| 65 | 0 | 63 |
| 下载次数 | 被引频次 | 阅读次数 |
精对苯二甲酸(PTA)装置氧化尾气成分复杂，含有多种含氧挥发性有机物、一氧化碳及含溴化合物，其净化处理面临严峻挑战。该复杂性源于前端工艺中存在的多种副反应，导致尾气中非甲烷总烃、苯系物和溴甲烷等污染物浓度显著超过国家标准限值。系统综述了PTA氧化尾气的回收法与销毁法处理技术发展现状，重点分析了冷凝回收与液体吸收2类回收技术，以及直接吸附、热氧化与催化氧化3类处理技术的优势与局限性。在回收方面，冷凝技术可实现有机物的高效分离与能量回收，但存在低温能耗高、设备腐蚀及二次污染等问题；液体吸收技术虽在传质效率和溶剂再生方面表现良好，却面临吸收剂损耗、系统结垢及废水处理等难题。在治理技术中，直接吸附技术操作灵活但再生频繁；热氧化(RTO)技术虽处理彻底，但能耗高且易产生NOx二次污染；催化氧化技术因其反应温度低、能耗少、无NOx生成等优势，成为当前研究与应用的重点。通过着重探讨催化氧化技术中所用的催化剂类型，包括贵金属催化剂、过渡金属氧化物催化剂和复合氧化物催化剂，分析了该技术用于PTA尾气净化中催化剂在含溴环境下的失活机制。最后，对PTA氧化尾气净化技术的未来发展进行了展望，指出通过催化剂创制、工艺耦合与智能控制等策略，可实现从“达标排放”到“资源化-零排放”的升级。
Abstract：The composition of the oxidation tail gas from the purified terephthalic acid(PTA) unit is intricate. It contains a variety of oxygenated volatile organic compounds(VOCs), carbon monoxide(CO), and bromine-containing compounds, posing a formidable challenge for its purification and treatment. This complexity is attributed to numerous side reactions occurring in the upstream processes. As a result, the concentrations of pollutants in the tail gas, such as total non-methane hydrocarbons(TNMHCs), benzene series compounds, and methyl bromide, significantly exceed the limits specified by national standards. This paper comprehensively reviews the current state-of-the-art in the recovery and treatment technologies for PTA oxidation tail gas. Special emphasis is placed on analyzing two types of recovery techniques, namely condensation recovery and liquid absorption, as well as three treatment methods: direct adsorption, thermal oxidation, and catalytic oxidation. Regarding recovery technologies, condensation techniques can effectively separate organic substances and recover energy. However, they are associated with issues such as high energy consumption at low temperatures, equipment corrosion, and potential secondary pollution. Liquid absorption technologies, despite exhibiting good performance in mass transfer efficiency and solvent regeneration, encounter problems such as absorbent loss, system fouling, and the challenge of wastewater treatment. Among the treatment technologies, direct adsorption offers operational flexibility but necessitates frequent regeneration. Thermal oxidation(RTO) can achieve thorough treatment; nonetheless, it consumes a large amount of energy and is likely to generate secondary pollution in the form of nitrogen oxides(NOx). Catalytic oxidation technology has emerged as the focus of current research and application due to its advantages of low reaction temperature, low energy consumption, and the absence of NOx formation. This paper delves into the types of catalysts employed in catalytic oxidation technology, including noble metal catalysts, transition metal oxide catalysts, and composite oxide catalysts. And the deactivation mechanism of the catalyst used in the purification of PTA tail gas under a bromine-containing environment was analyzed. Finally, the paper offers insights into the future development of PTA oxidation tail gas purification technologies. It is proposed that through strategies such as catalyst innovation, process integration, and intelligent control, it is possible to achieve an upgrade from “compliance discharge” to “resource utilization-zero discharge”.
[1] 林河海，中国芳烃产业链的一体化发展历史、盈利能力分析和未来发展[J].合成技术及应用，2020,35 (4):33-36.
[2] 李玉芳，伍小明.精对苯二甲酸国内市场分析[J].化学工业，2015,33 (11):27-30.
[3] 肖铭.我国乙二醇和精对苯二甲酸进出口分析[J].精细与专用化学品，2020,28 (9):6-9.
[4] 黄攀.我国PTA产业现状[J].合成技术及应用，2014,29 (3):24-27.
[5] 沈林.国内精对苯二甲酸(PTA)产业现状及发展趋势[J].化工管理，2019(20):1-2.
[6] 李西春，李媛.浅析国内精对苯二甲酸技术和生产现状[J].合成纤维，2021,50 (9):1-4.
[7] 王铭松.精对苯二甲酸产业及新技术发展应用[J].精细石油化工，2018,35 (3):71-75.
[8] 陈安尚，邱再明，韩继业，等.纳米级精对苯二甲酸钯炭催化剂研究[J].工业催化，2012,20 (11):57-60.
[9] 缪同.关于精对苯二甲酸(PTA)生产用钯碳催化剂的制备研究[J].当代化工研究，2018(9):113-114.
[10] 闫晓辉.毛细管气相色谱法分析精对苯二甲酸装置氧化单元尾气中的有机组分[J].河南化工，2005(1):32-33+47.
[11] 陈家桢，许金林.PTA装置氧化尾气中有机组分含量的测定[J].聚酯工业，2005(3):23-24.
[12] 陈雪非.PTA氧化尾气的能量回收及利用[J].聚酯工业，2011,24 (3):46-48.
[13] 崔国刚，李红坤，陈学佳，等.精对苯二甲酸装置氧化尾气综合处理方案[J].合成纤维，2017,46 (8):46-48+53.
[14] 王秉旺，孙柠.天津PTA装置氧化尾气处理技术探讨[J].聚酯工业，2019,32 (3):52-54.
[15] 陈红书，朱恩赞.吸附分离技术在大气污染防治中的应用研究[J].云南环境科学，2004 (3):48-50.
[16] 郝晓霞，王怀志，王筱喃，等.PTA尾气治理技术概述[J].当代化工，2013,42(2):187-189.
[17] 俞欢.PTA装置氧化尾气VOCs的治理[J].环境与发展，2017,29 (8):119-120.
[18] 张灿.浅析三室RTO技术处理VOCs废气[J].广州化工，2018,46 (14):95-96+102.
[19] 王振新.PX氧化反应尾气催化氧化处理系统工艺危害分析和对策措施[J].石油化工安全环保技术，2018,34 (2):35-38+69.
[20] HE C,CHENG J,ZHANG X,et al.Recent advances in the catalytic oxidation of volatile organic compounds:a review based on pollutant sorts and sources[J].Chemical Reviews,2019,119:4471-4568.
[21] LIU J,YANG L,DAI Z,et al.Zeolite-induced defect engineering for synthesis of CuBTC-derived novel carbon-zeolite bifunctional support catalyst for multicomponent VOCs catalytic oxidation removal[J].Chemical Engineering Journal,2024,500:156830.
[22] SHAN C,WANG Y,LI J,et al.Recent advances of vocs catalytic oxidation over spinel oxides:catalyst design and reaction mechanism[J].Environmental Science & Technology,2023,57:9495-9514.
[23] LIU X,ZENG J,WANG J,et al.Catalytic oxidation of methyl bromide using ruthenium-based catalysts[J].Catalysis Science & Technology,2016,6:4337-4344.
[24] GAO G,LIAO Y,LI W,et al.Active Surface RuOx species originating from size-driving self-dispersion process for toluene catalytic combustion[J].Chemical Engineering Journal,2022,441:136127.
[25] SUN K,KONG F,GONG X,et al.Hierarchical porous S-1 zeolite supported Pt catalyst for catalytic oxidation of various VOCs at low temperature with strong water resistance and excellent stability[J].Applied Catalysis A:General,2025,699:120284.
[26] YI J,LIU J,GAO B,et al.The comprehensive review of catalysts for catalytic oxidation of volatile organic compounds[J].Journal of Environmental Chemical Engineering,2025 13:115691.
[27] 王轩.非贵金属催化剂用于VOCs催化氧化工艺[J].安全、健康和环境，2023,23(10):16-24.
[28] ZENG J,SONG S,CHEN S,et al.Comparative study of Mn oxide catalysts on toluene oxidation:The effect of Mn valence electronic structures[J].Journal of Environmental Chemical Engineering,2025 12:112780.
[29] LOU B Z,SHAKOOR N,ADEEL M,et al.Catalytic oxidation of volatile organic compounds by non-noble metalcatalyst:current advancement and future prospectives[J].Journal of Cleaner Production,2022,363:132523.
[30] MA X,WANG W,ZHANG X,et al.MOF-derived FeOx with highly dispersed active sites as an efficient catalyst for enchaning catalytic oxidation of VOCs[J].Journal of Environmental Chemical Engineering,2024 12:111996.
[31] WANG J,SU J,ZHAO G,et al.A facile method for preparing the CeMnO3 catalyst with high activity and stability of toluene oxidation:The critical role of small crystal size and Mn3+-Ov-Ce4+ sites[J].Journal of Hazardous Materials,2024,470:134114.
[32] LIU M,ZHU D,LI S,et al.Enhanced oxygen vacancy over Mg-doped LaCo1-xMgxO3 perovskite catalysts for toluene catalytic combustion:Insight into the role of magnesium[J].Journal of Alloys and Compounds,2024,982:173621.
[33] FENG S Y,LIU J D,GAO B.Synergistic mechanism of Cu-Mn-Ce oxides in mesoporous ceramic base catalyst for VOCs microwave catalytic combustion[J].Chemical Engineering Journal,2022,429:132302.
[34] WU M,CHEN S,XIANG W.Oxygen vacancy induced performance enhancement of toluene catalytic oxidation using LaFeO3 perovskite oxides[J].Chemical Engineering Journal,2020,387:124101.
[35] MEI J,KE Y,YU Z,et al.Morphology-dependent properties of Co3O4/CeO2 catalysts for low temperature dibromomethane (CH2Br2) oxidation[J].Chemical Engineering Journal,2017,320:124-134.
[36] LV L,WANG S,DING Y,et al.Deactivation mechanism and anti-deactivation modification of Ru/TiO2 catalysts for CH3Br oxidation[J].Chemosphere,2020,257:127249.
基本信息:
中图分类号:X701
引用信息:
[1]王轩,徐伟,盛楠,等.精对苯二甲酸工艺氧化尾气净化技术评析与展望[J].安全、健康和环境,2025,25(10):38-46.
基金信息:
中国石化科技部项目(324069),PTA工艺高压氧化尾气净化技术开发