Theoretical study on potentiometric analysis applied to oxidation control of wet desulfurization slurry

FANG Xiaowei; HE Yudong; HUAN Xuanzhou; LI Xinghua; TAO Ming; WANG Ze

doi:10.19666/j.rlfd.202212201

English

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Theoretical study on potentiometric analysis applied to oxidation control of wet desulfurization slurry

Thermal Power Generation Vol. 52, Issue 8, Pages: 81-86(2023)

更新时间：2025-09-28

- Theoretical study on potentiometric analysis applied to oxidation control of wet desulfurization slurry
- 作者机构：
  
  1. 西安热工研究院有限公司
  2. 中国科学院过程工程研究所
- 作者简介：
- 基金信息：
- DOI：10.19666/j.rlfd.202212201
  CLC： X773
- Published：2023
- 稿件说明：
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FANG Xiaowei, HE Yudong, HUAN Xuanzhou, et al. Theoretical study on potentiometric analysis applied to oxidation control of wet desulfurization slurry[J]. Thermal Power Generation, 2023, 52(8): 81-86.
DOI：

FANG Xiaowei, HE Yudong, HUAN Xuanzhou, et al. Theoretical study on potentiometric analysis applied to oxidation control of wet desulfurization slurry[J]. Thermal Power Generation, 2023, 52(8): 81-86. DOI： 10.19666/j.rlfd.202212201.

摘要

氧化还原电位（ORP）分析法已逐渐应用于石灰石-石膏湿法脱硫浆液氧化控制领域，但目前缺乏相应的理论研究。首先基于密度泛函理论及酸解离平衡计算得到了浆液氧化过程中各电对标准电极电位E~θ(O_2(aq))/H_2O及E~θ(S(Ⅵ)/S(Ⅳ))，并获得了各反应的标准电动势；然后，以浆液氧化主反应2HSO_3~-+O_2→2H~++2SO_4~(2–)为基础，基于Nernst方程建立反应体系电动势理论计算模型，并通过实验研究发现，反应体系电动势实测值ORP与理论计算值EMF相差较大，表明Nernst方程不适用于浆液氧化体系；最后，通过逐步回归法建立了实测ORP与pH值、ln(c(Ca~(2+)))、ln(c(HSO_3~-))及ln(c(O_2))之间良好的多元线性拟合关系，该结果表明浆液氧化进程不仅与ORP有关，同时受pH值、钙离子及溶解氧浓度控制，因此以ORP为湿法脱硫浆液氧化控制指标时，应同时兼顾pH值、钙离子及溶解氧浓度的影响。

Abstract

Oxidation reduction potential(ORP) analysis method has been gradually used in the field of limestonegypsum wet desulfurization slurry oxidation control

but there is a lack of corresponding theoretical research. In this paper

firstly

the standard electrode potentials of each pair in the slurry oxidation process

E~θ(O_2(αq))/H_2O and E~θ(S(Ⅵ)/S(Ⅳ))

were obtained based on density functional theory and acid dissociation equilibrium calculation;and the standard electromotive force of each reaction was calculated. Then

based on the main reaction of slurry oxidation

2HSO_3~–+O_2→2H~++2SO_4~(2–)

the theoretical calculation model of the electromotive force of the reaction system was established by the Nernst equation. It was found that the measured ORP of the electromotive force of the reaction system was quite different from that by theoretical calculation

which meant the Nernst equation was not suitable for the slurry oxidation system. Finally

a good multivariate linear fitting relationship between the measured ORP

ln(c(Ca~(2+)))

ln(c(HSO_3~–)) and ln(c(O_2)) was established by the stepwise regression. The results indicated that the process of slurry oxidation was not only related to the single indicator of ORP

but also controlled by pH

calcium ion and dissolved oxygen concentration. When ORP is used as the oxidation control indicator of wet desulfurization slurry

the influence of pH

calcium ion and dissolved oxygen concentration should be taken into account at the same time.

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