采用小型光催化反应装置,以溶胶-凝胶法负载于玻璃纤维网上的固定膜TiO2为催化剂对布洛芬(IBP)进行光催化降解,分析了吸附、光解、IBP初始浓度、溶液初始pH和投加H2O2剂量对TiO2催化剂降解布洛芬的影响,并考察了IBP的矿化过程,对IBP降解中间产物进行定性分析。结果表明:吸附作用和在UV365下光解作用对降解布洛芬的影响不明显; IBP在较低浓度范围内,其降解呈伪一级反应,反应速率常数随初始浓度增大而减小; 随着溶液初始pH的增大,IBP的光催化降解速率逐渐降低; H2O2投加剂量对IBP光催化降解影响显著,这是IBP在水中存在状态和TiO2界面电荷性质受到pH影响所致,为提高光催化降解布洛芬速率,较适宜的H2O2投加剂量为2.5 mg/L左右。光催化对IBP有较好的矿化作用。LC-MS分析表明,·OH攻击作用是IBP光催化降解的基本途径。
Abstract
To reveal the photocatalytic degradation characteristics of ibuprofen(IBP), the effects of adsorption, photolysis, initial concentration, initial pH value and H2O2 dosage on the degradation of ibuprofen were explored by photoreactor with immobilized TiO2 catalyst supported on fiberglass net by solgel method. Mineralization and intermediates were also investigated. Results indicated that adsorption and photolysis under UV365 had little effects on IBP degradation. The degradation of IBP followed pseudlo-first-order kinetics under studied conditions, and the pseudo-first-order kinetic constants decreased with the increase of initial concentration. The photocatalytic degradation rate decreased with the increase of initial pH, for that the existing forms of IBP in the solution and the electric charge of TiO2 surface were controlled by pH. The photocatalytic degradation rate of IBP was significantly affected by H2O2 dosage, and the suitable, amount of H2O2 was about 2.5 mg/L. It was also indicated that TOC was removed effectively. According to the LC-MS data, hydroxylation addition to the parent pharmaceutical was proposed as the fundamental degradation pathway.
{{custom_sec.title}}
{{custom_sec.title}}
{{custom_sec.content}}
参考文献
[1] Richards S M, Cole S E. A toxicity and hazard assessment of fourteen pharmaceuticals to Xenopus laevis larvae[J]. Ecotoxicology,2006,15(8):647-656.
[2] Gmez M J, Mart1nez Bueno M J, Lacorte S,et al. Pilot survey monitoring pharmaceuticals and related compounds in a sewage treatment plant located on the Mediterranean coast[J]. Chemosphere, 2007,66(6): 993-1002.
[3] Boxall A B A, Kolpin D W, Halling-Sφrensen B, et al. Peer reviewed:are veterinary medicines causing environmental risks?[J]. Environmental Science & Technology, 2003, 37(15): 286A-294A.
[4] Winker M, Faika D, Gulyas H, et al. A comparison of human pharmaceutical concentrations in raw municipal wastewater and yellow water[J]. Science of the Total Environment, 2008,399(1):96-104.
[5] Nakada N, Shinohara H, Murata A, et al. Removal of selected pharmaceuticals and personal care products(PPCPs)and endocrine-disrupting chemicals(EDCs)during sand filtration and ozonation at a municipal sewage treatment plant[J]. Water Research, 2007,41(19):4373-4382.
[6] Hoffmann M R, Martin S T, Choi W Y, et al. Environmental applications of semiconductor photocatalysis[J]. Chemical Reviews, 1995, 95(1): 69-96.
[7] Herrmann J M. Heterogeneous photocatalysis: fundamentals and applications to the removal of various types of aqueous pollutants[J]. Catalysis Today, 1999, 53:115-129.
[8] Pera-Titus M, Garcia-Molina V, Banos A M,et al. Degradation of chlorophenols by means of advanced oxidation processes: a general review[J]. Applied Catalysis B: Environmental, 2004, 47(4): 219-256.
[9] Mendez-Arriaga F, Maldonado I M, Gimenez J, et al. Abatement of ibuprofen by solar photocatalysis process: Enhancement and scale up[J]. Catalysis Today, 2009,144: 112-116.
[10] Mendez-Arriaga F, Esplugas S, Gimenez J. Photocatalytic degradation of non-steroidal anti-inflammatory drugs with TiO2 and simulated solar irradiation[J]. Water Research,2008,42(3):585-594.
[11] 仇雁翎,赵建夫,李田,等. 热处理温度对TiO2光催化活性的影响[J]. 同济大学学报:自然科学版, 2008,36(6):764-768. Qiu Y L, Zhao J F, Li T,et al. Influence of heat treatment temperature on characteristics of TiO2 film photocatalyst[J].Journal of Tongji University:Natural Science, 2008,36(6):764-768.
[12] Yang H, Li G Y, An T C, et al. Photocatalytic degradation kinetics and mechanism of environmental pharmaceuticals in aqueous suspension of TiO2: a case of sulfa drugs[J]. Catalysis Today,2010,153:200-207.
[13] Abellan M N, Bayarri B, Gimenez J, et al. Photocatalytic degradation of sulfamethoxazole in aqueous suspension of TiO2[J]. Applied Catalysis B: Environmental, 2007,74:233-241.
[14] Jacobs E L, Fimmen L R, Chin Y P,et al. Fulvic acid mediated photolysis of ibuprofen in water[J]. Water Research, 2011,45(15): 4449-4458.
[15] Gratzel C K, Jirousek M, Gratzel M. Decomposition of organophosphorous compounds on photoactivated TiO2 surfaces[J]. Journal of Molecular Catalysis,1990, 60:375-387.
基金
收稿日期:2012-07-04 修回日期:2013-01-07
基金项目:江苏省环境科学与工程重点实验室开放课题(zd111201)
第一作者:林少华,副教授,博士。E-mail:franklinsh@126.com。
引文格式:林少华,杨娣娣,路婧婧,等. 布洛芬固定膜TiO2光催化降解特性研究[J]. 南京林业大学学报:自然科学版,2013,37(4):90-94.
PDF(679539 KB)
