Kinetics and role of active chlorine species in the degradation of carbamazepine by UV combined with chlorine

doi:10.16085/j.issn.1000-6613.2024-0742

Abstract

Abstract:

Carbamazepine (CBZ) is a widely utilized neuropathic drug but is recalcitrant in the aquatic environment. This study systematically explored the removal efficiency of CBZ in the UV/chlorine process. The results demonstrated that the degradation process of CBZ in the UV/chlorine system adhered to the pseudo-first-order kinetic model. As the pH was increased from 5 to 11, there was a decrease in reaction rate constant from 0.8259min^-1 to 0.0343min^-1, which might be attributed to variations in free radical species and apparent quantum yield. Free radical capture experiments revealed Cl· and ·OH as the primary species responsible for CBZ degradation, with steady-state kinetic modeling confirming their highest individual contribution among all free radicals. However, under specific conditions, other active species might surpass Cl· or ·OH in terms of individual contribution. Investigation into the impact of actual water matrix on CBZ degradation rate indicated that natural organic matter (NOM) significantly inhibited CBZ degradation due to internal filtration effects and competitive effect, while HCO₃^- only slightly hindered CBZ degradation and Cl^- had minimal influence on CBZ degradation process. UPLC-MS/MS detection identified 14 different degradation products, enabling us to propose a comprehensive pathway for CBZ degradation within the UV/chlorine system involving hydroxylation, deamination, multi-component recombination, double bond addition and C—N bond breaking processes. In conclusion, it could be concluded that UV/chlorine process was an effective water treatment technology to solve the problem of pharmaceutical wastewater pollution.

Key words: UV/chlorine, carbamazepine, advanced oxidation, steady-state kinetic prediction, individual contribution, transformation products

摘要：

卡马西平（carbamazepine，CBZ）是一种应用广泛的神经性药物，但其在水生环境中具有抗逆性。本研究系统性地分析了UV/氯工艺对CBZ的去除效能。研究结果表明CBZ在UV/氯体系内的降解过程符合假一级动力学模型，当pH从5增加到11时，反应速率常数从0.8259min^-1降低到0.0343min^-1，这可能与自由基种类的更替和表观量子产率的变化有关。自由基捕获实验结果表明Cl·和·OH是CBZ降解的主要物种，稳态动力学模型的计算结果也证实了Cl·和·OH是单体贡献最高的两种自由基；但在特定条件下，其他活性物质的单体贡献可能会超过Cl·或·OH。在考察实际水基质对CBZ降解速率的影响研究中发现天然有机物（NOM）的内过滤效应和竞争效应可以导致CBZ的降解被显著抑制，HCO₃^-则会轻度抑制CBZ降解，而Cl^-对CBZ的降解影响最小。通过UPLC-MS/MS检测获得14种不同的降解产物，并提出了CBZ在UV/氯体系内的降解路径，CBZ的降解主要包括了羟基化、脱氨、多组分重组、双键加成和C—N键断裂过程。综上可以推断UV/氯工艺是一种可以有效解决药物废水污染问题的水处理技术。

关键词: UV/氯, 卡马西平, 高级氧化, 稳态动力学预测, 单体贡献, 转化产物

CLC Number:

X522

MA Bingrui, DUAN Xuebin, CHEN Cheng, WANG Songxue, CHEN Lin, WANG Shoucheng, LI Jincheng, WU Guizhi, YAN Boyin. Kinetics and role of active chlorine species in the degradation of carbamazepine by UV combined with chlorine[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 4212-4222.

马丙瑞, 段学斌, 陈澄, 王松雪, 陈琳, 王守成, 李金成, 武桂芝, 闫博引. UV-氯联用降解卡马西平动力学及活性氯物种的功能[J]. 化工进展, 2025, 44(7): 4212-4222.

Figures/Tables 11

编号	反应	k/L·mol^-1·s^-1	编号	反应	k /L·mol^-1·s^-1
1	HClO $→ h v$ Cl·+·OH	ε=59L/(mol·cm) φ=1.45L/(mol·Einstein^①)	18	$C l 2 • -$ +OCl^- $→$ ClO·+2Cl^-	k₁₈=5.4×10⁸
1	HClO $→ h v$ Cl·+·OH	ε=59L/(mol·cm) φ=1.45L/(mol·Einstein^①)	19	O^·-+H₂O $→$ ·OH+OH^-	k₁₉=1.8×10⁶
2	ClO^- $→ h v$ Cl·+O·^-	ε=66L/(mol·cm) φ=0.97L/(mol·Einstein^①)	20	ClOH^·- $→$ OH·+Cl^-	k₂₀=6.1×10⁹s^-1
2	ClO^- $→ h v$ Cl·+O·^-	ε=66L/(mol·cm) φ=0.97L/(mol·Einstein^①)	21	ClOH^·- $→$ Cl·+OH^-	k₂₁=23s^-1
3	HClO $⇌$ H⁺+ClO^-	pK_a=7.5	22	ClOH^·-+H⁺ $→$ Cl·+H₂O	k₂₂=2.1×10¹⁰
4	OH+Cl^- $→$ ClOH^·-	k₄=4.3×10⁹	23	ClOH^·-+Cl^- $→$ $C l 2 • -$ +H₂O	k₂₃=1.0×10⁵
5	·OH+OH^- $→$ O^·-+H₂O	k₅=1.3×10¹⁰	24	·OH+CBZ $→$ 产品	k₂₄=8.2×10⁹
6	·OH+HOCl $→$ ClO·+H₂O	k₆=2.0×10⁹	25	Cl·+CBZ $→$ 产品	k₂₅=3.3×10¹⁰
7	·OH+OCl $→$ ClO·+OH^-	k₇=8.8×10⁹	26	ClO·+CBZ $→$ 产品	k₂₆=7.7×10⁸
8	Cl·+HOCl $→$ ClO·+H⁺+Cl^-	k₈=3.0×10⁹	27	$C l 2 • -$ +CBZ $→$ 产品	k₂₇=9.8×10⁷
9	Cl·+OCl^- $→$ Cl^-+ClO·	k₉=8.2×10⁹	28	·OH+HCO $3 -$ $→$ H₂O+CO₃^·-	k₂₈=8.5×10⁶
10	Cl·+Cl· $→$ Cl₂	k₁₀=1.0×10⁸	29	Cl·+HCO $3 -$ $→$ H₂O+CO₃^·-	k₂₉=2.2×10⁸
11	Cl·+Cl^- $→$ $C l 2 • -$	k₁₁=6.5×10⁹	30	$C l 2 • -$ +HCO $3 -$ $→$ 2Cl^-+H⁺+CO₃^·-	k₃₀=8.0×10⁷
12	Cl·+OH^- $→$ ClOH^·-	k₁₂=1.8×10¹⁰	31	Cl₃^·-+CBZ $→$ 产品	k₃₁=6.6×10⁶
13	ClO·+ClO· $→$ Cl₂O₂	k₁₃=2.5×10⁹	32	·OH+NOM $→$ 产品	k₃₂=2.5×10⁴L/(mgC·s)
14	2ClO·+OH^- $→$ OCl^-+H⁺+ClO₂	k₁₄=2.5×10⁹	33	Cl·+CBZ $→$ 产品	k₃₃=1.3×10⁸
15	ClO·+·OH $→$ OCl₂^-+H⁺	k₁₅=1.0×10⁹	34	ClO·+NOM $→$ 产品	k₃₄=4.6×10⁴L/(mgC·s)
16	$C l 2 • -$ $→$ Cl·+Cl^-	k₁₆=1.1×10⁵s^-1	35	OH+H₂PO₄^- $→$ H₂O+HPO₄^·-	k₃₅=2×10⁴
17	$C l 2 • -$ +OH^- $→$ ClOH^·-+Cl^-	k₁₇=4.5×10⁷	36	·OH+HCO₄^2- $→$ OH^-+HPO₄^·-	k₃₆=1.5×10⁵

编号	反应	k/L·mol^-1·s^-1	编号	反应	k /L·mol^-1·s^-1
1	HClO $→ h v$ Cl·+·OH	ε=59L/(mol·cm) φ=1.45L/(mol·Einstein^①)	18	$C l 2 • -$ +OCl^- $→$ ClO·+2Cl^-	k₁₈=5.4×10⁸
1	HClO $→ h v$ Cl·+·OH	ε=59L/(mol·cm) φ=1.45L/(mol·Einstein^①)	19	O^·-+H₂O $→$ ·OH+OH^-	k₁₉=1.8×10⁶
2	ClO^- $→ h v$ Cl·+O·^-	ε=66L/(mol·cm) φ=0.97L/(mol·Einstein^①)	20	ClOH^·- $→$ OH·+Cl^-	k₂₀=6.1×10⁹s^-1
2	ClO^- $→ h v$ Cl·+O·^-	ε=66L/(mol·cm) φ=0.97L/(mol·Einstein^①)	21	ClOH^·- $→$ Cl·+OH^-	k₂₁=23s^-1
3	HClO $⇌$ H⁺+ClO^-	pK_a=7.5	22	ClOH^·-+H⁺ $→$ Cl·+H₂O	k₂₂=2.1×10¹⁰
4	OH+Cl^- $→$ ClOH^·-	k₄=4.3×10⁹	23	ClOH^·-+Cl^- $→$ $C l 2 • -$ +H₂O	k₂₃=1.0×10⁵
5	·OH+OH^- $→$ O^·-+H₂O	k₅=1.3×10¹⁰	24	·OH+CBZ $→$ 产品	k₂₄=8.2×10⁹
6	·OH+HOCl $→$ ClO·+H₂O	k₆=2.0×10⁹	25	Cl·+CBZ $→$ 产品	k₂₅=3.3×10¹⁰
7	·OH+OCl $→$ ClO·+OH^-	k₇=8.8×10⁹	26	ClO·+CBZ $→$ 产品	k₂₆=7.7×10⁸
8	Cl·+HOCl $→$ ClO·+H⁺+Cl^-	k₈=3.0×10⁹	27	$C l 2 • -$ +CBZ $→$ 产品	k₂₇=9.8×10⁷
9	Cl·+OCl^- $→$ Cl^-+ClO·	k₉=8.2×10⁹	28	·OH+HCO $3 -$ $→$ H₂O+CO₃^·-	k₂₈=8.5×10⁶
10	Cl·+Cl· $→$ Cl₂	k₁₀=1.0×10⁸	29	Cl·+HCO $3 -$ $→$ H₂O+CO₃^·-	k₂₉=2.2×10⁸
11	Cl·+Cl^- $→$ $C l 2 • -$	k₁₁=6.5×10⁹	30	$C l 2 • -$ +HCO $3 -$ $→$ 2Cl^-+H⁺+CO₃^·-	k₃₀=8.0×10⁷
12	Cl·+OH^- $→$ ClOH^·-	k₁₂=1.8×10¹⁰	31	Cl₃^·-+CBZ $→$ 产品	k₃₁=6.6×10⁶
13	ClO·+ClO· $→$ Cl₂O₂	k₁₃=2.5×10⁹	32	·OH+NOM $→$ 产品	k₃₂=2.5×10⁴L/(mgC·s)
14	2ClO·+OH^- $→$ OCl^-+H⁺+ClO₂	k₁₄=2.5×10⁹	33	Cl·+CBZ $→$ 产品	k₃₃=1.3×10⁸
15	ClO·+·OH $→$ OCl₂^-+H⁺	k₁₅=1.0×10⁹	34	ClO·+NOM $→$ 产品	k₃₄=4.6×10⁴L/(mgC·s)
16	$C l 2 • -$ $→$ Cl·+Cl^-	k₁₆=1.1×10⁵s^-1	35	OH+H₂PO₄^- $→$ H₂O+HPO₄^·-	k₃₅=2×10⁴
17	$C l 2 • -$ +OH^- $→$ ClOH^·-+Cl^-	k₁₇=4.5×10⁷	36	·OH+HCO₄^2- $→$ OH^-+HPO₄^·-	k₃₆=1.5×10⁵

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