有机精馏釜残无害化处理与资源化转化研究进展与思考

doi:10.16085/j.issn.1000-6613.2022-1841

摘要/Abstract

摘要：

综述了化工精馏釜残危废的无害化处理技术以及不同种类及属性的化工精馏釜残特异的资源化利用方案和途径。从工程应用角度阐述和分析了精馏釜残不同的无害化处理技术的使用范畴、优缺点、技术现状和进展方向。根据不同精馏釜残的成分及物性特点，总结了不同种类精馏釜残的资源化利用方案。在此基础上针对目前产量大且组分复杂的酚基精馏釜残，提出对精馏釜残轻重组分进行多元化资源转化与无害化处理方案，并就此进行了综合分析，对精馏釜残资源化利用技术进行了初步的思考。

关键词: 精馏, 釜残, 有机危废, 无害化处理, 资源化转化

Abstract:

In this paper, the harmless treatment technology of chemical distillation stills and hazardous wastes, and the specific resource utilization schemes and approaches of chemical distillation stills with different types and properties were reviewed. From the point of engineering application, the application range, advantages and disadvantages, technical status and development direction of different harmless treatment technologies for distillation reactor residues were described and analyzed. According to the composition and physical properties of different rectification still residues, the resource utilization scheme of different kinds of rectification still residues was summarized. On this basis, in view of the phenol-based distillation residue with large output and complex components, a diversified resource conversion and harmless treatment plan for the light and heavy components of the distillation residue was proposed, and a comprehensive analysis and development thinking were carried out on the utilization technology of residual resources in distillation residues.

Key words: distillation, residue, organic waste, useless treatment, conversion

中图分类号:

杜金泽, 李源森, 蔡思超, 何林, 王成扬, 李鑫钢. 有机精馏釜残无害化处理与资源化转化研究进展与思考[J]. 化工进展, 2023, 42(2): 559-574.

DU Jinze, LI Yuansen, CAI Sichao, HE Lin, WANG Chengyang, LI Xingang. Recent advances and considerations for the harmless treatment and conversion of organic distillation residue[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 559-574.

图/表 14

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行业来源	危险废物种类	精馏釜残所含组分
石油化工业	石油精炼酸焦油和焦油	硫酸、磺酸、多环芳香烃、多环芳香烃低聚物
煤炭加工业	煤制气及煤气净化产生的焦油渣	萘、苊烯、芴、菲、荧蒽、蒽、芘等PAHs单体、沥青质
	煤炼焦轻油和萘的回收、苯精制、储存及废水池焦油渣和污泥	萘、苊烯、芴、菲、荧蒽、蒽、芘等PAHs单体、沥青质、煤灰、尘土
	焦炭生产过程及粗苯精制过程中产生的酸焦油、脱硫废液	硫酸、磺酸、多环芳香烃、多环芳香烃低聚物
	煤沥青改质过程中产生的闪蒸油	苯基萘、荧蒽、芘、苯基芴和䓛、氧芴、咔唑、二甲基蒽、等多环芳香烃
燃气生产业	煤生气行业产生的煤焦油渣	萘、苊烯、芴、菲、荧蒽、蒽、芘等 PAHs单体、多环芳香烃
基础化工业	乙烯制乙醛产生的残渣和次要馏分	次馏分：氯甲烷、氯乙烷、丁醛、乙酸；残渣：低聚物
	氯代物生产过程中的蒸馏残渣及重馏分	含氯多环芳香烃、胶质
	苯系物及含氮苯系物釜残及重馏分	多环芳香烃、含氮多环芳香烃
	使用羧酸肼生产 1,1-二甲基肼釜残	氰胺类化合物，含氯低聚物
	烯烃合成釜残及重组分	低聚聚合物、多环芳香烃
	醇类、羧酸类和酯类有机物釜残及重组分	低聚含氧聚合物、含氧多环芳香烃
石墨及其他非金属矿物制造业	电解铝及其他有色金属电解精炼过程中预焙阳极、碳块及其他碳素制品制造过程烟气处理所产生的含焦油废物	氟化氢、含硫化合物、苯系物
环境治理业	废矿物油再生过程中产生的酸焦油	硫酸、磺酸、多环芳香烃、多环芳香烃、含氧胶质、低聚物、泥沙

行业来源	危险废物种类	精馏釜残所含组分
石油化工业	石油精炼酸焦油和焦油	硫酸、磺酸、多环芳香烃、多环芳香烃低聚物
煤炭加工业	煤制气及煤气净化产生的焦油渣	萘、苊烯、芴、菲、荧蒽、蒽、芘等PAHs单体、沥青质
	煤炼焦轻油和萘的回收、苯精制、储存及废水池焦油渣和污泥	萘、苊烯、芴、菲、荧蒽、蒽、芘等PAHs单体、沥青质、煤灰、尘土
	焦炭生产过程及粗苯精制过程中产生的酸焦油、脱硫废液	硫酸、磺酸、多环芳香烃、多环芳香烃低聚物
	煤沥青改质过程中产生的闪蒸油	苯基萘、荧蒽、芘、苯基芴和䓛、氧芴、咔唑、二甲基蒽、等多环芳香烃
燃气生产业	煤生气行业产生的煤焦油渣	萘、苊烯、芴、菲、荧蒽、蒽、芘等 PAHs单体、多环芳香烃
基础化工业	乙烯制乙醛产生的残渣和次要馏分	次馏分：氯甲烷、氯乙烷、丁醛、乙酸；残渣：低聚物
	氯代物生产过程中的蒸馏残渣及重馏分	含氯多环芳香烃、胶质
	苯系物及含氮苯系物釜残及重馏分	多环芳香烃、含氮多环芳香烃
	使用羧酸肼生产 1,1-二甲基肼釜残	氰胺类化合物，含氯低聚物
	烯烃合成釜残及重组分	低聚聚合物、多环芳香烃
	醇类、羧酸类和酯类有机物釜残及重组分	低聚含氧聚合物、含氧多环芳香烃
石墨及其他非金属矿物制造业	电解铝及其他有色金属电解精炼过程中预焙阳极、碳块及其他碳素制品制造过程烟气处理所产生的含焦油废物	氟化氢、含硫化合物、苯系物
环境治理业	废矿物油再生过程中产生的酸焦油	硫酸、磺酸、多环芳香烃、多环芳香烃、含氧胶质、低聚物、泥沙

釜残类型	主要成分	复配合成方法	助剂应用	釜残利用率	发明单位或个人参考文献
渣油	多环芳烃等	渣油加水乳化	钻井润滑液	约100%	缪明富等^[54]
4-甲基吡啶釜残	4-甲基吡啶等	减压切分，60~160℃馏分	金属腐蚀抑制剂、缓蚀剂	约60%	王曰礼^[56]
4-甲基吡啶釜残	4-甲基吡啶等	4-甲基吡啶釜残与工业氯化苄反应后复配匀染剂、乙醇	钻井缓蚀剂	≥90%	郑家燊^[57]
浮选油釜残	松节油等	250~300℃加入熔融次等松香[松香：釜残=1∶(2~3)]	轮胎橡胶硫化用松焦油，橡胶软化剂	约100%	吉林省敦化林业局科技办公室^[58]
木浆浮油釜残	树脂酸、脂肪酸和中性物	与木浆浮油蒸馏轻组分一定比例混合	代替木焦油，橡胶软化剂	约100%	金琦等^[59]
三乙醇胺蒸馏釜残	四羟乙基乙二胺、一乙醇胺、二乙醇胺、三乙醇胺及其缩合物	与水以及表面活性剂复配	油田防垢剂	约100%	金淑梅^[55]
芳樟醇釜残液	半萜烯、芳樟醇等	无	塑料回收用，聚苯乙烯溶剂	约100%	陈广明等^[53]
十二烷基酚釜残	苯酚、苯雌酚、十二烷基酚、多侧链烷基酚	无	道路沥青增溶剂、增韧剂	约100%	天津大学、广东新华粤

釜残类型	主要成分	复配合成方法	助剂应用	釜残利用率	发明单位或个人参考文献
渣油	多环芳烃等	渣油加水乳化	钻井润滑液	约100%	缪明富等^[54]
4-甲基吡啶釜残	4-甲基吡啶等	减压切分，60~160℃馏分	金属腐蚀抑制剂、缓蚀剂	约60%	王曰礼^[56]
4-甲基吡啶釜残	4-甲基吡啶等	4-甲基吡啶釜残与工业氯化苄反应后复配匀染剂、乙醇	钻井缓蚀剂	≥90%	郑家燊^[57]
浮选油釜残	松节油等	250~300℃加入熔融次等松香[松香：釜残=1∶(2~3)]	轮胎橡胶硫化用松焦油，橡胶软化剂	约100%	吉林省敦化林业局科技办公室^[58]
木浆浮油釜残	树脂酸、脂肪酸和中性物	与木浆浮油蒸馏轻组分一定比例混合	代替木焦油，橡胶软化剂	约100%	金琦等^[59]
三乙醇胺蒸馏釜残	四羟乙基乙二胺、一乙醇胺、二乙醇胺、三乙醇胺及其缩合物	与水以及表面活性剂复配	油田防垢剂	约100%	金淑梅^[55]
芳樟醇釜残液	半萜烯、芳樟醇等	无	塑料回收用，聚苯乙烯溶剂	约100%	陈广明等^[53]
十二烷基酚釜残	苯酚、苯雌酚、十二烷基酚、多侧链烷基酚	无	道路沥青增溶剂、增韧剂	约100%	天津大学、广东新华粤

釜残类型	主要成分	复配合成方法	助剂应用	釜残利用率	参考文献发明单位或个人
玉米制醇工业釜残	山梨醇、二元醇、多元醇、多聚糖和有机酸等	除水、氨基磺酸催化磺化	水泥减水剂	≥90%	吴洪发等^[65]
渣油、环烷酸釜残	渣油、环烷酸等	渣油加水乳化；环烷酸釜残与碱液皂化反应	钻井润滑液；钻井液稳定剂	约100%	缪明富等^[54]
制药厂4-甲基吡啶釜残	大量吡啶类化合物	与盐酸反应上层生成物与OP乳化剂复配	钻井缓蚀剂	约90%	四川省石油管理局天然气研究所^[11]
制药厂4-甲基吡啶釜残	6-正丙基吡啶和6-乙基6-甲基毗咤	氯化苄和釜残反应后与甲醛的表面活性剂溶液复配	油井缓释液	约90%	孙克忠^[66]