炼油厂含硫高盐碱渣废水的生物处理技术研究
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摘要
本论文针对炼油厂油品精制过程中产生的液态烃和催化汽油碱渣废水,采用生物技术进行处理,并且利用空气氧化法对液态烃废碱液进行脱毒,此外,还采用硝化反硝化技术对催化汽油废碱液进行无害化处理。
本课题采用了SBR反应器对液态烃废碱液的生物处理过程进行了研究。在处理模拟废水时,控制反应条件如下：温度为30±2℃、进水pH值在7.0-8.5之间、曝气量为0.3L/min,对活性污泥成功进行了驯化,污泥的耐盐性能良好,对硫化物和有机物的降解效果稳定。在S2-负荷为0.1kg/(m3.d),系统的溶解氧充足的条件下,硫化物基本全部转化为SO42-,硫化物去除率达到100%。
液态烃废碱液中硫化物浓度为9180mg/L, COD浓度为63300mg/L,其碱度超过300000mg/L, TDS超过230000mg/L,其B/C<0.1,可生化性较差。GC-MS结果表明其主要有机成分为含硫有机化合物,组分超过了85%。
在SBR反应器中,控制反应器温度为30±2℃、保持系统中DO充足,在进水TDS浓度为40g/L、进水pH值为10.5的条件下,以液态烃废碱液为处理对象,对活性污泥成功进行了驯化,污泥的耐盐碱性能良好。总硫负荷为0.9kgS/(m3-d)时,硫化物的去除率接近100%, COD的去除率为83.8%。S2-主要转化为S042-,转化率为96%。进一步研究发现,SBR反应器对稀释3倍的废碱液处理效果比较稳定,此时污泥负荷应保持在0.75-1.15kgCOD/kgMLVSS·d之间。在废碱液稀释3倍进水条件下,总硫负荷为1.5kgS/(m3·d)时,含硫化合物的去除率保持在99%以上,出水中检测不出硫化物,S2-氧化为S042-的转化率下降,出水中夹杂大量单质S。
以Monod修正方程和Haldane方程对废碱液的生物降解数据进行拟合,得到生物降解液态烃碱渣的动力学方程,其中难降解物质S。为454mg/L.结合两种模型可以看到,废碱液中存在一定量的难生物降解物质,而且废碱液浓度过高会明显抑制微生物的活性。
采取空气氧化-生物处理法对合成废水及液态烃废碱液进行了脱毒研究。实验发现空气氧化-生物处理法可以有效的提高S2-转化为S042-的氧化率,从而降低单质硫的生成率。此外,两步法还可以有效的缩短反应时间,提高反应负荷。
对催化汽油废碱液的性质进行了分析,发现其COD浓度为370000mg/L,军发酚含量达到118000mg/L,同时也具备很高的碱度和TDS,可生化性较差。GC-MS结果表明废碱液中主要的成分为酚类化合物,占有机组分的比例达到76.9%,此外还含有20.1%的含硫有机物。
采取SBR工艺对催化汽油废碱液进行处理。经中和-萃取预处理后废碱液中COD浓度从370000mg/L下降到10500mg/L,酚的含量降低99.9%,B/C从小于0.1上升到0.4,具备较好的可生化性。利用SBR反应器对萃取后的废碱液进行生物处理,发现采用工业污泥的SBR-2系统的处理效果要明显好于采用市政污泥的SBR-1系统。
此外,采用A/O反应器考察以废碱液为单一碳源时A/O工艺对废碱液及氨氮废水的处理效果。研究发现以废碱液为碳源的处理效果稳定,废碱液中主要有机物均得到降解,出水NH3-N浓度低于检测限。为保证出水质量,废碱液的投加量与进水氨氮的浓度之比应为5。
Liquid hydrocarbon and catalytic gasoline spent caustic generated in the oil refining process of refinery were researched in this article with biological treatment method, liquid hydrocarbon spent caustic was detoxificated with air oxidation method, and the catalytic gasoline spent caustic was also disposed harmlessly by the use of nitrification and denitrification technology.
In this research, SBR reactor was adopted to study the biological treatment process of liquid hydrocarbon spent caustic.When the reaction condition was kept at the temperature of30℃, the pH value between7.0to8.5, and the aeration of0.3L/min in the simulated wastewater processing, the activated sludge was domesticated successfully, it achieved a good performance on salt-tolerance, and had a stable effect on the degradation of sulfide and organic matter. When the S2-load was0.1kg/(m3·d), and there was enough dissolved oxygen in the system, the sulfide were all converted to SO42-basically, and the removal rate of sulfide arrived at100%.
In the liquid hydrocarbon spent caustic, the sulfide concentration was9180mg/L, COD concentration was63300mg/L, alkalinity exceed300000mg/L, TDS was over230000mg/L, the B/C was below0.1, and it had poor biodegradability. GC-MS results showed that the main organic component of the spent caustic was sulfidic organic compound, and its rate exceeded85%.
In the experiment, the SBR reactor was controlled at temperature of30℃and kept with enough DO. When the influent TDS concentration was40g/L, and the influent pH value was10.5, liquid hydrocarbon spent caustic was researched as treatment objection. The activated sludge was domesticated successfully, and it had a good performance under halo-alkaline conditions. When the total sulfur load was0.9kgS/(m3·d), the sulfide removal efficiency arrived at about100%, and the COD removal rate was83.8%. S2-were mainly converted to SO42-, and the conversion rate was96%. Further studies showed that the SBR reactor had a relatively stable effect on the treatment of spent caustic diluted three times, and the sludge load should be kept between0.75-1.15kgCOD/kgMLVSS·d. When the influence was three times-diluted spent caustic, and the total sulfur load was1.5kgS/(m3·d). the removal efficiency of sulfur compounds were always above99%, there was not any sulfide detected in the effluent, the oxidation rate of S2-to SO42-declined, and there were a lot of elemental S mixed in the effluent.
The kinetic equation of liquid hydrocarbon caustic sludge biodegradation was obtainned by fitting the biodegradation data of spent caustic with the Monod correction equation and Haldane equation, and it showed that the Sn was454mg/L. It could be seen from the combination of these two models that there were a certain amount of substances which were diffcult to be biodegradable in the spent caustic, and the excessive concentration of spent caustic would inhibit microbial activity significantly.
In this study, the toxicity-reduction research of synthetic wastewater and liquid hydrocarbon spent caustic were carried out with air oxidation-biological treatment method. It was found that the air oxidation-biological treatment method could effectively increase the oxidation rate of S2-to SO42-, and thereby reduce the generation rate of elemental sulfur. In addition, the two-step method could also effectively shorten the reaction time, and improve the reaction load.
The characteristics of catalytic gasoline spent caustic was studied in this study, and it was found that its COD concentration was370000mg/L, volatile phenol content arrived at118000mg/L, the alkalinity and TDS were very high, and the biodegradability was poor. GC-MS results showed that the main component of spent caustic was phenolic compounds, wich take76.9%of all the organic components, and the additional20.1%were sulfidic organic compounds.
SBR process was taken to make treatment to catalytic gasoline spent caustic. After the pretreatment, COD removal efficiency of spent caustic was over97%, phenol content decreased by99.9%, and B/C rose to0.4which showed good biodegradability. After the biological treatment to pretreated spent caustic in SBR reactor, it was found that the effect of SBR-2system which take industrial sludge was abviously better than that of SBR-1system which use municipal sludge.
In addition, the effect of A/O process to spent caustic and ammonia wastewater which made spent caustic as the only carbon source was investigated with A/O reactor. The results showed that the treatment effect of the process which make spent caustic as the only carbon source was quite stable, the main organic matter in the spent caustic were all degradated. and the effluent NH3-N concentration was below the detection limit. In order to ensure the quality of effluent, the proportion of spent caustic to the concentration of the influent ammonia should be5.
本课题采用了SBR反应器对液态烃废碱液的生物处理过程进行了研究。在处理模拟废水时,控制反应条件如下：温度为30±2℃、进水pH值在7.0-8.5之间、曝气量为0.3L/min,对活性污泥成功进行了驯化,污泥的耐盐性能良好,对硫化物和有机物的降解效果稳定。在S2-负荷为0.1kg/(m3.d),系统的溶解氧充足的条件下,硫化物基本全部转化为SO42-,硫化物去除率达到100%。
液态烃废碱液中硫化物浓度为9180mg/L, COD浓度为63300mg/L,其碱度超过300000mg/L, TDS超过230000mg/L,其B/C<0.1,可生化性较差。GC-MS结果表明其主要有机成分为含硫有机化合物,组分超过了85%。
在SBR反应器中,控制反应器温度为30±2℃、保持系统中DO充足,在进水TDS浓度为40g/L、进水pH值为10.5的条件下,以液态烃废碱液为处理对象,对活性污泥成功进行了驯化,污泥的耐盐碱性能良好。总硫负荷为0.9kgS/(m3-d)时,硫化物的去除率接近100%, COD的去除率为83.8%。S2-主要转化为S042-,转化率为96%。进一步研究发现,SBR反应器对稀释3倍的废碱液处理效果比较稳定,此时污泥负荷应保持在0.75-1.15kgCOD/kgMLVSS·d之间。在废碱液稀释3倍进水条件下,总硫负荷为1.5kgS/(m3·d)时,含硫化合物的去除率保持在99%以上,出水中检测不出硫化物,S2-氧化为S042-的转化率下降,出水中夹杂大量单质S。
以Monod修正方程和Haldane方程对废碱液的生物降解数据进行拟合,得到生物降解液态烃碱渣的动力学方程,其中难降解物质S。为454mg/L.结合两种模型可以看到,废碱液中存在一定量的难生物降解物质,而且废碱液浓度过高会明显抑制微生物的活性。
采取空气氧化-生物处理法对合成废水及液态烃废碱液进行了脱毒研究。实验发现空气氧化-生物处理法可以有效的提高S2-转化为S042-的氧化率,从而降低单质硫的生成率。此外,两步法还可以有效的缩短反应时间,提高反应负荷。
对催化汽油废碱液的性质进行了分析,发现其COD浓度为370000mg/L,军发酚含量达到118000mg/L,同时也具备很高的碱度和TDS,可生化性较差。GC-MS结果表明废碱液中主要的成分为酚类化合物,占有机组分的比例达到76.9%,此外还含有20.1%的含硫有机物。
采取SBR工艺对催化汽油废碱液进行处理。经中和-萃取预处理后废碱液中COD浓度从370000mg/L下降到10500mg/L,酚的含量降低99.9%,B/C从小于0.1上升到0.4,具备较好的可生化性。利用SBR反应器对萃取后的废碱液进行生物处理,发现采用工业污泥的SBR-2系统的处理效果要明显好于采用市政污泥的SBR-1系统。
此外,采用A/O反应器考察以废碱液为单一碳源时A/O工艺对废碱液及氨氮废水的处理效果。研究发现以废碱液为碳源的处理效果稳定,废碱液中主要有机物均得到降解,出水NH3-N浓度低于检测限。为保证出水质量,废碱液的投加量与进水氨氮的浓度之比应为5。
Liquid hydrocarbon and catalytic gasoline spent caustic generated in the oil refining process of refinery were researched in this article with biological treatment method, liquid hydrocarbon spent caustic was detoxificated with air oxidation method, and the catalytic gasoline spent caustic was also disposed harmlessly by the use of nitrification and denitrification technology.
In this research, SBR reactor was adopted to study the biological treatment process of liquid hydrocarbon spent caustic.When the reaction condition was kept at the temperature of30℃, the pH value between7.0to8.5, and the aeration of0.3L/min in the simulated wastewater processing, the activated sludge was domesticated successfully, it achieved a good performance on salt-tolerance, and had a stable effect on the degradation of sulfide and organic matter. When the S2-load was0.1kg/(m3·d), and there was enough dissolved oxygen in the system, the sulfide were all converted to SO42-basically, and the removal rate of sulfide arrived at100%.
In the liquid hydrocarbon spent caustic, the sulfide concentration was9180mg/L, COD concentration was63300mg/L, alkalinity exceed300000mg/L, TDS was over230000mg/L, the B/C was below0.1, and it had poor biodegradability. GC-MS results showed that the main organic component of the spent caustic was sulfidic organic compound, and its rate exceeded85%.
In the experiment, the SBR reactor was controlled at temperature of30℃and kept with enough DO. When the influent TDS concentration was40g/L, and the influent pH value was10.5, liquid hydrocarbon spent caustic was researched as treatment objection. The activated sludge was domesticated successfully, and it had a good performance under halo-alkaline conditions. When the total sulfur load was0.9kgS/(m3·d), the sulfide removal efficiency arrived at about100%, and the COD removal rate was83.8%. S2-were mainly converted to SO42-, and the conversion rate was96%. Further studies showed that the SBR reactor had a relatively stable effect on the treatment of spent caustic diluted three times, and the sludge load should be kept between0.75-1.15kgCOD/kgMLVSS·d. When the influence was three times-diluted spent caustic, and the total sulfur load was1.5kgS/(m3·d). the removal efficiency of sulfur compounds were always above99%, there was not any sulfide detected in the effluent, the oxidation rate of S2-to SO42-declined, and there were a lot of elemental S mixed in the effluent.
The kinetic equation of liquid hydrocarbon caustic sludge biodegradation was obtainned by fitting the biodegradation data of spent caustic with the Monod correction equation and Haldane equation, and it showed that the Sn was454mg/L. It could be seen from the combination of these two models that there were a certain amount of substances which were diffcult to be biodegradable in the spent caustic, and the excessive concentration of spent caustic would inhibit microbial activity significantly.
In this study, the toxicity-reduction research of synthetic wastewater and liquid hydrocarbon spent caustic were carried out with air oxidation-biological treatment method. It was found that the air oxidation-biological treatment method could effectively increase the oxidation rate of S2-to SO42-, and thereby reduce the generation rate of elemental sulfur. In addition, the two-step method could also effectively shorten the reaction time, and improve the reaction load.
The characteristics of catalytic gasoline spent caustic was studied in this study, and it was found that its COD concentration was370000mg/L, volatile phenol content arrived at118000mg/L, the alkalinity and TDS were very high, and the biodegradability was poor. GC-MS results showed that the main component of spent caustic was phenolic compounds, wich take76.9%of all the organic components, and the additional20.1%were sulfidic organic compounds.
SBR process was taken to make treatment to catalytic gasoline spent caustic. After the pretreatment, COD removal efficiency of spent caustic was over97%, phenol content decreased by99.9%, and B/C rose to0.4which showed good biodegradability. After the biological treatment to pretreated spent caustic in SBR reactor, it was found that the effect of SBR-2system which take industrial sludge was abviously better than that of SBR-1system which use municipal sludge.
In addition, the effect of A/O process to spent caustic and ammonia wastewater which made spent caustic as the only carbon source was investigated with A/O reactor. The results showed that the treatment effect of the process which make spent caustic as the only carbon source was quite stable, the main organic matter in the spent caustic were all degradated. and the effluent NH3-N concentration was below the detection limit. In order to ensure the quality of effluent, the proportion of spent caustic to the concentration of the influent ammonia should be5.
引文
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