高铁酸盐处理难降解有机物磺化酚醛树脂

doi:10.16085/j.issn.1000-6613.2022-1485

化工进展 ›› 2023, Vol. 42 ›› Issue (6): 3302-3308.DOI: 10.16085/j.issn.1000-6613.2022-1485

高铁酸盐处理难降解有机物磺化酚醛树脂

杨红梅¹(), 高涛², 鱼涛¹, 屈撑囤¹^,²(), 高家朋¹

^1.西安石油大学，陕西省油气田环境污染控制与储层保护重点实验室，陕西西安 710065
^2.陕西延长石油(集团)有限责任公司研究院，陕西西安 710065
^3.中国石油安全环保技术研究院，石油石化污染物控制与处理国家重点实验室，北京 102206

收稿日期:2022-08-11 修回日期:2022-10-11 出版日期:2023-06-25 发布日期:2023-06-29
通讯作者: 屈撑囤
作者简介:杨红梅（1989—），女，硕士研究生，研究方向为油气田污染物控制。E-mail：gfyzyhm@163.com。
基金资助:
陕西省教育厅服务地方专项计划(22JC054)

Treatment of refractory organics sulfonated phenolic resin with ferrate

YANG Hongmei¹(), GAO Tao², YU Tao¹, QU Chengtun¹^,²(), GAO Jiapeng¹

^1.Shaanxi Key Laboratory of Environmental Pollution Control Technology＆Reservoir Protection of Oil and Gas Field, Xi’an Shiyou University, Xi’an 710065, Shaanxi, China
^2.Research Institute of Shaanxi Yanchang Petroleum (Group) Co. , Ltd. , Xi’an 710065, Shaanxi, China
^3.State Key Laboratory of Petrochemical Pollution Control and Treatment, PetroChina Institute of Safety and Environmental Protection Technology, Beijing 102206, China

Received:2022-08-11 Revised:2022-10-11 Online:2023-06-25 Published:2023-06-29
Contact: QU Chengtun

摘要/Abstract

摘要：

采用高铁酸盐处理难降解有机物磺化酚醛树脂（SMP），研究了各影响因素对SMP的COD_Cr去除率的影响，确定了最佳条件，当SMP初始浓度为0.05%（质量分数）时，高铁酸盐投量为1.2g/L、反应体系pH为13、反应2h，SMP的COD_Cr去除率为79.4%。高铁酸盐的投量对SMP的COD_Cr去除率有很大的影响，不同浓度的SMP应当选择不同的高铁酸盐投量。絮凝作用对SMP的去除效果占总去除率一定比例，但SMP的去除仍以氧化作用为主。结合紫外-可见分光光度法（UV-Vis）、凝胶渗透色谱（GPC）和气相色谱-质谱联用（GC-MS）分析可以断定SMP分子结构中磺甲基结构基本完全降解，SMP的大分子主链发生断裂生成分子量为1300左右的带有苯环结构的物质，当主链降解到一定程度后，苯环结构开始被氧化发生开环反应，生成烃类小分子有机物，最终氧化成 CO₂ 和 H₂O。

关键词: 高铁酸盐, 磺化酚醛树脂, 废水, 降解, 色谱

Abstract:

The refractory organic matter sulfonated phenolic resin (SMP) was treated with ferrate. The influences of various factors on the COD_Cr removal rate of SMP were studied. The optimal conditions were determined. When the initial concentration of SMP was 0.05% (mass ratio), the ferrate was 1.2g/L, the pH=13 and the reaction time was 2h, the COD_Cr removal rate of SMP was 79.4%. The amount of ferrate had a great influence on the COD_Cr removal rate. Different concentrations of SMP should choose different ferrate dosage. The removal rate of SMP was still dominated by oxidation and flocculation accounted for a low proportion of the total removal rate. Combined with UV-Vis, GPC and GC -MS analysis, it can be concluded that the sulphomethyl structure of SMP was completely degraded, and the macromolecular backbone of SMP was broken to generate substances with a molecular weight of about 1300 with a benzene ring. When the backbone was degraded to a certain degree, the benzene ring began to be oxidized and the ring-opening reaction occurred to form small molecular organic hydrocarbons, which were eventually oxidized to CO₂ and H₂O.

Key words: ferrate, sulfonated phenolic resin, waste water, degradation, chromatography

中图分类号:

X741

杨红梅, 高涛, 鱼涛, 屈撑囤, 高家朋. 高铁酸盐处理难降解有机物磺化酚醛树脂[J]. 化工进展, 2023, 42(6): 3302-3308.

YANG Hongmei, GAO Tao, YU Tao, QU Chengtun, GAO Jiapeng. Treatment of refractory organics sulfonated phenolic resin with ferrate[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3302-3308.

图/表 12

图1 反应时间对SMP的CODCr去除率的影响（0.05% SMP初始CODCr为653mg/L）

图2 反应体系pH对SMP的CODCr去除率的影响（0.05% SMP初始CODCr为653mg/L）

图3 SMP浓度对SMP的CODCr去除率的影响（0.01%、0.02%、0.05%、0.1%和0.2% SMP初始CODCr分别为234mg/L、373mg/L、653mg/L、997mg/L和1813mg/L）

图4 高铁酸盐在不同浓度时对SMP的氧化能力

图5 高铁酸盐在不同pH时对SMP的氧化能力

图6 氧化和絮凝作用对去除SMP的影响（pH=13）

图7 SMP分子结构图和SMP降解前后的紫外-可见吸收光谱图

表1 SMP降解产物的分子量分布

样品	M_n	M_w	M_z	M_w/M_n
SMP处理后	1.26×10³	1.33×10³	1.41×10³	1.06
SMP处理前	4.65×10⁴	6.03×10⁴	7.79×10⁴	1.29

图8 SMP氧化降解前的分子量分布

图9 SMP降解产物的分子量分布

图10 SMP降解产物的GC-MS谱图

表2 SMP降解产物组分分析

编号	停留时间/min	质量分数/%
1	0.592	1.53
2	0.708	24.89
3	1.258	15.96
4	1.342	27.72
5	1.667	0.61
6	12.067	0.84
7	12.950	2.97
8	14.375	0.32
9	14.625	24.17
10	28.250	0.98

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高铁酸盐处理难降解有机物磺化酚醛树脂

Treatment of refractory organics sulfonated phenolic resin with ferrate

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