焦化脱硫废杂盐资源化新技术

doi:10.16085/j.issn.1000-6613.2022-0426

摘要/Abstract

摘要：

由于HPF法焦炉煤气脱硫工艺会产生危害极大的脱硫废杂盐，本文以回避传统提盐法存在的工艺流程长、产品收率低等难题为出发点，提出硫酸铜沉淀硫氰酸根、微纳米气泡氧化硫代硫酸根、石灰表面强制沉淀硫酸根同步制氨的新技术。在实验室配制模拟脱硫废杂盐，优化新技术反应条件，实验表明，当[Cu²⁺]∶[SCN^-]摩尔比为1.2、温度为40℃、初始废液硫氰酸根浓度大于300g/L、反应80min后，SCN^-最佳去除率为99.20%；当pH=1、温度为50℃、初始废液硫代硫酸根浓度为50g/L、反应420min后，S₂O $3 2 -$ 去除率为95.18%；当[Ca²⁺]∶[SO $4 2 -$ ]摩尔比为1.5、反应温度为20℃、初始废液硫酸根浓度为500g/L，并加入5g直径5mm PP球充当研磨介质，反应240min后，SO $4 2 -$ 去除率为91.11%。

关键词: 脱硫废杂盐, 硫氰酸根, 气泡, 硫代硫酸根, 硫酸根

Abstract:

The HPF method will produce extremely hazardous desulfurization waste salt. In this paper, the new technology proposed included copper sulfate precipitation of thiocyanate, oxidation of thiosulfate by micro-nano bubbles, and simultaneous ammonia production by forced precipitation of sulfate by lime surface renewal as a starting point to avoid the drawbacks of long process flow and low product yield of the traditional salt extraction method. Optimization of reaction conditions for the new technology by formulating simulated desulfurization waste salt. Experiments showed that when the molar ratio of [Cu²⁺]∶[SCN^-] was 1.2, the temperature was 40℃, and the initial waste solution thiocyanate concentration was greater than 300g/L, the best removal rate of SCN^- was 99.20% after 80min of reaction. When the pH=1, the temperature was 50℃, the initial waste solution thiosulfate concentration was 50g/L, and the reaction was 420min, the removal efficiency of S₂O $3 2 -$ was 95.18%. When the molar ratio of [Ca²⁺]∶[SO $4 2 -$ ] was 1.5, the reaction temperature was 20℃, the initial sulfate concentration of the waste solution was 500g/L, and 5g of 5mm diameter PP balls were added as grinding media, the SO $4 2 -$ removal rate was 91.11% after 240min.

Key words: desulfurization waste salt, thiocyanate, bubble, thiosulfate, sulfate

中图分类号:

X705

陈磊, 田科, 曾力, 张俊丰, 黄妍, 何峰. 焦化脱硫废杂盐资源化新技术[J]. 化工进展, 2023, 42(1): 480-487.

CHEN Lei, TIAN Ke, ZENG Li, ZHANG Junfeng, HUANG Yan, HE Feng. New technology of coking desulfurization waste salt recycling technology[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 480-487.

图/表 7

图1 硫酸铜沉淀硫氰酸根的影响因素

图2 沉淀物XRD谱图1—[Cu2+]∶[SCN-]摩尔比为1.2的沉淀物；2—反应温度为40℃的沉淀物；3—初始废液SCN-浓度为300g/L的沉淀物；4—CuSCN标准谱图

图3 微纳米气泡氧化硫代硫酸根的影响因素

图4 铜离子、硫氰酸根、硫酸根对硫代硫酸根去除率的影响

图5 石灰表面强制更新去除硫酸根的影响因素

图6 铜离子、硫氰酸根、硫代硫酸根对硫酸根去除率的影响

图7 沉淀物XRD谱图

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