超临界水氧化含油污泥技术研究
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摘要
超临界水氧化技术(Supercritical Water Oxidation,SCWO)是一种能够彻底破坏有机物结构的新型氧化技术。大多数有机污染物和氧气都能够极好地溶解在超临界水(Supercritical Water,SCW)中,形成一个有机物氧化的良好环境。从而可以很好地将废物中所含的有机物用氧化剂分解成水、CO2等简单无害的小分子化合物。
本文以过氧化氢作氧化剂,使用自行设计的实验装置,以实际油田含油污泥和模拟的含油污泥为研究对象,研究超临界水氧化法处理油田含油污泥。实验研究了反应温度、反应压力、反应停留时间、氧化剂量等因素对含油污泥中有机物去除率的影响,并且提出了以HCHO作共氧化剂、NaHCO3在低温时作催化剂来促进含油污泥中有机物去除率。并对超临界水氧化反应机理进行了讨论。
实验结果表明:最佳反应温度420℃—440℃;最佳反应压力24MPa—30MPa;反应停留时间10min—15min;氧化剂过氧比,过氧化氢量与化学需求量之比为4—7;含油污泥量,污泥中所含有机物COD为2000mg/L—6000mg/L;最佳pH值为10。HCHO具有很好的共氧化作用,在反应温度440℃、反应压力24MPa、反应时间10min、氧化剂过氧比为4、初始油田含油污泥COD为2000mg/L、15mg/L共氧化剂HCHO条件下,油田含油污泥COD去除率达99.9%,最后出水COD<10mg/L。超临界水氧化含油污泥为自由基反应机理,反应中间产物为醋酸和一氧化碳。含油污泥的超临界水氧化反应经过醋酸、一氧化碳中间步骤,然后再进一步氧化分解为二氧化碳和水。
Supercritical water oxidation technology is a new type technology of the complete destruction of the organic matter structure. Most organic pollutants and oxygen can dissolve in supercritical water, and they can form a good environment. Thus the organic matter in the waste can be decomposed by oxidants into water, carbon dioxide and simple small molecule compounds.
Hydrogen peroxide is the oxidant in this paper, self-designed experimental device is used, the actual oily sludge and the simulation oily sludge are destruction by hydrogen peroxide in supercritical water. The reaction temperature, the reaction pressure, the reaction residence time and oxidants are study on the removal rate of organic matter of oily sludge. Formaldehyde has been used as a co-oxidant, sodium bicarbonate has been used as catalyst to promote organic matter removal rate of oily sludge at low temperature. And supercritical water oxidation reaction mechanism was discussed.
The experimental results show that: the best reaction temperature is 420℃—440℃; best reaction pressure is 24MPa—30MPa; best reaction residence time is 10min—15min; the initial hydrogen peroxide, th ratio of the actual amount and theoretical demand is 4—7; oily sludge volume, initial COD is 2000mg/L—6000mg/L; optimum pH value is 10; the co-oxidative effect of formaldehyde on oil-field sludge is characterized for oilfield sludge concentrations (50000mg/L) and formaldehyde concentration (15mg/L) for a range of temperatures (380℃-440℃), the COD removal rate is 99.9% at T=440℃, p=24MPa,τ=10min, [COD]initial=2000mg/L, with formaldehyde in supercritical water, and finally effluent COD <10mg/L. Radical reaction mechanism is the mechanism of supercritical water oxidation oily sludge, acetic acid and carbon monoxide are the reaction intermediate product. First acetic acid and carbon monoxide are generated in supercritical water, and then further oxidized to carbon dioxide and water.
本文以过氧化氢作氧化剂,使用自行设计的实验装置,以实际油田含油污泥和模拟的含油污泥为研究对象,研究超临界水氧化法处理油田含油污泥。实验研究了反应温度、反应压力、反应停留时间、氧化剂量等因素对含油污泥中有机物去除率的影响,并且提出了以HCHO作共氧化剂、NaHCO3在低温时作催化剂来促进含油污泥中有机物去除率。并对超临界水氧化反应机理进行了讨论。
实验结果表明:最佳反应温度420℃—440℃;最佳反应压力24MPa—30MPa;反应停留时间10min—15min;氧化剂过氧比,过氧化氢量与化学需求量之比为4—7;含油污泥量,污泥中所含有机物COD为2000mg/L—6000mg/L;最佳pH值为10。HCHO具有很好的共氧化作用,在反应温度440℃、反应压力24MPa、反应时间10min、氧化剂过氧比为4、初始油田含油污泥COD为2000mg/L、15mg/L共氧化剂HCHO条件下,油田含油污泥COD去除率达99.9%,最后出水COD<10mg/L。超临界水氧化含油污泥为自由基反应机理,反应中间产物为醋酸和一氧化碳。含油污泥的超临界水氧化反应经过醋酸、一氧化碳中间步骤,然后再进一步氧化分解为二氧化碳和水。
Supercritical water oxidation technology is a new type technology of the complete destruction of the organic matter structure. Most organic pollutants and oxygen can dissolve in supercritical water, and they can form a good environment. Thus the organic matter in the waste can be decomposed by oxidants into water, carbon dioxide and simple small molecule compounds.
Hydrogen peroxide is the oxidant in this paper, self-designed experimental device is used, the actual oily sludge and the simulation oily sludge are destruction by hydrogen peroxide in supercritical water. The reaction temperature, the reaction pressure, the reaction residence time and oxidants are study on the removal rate of organic matter of oily sludge. Formaldehyde has been used as a co-oxidant, sodium bicarbonate has been used as catalyst to promote organic matter removal rate of oily sludge at low temperature. And supercritical water oxidation reaction mechanism was discussed.
The experimental results show that: the best reaction temperature is 420℃—440℃; best reaction pressure is 24MPa—30MPa; best reaction residence time is 10min—15min; the initial hydrogen peroxide, th ratio of the actual amount and theoretical demand is 4—7; oily sludge volume, initial COD is 2000mg/L—6000mg/L; optimum pH value is 10; the co-oxidative effect of formaldehyde on oil-field sludge is characterized for oilfield sludge concentrations (50000mg/L) and formaldehyde concentration (15mg/L) for a range of temperatures (380℃-440℃), the COD removal rate is 99.9% at T=440℃, p=24MPa,τ=10min, [COD]initial=2000mg/L, with formaldehyde in supercritical water, and finally effluent COD <10mg/L. Radical reaction mechanism is the mechanism of supercritical water oxidation oily sludge, acetic acid and carbon monoxide are the reaction intermediate product. First acetic acid and carbon monoxide are generated in supercritical water, and then further oxidized to carbon dioxide and water.
引文
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[2] Mait Kriipsalu, Marcia Marques, Diauddin R. Nammari, etal. Bio-treatment of oil sludge: The contribution of amendment material to the content of target contaminants, and biodegradation dynamics [J]. Hazardous Materials, 2007, 148(3):616-622
[3] M. J. Ayotamuno, R. N. Okparanma, E. K. Nweneka, et al. Bio-remediation of a sludge containing hydrocarbons [J]. Applied Energy, 2007, 84(9): 936-943
[4] Bambang VERIANSYAH and Jae-Duck KIM. Supercritical water oxidation for the destruction of toxic organic wastewaters: A review [J]. Environmental Sciences 2007, 19(5): 513-522
[5] Onur ?. S??üt and Mesut Akgün. Treatment of textile wastewater by SCWO in tube reactor [J]. Supercrit Fluids. 2007, 43(1):106-111
[6]国家环保局,水和废水监测分析方法[M].第三版北京:中国环境科学出版社,1989
[7]中国石油天然气总公司发布.碎屑岩油藏注水水质推荐指标及分析方法[M].北京:石油工业出版社,1996,1-2
[8]邹斌,魏平方,邓皓.新型絮凝剂室内评价试验[J].油气田环境保护,2000,10(1):26-28
[9]刘万毅,吴尚芝.复合絮凝剂PAFCS的絮凝研究[J].工业水处理,1996,16(4):29~30
[10]刘晓娟,张宁生.油田含油污泥微波处理实验研究[J].油田化学,2004,21(3):287-289
[11]卢广平,陈宝智,王敬.絮凝剂对含油污泥过滤性能的影响[J].环境保护科学,2005,31(3):34~37
[12] Paspek Stephen C. Jr. et al. Method for rendering oily sludges environmentally acceptable. US 4786401
[13] Shanableh A.Earnest F.Gloyna,Supercritical water oxidation-wasterwaters and sludges [J]. Wat. Sci. Tech1991, 23: 389-398.
[14] Lee D S. Gloyna E F. Supercritical water oxidation microreactor system. Paper presented at Water Poll,Control Fed. Specialty Conf, New Orleans,Louis-iana. 1988, April 17-19.
[15] Helling R K. Tester J W. Oxidation of simple com-pounds and mixtures in supercritical water carbon monoxide, ammonia and ethanol [J]. Environ. Sci. Tecnol, 1988, 22: 1319-1324.
[16] Thornton T D, LaDue D E. Savage P E. Phenol oxidation in supercritical water: formation of dibenzofuran dibenzo-p-dioxin and related compounds [J]. Environ. Sci. Technol. 1991, 25: 1507-1510.
[17] Emmanuel Fauvel, Christophe Joussot-Dubien, Pierrette Guichardon, et al. Adouble-wall reactor for hydrothermal oxidation with supercritical water flow across the inner porous tube [J]. Supercritical Fluids. 2004, 28: 47–56
[18] Ding Z Y. Supercritical water oxidation of NH3 over a MnO2/CeO2 catalyst [J]. Industrial Engineering Chemistry Research. 1998, 37(5):1707-1716.
[19]王涛,杨明,向波涛,等.超临界水氧化法去除尿液中有机物的探索[J].航天医学与医学工程,1997,10(5):370-372.
[20]向波涛,王涛,刘军,等.超临界水氧化法处理含硫废水研究[[J].化工环保,1999,(2):75-79.
[21]丁军委,陈丰秋,吴素芳,等.苯胺在超临界水中氧化反应动力学的研究[J].高校化学工程学报,2001,2:66-70.
[22]王涛,何胜悦,刘崇义,等.超临界水氧化法处理对苯二酚废水的初步研究[J].化工学报,1996,47(3):381-384.
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