气相测定超纯水中痕量过氧化氢的试验研究

doi:10.19965/j.cnki.iwt.2025-0205

摘要/Abstract

摘要：

在超纯水精处理系统，由真空紫外线产生的痕量H₂O₂会加速下游工艺高分子材料的降解和老化，因此在线测定痕量H₂O₂成为保障系统运行与控制微污染的必要措施。开发了一种基于氢氧合成反应的新型气体计量法，通过测量氢化反应筒入口与出口H₂和O₂的质量浓度，可以分析流经反应筒的超纯水中H₂O₂的浓度。选择载Pd的离子交换树脂作为反应筒填充触媒，H₂和O₂在Pd金属表面高选择性发生多相催化加氢反应。结果表明，样本空白试验的检出限低至0.22 μg/L，对照试验显示测量值与参考值的相对误差在5%之内，具有较强的线性相关性（R ²为0.999 8）。测定方法不仅为半导体高端制程清洗水中微污染物H₂O₂的定量分析提供了有效手段，还为构建深度脱除H₂O₂和DO的新型超纯水制备系统提供了设计方法。

关键词: 超纯水, 过氧化氢, 微污染, 纳米粒子, 气体计量法

Abstract:

In the ultrapure water polishing system, the trace H₂O₂ produced by vacuum ultraviolet radiation will accelerate the degradation and aging of the downstream process polymer materials. Therefore, online determination of trace H₂O₂ has become a necessary measure to ensure system operation and control of micro-contamination. A new gasometric method based on hydrogen-oxygen synthesis reaction was developed, which analyzed the concentration of H₂O₂ in ultrapure water flowing through the reactor by measuring the mass concentration of H₂ and O₂ at the inlet and outlet of the hydrogenation reactor. Specifically, the palladium-loaded ion exchange resin was selected as the catalyst packed in the reactor, and H₂ and O₂ were highly selective for heterogeneous catalytic hydrogenation on the palladium metal surface. The results showed that the detection limit of the sample blank experiment was as low as 0.22 μg/L. The control experiment showed that the relative error between the measured value and the reference value was within 5%, with a strong linear correlation (R ²=0.999 8). The proposed determination method could not only provide an effective approach for the quantitative analysis of micro-contamination H₂O₂ in the ultrapure water of semiconductor advanced processes, but also provide a design method for constructing a new ultrapure water preparation system for deep removal of H₂O₂ and DO.

Key words: ultrapure water, hydrogen peroxide, micro-contamination, nanoparticles, gasometric method

中图分类号:

TU991.2

郑伟, 吴东利, 温鑫, 薛佳卉, 刘澈, 申颖洁. 气相测定超纯水中痕量过氧化氢的试验研究[J]. 工业水处理, 2026, 46(1): 168-177.

Wei ZHENG, Dongli WU, Xin WEN, Jiahui XUE, Che LIU, Yingjie SHEN. Experimental study on the determination of trace hydrogen peroxide in ultrapure water by gasometric method[J]. Industrial Water Treatment, 2026, 46(1): 168-177.

https://www.iwt.cn/CN/Y2026/V46/I1/168

图/表 13

图1 超纯水试验线精处理系统工艺示意

Fig.1 Schematic diagram of polishing system for ultrapure water preparation demonstration line

图2 HPA-DC2分析仪原理示意

Fig.2 Schematic diagram of HPA-DC2 analyzer principle

表1 H₂-O₂合成H₂O过程中存在的几种化学反应的热力学数据

Table 1 Thermodynamic data of several chemical reactions in H₂-O₂ synthesis of H₂O

化学方程式	ΔH/（kJ· mol^-1）	ΔG ^θ/（kJ·mol^-1）	反应式序号
H₂+1/2O₂→H₂O	241.6	-237.2	（1）
H₂+O₂→H₂O₂	135.8	-120.4	（2）
H₂O₂→H₂O+1/2O₂	105.8	-116.8	（3）
H₂O₂+H₂→2H₂O	211.5	-353.8	（4）

图3 Pd金属表面氢氧合成反应的基元步骤

Fig.3 Schematic diagram of the main elementary steps in the hydrogen-oxygen synthesis reaction

图4 氢氧合成反应对H₂O₂浓度测定的影响

Fig.4 Effects of hydrogen-oxygen synthesis reaction on the determination of H₂O₂

图5 H₂吸收量对H₂O₂测定值的影响

Fig.5 Effects of hydrogen absorption on H₂O₂measurement value

表2 高溶氧背景值下不同O₂处理方法获得的H₂O₂测定浓度

Table 2 Determination of H₂O₂ concentration by different treatment methods for O₂ under high DO background values

项目	开启MGA（吸收H₂）	开启MGA（解吸O₂）	关闭MGA
反应筒进口DO₁	7.9 mg/L	112.6 μg/L	7.9 mg/L
反应筒出口DO₂	7.8 mg/L	118.8 μg/L	7.9 mg/L
差值溶氢（Δ［DH］_1-2）	13.39 μg/L	0.10 μg/L	1.54 μg/L
差值溶氧（ΔDO_2-1）	100.16 μg/L	6.21 μg/L	无法获得
H₂O₂测定质量浓度	15.42 μg/L	15.53 μg/L	无法获得

表3 Dextens分析仪溶氢水测定值的离散分析

Table 3 Discrete analysis results of measurement data of dissolved hydrogen water using the Dextens analyzer

H₂质量浓度/（μg·L^-1）	S	RSD/%
0.05	0.011	22.00
0.08	0.009	10.75
0.12	0.010	8.21
0.20	0.014	7.15
0.31	0.018	5.89
0.49	0.019	3.92
0.78	0.016	2.11
1.23	0.024	1.97
1.95	0.044	2.24
3.08	0.045	1.47
4.86	0.054	1.11
7.68	0.071	0.92
12.14	0.102	0.84
19.13	0.151	0.79
29.98	0.225	0.75

图6 空白试样背景噪声分布图

Fig.6 Distribution map of background noise in blank samples

表4 H₂O₂测定值相对误差分析

Table 4 Analysis of relative error in H₂O₂ measurement values

样本编号	1	2	3	4	5	6	7	8
计算质量浓度/（μg·L^-1）	0.00	1.00	3.00	6.00	12.00	24.00	48.00	72.00
响应质量浓度/（μg·L^-1）	0.32	0.82	2.84	5.75	11.65	23.59	45.65	68.18
测量质量浓度/（μg·L^-1）	0.48	1.00	3.09	6.09	12.18	24.50	47.27	70.53
绝对误差（AE）/（μg·L^-1）	0.48	0.00	0.09	0.09	0.18	0.50	-0.73	-1.47
相对误差（RE）		-0.47%	2.85%	1.49%	1.49%	2.10%	-1.51%	-2.04%

图7 不同配制浓度H₂O₂对测量结果的散点回归分析

Fig.7 Scatter regression plots of measurement results with different configurations concentrations of H₂O₂

表5 加标回收率的测定试验

Table 5 Determination test of recovery rate of added standard

测量次数

样品本底值/（μg·L^-1）

加入量/（μg·L^-1）

实测值/

（μg·L^-1）

图8 混流比率对H₂O₂脱除塔出水中H₂O₂和O₂浓度的影响

Fig.8 Influence of mixed flow ratio on the concentrations of H₂O₂ and O₂ in the effluent of H₂O₂ removal tower

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