21]唐朝春,陈惠民,刘名,等.利用吸附法除磷研究进展[J].工业水处理,2015,35(7):1-4.TANG C C,CHEN H M,LIU M,et al.Research progress in the use of adsorption for dephosphorization[J].Industrial Water Treatment,2015,35(7):1-4.
[22]周宏光.载纳米水合氧化铁复合半焦的研制及其除磷性能研究[D].重庆:西南大学,2014.ZHOU H G.Preparation of bio-char supported namo ferric oxide composite and its performance on the removal of phosphate from water[D].Chongqing:Southwest University,2014.
[23]张玲,李梦雪,周奇.镧铁复合吸附剂的制备及除磷性能[J].上海大学学报(自然科学版),2013,19(4):331-335.ZHANG L,LI M X,ZHOU Q.Preparation and phosphorus removal of complex phosphate adsorbent from lanthanum and iron[J].Journal of Shanghai University(Natural Science),2013,19(4):331-335.
[24]陆岩,刘艳磊,姜恒,等.氧化镧对磷酸根的吸附及其机理研究[J].化工科技,2014,22(1):45-48.LU Y,LIU Y L,JIANG Heng,et al.Adsortion and mechanism of lanthanum oxide for phosphate[J].Scinence&Technology in Chemical Industry,2014,22(1):45-48.
[25]冯群英.饮用水深度除磷技术研究[D].北京:北京工业大学,2007.FENG Q Y.Study on advanced treatment technioue of phosphours removal in drinking water[D].Beijing:Beijing University of Technology,2007.
[26]MUSTAFA S,ZAMAN M I,KHAN S.Temperature effect on the mechanism of phosphate anions sorption byβ-Mn O2[J].Chemical Engineering Journal,2008,141(1):51-57.
[27]AWUAL M R,JYO A,IHARA T,et al.Enhanced trace phosphate removal from water by zirconium(Ⅳ)loaded fibrous adsorbent[J].Water Research,2011,45(15):4592-4600.
[28]ZHANG G,LIU H,LIU R,et al.Removal of phosphate from water by a Fe-Mn binary oxide adsorbent[J].Journal of Colloid and Interface Science,2009,335(2):168-174.
[29]TIAN S,JIANG P,NING P,et al.Enhanced adsorption removal of phosphate from water by mixed lanthanum/aluminum pillared montmorillonite[J].Chemical Engineering Journal,2009,151(1/3):141-148.
[30]LONG F,GONG J,ZENG G,et al.Removal of phosphate from aqueous solution by magnetic Fe-Zr binary oxide[J].Chemical Engineering Journal,2011,171(2):448-455.
[31]LIU H,SUN X,YIN C,et al.Removal of phosphate by mesoporous Zr O2[J].Journal of Hazardous Materials,2008,151(2/3):616-622.
[32]XUE Y,HOU H,ZHU S.Characteristics and mechanisms of phosphate adsorption onto basic oxygen furnace slag[J].Journal of Hazardous Materials,2009,162(2/3):973-980.
[33]HUANG W,WANG S,ZHU Z,et al.Phosphate removal from wastewater using red mud[J].Journal of Hazardous Materials,2008,158(1):35-42.
[34]李艳君,王莉红,兰尧中.活性氧化铝除磷吸附剂的试验研究[J].昆明冶金高等专科学校学报,2009,25(1):59-60,65.LI Y J,WANG L H,LAN Y Z.Experimental study on phosphorus removal by activated alumina adsorbents[J].Journal of Kunming Metallurgy College,2009,25(1):59-60,65.
[35]徐小明.CMC-Co Fe2O4磁性吸附剂的制备及吸附回收磷的实验研究[D].哈尔滨:哈尔滨工程大学,2013.XU X M.Synthesis of magnetic CMC-Co Fe2O4 compounds and research on the phosphate removal and recovery from wastewater[D].Harbin:Harbin Engineering University,2013.
[36]陈丽萍,段毅文.聚合羟基铝改性杭锦2#土对磷酸根的吸附性能研究[J].非金属矿,2010,33(1):54-57.CHEN L P,DUAN Y W.Study on adsorption of polyhydroxyl aluminium modified hangjin 2#clay to phosphate[J].Non-Metallic Mines,2010,33(1):54-57.
[2]苗文凭,林海,卢晓君.粉煤灰吸附除磷的改性研究[J].环境工程学报,2008,2(4):502-506.MIAO W P,LIN H,LU X J.Adsorption of phosphate using modified fly ash from water solution[J].Chinese Journal of Environmental Engineering,2008,2(4):502-506.
[3]LEE S Y,CHUN S J,KANG I A,et al.Preparation of cellulose nanofibrils by high-pressure homogenizer and cellulose-based composite films[J].Journal of Industrial&Engineering Chemistry,2009,15(1):50-55.
[4]PARALIKAR S A,SIMONSEN J,LOMBARDI J.Poly(vinyl alcohol)/cellulose nanocrystal barrier membranes[J].Journal of Membrane Science,2008,320(1):248-258.
[5]JEAN B,DUBREUILF,HEUX L,et al.Structural details of cellulose nanocrystals/polyelectrolytes multilayers probed by neutron reflectivity and AFM[J].Langmuir,2008,24(7):3452-3458.
[6]唐丽荣,王炜彬,王清华,等.基于芳香基双硫键的乙酸酯化纳米纤维素/聚(脲-氨酯)自愈合材料[J].化工进展,2017,36(4):1381-1387.TANG L R,WANG W B,WANG Q H,et al.Esterified cellulose nanocrystals/poly(urea-urethane)self-healing materials based on aromatic disulfide bonds[J].Chemical Industry and Engineering Progress,2017,36(4):1381-1387.
[7]HE X,CHENG L,WANG Y,et al.Aerogels from quaternary ammonium-functionalized cellulose nanofibers for rapid removal of Cr(Ⅵ)from water[J].Carbohydrate Polymers,2014,111(20):683-687.
[8]WANG Y,ZHANG X,HE X,et al.In situ synthesis of Mn O2 coated cellulose nanofibers hybrid for effective removal of methylene blue[J].Carbohydrate Polymers,2014,110(18):302-308.
[9]YUAN G H,PRABAKAEAN M,SUN Q L,et al.Cyclodextrin functionalized cellulose nanofiber composites for the faster adsorption of toluene from aqueous solution[J].Journal of the Taiwan Institute of Chemical Engineers,2017,70:352-358.
[10]胡正生,康长安,乔支卫.市政污水除磷技术研究进展[J].科技资讯,2012(8):145-147.HU Z S,KANG C A,QIAO Z W.Discussion on phosphate removal from municipal wastewater[J].Science and Technology Information,2012(8):145-147.
[11]DAI J,YANG H,YAN H,et al.Phosphate adsorption from aqueous solutions by disused adsorbents:chitosan hydrogel beads after the removal of copper(Ⅱ)[J].Chemical Engineering Journal,2011,166(3):970-977.
[12]ZHANG L,WAN L,CHANG N,et al.Removal of phosphate from water by activated carbon fiber loaded with lanthanum oxide[J].Journal of Hazardous Materials,2011,190(1):848-855.
[13]IIZUKA A,SASAKI T,HONGO T,et al.Phosphorus adsorbent derived from concrete sludge(PAde CS)and its phosphorus recovery performance[J].Industrial&Engineering Chemistry Research,2012,51(34):11266-11273.
[14]YADAV D,KAPUR M,KUMAR P,et al.Adsorptive removal of phosphate from aqueous solution using rice husk and fruit juice residue[J].Process Safety&Environmental Protection,2015,94:402-409.
[15]朱加乐,王欣泽,沈剑,等.十四烷基三甲基溴化铵改性活性炭吸附水中硝酸盐和磷酸盐[J].化工进展,2017,36(7):2676-2683.ZHU J L,WANG X Z,SHEN J,et al.Adsorption of nitrate and phosphate by MTAB-modified activated carbon[J].Chemical Industry and Engineering Progress,2017,36(7):2676-2683.
[16]陈爱燕,程翔,黄新瑞,等.Zn-Al类水滑石磷吸附剂的制备及其吸附性能[J].化工学报,2008,59(9):2270-2275.CHEN A Y,CHENG X,HUANG X R,et al.Synthesis of Zn-Al hydrotalcite-like compounds as phosphate adsorbent and its adsorption capacity[J].Journal of Chmeical Industry and Engineering(China),2008,59(9):2270-2275.
[17]韩强,杜晓丽,崔申申,等.颗粒态铁锰复合氧化物对磷的吸附特征及影响因素[J].化工进展,2017,36(6):2311-2317.HAN Q,DU X L,CUI S S,et al.Adsorptive characteristics and effect parameters of granular Fe-Mn binary oxide for phosphate[J].Chemical Industry and Engineering Progress,2017,36(6):2311-2317.
[18]ZHANG X,WANG Y,ZHAO J,et al.Mechanically strong and thermally responsive cellulose nanofibers/poly(N-isopropylacrylamide)composite aerogels[J].ACS Sustainable Chemistry&Engineering,2016,4(8):4321-4327.
[19]CUI G,LIU M,CHEN Y,et al.Synthesis of a ferric hydroxide-coated cellulose nanofiber hybrid for effective removal of phosphate from wastewater[J].Carbohydrate Polymers,2016,154:40-47.
[20]魏静.细菌纤维素/镧系氧化物纳米纤维的制备及性能研究[D].南京:南京理工大学,2015.WEI J.Synthesis and properties of the bacterial cellulose/Lanthanum metal compounds nanofibers[D].Nanjing:Nanjing University of Science&Technology,2015.
[21]唐朝春,陈惠民,刘名,等.利用吸附法除磷研究进展[J].工业水处理,2015,35(7):1-4.TANG C C,CHEN H M,LIU M,et al.Research progress in the use of adsorption for dephosphorization[J].Industrial Water Treatment,2015,35(7):1-4.
[22]周宏光.载纳米水合氧化铁复合半焦的研制及其除磷性能研究[D].重庆:西南大学,2014.ZHOU H G.Preparation of bio-char supported namo ferric oxide composite and its performance on the removal of phosphate from water[D].Chongqing:Southwest University,2014.
[23]张玲,李梦雪,周奇.镧铁复合吸附剂的制备及除磷性能[J].上海大学学报(自然科学版),2013,19(4):331-335.ZHANG L,LI M X,ZHOU Q.Preparation and phosphorus removal of complex phosphate adsorbent from lanthanum and iron[J].Journal of Shanghai University(Natural Science),2013,19(4):331-335.
[24]陆岩,刘艳磊,姜恒,等.氧化镧对磷酸根的吸附及其机理研究[J].化工科技,2014,22(1):45-48.LU Y,LIU Y L,JIANG Heng,et al.Adsortion and mechanism of lanthanum oxide for phosphate[J].Scinence&Technology in Chemical Industry,2014,22(1):45-48.
[25]冯群英.饮用水深度除磷技术研究[D].北京:北京工业大学,2007.FENG Q Y.Study on advanced treatment technioue of phosphours removal in drinking water[D].Beijing:Beijing University of Technology,2007.
[26]MUSTAFA S,ZAMAN M I,KHAN S.Temperature effect on the mechanism of phosphate anions sorption byβ-Mn O2[J].Chemical Engineering Journal,2008,141(1):51-57.
[27]AWUAL M R,JYO A,IHARA T,et al.Enhanced trace phosphate removal from water by zirconium(Ⅳ)loaded fibrous adsorbent[J].Water Research,2011,45(15):4592-4600.
[28]ZHANG G,LIU H,LIU R,et al.Removal of phosphate from water by a Fe-Mn binary oxide adsorbent[J].Journal of Colloid and Interface Science,2009,335(2):168-174.
[29]TIAN S,JIANG P,NING P,et al.Enhanced adsorption removal of phosphate from water by mixed lanthanum/aluminum pillared montmorillonite[J].Chemical Engineering Journal,2009,151(1/3):141-148.
[30]LONG F,GONG J,ZENG G,et al.Removal of phosphate from aqueous solution by magnetic Fe-Zr binary oxide[J].Chemical Engineering Journal,2011,171(2):448-455.
[31]LIU H,SUN X,YIN C,et al.Removal of phosphate by mesoporous Zr O2[J].Journal of Hazardous Materials,2008,151(2/3):616-622.
[32]XUE Y,HOU H,ZHU S.Characteristics and mechanisms of phosphate adsorption onto basic oxygen furnace slag[J].Journal of Hazardous Materials,2009,162(2/3):973-980.
[33]HUANG W,WANG S,ZHU Z,et al.Phosphate removal from wastewater using red mud[J].Journal of Hazardous Materials,2008,158(1):35-42.
[34]李艳君,王莉红,兰尧中.活性氧化铝除磷吸附剂的试验研究[J].昆明冶金高等专科学校学报,2009,25(1):59-60,65.LI Y J,WANG L H,LAN Y Z.Experimental study on phosphorus removal by activated alumina adsorbents[J].Journal of Kunming Metallurgy College,2009,25(1):59-60,65.
[35]徐小明.CMC-Co Fe2O4磁性吸附剂的制备及吸附回收磷的实验研究[D].哈尔滨:哈尔滨工程大学,2013.XU X M.Synthesis of magnetic CMC-Co Fe2O4 compounds and research on the phosphate removal and recovery from wastewater[D].Harbin:Harbin Engineering University,2013.
[36]陈丽萍,段毅文.聚合羟基铝改性杭锦2#土对磷酸根的吸附性能研究[J].非金属矿,2010,33(1):54-57.CHEN L P,DUAN Y W.Study on adsorption of polyhydroxyl aluminium modified hangjin 2#clay to phosphate[J].Non-Metallic Mines,2010,33(1):54-57.