罐底油泥中原油回收的工艺技术研究
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摘要
原油生产,炼制,运输过程中会产生大量的含油污泥,这些含油污泥充分乳化而难以自然沉降,如不加以处理而直接堆放,不仅会造成环境污染,也是对污泥中所含原油的一种浪费。本研究针对含油污泥中危害严重,含油量大,回收价值高,且难以处理的罐底油泥,采用冻融法和热化学清洗法对其进行处理,既可解决罐底油泥的环境污染问题,又可回收石油资源,因此有着重要的研究价值。
研究认为在两个系统运行涉及到的众多因素中,冻融法的关键是冰体生长条件的控制,热化学清洗法的关键是药剂的筛选和使用。
(1)选用采自辽河油田的罐底油泥为研究对象,运用热重,热值分析,光谱分析等多种手段,分析得到样品含水50.62%,含油39.3%,含泥沙9.98%,土壤残油率22.7%。主要油分为沸点在300-400℃间的烃类,油泥热值为15347.2 kJ/kg。
(2)在不使用药剂的情况下,确定冻融法最佳工艺条件为:调节样品含水率至70%,冷冻温度为-16±0.5℃,冷冻时间为8h,融解温度20-25℃。在此条件下,土壤残油率降至2.6%,二级冻融后,土壤残油率降至0.5%;热化学清洗法最佳工艺条件为:调节样品含水率至65%,清洗温度60℃,清洗时间30min,搅拌器转速200 r/min。此时,土壤残油率降至4.4%。
(3)热化学清洗法在最佳工艺条件下,对清洗药剂筛选复配的研究表明,当选定清洗剂的理想配方为LAS:Na_2CO_3=1:2(质量比)时,样品残油率降为1.7%,二级清洗后降至0.19%,可直接作为农用污泥排放。回收原油热值达到39186.3KJ/kg,接近原油平均热值41868.5 kJ/kg。
(4)通过测定Zeta电位值和COD值,为冻融法融水筛选得到高效无机絮凝剂PFS和有机高分子絮凝剂CPAM分别可使融水COD从455 mg/L降至201 mg/L和211 mg/L。两者组合使用,有效降低融水COD至177 mg/L;为热化学清洗法筛选得到高效无机絮凝剂PAC和有机高分子絮凝剂CPAM分别可使清洗液COD从降至167 mg/L和208mg/L。两者组合使用,有效降低融水COD至149mg/L。
(5)构建冻融技术处理罐底油泥工艺流程。设计一种新型悬浮式连续冷冻/融化罐底油泥处理工艺装置,该装置具有操作简便,处理效率高,节省资源等特点。
Sludge, which is discharged from the process of oil crude production and transport, can not be free settled because of its sufficient emulsification. It can get the environment polluted, and also be a waste of crude oil resource while the oily sludge is discharged directly without any disposal. Study focuses on treating oily sludge of tank bottom which is harmful, oily, valuable and difficult to dispose. Freeze/thaw method and thermochemical cleaning method are considered to be the valuable methods that studied to treat the oily sludge and recycle oil.
Controling the growth of ice crystal and choosing the right reagent are the core factors in these two methods.
(1) The sample is taken from oil tank bottom of Liao River Oil field, new test approaches are attempted on the base analyse of nature and chemical compositions of the sample. Water content, oil conten, sand content and the residual oil rate in solid are 50.62%, 39.3%, 9.98% and 22.7%, respectively. Boiling points of hydrocarbon in oil are between 300-400℃, the heating value of the sludge is 15347.2 kJ/kg.
(2) The study observes the performances of freeze/thaw method and thermochemical cleaning method on oily sludge treatment without using reagent and determines the best initial parameters: for freeze/thaw method, the best water content, freezing temperature, freezing time and thawing temperature are 70%, -16±0.5℃, 8 h and 20-25°C, respectively. The best residual oil rate in solid could reach 2.6%, 0.5% could be reached while using the second level of freeze/thaw method; For thermochemical cleaning method, the best water content is 65%, washing temperature is 60°C, washing time is 30 min, agitation speed is 200 r/min and the residual oil rate in solid could reach 4.4%.
(3) Under the best technologcial conditions, LAS:Na_2CO_3=1:2(mass ratio) are selected. The residual oil rates reduced to 1.7% when LAS:Na_2CO_3=1:2 and to 0.19% while using the second level washing. The heating value is 39186.3 kJ/kg which closes to the average heating value of oil.
(4) In the flocculation experiment of the thawing water and waste water, Zeta electric potential and COD were measured to select the optimum inorganic flocculate solution and organic macromolecule. PFS and CPAM are chosen in freeze/thaw method and the COD could reach 177 when they were combined. PAC and CPAM are chosen in thermochemical cleaning method and the COD could reach 149 when they were combined.
(5) Based on freeze/thaw principle and basal experiments, an oily sludge floating freeze/thaw treatment equipment which is high performance, low cost and convenient to operate are designed.
研究认为在两个系统运行涉及到的众多因素中,冻融法的关键是冰体生长条件的控制,热化学清洗法的关键是药剂的筛选和使用。
(1)选用采自辽河油田的罐底油泥为研究对象,运用热重,热值分析,光谱分析等多种手段,分析得到样品含水50.62%,含油39.3%,含泥沙9.98%,土壤残油率22.7%。主要油分为沸点在300-400℃间的烃类,油泥热值为15347.2 kJ/kg。
(2)在不使用药剂的情况下,确定冻融法最佳工艺条件为:调节样品含水率至70%,冷冻温度为-16±0.5℃,冷冻时间为8h,融解温度20-25℃。在此条件下,土壤残油率降至2.6%,二级冻融后,土壤残油率降至0.5%;热化学清洗法最佳工艺条件为:调节样品含水率至65%,清洗温度60℃,清洗时间30min,搅拌器转速200 r/min。此时,土壤残油率降至4.4%。
(3)热化学清洗法在最佳工艺条件下,对清洗药剂筛选复配的研究表明,当选定清洗剂的理想配方为LAS:Na_2CO_3=1:2(质量比)时,样品残油率降为1.7%,二级清洗后降至0.19%,可直接作为农用污泥排放。回收原油热值达到39186.3KJ/kg,接近原油平均热值41868.5 kJ/kg。
(4)通过测定Zeta电位值和COD值,为冻融法融水筛选得到高效无机絮凝剂PFS和有机高分子絮凝剂CPAM分别可使融水COD从455 mg/L降至201 mg/L和211 mg/L。两者组合使用,有效降低融水COD至177 mg/L;为热化学清洗法筛选得到高效无机絮凝剂PAC和有机高分子絮凝剂CPAM分别可使清洗液COD从降至167 mg/L和208mg/L。两者组合使用,有效降低融水COD至149mg/L。
(5)构建冻融技术处理罐底油泥工艺流程。设计一种新型悬浮式连续冷冻/融化罐底油泥处理工艺装置,该装置具有操作简便,处理效率高,节省资源等特点。
Sludge, which is discharged from the process of oil crude production and transport, can not be free settled because of its sufficient emulsification. It can get the environment polluted, and also be a waste of crude oil resource while the oily sludge is discharged directly without any disposal. Study focuses on treating oily sludge of tank bottom which is harmful, oily, valuable and difficult to dispose. Freeze/thaw method and thermochemical cleaning method are considered to be the valuable methods that studied to treat the oily sludge and recycle oil.
Controling the growth of ice crystal and choosing the right reagent are the core factors in these two methods.
(1) The sample is taken from oil tank bottom of Liao River Oil field, new test approaches are attempted on the base analyse of nature and chemical compositions of the sample. Water content, oil conten, sand content and the residual oil rate in solid are 50.62%, 39.3%, 9.98% and 22.7%, respectively. Boiling points of hydrocarbon in oil are between 300-400℃, the heating value of the sludge is 15347.2 kJ/kg.
(2) The study observes the performances of freeze/thaw method and thermochemical cleaning method on oily sludge treatment without using reagent and determines the best initial parameters: for freeze/thaw method, the best water content, freezing temperature, freezing time and thawing temperature are 70%, -16±0.5℃, 8 h and 20-25°C, respectively. The best residual oil rate in solid could reach 2.6%, 0.5% could be reached while using the second level of freeze/thaw method; For thermochemical cleaning method, the best water content is 65%, washing temperature is 60°C, washing time is 30 min, agitation speed is 200 r/min and the residual oil rate in solid could reach 4.4%.
(3) Under the best technologcial conditions, LAS:Na_2CO_3=1:2(mass ratio) are selected. The residual oil rates reduced to 1.7% when LAS:Na_2CO_3=1:2 and to 0.19% while using the second level washing. The heating value is 39186.3 kJ/kg which closes to the average heating value of oil.
(4) In the flocculation experiment of the thawing water and waste water, Zeta electric potential and COD were measured to select the optimum inorganic flocculate solution and organic macromolecule. PFS and CPAM are chosen in freeze/thaw method and the COD could reach 177 when they were combined. PAC and CPAM are chosen in thermochemical cleaning method and the COD could reach 149 when they were combined.
(5) Based on freeze/thaw principle and basal experiments, an oily sludge floating freeze/thaw treatment equipment which is high performance, low cost and convenient to operate are designed.
引文
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