Fe2+/Mn2+活化亚硫酸盐降解盐酸土霉素的机理研究

doi:10.11949/0438-1157.20231088

摘要/Abstract

摘要：

盐酸土霉素常被用于治疗畜禽疾病，但是它不能被畜禽完全代谢，残留的盐酸土霉素进入水体危害水环境的健康。铁锰作为常见的过渡金属，通常以二价态活化亚硫酸盐来降解有机污染物，反应条件温和、操作简单，但是单独的二价铁与二价锰氧化还原电势低，活化亚硫酸盐效果较差。本研究采用Fe²⁺/Mn²⁺共活化Na₂SO₃降解水中的盐酸土霉素，考察药剂用量、pH、溶解氧、氯离子、碳酸根及腐殖酸对Fe²⁺/Mn²⁺/Na₂SO₃体系降解盐酸土霉素的影响；通过焦磷酸盐实验、自由基淬灭实验和EPR实验分析Fe²⁺/Mn²⁺/Na₂SO₃体系中的活性物种；利用紫外可见光谱、傅里叶红外光谱、气相色谱-质谱联用仪识别盐酸土霉素的官能团及其降解中间产物的变化，推断盐酸土霉素的降解途径。结果表明：当Fe²⁺/Mn²⁺/Na₂SO₃浓度比为1∶4∶20（浓度分别为0.1、0.4和2 mmol/L）时，在反应45 min、pH为9.0条件下，盐酸土霉素的去除率和矿化率最高，分别达到94%和49%。随着溶解氧从9 mg/L下降至1.89 mg/L，盐酸土霉素去除率从94%下降至17%；氯离子、腐殖酸和碳酸根均对盐酸土霉素的降解产生抑制作用。Mn（Ⅲ）和 $S O_{4}^{• -}$ 是降解盐酸土霉素的主要活性氧化剂，盐酸土霉素的降解经过电子转移、开环与酰基化等过程。

关键词: Fe²⁺/Mn²⁺/Na₂SO₃体系, 盐酸土霉素, 活化, 自由基, 氧化

Abstract:

Oxytetracycline hydrochloride is often used in the treatment of livestock and poultry diseases, however, it cannot be completely metabolized. The residual oxytetracycline hydrochloride entering water poses a threat to the health of water environment. Bivalent iron and bivalent manganese, as common transition metals, can usually activate sulfides to degrade organic pollutants. Its reaction conditions are mild and the operation is simple. However, the redox potential of single divalent iron and single divalent manganese is low, and the performance of activating sulfide is poor. In this experiment, Fe²⁺/Mn²⁺coactivating Na₂SO₃ was used to degrade oxytetracycline hydrochloride in water. The effects of reagent dosage, pH, dissolved oxygen, chloride ion, carbonate ions and humic acid on the degradation of oxytetracycline hydrochloride in the Fe²⁺/Mn²⁺/Na₂SO₃ system were investigated. The oxidizing active substances in the Fe²⁺/Mn²⁺/Na₂SO₃ system were analyzed using pyrophosphate test, free radical quenching test and EPR experiment. The changes of functional groups and degradation intermediates of oxytetracycline hydrochloride were identified by UV-Vis spectroscopy, Fourier transform infrared spectroscopy and gas chromatography-mass spectrometry, and the degradation pathway of oxytetracycline hydrochloride was inferred. The results showed that when the concentration ratio of Fe²⁺/Mn²⁺/Na₂SO₃ was 1∶4∶20 (the concentrations were 0.1, 0.4 and 2 mmol/L, respectively),the reaction time was 45 min and the pH was 9.0, removal efficiency and mineralization rate of oxytetracycline hydrochloride were the highest, and up to 94% and 49%, respectively. When dissolved oxygen decreased from 9 mg/L to 1.89 mg/L, removal efficiency of oxytetracycline hydrochloride decreased from 94% to 17%. Chlorine ions, humic acids and carbonate ions all had inhibitory effects on the degradation of oxytetracycline hydrochloride. Mn (Ⅲ) and $S O_{4}^{• -}$ were main active oxidants for the degradation of oxytetracycline hydrochloride, and the degradation underwent the processes of electron transfer, ring opening and acylation.

Key words: Fe²⁺/Mn²⁺/sulfite system, oxytetracycline hydrochloride, activation, radical, oxidation

中图分类号:

X 523

贾艳萍, 阴东旭, 徐静仪, 张海丰, 张兰河. Fe²⁺/Mn²⁺活化亚硫酸盐降解盐酸土霉素的机理研究[J]. 化工学报, 2024, 75(2): 647-658.

Yanping JIA, Dongxu YIN, Jingyi XU, Haifeng ZHANG, Lanhe ZHANG. Mechanism study of oxytetracycline hydrochloride degradation through activating sulfite by Fe²⁺/Mn²⁺[J]. CIESC Journal, 2024, 75(2): 647-658.

图/表 11

图1 盐酸土霉素结构示意图

Fig.1 Schematic diagram of the structure of oxytetracycline hydrochloride

图2 Fe2+/Mn2+/Na2SO3体系反应装置示意图

Fig.2 Schematic diagram of reaction setup of Fe2+/Mn2+/sulfite system

图3 在不同反应体系中盐酸土霉素浓度、pH和矿化率的变化

Fig.3 The changes of oxytetracycline hydrochloride concentration, pH and mineralization rate in different reaction systems

图4 焦磷酸盐对照实验

Fig.4 Comparison diagram of pyrophosphate experiment

图5 pH和DO对盐酸土霉素降解效果的影响

Fig.5 Effect of pH and DO on the degradation of oxytetracycline hydrochloride

图6 氯离子、腐殖酸与碳酸根对盐酸土霉素降解效果的影响

Fig.6 Effects of chloride ions, humic acid and carbonate on the degradation of oxytetracycline hydrochloride

图7 Fe2+/Mn2+/Na2SO3体系活性物质鉴定

Fig.7 Identification of active substance in Fe2+/Mn2+/Na2SO3 system

图8 盐酸土霉素的紫外可见光谱和红外光谱

Fig.8 UV-Vis and IR spectra of oxytetracycline hydrochloride

图9 进水和出水气-质联用谱图

Fig.9 Gas-mass spectrometry of influent and effluent

表1 OTH降解过程的中间产物

Table 1 Intermediate products in the degradation process of OTH

产物	保留时间/min	m/z	分子式	产物	保留时间/min	m/z	分子式
1	4.295	106	C₈H₁₀	10	9.585	138	C₈H₁₀O₂
2	4.900	108	C₇H₈O	11	13.525	206	C₁₄H₂₂O
3	5.955	144	C₈H₁₆O₂	12	18.705	278	C₁₆H₂₂O₄
4	6.385	134	C₁₀H₁₄	13	20.050	196	C₁₀H₁₂O₄
5	7.260	108	C₇H₈O	14	23.385	154	C₉H₁₄O₂
6	7.360	136	C₁₀H₁₆	15	24.215	424	C₂₉H₄₄O₂
7	7.940	152	C₁₀H₁₆O	16	24.640	208	C₁₃H₂₀O₂
8	8.975	134	C₉H₁₀O	17	26.645	180	C₁₁H₁₆O₂
9	9.150	138	C₉H₁₄O

图10 盐酸土霉素的降解途径

Fig.10 Degradation pathway of oxytetracycline hydrochloride

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Fe²⁺/Mn²⁺活化亚硫酸盐降解盐酸土霉素的机理研究

Mechanism study of oxytetracycline hydrochloride degradation through activating sulfite by Fe²⁺/Mn²⁺

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