镍铁层状双金属氢氧化物催化臭氧去除双酚A的试验
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摘要
采用共沉淀的方法合成镍铁层状双金属氢氧化物,通过X射线衍射(XRD)研究不同镍铁金属摩尔比例对镍铁层状双金属氢氧化物晶型的影响;设计单因素试验,研究催化剂投加量、pH、臭氧浓度、镍铁金属摩尔比例等因素对双酚A(BPA)去除效果的影响;探讨催化臭氧氧化去除BPA的反应机理。XRD图显示当镍铁金属摩尔比为3∶1时,镍铁层状双金属氢氧化物的结晶度最好。试验结果表明:在BPA初始浓度为10 mg/L、pH值为8.2、臭氧浓度为9.0 mg/L、催化剂投加量为0.3 g/L、镍铁金属摩尔比例为3∶1的条件下,含BPA废水的总有机碳(TOC)去除率高达89%。通过羟基自由基抑制剂反应试验,观察到TOC和BPA的去除率均有所降低,说明催化臭氧反应过程中存在羟基自由基氧化作用。
Ni-Fe layered double hydroxides were synthesized by co-precipitation method. Ni-Fe layered double hydroxides were characterized to study the crystal structure with different metal molar ratios by X-ray diffraction(XRD). By designing the single factor experiments, the effects of catalyst dosage, pH, ozone concentration, and metal molar ratio were investigated on the removal of bisphenol A(BPA). In addition, the reaction mechanism of catalytic ozonation was also discussed. XRD showed that the crystallinity of Ni-Fe layered double hydroxides was good when the molar ratio of Ni∶Fe was 3∶1. The total organic carbon(TOC) removal rate of BPA-contaminated wastewater was 89% and BPA was basically completely removed under pH value of 8.2, ozone concentration of 9.0 mg/L, catalyst dosage of 0.3 g/L, and nickel-iron metal molar ratio of 3∶1. By a free radical inhibitor reaction test, removal rates of TOC and BPA were decreased, indicating that catalytic ozone reaction conformed to hydroxyl radical reaction mechanism.
Ni-Fe layered double hydroxides were synthesized by co-precipitation method. Ni-Fe layered double hydroxides were characterized to study the crystal structure with different metal molar ratios by X-ray diffraction(XRD). By designing the single factor experiments, the effects of catalyst dosage, pH, ozone concentration, and metal molar ratio were investigated on the removal of bisphenol A(BPA). In addition, the reaction mechanism of catalytic ozonation was also discussed. XRD showed that the crystallinity of Ni-Fe layered double hydroxides was good when the molar ratio of Ni∶Fe was 3∶1. The total organic carbon(TOC) removal rate of BPA-contaminated wastewater was 89% and BPA was basically completely removed under pH value of 8.2, ozone concentration of 9.0 mg/L, catalyst dosage of 0.3 g/L, and nickel-iron metal molar ratio of 3∶1. By a free radical inhibitor reaction test, removal rates of TOC and BPA were decreased, indicating that catalytic ozone reaction conformed to hydroxyl radical reaction mechanism.
引文
[1] DIAMANTIKANDARAKIS E, BOURGUIGNON J P, GIUDICE L C, et al. Endocrine-disrupting chemicals: An Endocrine Society scientific statement[J]. Endocrine Reviews, 2009, 30(4): 293-342.
[2] 纪桂霞, 王学连, 周海东,等. PPCPs在水环境中的风险控制研究进展[J]. 能源研究与信息, 2015, 31(3):142-147.
[3] 徐红燕, 周仕林, 陶红,等. 废水中邻苯二甲酸酯降解的研究进展[J]. 上海理工大学学报, 2010, 32(5):418-422.
[4] ERJAVEC B, KAPLAN , et al. Catalytic wet air oxidation of bisphenol A model solution in a trickle-bed reactor over titanate nanotube-based catalysts[J]. Applied Catalysis B Environmental, 2013, 22(6): 342-352.
[5] ROCHA S, DOMINGUES V F, PINHO C, et al. Occurrence of bisphenol A, estrone, 17β-estradiol and 17α-ethinylestradiol in Portuguese rivers[J]. Bulletin of Environmental Contamination & Toxicology, 2013, 90(1): 73-78.
[6] 龚剑, 冉勇, 杨余, 等. 珠江广州河段表层水中雌激素化合物的污染状况[J]. 环境化学, 2008, 27(2): 242-244.
[7] WELSHONS W V, NAGEL S C, VOM SAAL F S. Large effects from small exposures. III. Endocrine mechanisms mediating effects of bisphenol A at levels of human exposure[J]. Endocrinology, 2006, 147(6 Suppl): 56-69.
[8] DORN P B, CHOU C S, GENTEMPO J J. Degradation of bisphenol A in natural waters[J]. Chemosphere, 1987, 16(7): 1501-1507.
[9] 全学军, 程治良, 杨露, 等. 多层光源内置式气-液-固循环流化床光催化降解双酚A[J]. 环境科学学报, 2011, 31(6): 1233-1240.
[10] IOAN I, WILSON S, LUNDANES E, et al. Comparison of Fenton and sono-Fenton bisphenol A degradation[J]. Journal of Hazardous Materials, 2007, 142(1): 559-563.
[11] UMAR M, RODDICK F, FAN L, et al. Application of ozone for the removal of bisphenol A from water and wastewater——A review[J]. Chemosphere, 2013, 90(8): 2197-2207.
[12] NI C H, CHEN J N, YANG P Y. Catalytic ozonation of 2-dichlorophenol by metallic ions[J]. Water Science & Technology, 2003, 47(1): 77-82.
[13] HAGINIWA J, HIGUCHI Y, HIROSE M. Oxidation of Ferrous ions by ozone in acidic solutions[J]. Inorganic Chemistry, 1992, 23(48): 459-522.
[14] 李梦澜, 李海青, 李刚. 纳米α-MnO2催化臭氧氧化降解水中双酚A [J]. 化工环保, 2014, 34(5): 484-487.
[15] 郝玉兰, 周延明, 刘钊, 等纳米二氧化钛介孔微球光催化降解水中BPA的机理[J]. 光谱实验室, 2012, 29(2): 1128-1132.
[16] PARK J S, CHOI H, AHN K H. The reaction mechanism of catalytic oxidation with hydrogen peroxide and ozone in aqueous solution[J]. Water Science & Technology, 2003, 47(1): 179-184.
[17] 李亚如, 许智华, 张道方. 铁改性活性炭对水中镉的吸附和再生实验研究[J]. 能源研究与信息, 2014(4): 187-191.
[18] 耿媛媛, 侯永江, 杜金梅, 等. 多相催化臭氧化技术中催化剂的研究进展[J]. 工业水处理, 2011, 31(2): 8-12.
[19] 施炜, 胡军, 倪哲明, 等. 层间水分子含量对铜铁水滑石超分子作用力的影响[J]. 物理化学学报, 2012, 28(8): 1869-1876.
[20] KUMBHAR P S, SANCHEZ-VALENTE J, MILLET J M M, et al. Mg-Fe hydrotalcite as a catalyst for the reduction of aromatic nitro compounds with hydrazine hydrate[J]. Journal of Catalysis, 2000, 191(2): 467-473.
[21] BADER H, HOIGN J. Determination of ozone in water by the indigo method[J]. Water Research, 1981, 15(4): 449-456.
[22] MULLET M, FIEVET P, SZYMCZYK A, et al. A simple and accurate determination of the point of zero charge of ceramic membranes[J]. Desalination, 1999, 34(1): 41-48.
[23] 王岚, 陈慧琴, 陈欣妍, 等镍铁和镁铁水滑石的合成及热稳定性研究[J]. 合成化学, 2003, 11(6): 524-526.
[24] CAVANI F, TRIFIRò F, VACCARI A. Hydrotalcite-type anionic clays: Preparation, properties and applications[J]. Catalysis Today, 1991, 11(2): 173-301.
[25] 周彤, 李峰, 战可涛, 等. 层状前体镍铁水滑石及磁性材料的制备及表征[J]. 化学学报, 2002, 60(6): 1078-1083.
[26] ZHANG H, HUANG C H. Oxidative transformation of triclosan and chlorophene by manganese oxides[J]. Environmental Science & Technology, 2003, 37(11): 2421-2430.
[27] STONE A T. Reductive Dissolution of manganese(III/Iv) oxides by substituted phenols[J]. Environmental science & technology, 1987, 21(10): 979-988.
[28] 刘昕, 罗婷玉, 姚坚, 等. 纳米态β-MnO2催化臭氧降解BPA的研究[J]. 化学研究与应用, 2016, 28(9): 1220-1224.
[29] 汤茜, 周玲妹, 陆丽, 等. 活性炭负载Fe3+催化臭氧氧化水中双酚A [J]. 辽宁化工, 2014(6): 664-667.
[30] 李越. 负载型催化剂催化臭氧化降解水中水杨酸的研究 [D].泰安:山东农业大学, 2014.
[31] CHEN C, YU J, YOZA B A, et al. A novel "wastes-treat-wastes" technology: Role and potential of spent fluid catalytic cracking catalyst assisted ozonation of petrochemical wastewater [J]. Journal of Environmental Management, 2015, 152:58-65.
[32] 李海燕, 曲久辉. 饮用水中DBP的臭氧氧化效能与影响因素[J]. 环境化学, 2004, 23(3): 278-282.【专家点评】 文章采用共沉淀的方法合成镍铁层状双金属氢氧化物,通过 X 射线衍射(XRD)研究不同镍铁金属摩尔比对镍铁层状双金属氢氧化物晶型的影响。在制备催化剂的基础上,研究了催化剂投加量、pH、臭氧浓度、镍铁金属摩尔比例等因素对双酚 A(BPA)去除效果的影响。论文写作规范,论述清楚,分析合理。研究结果为臭氧化催化剂的开发与应用提供了科学数据支撑,具有较好的应用价值。
[2] 纪桂霞, 王学连, 周海东,等. PPCPs在水环境中的风险控制研究进展[J]. 能源研究与信息, 2015, 31(3):142-147.
[3] 徐红燕, 周仕林, 陶红,等. 废水中邻苯二甲酸酯降解的研究进展[J]. 上海理工大学学报, 2010, 32(5):418-422.
[4] ERJAVEC B, KAPLAN , et al. Catalytic wet air oxidation of bisphenol A model solution in a trickle-bed reactor over titanate nanotube-based catalysts[J]. Applied Catalysis B Environmental, 2013, 22(6): 342-352.
[5] ROCHA S, DOMINGUES V F, PINHO C, et al. Occurrence of bisphenol A, estrone, 17β-estradiol and 17α-ethinylestradiol in Portuguese rivers[J]. Bulletin of Environmental Contamination & Toxicology, 2013, 90(1): 73-78.
[6] 龚剑, 冉勇, 杨余, 等. 珠江广州河段表层水中雌激素化合物的污染状况[J]. 环境化学, 2008, 27(2): 242-244.
[7] WELSHONS W V, NAGEL S C, VOM SAAL F S. Large effects from small exposures. III. Endocrine mechanisms mediating effects of bisphenol A at levels of human exposure[J]. Endocrinology, 2006, 147(6 Suppl): 56-69.
[8] DORN P B, CHOU C S, GENTEMPO J J. Degradation of bisphenol A in natural waters[J]. Chemosphere, 1987, 16(7): 1501-1507.
[9] 全学军, 程治良, 杨露, 等. 多层光源内置式气-液-固循环流化床光催化降解双酚A[J]. 环境科学学报, 2011, 31(6): 1233-1240.
[10] IOAN I, WILSON S, LUNDANES E, et al. Comparison of Fenton and sono-Fenton bisphenol A degradation[J]. Journal of Hazardous Materials, 2007, 142(1): 559-563.
[11] UMAR M, RODDICK F, FAN L, et al. Application of ozone for the removal of bisphenol A from water and wastewater——A review[J]. Chemosphere, 2013, 90(8): 2197-2207.
[12] NI C H, CHEN J N, YANG P Y. Catalytic ozonation of 2-dichlorophenol by metallic ions[J]. Water Science & Technology, 2003, 47(1): 77-82.
[13] HAGINIWA J, HIGUCHI Y, HIROSE M. Oxidation of Ferrous ions by ozone in acidic solutions[J]. Inorganic Chemistry, 1992, 23(48): 459-522.
[14] 李梦澜, 李海青, 李刚. 纳米α-MnO2催化臭氧氧化降解水中双酚A [J]. 化工环保, 2014, 34(5): 484-487.
[15] 郝玉兰, 周延明, 刘钊, 等纳米二氧化钛介孔微球光催化降解水中BPA的机理[J]. 光谱实验室, 2012, 29(2): 1128-1132.
[16] PARK J S, CHOI H, AHN K H. The reaction mechanism of catalytic oxidation with hydrogen peroxide and ozone in aqueous solution[J]. Water Science & Technology, 2003, 47(1): 179-184.
[17] 李亚如, 许智华, 张道方. 铁改性活性炭对水中镉的吸附和再生实验研究[J]. 能源研究与信息, 2014(4): 187-191.
[18] 耿媛媛, 侯永江, 杜金梅, 等. 多相催化臭氧化技术中催化剂的研究进展[J]. 工业水处理, 2011, 31(2): 8-12.
[19] 施炜, 胡军, 倪哲明, 等. 层间水分子含量对铜铁水滑石超分子作用力的影响[J]. 物理化学学报, 2012, 28(8): 1869-1876.
[20] KUMBHAR P S, SANCHEZ-VALENTE J, MILLET J M M, et al. Mg-Fe hydrotalcite as a catalyst for the reduction of aromatic nitro compounds with hydrazine hydrate[J]. Journal of Catalysis, 2000, 191(2): 467-473.
[21] BADER H, HOIGN J. Determination of ozone in water by the indigo method[J]. Water Research, 1981, 15(4): 449-456.
[22] MULLET M, FIEVET P, SZYMCZYK A, et al. A simple and accurate determination of the point of zero charge of ceramic membranes[J]. Desalination, 1999, 34(1): 41-48.
[23] 王岚, 陈慧琴, 陈欣妍, 等镍铁和镁铁水滑石的合成及热稳定性研究[J]. 合成化学, 2003, 11(6): 524-526.
[24] CAVANI F, TRIFIRò F, VACCARI A. Hydrotalcite-type anionic clays: Preparation, properties and applications[J]. Catalysis Today, 1991, 11(2): 173-301.
[25] 周彤, 李峰, 战可涛, 等. 层状前体镍铁水滑石及磁性材料的制备及表征[J]. 化学学报, 2002, 60(6): 1078-1083.
[26] ZHANG H, HUANG C H. Oxidative transformation of triclosan and chlorophene by manganese oxides[J]. Environmental Science & Technology, 2003, 37(11): 2421-2430.
[27] STONE A T. Reductive Dissolution of manganese(III/Iv) oxides by substituted phenols[J]. Environmental science & technology, 1987, 21(10): 979-988.
[28] 刘昕, 罗婷玉, 姚坚, 等. 纳米态β-MnO2催化臭氧降解BPA的研究[J]. 化学研究与应用, 2016, 28(9): 1220-1224.
[29] 汤茜, 周玲妹, 陆丽, 等. 活性炭负载Fe3+催化臭氧氧化水中双酚A [J]. 辽宁化工, 2014(6): 664-667.
[30] 李越. 负载型催化剂催化臭氧化降解水中水杨酸的研究 [D].泰安:山东农业大学, 2014.
[31] CHEN C, YU J, YOZA B A, et al. A novel "wastes-treat-wastes" technology: Role and potential of spent fluid catalytic cracking catalyst assisted ozonation of petrochemical wastewater [J]. Journal of Environmental Management, 2015, 152:58-65.
[32] 李海燕, 曲久辉. 饮用水中DBP的臭氧氧化效能与影响因素[J]. 环境化学, 2004, 23(3): 278-282.【专家点评】 文章采用共沉淀的方法合成镍铁层状双金属氢氧化物,通过 X 射线衍射(XRD)研究不同镍铁金属摩尔比对镍铁层状双金属氢氧化物晶型的影响。在制备催化剂的基础上,研究了催化剂投加量、pH、臭氧浓度、镍铁金属摩尔比例等因素对双酚 A(BPA)去除效果的影响。论文写作规范,论述清楚,分析合理。研究结果为臭氧化催化剂的开发与应用提供了科学数据支撑,具有较好的应用价值。