辽河油田含油污泥综合处理技术
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摘要
在稠油污水处理流程中,气浮已经成为关键和不可缺少的单元工艺,目前辽河油田日产稠油污水8.5×104m3,年产污泥(浮渣)58×104m3,其处置问题日益突出。浮渣的主要成分为水(97%)、粘土矿物(2%)和油(1%),其中重质油组分较多,主要是沥青质和胶质。呈半固体状态的浮渣是含油污水处理系统的最末端废弃物,已被列入《国家危险废物名录》,成为国家强制性管理的固体废弃物。对含油浮渣的处置,国内外迄今为止尚无有效方法。为解决含油浮渣的无害化问题,本项目以辽河油田的6个典型联合站浮渣为研究对象,根据其理化特性,采取物理、化学等技术手段,开展了预处理、减量化、无害化等分阶段、分目标的技术探索与工业实践。
实验结果表明:(1)含油浮渣的主要特点是含水率高,油成分主要为胶质、沥青质等重质成分,固体物质多为粘土矿物。在絮凝剂的作用下三种物质形成稳定絮凝团,粘稠度大,流动性差,各种组分不易分离,因此浮渣的物理结构和表面性质使其在界面机制、分离难度等方面都具有特殊性,不利于浮渣的减量化、无害化处理和资源化利用,区别于其它种类的含油污泥;(2)含油浮渣的稳定性源于絮凝团结构的稳定性,只有破坏絮凝团结构,才能对浮渣进行进一步的深度处理。实验结果表明,物理、化学及机械等方法均有利于絮凝团的解体,但可破坏铝盐凝聚作用的化学药剂,能最有效地实现浮渣的絮凝团破坏。浮渣结构破坏后,液/固分离效果明显,可进行石油的清洗、压滤和焚烧处理。因此反絮凝-液化处理,是浮渣处理的有效方法和技术前提;(3)浮渣中石油的清洗效率取决于石油和粘土矿物的理化性质,尤其是粘土矿物的表面性质对油的吸附/解吸具有重要影响。采用高效化学清洗药剂,可使含油浮渣中固体颗粒的吸附油得到有效清除;基于自行设计的清洗装置,控制搅拌频率、旋流速度及搅混半径,并调控反应体系的反应温度及变化过程,可实现油的清洗和分离;(4)含油浮渣减量化的主要手段是板框压滤,提高减量化效率的重要途径是破解絮凝团结构,提高游离水比例,并采用静态间歇或动态连续沉降进行污泥浓缩,以提高压滤效率。实验结果表明,通过液化(反絮凝)—浓缩(固液分离)—压滤工艺对含油浮渣进行减量处理,含油浮渣的含水率下降了17~24%,浮渣含水率达到80%以下,体积减量8~10倍,压滤时效提高一倍,总体处理费用与现有技术相当;(5)减量化没有解决浮渣的最后出路问题,在此基础上探索浮渣的焚烧技术方法具有重要意义。
Gas floatation has already become the necessary technics in the viscous oil produced water treatment process and the output of floating sludge increased particularly. Currently 5.8×104m3floating sludge was produced every year,comprised water(97%), secondary mineral(2%) and petrolum(1%). Among them resin and bitumen are dominating oil component. No efficacious technics could be applied to the sludge treatment so far and this thorny problem on the environmental protection floored the Liaohe oil field. Six kind of floating sludge sampling from 6 produced water treatment station was investigated. Based on the analysis results, treatment methods were applied, such as reverse flocculation, pressure filter and rotary hearth incinerator. Results were as follows:
(1) Petroleum, secondary mineral and water agglomerate and form floating sludge. So the sludge was viscidity and the components could not be separated easily. The physical construction and surface character lead to the special interface attribute and deoil difficulty. So the deconstruction of floc is essential for the floating sludge treatment.
(2) The stability of sludge depends on the structure of floc. It is necessary to destroy the framework of floc. In the experiment, physical, chemical and dynamical measures were taken to break the floc. The results showed that the reverse flocuation is the necessary pretreatment. Water could separted from the floc after its deconstruction.
(3) Pressure filter is still the most effective path to reduce the volume of sludge. the process of reverse flocuation-sludge thicking-presure filter could decrease the water concerntration below 80% and reduced the volume to 1/10-1/8.
(4) Batch refuse incinerator and rotary hearth incinerator were applied in this study.Industry pilotting experiment show that sludge could be treated by incinerator safely.
实验结果表明:(1)含油浮渣的主要特点是含水率高,油成分主要为胶质、沥青质等重质成分,固体物质多为粘土矿物。在絮凝剂的作用下三种物质形成稳定絮凝团,粘稠度大,流动性差,各种组分不易分离,因此浮渣的物理结构和表面性质使其在界面机制、分离难度等方面都具有特殊性,不利于浮渣的减量化、无害化处理和资源化利用,区别于其它种类的含油污泥;(2)含油浮渣的稳定性源于絮凝团结构的稳定性,只有破坏絮凝团结构,才能对浮渣进行进一步的深度处理。实验结果表明,物理、化学及机械等方法均有利于絮凝团的解体,但可破坏铝盐凝聚作用的化学药剂,能最有效地实现浮渣的絮凝团破坏。浮渣结构破坏后,液/固分离效果明显,可进行石油的清洗、压滤和焚烧处理。因此反絮凝-液化处理,是浮渣处理的有效方法和技术前提;(3)浮渣中石油的清洗效率取决于石油和粘土矿物的理化性质,尤其是粘土矿物的表面性质对油的吸附/解吸具有重要影响。采用高效化学清洗药剂,可使含油浮渣中固体颗粒的吸附油得到有效清除;基于自行设计的清洗装置,控制搅拌频率、旋流速度及搅混半径,并调控反应体系的反应温度及变化过程,可实现油的清洗和分离;(4)含油浮渣减量化的主要手段是板框压滤,提高减量化效率的重要途径是破解絮凝团结构,提高游离水比例,并采用静态间歇或动态连续沉降进行污泥浓缩,以提高压滤效率。实验结果表明,通过液化(反絮凝)—浓缩(固液分离)—压滤工艺对含油浮渣进行减量处理,含油浮渣的含水率下降了17~24%,浮渣含水率达到80%以下,体积减量8~10倍,压滤时效提高一倍,总体处理费用与现有技术相当;(5)减量化没有解决浮渣的最后出路问题,在此基础上探索浮渣的焚烧技术方法具有重要意义。
Gas floatation has already become the necessary technics in the viscous oil produced water treatment process and the output of floating sludge increased particularly. Currently 5.8×104m3floating sludge was produced every year,comprised water(97%), secondary mineral(2%) and petrolum(1%). Among them resin and bitumen are dominating oil component. No efficacious technics could be applied to the sludge treatment so far and this thorny problem on the environmental protection floored the Liaohe oil field. Six kind of floating sludge sampling from 6 produced water treatment station was investigated. Based on the analysis results, treatment methods were applied, such as reverse flocculation, pressure filter and rotary hearth incinerator. Results were as follows:
(1) Petroleum, secondary mineral and water agglomerate and form floating sludge. So the sludge was viscidity and the components could not be separated easily. The physical construction and surface character lead to the special interface attribute and deoil difficulty. So the deconstruction of floc is essential for the floating sludge treatment.
(2) The stability of sludge depends on the structure of floc. It is necessary to destroy the framework of floc. In the experiment, physical, chemical and dynamical measures were taken to break the floc. The results showed that the reverse flocuation is the necessary pretreatment. Water could separted from the floc after its deconstruction.
(3) Pressure filter is still the most effective path to reduce the volume of sludge. the process of reverse flocuation-sludge thicking-presure filter could decrease the water concerntration below 80% and reduced the volume to 1/10-1/8.
(4) Batch refuse incinerator and rotary hearth incinerator were applied in this study.Industry pilotting experiment show that sludge could be treated by incinerator safely.
引文
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[8]冯志力,张洪林等.复配絮凝剂的筛选及其在炼油污泥中的应用.辽宁城乡环境科技,2003(10)25-28
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[3] K.Yake. Fixed technology and contaminated soil-petroleum industry. Proceedings of water, air and soil polluction and protection. Paris.1994 .198-203
[4] Heuer , et al Process for the Recovery oil from Waste Oil Sludges.WO9304800,1992
[5] W.J.Hahn.Biological Treatment of Petroleum Oily Sludge.SPE .23997,519-530
[6]王毓仁等.国外炼油厂含油污泥处理技术.炼油设计,1999,29(9):51-56
[7]张秀霞,耿春香等.溶剂萃取-蒸汽蒸馏法处理含油污泥.上海环境科学,2000(5):16-18
[8]冯志力,张洪林等.复配絮凝剂的筛选及其在炼油污泥中的应用.辽宁城乡环境科技,2003(10)25-28
[9] Bock,et al.Unique and Effective Separation Technique for Oil Contaminated Sludge. USA,US 4 938 877.1989
[10] Bruno Sander,et al. Dewatering of Petroleum Sludges with Recovery of the Oil Component.USA,US 4 417 976.1981
[11] Sanjay R Srivatsa,et al. Recovery of Oily Sludge .USA,US 4 383 927.1983
[12]赵玉鹏.含油污泥无害化处理研究.石油规划设计,1999,10(2):29-31
[13]芈振明等.固体废物的处理与处置,修订版.北京:高等教育出版社,1992,1-2
[14]何强.环境学导论,第二版.北京:清华大学出版社,1993,252-254
[15]吴芳云等.石油环境工程,第一版.北京:石油工业出版社,2002,665-668
[16]姜昌亮.石油工业环境保护,第一版.北京:石油工业出版社,2000,21-24
[17]唐淑清,刘志群,芦庆生等.工业无烟油泥煤研究.环境保护科学,1998,(4):28-31
[18] Roberta Schutte.process for reducing sludge accumulation in the hot water extraction process for oil sands.US5492628,1994
[19] W.J.Hahn.High-Temperature reprocessing of petroleum oily sludge.SPE Production & Facilities,1994,179-182
[20]赵乐军.污泥填埋技术应用进展.中国给水排水,2004,20:4-7
[21]郭宏昶等.炼油企业固体废物填埋场设计的若干问题.炼油设计,2000,(5):26-28
[22] Hong Dong Combustion method for the treatment of oil contaminated soil. Proceedings of water, air and soil pollution and protection. Paris, 1994, 289-293
[23] S.Sankaran,S.Pandey and K.Sumathy,Experimental Investigation on Waste Hest Recovery By Refinery Oil Sludge Incineration Using Fluidised-bed Technique,SCI.HEALH,A33(5),829~845,1998
[24] Arecco,A method for pretreating sludge of petroleum origin in readingess for destruction in an incinerator,and a system for impoementing the method,EP 550 790 A2
[25]刘晓娟等.油气田污泥无害化处理途径探讨.油气田环境保护,2004,(6):32-36
[26]周高华等.含油污泥脱水设备与技术.机械化工,2003,(5):306-312
[27] Iwata Y,Method of treating oil sludge,US5888375,1999
[28]龙安厚.大庆油田废钻井液固化处理研究.钻井液与完井液,2003,(2):4-5
[29]刘光全.含油污泥处理技术研究.重庆环境科学,1999,21(3):49-52
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