负载型零价过渡金属在双氧化体系下降解高稳定油田污染物

doi:10.19965/j.cnki.iwt.2023-1135

摘要/Abstract

摘要：

过硫酸盐单一氧化技术在过渡金属活化下可有效降解有机污染物，但存在氧化剂投加量过大、pH适用范围窄和金属离子浸出造成二次污染等问题。为了应对上述问题，采用浸渍还原法将过渡金属Cu负载至水滑石（LDHs）载体上，得到高分散负载型零价铜固体催化剂（Cu⁰@LDHs）。通过Cu⁰@LDHs活化过氧化氢-过硫酸钠（H₂O₂-Na₂S₂O₈）双氧化体系降解油田高聚物羟丙基瓜尔胶（HPG）。对反应条件的优化结果表明，在pH为3~11的范围内，H₂O₂-Na₂S₂O₈双氧化体系对HPG均能保持较高的降解效果，25 min内降解率皆高于76.30%，且120 min后COD去除率最高可达93.91%。Cu⁰@LDHs循环再生5次后仍能保持良好的催化活性，其对HPG的降解效率能保持在80%以上。在此过程中，·OH和SO₄ ^·-是主要活性物种并且二者间存在协同作用。反应前后Cu⁰@LDHs的XRD、SEM、BET表征结果表明，该催化剂所表现出的高活性主要归结于高度分散在水滑石载体表面的Cu⁰具有良好的活性以及稳定性。

关键词: 过氧化氢-过硫酸钠, 双氧化体系, 羟丙基瓜尔胶, 负载型零价金属催化剂

Abstract:

The peroxydisulfate single-oxidation technology can effectively degrade organic pollutants under the activation of transition metals. However, there are issues such as excessive oxidant dosage, narrow pH range, and secondary pollution caused by metal ions leaching. To address these problems, a highly dispersed supported zero-valent copper catalyst(Cu⁰@LDHs) was obtained by loading transition metal copper onto hydrotalcite(LDHs) carriers by the impregnation-reduction method. Cu⁰@LDHs was used to activate the hydrogen peroxide-sodium persulfate(H₂O₂-Na₂S₂O₈) dual-oxidation system for the degradation of oilfield hydroxypropyl guar gum (HPG). Based on the optimization of reaction conditions, it was found that within the pH range of 3 to 11, the H₂O₂-Na₂S₂O₈ dual-oxidation system still maintained a high degradation effect on HPG, with degradation rates higher than 76.30% at 25 min, and COD removal rate of 93.91% after 120 min. Cu⁰@LDHs maintained good catalytic activity even after 5 cycles of regeneration, with HPG degradation efficiency of above 80%. During this process, ·OH and SO₄ ^·- were identified as the main active species, and there was a synergistic effect between them. XRD, SEM, and BET characterization of Cu⁰@LDHs before and after the reaction indicated that the high activity of the catalyst was mainly attributed to the highly dispersed Cu⁰ on the surface of the hydrotalcite carrier, which exhibited excellent activity and stability.

Key words: hydrogen peroxide-sodium persulfate, dual-oxidation system, hydroxypropyl guar gum, supported zero-valent metal catalyst

中图分类号:

X741

白兵兵, 杨晨晔, 豆龙龙, 周瑞, 张洁, 汤颖. 负载型零价过渡金属在双氧化体系下降解高稳定油田污染物[J]. 工业水处理, 2024, 44(12): 123-130.

Bingbing BAI, Chenye YANG, Longlong DOU, Rui ZHOU, Jie ZHANG, Ying TANG. The degradation of highly stable oilfield pollutants by supported zero-valent transition metals in a dual-oxidation system[J]. Industrial Water Treatment, 2024, 44(12): 123-130.

https://www.iwt.cn/CN/Y2024/V44/I12/123

图/表 13

图1 不同氧化体系对HPG的降解效果

Fig.1 Effect of different oxidation systems on the degradation of HPG

图2 催化剂种类对降解效果的影响

Fig.2 Effect of catalyst type on degradation

图3 氧化剂投加量对降解效果的影响

Fig.3 Effect of oxidant dosage on degradation

图4 催化剂投加量对降解效果的影响

Fig.4 Effect of catalyst dosage on degradation

图5 pH对降解效果的影响

Fig.5 Effect of pH on degradation

图6 经H₂O₂-Na₂S₂O₈双氧化体系降解前后COD的变化

Fig.6 Changes of COD before and after degradation in the H₂O₂-Na₂S₂O₈ double oxidation system

图7 Cu⁰@LDHs的再生效果

Fig.7 Regeneration effect of Cu⁰@LDHs

图8 活性物种捕获实验

Fig.8 Active species capture experiments

图9 Cu⁰@LDHs反应前后的XRD

Fig.9 XRD patterns of Cu⁰@LDHs before and after reaction

图10 LDHs（a）、反应前Cu⁰@LDHs（b）、反应后Cu⁰@LDHs（c）的SEM

Fig.10 SEM of LDHs（a），Cu⁰@LDHs before reaction（b）， Cu⁰@LDHs after reaction（c）

表1 催化剂的孔结构性质

Table 1 Pore structure properties of catalysts

催化剂

比表面积/

（cm²·g^-1）

孔体积/

（cm³·g^-1）

图11 不同催化剂的氮气吸附-脱附等温线

Fig.11 Nitrogen adsorption-desorption isotherms of different catalysts

图12 Cu⁰@LDHs活化H₂O₂-Na₂S₂O₈双氧化体系降解HPG机理

Fig.12 Mechanism of HPG degradation by Cu⁰@LDHs activated H₂O₂-Na₂S₂O₈ double oxidation system

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