丙烯酸-甲基丙烯酸羟乙酯共聚物纤维负载型Fenton催化剂制备工艺对催化活性的影响
|
摘要
为改善纤维负载型Fenton反应催化剂的重复使用性,以丙烯酸为主要单体,以甲基丙烯酸羟乙酯为辅助单体,采用沉淀聚合法合成丙烯酸-甲基丙烯酸羟乙酯共聚物,采用湿法纺丝并负载Fe2+制备纤维负载型Fenton催化剂,并通过亚甲基蓝去除实验考察溶剂组成、凝固浴组成以及凝固浴温度等因素对该催化剂重复使用性的影响.结果表明:当溶剂中NaOH与H_2O质量之比为0.3∶9.7、凝固浴中H_2SO_4与H_2O体积之比为2∶8、凝固浴温度为20℃时,所得纤维与Fe~(2+)形成络合物的催化活性最佳,在H_2O_2和O_3存在条件下,1 min内亚甲基蓝去除效率即可达到97%,且第3次使用催化剂4 min时亚甲基蓝去除效率仍可达95%.
To improve the reusability of catalyst based on fiber supported Fe~(2+), the copolymer of acrylic acid and hydroxyethyl methacrylate was synthesized via precipitation polymerization by using acrylic acid as a main monomer and hydroxyethyl methacrylate as a auxiliary monomer. Its fiber was prepared by wet spinning, and the Fenton catalyst was prepared by loading Fe~(2+)on the fiber. The effects of the composition of solvent, the composition of coagulation bath and the temperature of coagulation bath on the reusability of catalyst were investigated by evaluating the removal efficiency of Methylene Blue. The results showed that the catalyst of Fe~(2+) coordinated fiber exhibited the best catalytic performance when the mass ratio of NaOH to H_2O was equal to 0.3 ∶ 9.7, the volume ratio of H_2SO_4 to H_2O was equal to 2 ∶ 8, and the coagulation bath temperature was 20 ℃. When the catalyst was used for the first time, 97% of MB could be removed from its solution within 1 min in the presence of H_2O_2 and O_3 while for the third time, 95% of MB could be removed within 4 min.
To improve the reusability of catalyst based on fiber supported Fe~(2+), the copolymer of acrylic acid and hydroxyethyl methacrylate was synthesized via precipitation polymerization by using acrylic acid as a main monomer and hydroxyethyl methacrylate as a auxiliary monomer. Its fiber was prepared by wet spinning, and the Fenton catalyst was prepared by loading Fe~(2+)on the fiber. The effects of the composition of solvent, the composition of coagulation bath and the temperature of coagulation bath on the reusability of catalyst were investigated by evaluating the removal efficiency of Methylene Blue. The results showed that the catalyst of Fe~(2+) coordinated fiber exhibited the best catalytic performance when the mass ratio of NaOH to H_2O was equal to 0.3 ∶ 9.7, the volume ratio of H_2SO_4 to H_2O was equal to 2 ∶ 8, and the coagulation bath temperature was 20 ℃. When the catalyst was used for the first time, 97% of MB could be removed from its solution within 1 min in the presence of H_2O_2 and O_3 while for the third time, 95% of MB could be removed within 4 min.
引文
[1]高婷,李天任,韩名超,等.马来酸酐/丙烯酸水凝胶对亚甲基蓝染料的吸附[J].吉林大学学报,2017,55(4):1037-1043.GAO T,LI T R,HAN M C,et al.Adsorption of Methylene Blue dye by maleic anhydride/acrylic acid hydrogel[J].Journal of Jilin University,2017,55(4):1037-1043(in Chinese).
[2]殷晓春,吴建军,赵翊,等.高分子改性黄原胶/羟基磷灰石复合水凝胶的制备及其吸附金属离子性能[J].环境科学学报,2017,37(2):633-641.YIN X C,WU J J,ZHAO Y,et al.Preparation of polymer modified xanthan gum/hydroxyapatite composite hydrogel and its absorption for metal ions[J].Acta Scientiae Circumstantiae,2017,37(2):633-641(in Chinese).
[3]俞洁,郑继东,陆泉芳,等.壳聚糖/聚乙二醇/丙烯酸吸附剂对Cu2+、Co2+和Ni2+的吸附选择性和重复利用性[J].环境科学学报,2017,37(3):1003-1012.YU J,ZHENG J D,LU Q F,et al.Adsorption selectivity and reusability of chitosan/poly(ethylene glycol)/acrylic acid adsorbent for Cu2+,Co2+and Ni2+[J].Acta Scientiae Circumstantiae,2017,37(3):1003-1012(in Chinese).
[4]CLEMONS C,SEDLMAIR J,ILLMAN B,et al.Chemically imaging the effects of the addition of nanofibrillated cellulose on the distribution of poly(acrylic acid)in poly(vinyl alcohol)[J].Polymer,2013,54(8):2058-2061.
[5]FEI J,GU L.PVA/PAA thermo-crosslinking hydrogel fiber:Preparation and pH-sensitive properties in electrolyte solution[J].European Polymer Journal,2002,38(8):1653-1658.
[6]张滕,王勇梅,彭昌盛,等.染料废水的处理方法及研究进展[J].环保科技,2016,22(1):36-40.ZHANG T,WANG Y M,PENG C S,et al.Review on the treatment of dye wastewater[J].Environmental Protection and Technology,2016,22(1):36-40(in Chinese).
[7]TERINTE N,MANDA B M K,TAYLOR J,et al.Environmental assessment of coloured fabrics and opportunities for value creation:Spin-dyeing versus conventional dyeing of modal fabrics[J].Journal of Cleaner Production,2014,72(6):127-138.
[8]BABUPONNUSAMI A,MUTHUKUMAR K.A review on Fenton and improvements to the Fenton process for wastewater treatment[J].Journal of Environmental Chemical Engineering,2014,2(1):557-572.
[9]ZHANG G,OKAJIMA I,SAKO T.Decomposition and decoloration of dyeing wastewater by hydrothermal oxidation[J].Journal of Supercritical Fluids,2016,112(1):136-142.
[10]LUISA M,PASTRANA M,PEREIRA N,et al.Degradation of diphenhydramine by photo-Fenton using magnetically recoverable iron oxide nanoparticles as catalyst[J].Chemical Engineering Journal,2015,261:45-52.
[11]WANG N,ZHENG T,ZHANG G,et al.A review on Fentonlike processes for organic wastewater treatment[J].Journal of Environmental Chemical Engineering,2016,4(1):762-787.
[12]DENG J,SHAO Y,GAO N,et al.Co Fe2O4magnetic nanoparticles as a highly active heterogeneous catalyst of oxone for the degradation of diclofenac in water[J].Journal of Hazardous Materials,2013,262:836-844.
[13]NAVALON S,ALVARO M,GARCIA H.Chem inform abstract:Heterogeneous Fenton catalysts based on clays,silicas and zeolites[J].Cheminform,2015,42(1):1-26.
[14]崔丰元.均相芬顿氧化技术在废水处理中的应用研究[J].环境科学与管理,2015,40(4):83-85.CUI F Y.Application of homogeneous Fenton oxidation technology in wastewater treatment[J].Environmental Science and Management,2015,40(4):83-85(in Chinese).
[15]周亚梁,黄东月.芬顿反应技术的类型及研究进展[J].广东化工,2013,40(1):74.ZHOU Y L,HUANG D Y.Types and research progress of Fenton reaction technology[J].Guangdong Chemical Industry,2013,40(1):74(in Chinese).
[16]CHENG M,MA W,LI J,et al.Visible-light-assisted degradation of dye pollutants over Fe(Ⅲ)-loaded resin in the presence of H2O2at neutral pH values[J].Environmental Science and Technology,2004,38(5):1569-1575.
[17]张潇逸,何青春,蒋进元,等.类芬顿处理技术研究进展综述[J].环境科学与管理,2015(6):58-61.ZHANG X Y,HE Q C,JIANG J Y,et al.Study progress of class-Fenton treatment technology[J].Environmental Science and Management,2015(6):58-61(in Chinese).
[18]宋应民,耿春茂,许容花,等.非均相类芬顿催化剂的制备及其应用效果研究[J].广东化工,2014,41(13):82-101.SONG Y M,GENG C M,XU R H,et al.Study on the preparation of heterogeneous catalyst for fenton reaction and the effect of its application[J].Guangdong Chemical Industry,2014,41(13):82-101(in Chinese).
[19]HE J,YANG X,MEN B,et al.Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials:A review[J].Journal of Environmental Sciences,2016,39(1):97-109.
[20]王延相,季保华,刘焕章.湿法纺聚丙烯腈原丝凝固过程的研究[J].功能材料,2005,36(9):1438-1441.WANG Y X,JI B H,LIU H Z.Study on the effect of coagulation conditions in wet spinning process of polyacrylonitrile fibers[J].Journal of Functional Materials,2005,36(9):1438-1441(in Chinese).
[2]殷晓春,吴建军,赵翊,等.高分子改性黄原胶/羟基磷灰石复合水凝胶的制备及其吸附金属离子性能[J].环境科学学报,2017,37(2):633-641.YIN X C,WU J J,ZHAO Y,et al.Preparation of polymer modified xanthan gum/hydroxyapatite composite hydrogel and its absorption for metal ions[J].Acta Scientiae Circumstantiae,2017,37(2):633-641(in Chinese).
[3]俞洁,郑继东,陆泉芳,等.壳聚糖/聚乙二醇/丙烯酸吸附剂对Cu2+、Co2+和Ni2+的吸附选择性和重复利用性[J].环境科学学报,2017,37(3):1003-1012.YU J,ZHENG J D,LU Q F,et al.Adsorption selectivity and reusability of chitosan/poly(ethylene glycol)/acrylic acid adsorbent for Cu2+,Co2+and Ni2+[J].Acta Scientiae Circumstantiae,2017,37(3):1003-1012(in Chinese).
[4]CLEMONS C,SEDLMAIR J,ILLMAN B,et al.Chemically imaging the effects of the addition of nanofibrillated cellulose on the distribution of poly(acrylic acid)in poly(vinyl alcohol)[J].Polymer,2013,54(8):2058-2061.
[5]FEI J,GU L.PVA/PAA thermo-crosslinking hydrogel fiber:Preparation and pH-sensitive properties in electrolyte solution[J].European Polymer Journal,2002,38(8):1653-1658.
[6]张滕,王勇梅,彭昌盛,等.染料废水的处理方法及研究进展[J].环保科技,2016,22(1):36-40.ZHANG T,WANG Y M,PENG C S,et al.Review on the treatment of dye wastewater[J].Environmental Protection and Technology,2016,22(1):36-40(in Chinese).
[7]TERINTE N,MANDA B M K,TAYLOR J,et al.Environmental assessment of coloured fabrics and opportunities for value creation:Spin-dyeing versus conventional dyeing of modal fabrics[J].Journal of Cleaner Production,2014,72(6):127-138.
[8]BABUPONNUSAMI A,MUTHUKUMAR K.A review on Fenton and improvements to the Fenton process for wastewater treatment[J].Journal of Environmental Chemical Engineering,2014,2(1):557-572.
[9]ZHANG G,OKAJIMA I,SAKO T.Decomposition and decoloration of dyeing wastewater by hydrothermal oxidation[J].Journal of Supercritical Fluids,2016,112(1):136-142.
[10]LUISA M,PASTRANA M,PEREIRA N,et al.Degradation of diphenhydramine by photo-Fenton using magnetically recoverable iron oxide nanoparticles as catalyst[J].Chemical Engineering Journal,2015,261:45-52.
[11]WANG N,ZHENG T,ZHANG G,et al.A review on Fentonlike processes for organic wastewater treatment[J].Journal of Environmental Chemical Engineering,2016,4(1):762-787.
[12]DENG J,SHAO Y,GAO N,et al.Co Fe2O4magnetic nanoparticles as a highly active heterogeneous catalyst of oxone for the degradation of diclofenac in water[J].Journal of Hazardous Materials,2013,262:836-844.
[13]NAVALON S,ALVARO M,GARCIA H.Chem inform abstract:Heterogeneous Fenton catalysts based on clays,silicas and zeolites[J].Cheminform,2015,42(1):1-26.
[14]崔丰元.均相芬顿氧化技术在废水处理中的应用研究[J].环境科学与管理,2015,40(4):83-85.CUI F Y.Application of homogeneous Fenton oxidation technology in wastewater treatment[J].Environmental Science and Management,2015,40(4):83-85(in Chinese).
[15]周亚梁,黄东月.芬顿反应技术的类型及研究进展[J].广东化工,2013,40(1):74.ZHOU Y L,HUANG D Y.Types and research progress of Fenton reaction technology[J].Guangdong Chemical Industry,2013,40(1):74(in Chinese).
[16]CHENG M,MA W,LI J,et al.Visible-light-assisted degradation of dye pollutants over Fe(Ⅲ)-loaded resin in the presence of H2O2at neutral pH values[J].Environmental Science and Technology,2004,38(5):1569-1575.
[17]张潇逸,何青春,蒋进元,等.类芬顿处理技术研究进展综述[J].环境科学与管理,2015(6):58-61.ZHANG X Y,HE Q C,JIANG J Y,et al.Study progress of class-Fenton treatment technology[J].Environmental Science and Management,2015(6):58-61(in Chinese).
[18]宋应民,耿春茂,许容花,等.非均相类芬顿催化剂的制备及其应用效果研究[J].广东化工,2014,41(13):82-101.SONG Y M,GENG C M,XU R H,et al.Study on the preparation of heterogeneous catalyst for fenton reaction and the effect of its application[J].Guangdong Chemical Industry,2014,41(13):82-101(in Chinese).
[19]HE J,YANG X,MEN B,et al.Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials:A review[J].Journal of Environmental Sciences,2016,39(1):97-109.
[20]王延相,季保华,刘焕章.湿法纺聚丙烯腈原丝凝固过程的研究[J].功能材料,2005,36(9):1438-1441.WANG Y X,JI B H,LIU H Z.Study on the effect of coagulation conditions in wet spinning process of polyacrylonitrile fibers[J].Journal of Functional Materials,2005,36(9):1438-1441(in Chinese).