化工学报 ›› 2023, Vol. 74 ›› Issue (9): 3912-3920.DOI: 10.11949/0438-1157.20230702

• 能源和环境工程 • 上一篇    下一篇

炼化碱渣湿式氧化预处理过程DOM的化学转化特征

杨百玉(), 寇悦, 姜峻韬, 詹亚力, 王庆宏, 陈春茂()   

  1. 中国石油大学(北京)化学工程与环境学院,重质油国家重点实验室,北京 102249
  • 收稿日期:2023-07-07 修回日期:2023-09-08 出版日期:2023-09-25 发布日期:2023-11-20
  • 通讯作者: 陈春茂
  • 作者简介:杨百玉(1997—),女,硕士研究生,xxwldyby@163.com
  • 基金资助:
    国家自然科学基金面上项目(22278436)

Chemical conversion of dissolved organic matter in petrochemical spent caustic along a wet air oxidation pretreatment process

Baiyu YANG(), Yue KOU, Juntao JIANG, Yali ZHAN, Qinghong WANG, Chunmao CHEN()   

  1. State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering and Environment, China University of Petroleum, Beijing 102249, China
  • Received:2023-07-07 Revised:2023-09-08 Online:2023-09-25 Published:2023-11-20
  • Contact: Chunmao CHEN

摘要:

湿式氧化工艺(WAO)是炼化企业预处理高浓度碱渣的有效手段。基于3D-EEM、GC-MS以及Orbitrap MS组合分析,在分子水平上研究了碱渣中溶解性有机物(dissolved organic matter,DOM)在WAO过程的化学转化特征。研究发现:WAO过程主要发生加氧去氢(+1O-2H和+2O-2H)、加氧(+3O)以及脱烷基化(-C2H6)反应,芳香性DOM分子结构由高环(≥5环)向低环(3环/4环)转化;弱极性DOM由硫基苯甲醛、3,4-双(乙氧基甲基)噻吩等转化为硫酸盐、噻吩甲酸和硫醚等小分子化合物;强极性DOM则由具有较低不饱和度(DBEwa 3.727)和O/Cwa (0.386)的O2~4类和O3S1类化合物转化为具有较高不饱和度(DBEwa 5.911)和O/Cwa (0.537)的O5~9类和O4~9S1类化合物。WAO预处理后极性DOM种类由1792种增至4909种,水质的可生化性提升了35%。

关键词: 废水, 污染, 降解, 炼化碱渣, 湿式氧化, 溶解性有机物, 化学转化

Abstract:

Wet air oxidation (WAO) is an effective pretreatment process for high-concentration petrochemical spent caustics. In this study, an integrated analysis based on three-dimensional excitation-emission matrix fluorescence spectroscopy (3D-EEM), gas chromatography-mass spectrometry (GC-MS) and orbitrap mass spectrometry (Orbitrap MS) was established to investigate chemical conversion behaviors of petrochemical spent caustic along a WAO process at molecular level. Oxygen-dehydrogenation (+1O-2H and +2O-2H), oxygenation (+3O) and dealkylation (-C2H6) reactions happened in WAO process, resulting in a very significant change of DOM constituents. The molecular structures of fluorescent DOM converted from high ring number (≥5 rings) to low ring number (3 or 4 rings). Weak polar DOM, mainly thiobenzaldehyde and 3,4-bis(ethoxymethyl)-thiophene, is converted to sulfates, thiophenic acid and thioethers. The polar DOM, mainly O2—4 and O3S1 species with low unsaturation (DBEwa 3.727) and O/Cwa (0.386), is converted into O5—9 and O4—9S1 species with high unsaturation (DBEwa 5.911) and O/Cwa (0.537). Compound types of polar DOM increased from 1792 to 4909 by WAO pretreatment and the biodegradability of effluent improved by 35%.

Key words: waste water, pollution, degradation, petrochemical spent caustic, wet air oxidation, dissolved organic matter, chemical conversion

中图分类号: