碱辅助四氧化三锰降解磷酸三丁酯及磷元素回收研究

doi:10.11949/0438-1157.20230574

摘要/Abstract

摘要：

磷酸三丁酯（TBP）有机危废的无机化和资源化处置技术是一项重要的环保需求。基于化学链燃烧（CLC）的原理和TBP碱水解的机理构建碱辅助Mn₃O₄热氧化降解TBP的反应体系，开发TBP无机化同步磷元素资源化的新工艺。在TBP、NaOH、Mn₃O₄为1 ml∶6 g∶13 g的较优比例下，220℃反应3 h后，磷元素从TBP向无机相转移的转化率可达到77.47%，同时TBP降解后气相产物中非甲烷总烃（NMHC）浓度仅为27.28 mg/m³，低于相关环境标准限值。采用乙醇沉淀法分离回收无机磷产物，通过X射线衍射（XRD）分析得知，含磷产物的主要成分为Na₃PO₄、NaPO₃、Na₂HPO₄和Na₃PO₄·8H₂O。根据TBP降解中间产物的质谱分析结果提出了TBP降解和磷元素迁移的可能路径。电子顺磁共振（EPR）分析证实羟基自由基（·OH）和超氧自由基（ $\cdot O_{2}^{-}$ ）对TBP的降解过程具有重要的促进作用。

关键词: 磷酸三丁酯, 催化, 自由基, 废物处理, 回收

Abstract:

The inorganic and resource disposal technology of tributyl phosphate (TBP) organic hazardous waste is an important environmental protection demand. Based on the principle of chemical looping combustion (CLC) and the mechanism of alkaline hydrolysis of TBP, a reaction system of alkali-assisted thermal oxidation TBP by Mn₃O₄ was constructed. A process of TBP degradation with simultaneous phosphorus recovery was developed. Under an optimal feed ratio of TBP, NaOH and Mn₃O₄ (1 ml∶6 g∶13 g), the conversion rate of P from TBP to inorganic phase could reach 77.47%, and the non-methane hydrocarbon (NMHC) concentration of gas products was only 27.28 mg/m³, which was lower than the relevant environmental standard limit. Inorganic phosphorus products were separated and recovered by ethanol precipitation. X-Ray diffraction (XRD) analysis showed that the main components of phosphorus-containing products included Na₃PO₄, NaPO₃, Na₂HPO₄ and Na₃PO₄·8H₂O. According to mass spectrometry analysis of TBP degradation intermediates, the possible pathways of TBP degradation and phosphorus migration were proposed. Electron paramagnetic resonance (EPR) analysis revealed that hydroxyl radical (·OH) and superoxide radical ( $\cdot O_{2}^{-}$ ) played important roles in promoting the degradation of TBP.

Key words: tributyl phosphate, catalysis, radical, waste treatment, recovery

中图分类号:

X 783

童文华, 李义隆, 张永奎, 王雅博. 碱辅助四氧化三锰降解磷酸三丁酯及磷元素回收研究[J]. 化工学报, 2023, 74(10): 4277-4285.

Wenhua TONG, Yilong LI, Yongkui ZHANG, Yabo WANG. Study on alkali-assisted degradation of tributyl phosphate by manganese tetroxide and phosphorus recovery[J]. CIESC Journal, 2023, 74(10): 4277-4285.

图/表 8

图1 碱辅助CLC反应体系处理TBP的反应装置

Fig.1 Reaction apparatus for TBP treatment by alkali-assisted CLC reaction system

图2 从反应产物洗涤液中提取的水溶性含磷组分的XRD谱图

Fig.2 XRD pattern of the water-soluble phosphorus-containing components extracted from the washing solution of reaction product

图3 NaOH使用量的优化实验结果

Fig.3 Experimental results for the optimization of NaOH dosage

图4 反应前后载氧体Mn3O4的晶体结构变化

Fig.4 Crystal structure changes of oxygen carrier Mn3O4 before and after reaction

图5 碱辅助CLC技术处理TBP及磷元素回收的工艺流程

Fig.5 Process flow chart of alkali-assisted CLC technology for TBP treatment and phosphorus recovery

图6 碱辅助四氧化三锰降解TBP的可能路径

Fig.6 Possible pathway of alkali-assisted TBP degradation by Mn3O4

图7 氧空位和自由基检测结果

Fig.7 Results of oxygen vacancy and free radical detection

表1 碱辅助四氧化三锰降解TBP可能产生的最终产物

Table 1 Possible end products of alkali-assisted TBP degradation by Mn3O4

序号	化合物名称	分子量	分子结构	检测情况	文献
1	甲基-次磷酸单丁酯	136		√	—
2	次磷酸单丁酯	122		√	—
3	磷酸	98		√	[17, 28-29]
4	4-戊烯-2-酮	84		√	—
5	亚磷酸	82		√	—
6	1-丁醇	74		√	[17, 28-29]
7	丁酮	72		√	—
8	3-甲基-1-丁烯	69		√	—
9	乙酸	60		√	[28-29]
10	丁烷	58		√	—
11	丁烯	56		√	[13, 30]
12	丙烷	44		√	—
13	一氧化碳	28	C≡O	√	—

参考文献 30

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