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    高铁酸盐活化过二硫酸盐高效降解水中的盐酸四环素

    Efficient degradation of tetracycline hydrochloride in wastewater through peroxysulphate activation using ferrate

    • 摘要: 文中分别以活性炭、铁粉、硫化亚铁、七水合硫酸亚铁、高铁酸钾活化过二硫酸盐降解盐酸四环素,对比了其对盐酸四环素的降解效能。研究了盐酸四环素的初始浓度、过二硫酸盐浓度、高铁酸盐浓度、溶液初始pH、反应温度和共存离子等因素对盐酸四环素降解的影响。在单因素实验基础上,应用响应面法对盐酸四环素的降解工艺进行了优化。利用自由基淬灭实验,推测了FeS+ Na2S2O8、K2FeO4+Na2S2O8两种降解体系中的主要活性物种。用高效液相色谱-质谱(HPLC-MS)对高铁酸盐活化过二硫酸盐降解盐酸四环素的产物进行了鉴定,推测了盐酸四环素的可能降解路径。结果表明:FeS、K2FeO4为过二硫酸盐的较好的活化剂,且以K2FeO4为活化剂时盐酸四环素在较宽的质量浓度范围(10~80 mg·L−1)内均具有较高的降解率。溶液中共存的\mathrmSO_4^2- 、Cl−、\rmHPO^2-_4 对盐酸四环素的降解均具有不同程度的抑制作用。在最佳工艺参数下,盐酸四环素在50 min内的降解率可达99.97%。FeS+Na2S2O8、K2FeO4+Na2S2O8两种降解体系中均存在\mathrmSO_4^- ·、·OH和lO2,且·OH和lO2对盐酸四环素降解的贡献较大。盐酸四环素的降解的可能路径有8条,主要涉及抽氢、加氢、羟基化、脱甲基、脱羰基、脱羟基、脱胺基、脱水、C═C双键氧化、C─N键断裂、开环等过程。

       

      Abstract: The degradation of tetracycline hydrochloride through peroxysulphate activation using activated carbon, iron powder, ferrous sulfide, ferrous sulfate heptahydrate, and potassium ferrate were carried out, respectively. And, the effects of initial tetracycline hydrochloride concentration, peroxysulphate concentration, ferrate concentration, initial solution pH, reaction temperature, and co-existing ions on degradation of tetracycline hydrochloride were investigated. Besides, the main active species in FeS+Na2S2O8 and K2FeO4+Na2S2O8 system were speculated by radical scavenging experiments. The degradation products of tetracycline hydrochloride in K2FeO4+Na2S2O8 system were identified by HPLC-MS. The results showed that FeS and K2FeO4 were the optimal activators of peroxysulphate. When K2FeO4 acted as an activator for peroxymonosulfate, the higher degradation efficiencies of tetracycline hydrochloride were gained in wide concentration range of tetracycline hydrochloride from 10 mg·L−1 to 80 mg·L−1. The co-existing ions of \mathrmSO_4^2- , Cl− and \rmHPO^2-_4 inhibited the degradation of tetracycline hydrochloride. The degradation efficiency reached 99.97% under the optimal conditions in 50 min. \mathrmSO_4^- ·、·OH and lO2 were detected in FeS+Na2S2O8 and K2FeO4+Na2S2O8 system, and ·OH and lO2 mainly accounted for degradation of tetracycline hydrochloride. The degradation of tetracycline hydrochloride via peroxymonosulfate activation with ferrate could happen through eight distinct pathways, which referred to hydrogen extraction, hydrogenation, hydroxylation, demethylation, decarbonylation, dealkylation, deamination, dehydration, oxidation of C═C bond, bond rupture of C─N and ring opening, etc.

       

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