延长石油集团炼油碱渣处理技术开发与应用研究
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摘要
石油炼制过程中为了满足液化气及油品的质量要求,通常对液化气和液态烃进行碱洗精制,以脱除其中的杂质。碱洗后的废碱液常称为炼油碱渣,由于其中含有酚类物质和有机硫化物等大量有毒有机物,化学需氧量COD高,生物降解性差,因此会给环境造成严重的污染。
为解决延长石油集团炼化公司炼油碱渣废水处理的技术难题,本研究在对国内外已有的碱渣处理工艺技术分析对比的基础上,提出了组合工艺对炼化公司炼油碱渣进行综合处理。通过研究得到了预处理(氧化/中和/洗涤)—生化处理(QBR废碱液生化处理/QBF废气生化处理)的工艺路线,该工艺可将进料废碱渣的COD由高达几万甚至几十万mg/L降低至500mg/L以下,硫化物由高达5283mg/L处理至未检出水平,酚含量由几千至几万mg/L降低至1-2mg/L,油类物质降低至约1-3mg/L
该组合工艺已用于炼化公司实际生产,达到了预期的处理效果,研究结果具有显著的社会和环境效益。
In order to meet the quality requirements of petroleum gas and oil in the process of refining, it was usually refined by using alkali to wash to remove the impurities. The refinery alkaline was produced after leading alkaline causing serious environmental pollution because of the high content of toxic organic compounds such as phenol and organic sulfur compounds which resulted in the poor biodegradation and high chemical oxygen demand(COD).
In this paper we studied on the alkaline treatment technology on the basis of the analysis and comparison of refining process existed to solve the key technical problem in the project of YanChang petroleum refining & petrochemical company. Combination process with comprehensive handling refinery alkaline was proposed. The process contained pretreatment with oxidation & neutralization & washing and biochemical treatment with QBR alkaline biochemical treatment& QBF exhaust gas biochemical treatment. COD was reduced to under 500mg/L from tens of thousands even hundreds of thousands pre treatment while phenols was reduced to under 1or 2mg/L from thousands even tens of thousands pre treatment. The sulfide which was as high as 5283 mg/L pre treatment failed to detect after treatment. And oily substances were reduced to under 1or 3mg/L.
This combination technology had been already utilized in the actual production and achieved its desired effect. The result had significant social and environmental benefits.
为解决延长石油集团炼化公司炼油碱渣废水处理的技术难题,本研究在对国内外已有的碱渣处理工艺技术分析对比的基础上,提出了组合工艺对炼化公司炼油碱渣进行综合处理。通过研究得到了预处理(氧化/中和/洗涤)—生化处理(QBR废碱液生化处理/QBF废气生化处理)的工艺路线,该工艺可将进料废碱渣的COD由高达几万甚至几十万mg/L降低至500mg/L以下,硫化物由高达5283mg/L处理至未检出水平,酚含量由几千至几万mg/L降低至1-2mg/L,油类物质降低至约1-3mg/L
该组合工艺已用于炼化公司实际生产,达到了预期的处理效果,研究结果具有显著的社会和环境效益。
In order to meet the quality requirements of petroleum gas and oil in the process of refining, it was usually refined by using alkali to wash to remove the impurities. The refinery alkaline was produced after leading alkaline causing serious environmental pollution because of the high content of toxic organic compounds such as phenol and organic sulfur compounds which resulted in the poor biodegradation and high chemical oxygen demand(COD).
In this paper we studied on the alkaline treatment technology on the basis of the analysis and comparison of refining process existed to solve the key technical problem in the project of YanChang petroleum refining & petrochemical company. Combination process with comprehensive handling refinery alkaline was proposed. The process contained pretreatment with oxidation & neutralization & washing and biochemical treatment with QBR alkaline biochemical treatment& QBF exhaust gas biochemical treatment. COD was reduced to under 500mg/L from tens of thousands even hundreds of thousands pre treatment while phenols was reduced to under 1or 2mg/L from thousands even tens of thousands pre treatment. The sulfide which was as high as 5283 mg/L pre treatment failed to detect after treatment. And oily substances were reduced to under 1or 3mg/L.
This combination technology had been already utilized in the actual production and achieved its desired effect. The result had significant social and environmental benefits.
引文
[1]吴爱明.催化湿式氧化法处理炼油碱渣废水的研究[D].湘潭市：湘潭大学,2007年.
[2]乌锡康.有机废水治理技术[M].北京：烃加工出版社(第一版).1999.
[3]钱伯章等译,美国石油学会编.炼油厂废水处理手册[M].烃加工出版社.1986.
[4]张方西.含酚废水的处理与利用[M].北京：化学工业出版社.1983.
[5]马凤荣,牟彤,白冰,等。高浓度废水处理技术在柴油碱渣处理中的应用[J],油气田环境保护,2006,2：19-21.
[6]孙连阁.乙烯废碱液中硫化物和直机恤处理及相未机理研究[D].大庆：大庆石油学院,2003.
[7]赵彦永.废碱液处理[J].石油化工环境保护,1997,1：30-33.
[8]张武平,袁萍.乙烯脱硫废碱液的综合治理[J].辽宁化工,1998,27(5)：259～61.
[9]韩建华.炼油厂含硫碱渣处理工艺[J].石油化工环境保护.2000,1：34-41.
[10]谢晋巧,钱宇.炼油厂废碱液治理技术的研究[JJ.石油化工环境保护,1998,1：37～2.
[11]于然旺,董明会.乙烯装置废碱液处理的现状与展望[J].乙烯工业,2004,16(2)：54～57.
[12]齐刚,李淑英,王斌,等.模型试验法评价石化工业废水的可生化性[J].北方环境,2004,29(4)：27～28.
[13]赵华,曹青青,刘侃.炼油碱渣处理技术现状与展望[J].化工科技,2009,17(2)：71-74.
[14]唐晓东.炼油废碱液的综合利[J].油气田环境保护用,2000,2(10)41-45.
[15]杨英,李福华,陈嵩等,石化炼油厂碱渣废水处理工艺的选择[J].环境科学导刊,2007,26(6)：61～63.
[16]刘鸿雁,刘亚玲.模型试验法评价乙烯废碱液的可生化性[J].黑龙江环境通报,2002,28(2)：64～65.
[17]杨少霞,冯玉杰,万家峰,蔡伟民.湿式催化氧化技术的研究与发展概况[J].哈尔滨工业大学学报,2002,34：540～544.
[18]谭亚军,蒋展鹏,祝万鹏等.用于有机污染物湿式氧化的Cu系催化剂活性研究[J].化工环保,2000,20：6～10.
[19]谭亚军,蒋展鹏,祝万鹏等.有机污染物湿式催化氧化降解中Cu系催化剂的稳定性[J].环境科学,2000,21：82～85.
[20]宾月景,祝万鹏,蒋展鹏等.催化湿式催化剂及处理技术研究[J].环境科学,1999,20：42-44.
[21]曾新平,唐文伟,赵建夫等.湿式氧化处理高浓度难降解有机废水研究[J].环境科学学报,2004,24(6)：945-949.
[22]J N Foussard. Wet peroxide oxidation for indust rial waste water t reatment [J]. Genic Renact,1991,16 (5):177-179.
[23]张振择.碱渣处理装置的现状与展望[J].石油化工环境保护,1998,2：13～17.
[24]何爱明,张静,李聪敏.碱渣处理工艺应用[J].天然气与石油,2008,28(6)：31-34.
[25]肖晔远,史云鹏.湿式氧化处理污水的应用现状及展望[J].工业用水与废水,2002,32：5-7.
[26]邓德刚,韩建华.碱渣缓和湿式氧化处理工艺的工业应用[C].中国石化集团公司炼油行业环保专业技术协作组2002年年会论文集.2002.
[27]刘建荣等.催化氧化处理含酚废水[J].中国给水排水,1992,8：44～47.
[28]卢义程等,高浓度乳化废水处理中铜系催化剂催化活性比较[J].上海环境科学,2002,12(4)：199～01.
[29]余政哲,孙德智,史鹏飞,等.化学沉淀与高级氧化法处理乙烯裂解废碱液的研究[J].化工环保2004,24(2)：90-93.
[30]邱皖龙.乙烯装置碱洗和废碱处理单元工业改造[D].天津：天津大学,2007.
[31]殷杰,唐娜.碳化法处理石油废碱渣研究进展[J].天津化工,2010,2(24)：1-3.
[32]常伟先,靳建军,凌南等,碱渣处理装置工艺设计[J].石油与天然气化工,2005,34(4)273-275.
[33]杨琦.国外对污水湿式氧化处理的研究进展[J].环境科学研究,1998,11(4)：62.
[34]Liu Yogsong. Treatment of Phenol-containing waster water by sequencing contact stabilization process. Water Treatment,1990,5(1)),77～86.
[35]Stephenson T, Mann A, Upton J, The small footprint waste water treatment process. Chem. Ind.,1993,14(3):533-536.
[36]Moore R, Quarmby J, Stephenson T, The effects of media size on the performance of biological aerated filters. Wat. Res.,2001,35(10):2514～2522.
[37]牟彤,白冰,崔利.高效生物处理技术在炼油厂碱渣废水处理中的应用[J].油气田环境保护,2007,17(1)：23～26.
[38]曹志钦.石油化工废碱液在造纸厂的应用[J].油气田环境保护,1999,9(1)：31-34.
[39]杜龙弟,赵智武,荣国海,等.乙烯废碱液的苛化法再生工艺研究[J].乙烯工业,2004,16(4)：29-33.
[40]姜海.炼油工业含硫废水提制工业硫化碱的研究[J].石油与天然气化工,1995,24(3)：9-12.
[41]Davis, Donald G., "Potentiometric Titrations" in Standard Methods of Chemical Analysis, Vol. Ⅲ A, F. J. Welcher, ed. Van Nostrand Reinhold Co., New York,1966.
[42]Ewing, Galen W., Instrumental Methods of Chemical Analysis, McGraw-Hill, New York, 1969.
[43]Liu C. H. and Shen, Samuel, Argentometric Titration of Sulfide in Alkaline Solutions, Analytical Chemistry,1964.36:1652.
[44]Gorden, G.E., Colorimetric Determination of Phenolic Materials in Refinery Waste Water. Analytical Chemistry,1960.32:1325.
[45]Mohler, E.F., and Jacob, L.H., Determination of Phenolic Type Compounds in Water and Waste Water-Comparison of Analytical Methods. Analytical Chemistry,1957,29:1369
[46]Standard Method for the Examination of Water and Waste Water,16th Edition,1985: 556-561.
[47]ASTM Standards, Part 23, Water; Atmospheric Analysis,1973. Method D-1783-70:535.
[48]田进军,丁坷,王晨,等.湿式空气氧化法处理硫化钠废碱液[J].青岛科技大学学报,2004,25(3)：210～13.
[49]于深乔.从炼油碱渣中回收环烷酸[J].化工环保,1990,1(6)：343-347.
[50]余政哲,孙德智,史鹏飞,等.两步沉淀法处理乙烯废碱液的实验研究[J].现代化工,2003,23：131-133.
[2]乌锡康.有机废水治理技术[M].北京：烃加工出版社(第一版).1999.
[3]钱伯章等译,美国石油学会编.炼油厂废水处理手册[M].烃加工出版社.1986.
[4]张方西.含酚废水的处理与利用[M].北京：化学工业出版社.1983.
[5]马凤荣,牟彤,白冰,等。高浓度废水处理技术在柴油碱渣处理中的应用[J],油气田环境保护,2006,2：19-21.
[6]孙连阁.乙烯废碱液中硫化物和直机恤处理及相未机理研究[D].大庆：大庆石油学院,2003.
[7]赵彦永.废碱液处理[J].石油化工环境保护,1997,1：30-33.
[8]张武平,袁萍.乙烯脱硫废碱液的综合治理[J].辽宁化工,1998,27(5)：259～61.
[9]韩建华.炼油厂含硫碱渣处理工艺[J].石油化工环境保护.2000,1：34-41.
[10]谢晋巧,钱宇.炼油厂废碱液治理技术的研究[JJ.石油化工环境保护,1998,1：37～2.
[11]于然旺,董明会.乙烯装置废碱液处理的现状与展望[J].乙烯工业,2004,16(2)：54～57.
[12]齐刚,李淑英,王斌,等.模型试验法评价石化工业废水的可生化性[J].北方环境,2004,29(4)：27～28.
[13]赵华,曹青青,刘侃.炼油碱渣处理技术现状与展望[J].化工科技,2009,17(2)：71-74.
[14]唐晓东.炼油废碱液的综合利[J].油气田环境保护用,2000,2(10)41-45.
[15]杨英,李福华,陈嵩等,石化炼油厂碱渣废水处理工艺的选择[J].环境科学导刊,2007,26(6)：61～63.
[16]刘鸿雁,刘亚玲.模型试验法评价乙烯废碱液的可生化性[J].黑龙江环境通报,2002,28(2)：64～65.
[17]杨少霞,冯玉杰,万家峰,蔡伟民.湿式催化氧化技术的研究与发展概况[J].哈尔滨工业大学学报,2002,34：540～544.
[18]谭亚军,蒋展鹏,祝万鹏等.用于有机污染物湿式氧化的Cu系催化剂活性研究[J].化工环保,2000,20：6～10.
[19]谭亚军,蒋展鹏,祝万鹏等.有机污染物湿式催化氧化降解中Cu系催化剂的稳定性[J].环境科学,2000,21：82～85.
[20]宾月景,祝万鹏,蒋展鹏等.催化湿式催化剂及处理技术研究[J].环境科学,1999,20：42-44.
[21]曾新平,唐文伟,赵建夫等.湿式氧化处理高浓度难降解有机废水研究[J].环境科学学报,2004,24(6)：945-949.
[22]J N Foussard. Wet peroxide oxidation for indust rial waste water t reatment [J]. Genic Renact,1991,16 (5):177-179.
[23]张振择.碱渣处理装置的现状与展望[J].石油化工环境保护,1998,2：13～17.
[24]何爱明,张静,李聪敏.碱渣处理工艺应用[J].天然气与石油,2008,28(6)：31-34.
[25]肖晔远,史云鹏.湿式氧化处理污水的应用现状及展望[J].工业用水与废水,2002,32：5-7.
[26]邓德刚,韩建华.碱渣缓和湿式氧化处理工艺的工业应用[C].中国石化集团公司炼油行业环保专业技术协作组2002年年会论文集.2002.
[27]刘建荣等.催化氧化处理含酚废水[J].中国给水排水,1992,8：44～47.
[28]卢义程等,高浓度乳化废水处理中铜系催化剂催化活性比较[J].上海环境科学,2002,12(4)：199～01.
[29]余政哲,孙德智,史鹏飞,等.化学沉淀与高级氧化法处理乙烯裂解废碱液的研究[J].化工环保2004,24(2)：90-93.
[30]邱皖龙.乙烯装置碱洗和废碱处理单元工业改造[D].天津：天津大学,2007.
[31]殷杰,唐娜.碳化法处理石油废碱渣研究进展[J].天津化工,2010,2(24)：1-3.
[32]常伟先,靳建军,凌南等,碱渣处理装置工艺设计[J].石油与天然气化工,2005,34(4)273-275.
[33]杨琦.国外对污水湿式氧化处理的研究进展[J].环境科学研究,1998,11(4)：62.
[34]Liu Yogsong. Treatment of Phenol-containing waster water by sequencing contact stabilization process. Water Treatment,1990,5(1)),77～86.
[35]Stephenson T, Mann A, Upton J, The small footprint waste water treatment process. Chem. Ind.,1993,14(3):533-536.
[36]Moore R, Quarmby J, Stephenson T, The effects of media size on the performance of biological aerated filters. Wat. Res.,2001,35(10):2514～2522.
[37]牟彤,白冰,崔利.高效生物处理技术在炼油厂碱渣废水处理中的应用[J].油气田环境保护,2007,17(1)：23～26.
[38]曹志钦.石油化工废碱液在造纸厂的应用[J].油气田环境保护,1999,9(1)：31-34.
[39]杜龙弟,赵智武,荣国海,等.乙烯废碱液的苛化法再生工艺研究[J].乙烯工业,2004,16(4)：29-33.
[40]姜海.炼油工业含硫废水提制工业硫化碱的研究[J].石油与天然气化工,1995,24(3)：9-12.
[41]Davis, Donald G., "Potentiometric Titrations" in Standard Methods of Chemical Analysis, Vol. Ⅲ A, F. J. Welcher, ed. Van Nostrand Reinhold Co., New York,1966.
[42]Ewing, Galen W., Instrumental Methods of Chemical Analysis, McGraw-Hill, New York, 1969.
[43]Liu C. H. and Shen, Samuel, Argentometric Titration of Sulfide in Alkaline Solutions, Analytical Chemistry,1964.36:1652.
[44]Gorden, G.E., Colorimetric Determination of Phenolic Materials in Refinery Waste Water. Analytical Chemistry,1960.32:1325.
[45]Mohler, E.F., and Jacob, L.H., Determination of Phenolic Type Compounds in Water and Waste Water-Comparison of Analytical Methods. Analytical Chemistry,1957,29:1369
[46]Standard Method for the Examination of Water and Waste Water,16th Edition,1985: 556-561.
[47]ASTM Standards, Part 23, Water; Atmospheric Analysis,1973. Method D-1783-70:535.
[48]田进军,丁坷,王晨,等.湿式空气氧化法处理硫化钠废碱液[J].青岛科技大学学报,2004,25(3)：210～13.
[49]于深乔.从炼油碱渣中回收环烷酸[J].化工环保,1990,1(6)：343-347.
[50]余政哲,孙德智,史鹏飞,等.两步沉淀法处理乙烯废碱液的实验研究[J].现代化工,2003,23：131-133.