Experimental study on oxidation characteristics of sulfite under high salt water condition

doi:10.11949/j.issn.0438-1157.20181237

Abstract

Abstract:

Under the background of “Water pollution control action plan”, zero discharge of desulfurization wastewater has become the development trend of the era. The use of flue gas waste heat concentrated desulfurization wastewater to reduce desulfurization wastewater has attracted industry attention. During the pre-concentration of the flue gas, less SO₂ is transferred to the liquid phase to produce SO₃ ^2-, HSO₃ ^-, SO₄ ^2-. The sulfite nature is unstable and subsequent treatment will be affected. To explore the oxidation characteristics of sulfite under high salt water conditions in this process, the oxidation characteristics of sulfites were studied by oxidation-reduction potential(ORP) and dissolved oxygen. The study found that flue gas oxygen content promoted sulfite oxidation. The concentration ratio of desulfurization wastewater is positively correlated with the ORP value, which is beneficial to the oxidation of sulfite. Better sulfite oxidation during pre-concentration of flue gas, the oxidation rate can reach 94.7%, and no forced oxidation is required. This study is of great significance for controlling fouling during flue gas enrichment and reducing adverse effects on subsequent treatment.

Key words: oxidation of sulfite, desulfurization wastewater, ORP, dissolved oxygen

摘要：

在“水十条”背景下，脱硫废水零排放已是大势所趋，利用烟气余热浓缩脱硫废水将脱硫废水减量化引起业内关注。在烟气预浓缩过程中有较少的SO₂转移至液相，产生SO₃ ^2-、HSO₃ ^-、SO₄ ^2-。其中亚硫酸盐性质不稳定，会影响后续处理。为探究此过程中高盐水条件下亚硫酸盐的氧化特性，通过氧化还原电位（ORP）和溶解氧联合监控，对亚硫酸盐的氧化特性进行研究。研究发现：烟气含氧量促进亚硫酸盐氧化；脱硫废水浓缩倍率同ORP值呈正相关，有利于亚硫酸盐的氧化；烟气预浓缩过程中亚硫酸盐氧化情况较好，氧化率可达94.7%，不需要进行强制氧化。此研究对烟气浓缩过程中控制结垢及减少对后续处理的不良影响具有重要的价值。

关键词: 亚硫酸盐氧化, 脱硫废水, 氧化还原电位, 溶解氧

CLC Number:

X 703

Shuangchen MA, Zixuan FAN, Zhongcheng WAN, Jianing CHEN, Jingrui ZHANG, Caini MA. Experimental study on oxidation characteristics of sulfite under high salt water condition[J]. CIESC Journal, 2019, 70(5): 1964-1972.

马双忱, 范紫瑄, 万忠诚, 陈嘉宁, 张净瑞, 马采妮. 高盐水条件下亚硫酸盐氧化特性实验研究[J]. 化工学报, 2019, 70(5): 1964-1972.

Figures/Tables 12

Fig.1 Schematic diagram of flue gas desulfurization and mass transfer

Table 1 Experimental agents

药品名	纯度	生产厂家
硫酸	AR	天津（香港）新通精细化工有限公司
碘化钾	AR	天津（香港）新通精细化工有限公司
氯化钠	AR	天津（香港）新通精细化工有限公司
氯化镁	AR	天津（香港）新通精细化工有限公司
三氯化铁	AR	天津市北方天医化学试剂厂
硫代硫酸钠标准溶液（0.1 mol/L）		天津华特化研科技有限公司
盐酸		天津（香港）新通精细化工有限公司
铬黑T		天津（香港）新通精细化工有限公司
可溶性淀粉		天津市光复精细化工研究所
SO₂	99.995%	保定华威气体科技有限公司
N₂	99.996%	保定华威气体科技有限公司
O₂	99.9%	保定华威气体科技有限公司

Fig.2 Diagram of experimental device

Fig.3 Each data in different oxygen contents in flue gas

Table 2 Definition and calculation of parameters related to titration experiments

项目	定义	参数
$S O 4 2 -$ /(mg/L)[border:border-top:solid;]	$C 1 = (V 2 - V 1) × 0.010 V × 96.06 × 1000$ [border:border-top:solid;]	V ₁——水样测定所耗EDTA标准滴定溶液的用量，ml V ₂——滴定空白所耗EDTA标准滴定溶液的用量，ml V——所取水样量,ml 0.010——EDTA标准滴定溶液的浓度,mol/L 96.06——硫酸根（SO₄ ^2－）摩尔质量，g/mol
$S O 3 2 -$ /(mg/L)	$C 2 = (V 2 - V 1) × 0.05 × 40 V × 1000$	V ₁——试样消耗硫代硫酸钠标准溶液量，ml V ₂——蒸馏水消耗硫代硫酸钠标准溶液量，ml 0.05——硫代硫酸钠标准溶液浓度，mol/L V ——试样体积，ml
S元素/mg	$m = C 1 × 0.4 × 3296 + C 2 × 0.4 × 3280$	0.4——烟气模拟实验所用到去离子水体积，L 32/96—— $S O 4 2 -$ 中硫元素所占比例 32/80— $S O 3 2 -$ 中硫元素所占比例
溶解率/%	$ω = m 55 × 100 %$	55——烟气模拟实验中通入SO₂总质量，mg
$S O 3 2 -$ 氧化率/%	$α = C 1 × 0.4 × 3296 / m$

Table 2 Definition and calculation of parameters related to titration experiments

项目	定义	参数
$S O 4 2 -$ /(mg/L)[border:border-top:solid;]	$C 1 = (V 2 - V 1) × 0.010 V × 96.06 × 1000$ [border:border-top:solid;]	V ₁——水样测定所耗EDTA标准滴定溶液的用量，ml V ₂——滴定空白所耗EDTA标准滴定溶液的用量，ml V——所取水样量,ml 0.010——EDTA标准滴定溶液的浓度,mol/L 96.06——硫酸根（SO₄ ^2－）摩尔质量，g/mol
$S O 3 2 -$ /(mg/L)	$C 2 = (V 2 - V 1) × 0.05 × 40 V × 1000$	V ₁——试样消耗硫代硫酸钠标准溶液量，ml V ₂——蒸馏水消耗硫代硫酸钠标准溶液量，ml 0.05——硫代硫酸钠标准溶液浓度，mol/L V ——试样体积，ml
S元素/mg	$m = C 1 × 0.4 × 3296 + C 2 × 0.4 × 3280$	0.4——烟气模拟实验所用到去离子水体积，L 32/96—— $S O 4 2 -$ 中硫元素所占比例 32/80— $S O 3 2 -$ 中硫元素所占比例
溶解率/%	$ω = m 55 × 100 %$	55——烟气模拟实验中通入SO₂总质量，mg
$S O 3 2 -$ 氧化率/%	$α = C 1 × 0.4 × 3296 / m$

Table 3 Desulfurization wastewater quality

检测项目	检测结果		平均值
pH	8.02	8.03	8.025
化学需氧量/(mg/L)	502.08	585.76	543.92
悬浮物/(mg/L)	462.67	572.67	517.67
铁/(mg/L)	0.09	0.43	0.26
铜/(mg/L)	0.02	0.03	0.025
锌/(mg/L)	未检出	未检出
镍/(mg/L)	0.03	0.01	0.02
锰/(mg/L)	7.18	1.59	4.385
铬/(μg/L)	0.49	1.25	0.87
镉/(μg/L)	0.66	0.35	0.505
铅/(μg/L)	10.7	7.27	8.985
汞/(μg/L)	0.63	0.63	0.63
砷/(μg/L)	未检出	未检出
氟离子/(mg/L)	65.82	48.21	57.015
氯离子/(mg/L)	18753.71	14119.62	16436.67
硫酸盐/(mg/L)	12495.05	8824.2	10659.63

Fig.4 ORP of desulfurization wastewater with different concentration times changes with time

Fig.5 Change of ORP with time in constant-price salt NaCl system

Fig.6 Variation of ORP over time in variable salt FeCl3 system

Fig.7 Variation of dissolved oxygen with time in different concentration multiple desulfurization wastewater

Fig.8 Oxygen total mass transfer coefficient of different concentration multiple desulfurization wastewater

Fig.9 Changes in sulfite concentration at different concentration times

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