厌氧消化-SBR-絮凝组合工艺处理牛粪废水研究
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摘要
随着我国畜禽养殖业的快速发展以及不可再生能源的短缺,迫切需要研究、解决日益严重的畜禽粪便废水污染及生物能源再利用问题。本文既是结合牛粪废水的特点,采用厌氧消化-SBR-絮凝组合工艺对其进行综合处理,克服以往单独以处理废水为目的的做法,达到既可以获得可再生能源,又能够治理废水污染的双重目的,具有重要的经济、社会效益。
牛粪废水的厌氧消化是本文研究的核心。为了高温厌氧消化过程的快速启动和平稳运行,获得更多的厌氧消化气,本文首先进行了接种物的筛选、培养和驯化研究,重点考察了接种物种类、培养条件等因素对废水厌氧消化性能的影响。结果表明:采用生活污水处理厂的二沉池污泥与厌氧消化污泥混合物来培养接种物效果良好,具体表现在:厌氧消化反应启动较快,产气过程较平稳,产气持续时间长,产气量大;体系的pH值比较稳定,对挥发性酸的积累具有更强的缓冲能力;对COD的去除率也相对较高。
在此基础上,采用选定的接种物,实验研究了温度、进水有机物浓度以及微量元素等对牛粪废水厌氧消化过程中甲烷产率及COD去除率的影响。结果显示:温度对牛粪废水厌氧消化产气状况影响较大,相对室温而言,高温厌氧消化产气量高,且其中甲烷含量也比较高(63%),经厌氧消化后,废水COD去除率达57%。进水COD浓度对沼气产量有一定的影响,随着进料COD浓度增加,虽然总产气量增加,但是单位质量COD的产气量(甲烷转化率)以及COD去除率有所减小;微量元素的加入对低浓度废水影响不大,但对高浓度废水高温厌氧消化情况有一定改善,且不同微量元素对厌氧消化过程影响不同,微量元素Fe~(2+),Mg~(2+)、Ni~(2+)的适宜添加量不大于0.5 mmol/L。
结合牛粪废水高温厌氧消化的实验研究结果,利用Stover-Kineannon动力学模型,建立了牛粪废水高温厌氧消化动力学方程,其中:最大反应速率常数U_(max)=13.18 gCOD/(L_(溶液)·d),饱和常数K_b=13.77 gCOD/(L_(溶液)·d)。另外,通过研究高温厌氧消化过程中甲烷产率的动力学关系,得到甲烷最大产率常数M_(max)=18.11L_(gas)/(L_(溶液)·d);甲烷产率系数M_b=49.31 gCOD/(L_(溶液)·d)。这些动力学研究成果,对厌氧消化反应器的设计及运行具有重要的理论意义。
考虑到牛粪废水经高温厌氧消化后有机物含量仍然较高,本文采用自制的SBR反应器对厌氧消化液做进一步处理,重点研究了普通絮状活性污泥的培养、颗粒污泥的培养、两种污泥对污染物去除能力的对比、SBR絮状污泥处理过程中各参数对处理效果的影响以及SBR工艺处理高温厌氧消化液的动力学行为。结果表明:当高温厌氧消化液的COD在0.5～1.6 g/L之间变化时,SBR反应器表现出较强的抗负荷冲击能力;两种污泥对厌氧消化液中污染物去除能力都比较高,其中采用颗粒污泥进行处理,SBR出水悬浮物含量较低,且对COD、总氮(TKN)的去除略优于絮状活性污泥;另外,结合SBR絮状活性污泥处理厌氧消化液实际情况,建立了SBR反应器中COD降解的动力学方程。
最后,针对SBR处理出水仍有较多细小纤维素等悬浮物的特点,本文采用化学絮凝方法,对SBR净化水进行二级处理,旨在降低废水色度、悬浮物含量以及有机物浓度等。实验考察了絮凝剂种类、絮凝剂用量、搅拌速度、絮凝沉淀时间等因素对废水处理效果的影响,得出较佳的絮凝条件,即:采用聚合氯化铝作为絮凝剂、絮凝剂浓度1.5g/L、搅拌速度120r/min、慢速搅拌时间2.5min、沉淀时间20min。在此条件下,处理水的COD浓度低于400mg/L、悬浮物含量144mg/L、色度为48。
本文利用高温厌氧消化并结合SBR-絮凝法对经过预处理的牛粪废水进行处理,既获得了可再生能源-甲烷,又使废水达到了理想的处理效果,处理出水COD、色度、悬浮物等指标可以达到国家规定的畜禽养殖业污染物排放标准(GB18596-2001),为处理类似的畜禽粪便废水及再生能源的回收提供了新的组合工艺及理论依据。
The pollution of the dejection wastewater discharged from breed farms become severely and needed to be solved urgently in China. Based on the characters of the wastewater, the technology of thermophillic anaerobic digestion-SBR-flocculation was studied to treat them in this paper. Not only the reproducible energy was obtained but also the environmental pollutions were treated, it has important social and economic benefits.
The thermophilic anaerobic digestion of cow manure wastewater was the kernel part of this paper. In order to make the biochemistry reaction running smoothly and quickly, the inocula used in the experiments were selected and cultivated firstly, and the effects of the inocula's species, the cultivating conditions etc on the process of the wastewater thermophilic anaerobic digestion were discussed. Results showed that the anaerobic digestion reaction inoculated with the inocula cultivated with mixed sludge start up more quickly, biogas production more steady and last longer than that of the anaerobic digestion inoculated with inocula domesticated with single sludge, and the pH was more steady, COD removal efficiency higher too.
On the basis of the effects of inocula on the biochemistry's reaction, the selected incula was adopted and the effects of temperature, COD concentration and trace elements were studied. Results indicated that the temperature has greater impact on the system's operation. The biogas production, the percentage of methane in the biogas (63%) and the COD removal efficiency (57%) of thermophilic anaerobic digestion were higher than that of room temperature.
There wre some effects of COD concentration on the biogas production. With the increasing of COD concentration, total biogas production increased, while the biogas produced by per-unit quality of COD was decreased. The addition of trace elements had little effect on the lower COD concentration wastewater, but it could improve the treatment efficiency of higher COD wastewater. The appropriate quantity of Fe~(2+), Mg~(2+) or Ni~(2+) was about 0.5 mmol/L to the higher COD wastewater.
Combined with the results of thermophilic anaerobic digestion of cow manure wastewater, a kinetics equation based on the Stover-Kincannon model was obtained with the maximum reaction rate constant U_(max) as 13.18 gCOD/(L_(溶液)·d) and the saturation constant K_b as 13.77 gCOD/(L_(溶液)·d). In the same way, the maximum constant of methane production rate (M_(max)=18.11 L_(gas)/(L_(溶液)·d)) and coefficient of methane yield (M_b= 49.31 gCOD/(L_(溶液)·d)) were obtained too by studying the dynamics of the methane production rate. These research results have very important theoretical significance on the design and operations of anaerobic digestion reactor.
The concentration of COD, suspended substance were still higher than that of the discharge standard after the wastewater was treated by thermophilic anaerobic digestion and the SBR made by ourselves was used to treat them furthermore. The cultivation of popular active sludge and granular sludge, the COD removal efficiency of the two types sludge, the factors that affect the disposal efficiency of popular active sludge and the SBR kinetics were studied in this stage. Results showed that the SBR have a certain ability to resist the impact of organic loading rate when the COD concentration ranged from 0.5 g/L to 1.6 g/L. Both of the two types sludge have high removal efficiencies on organic compounds of the wastewater. The difference between them was that the suspended substance was lower, the removal efficiencies of COD and TKN a little higher of the water treated by granular sludge than that of treated by popular active sludge. In addition to that, the kinetics equation of SBR was established based on the actual situation of treating the effluent of the cow manure wastewater treated by the method of thermophilic anaerobic digestion.
Because the water treated by SBR still contained lots of celluloses and other tiny suspended substances, a process of flocculation as the secondary treatment was adopted to decrease the color, the suspended substances and the organic compounds concentration. The effects of the coagulant categories, dosage of coagulant, stirring speed, stirring time and settlement time were investigated, and the better flocculation conditions were obtained as coagulant dosage 1.5 g/L, stirring speed 120 r/min, stirring time 2.5 min and settlement time 20 min. After being treated under these conditions, COD concentration lower than 400 mg/L, suspended substance about 144 mg/L and the color about 50.
Not only the reproducible energy was obtained but also the ideal treatment effects of cow manure wastewater were obtained by the process of thermophilic anaerobic digestion combined with SBR and flocculation. The COD, suspended substances and color all met the discharge standard of water pollutants for farm breeds (GB18596-2001) after being treated by this method. A new integrated technology and theoretical basis were provided for the treatment of the similar wastewater.
牛粪废水的厌氧消化是本文研究的核心。为了高温厌氧消化过程的快速启动和平稳运行,获得更多的厌氧消化气,本文首先进行了接种物的筛选、培养和驯化研究,重点考察了接种物种类、培养条件等因素对废水厌氧消化性能的影响。结果表明:采用生活污水处理厂的二沉池污泥与厌氧消化污泥混合物来培养接种物效果良好,具体表现在:厌氧消化反应启动较快,产气过程较平稳,产气持续时间长,产气量大;体系的pH值比较稳定,对挥发性酸的积累具有更强的缓冲能力;对COD的去除率也相对较高。
在此基础上,采用选定的接种物,实验研究了温度、进水有机物浓度以及微量元素等对牛粪废水厌氧消化过程中甲烷产率及COD去除率的影响。结果显示:温度对牛粪废水厌氧消化产气状况影响较大,相对室温而言,高温厌氧消化产气量高,且其中甲烷含量也比较高(63%),经厌氧消化后,废水COD去除率达57%。进水COD浓度对沼气产量有一定的影响,随着进料COD浓度增加,虽然总产气量增加,但是单位质量COD的产气量(甲烷转化率)以及COD去除率有所减小;微量元素的加入对低浓度废水影响不大,但对高浓度废水高温厌氧消化情况有一定改善,且不同微量元素对厌氧消化过程影响不同,微量元素Fe~(2+),Mg~(2+)、Ni~(2+)的适宜添加量不大于0.5 mmol/L。
结合牛粪废水高温厌氧消化的实验研究结果,利用Stover-Kineannon动力学模型,建立了牛粪废水高温厌氧消化动力学方程,其中:最大反应速率常数U_(max)=13.18 gCOD/(L_(溶液)·d),饱和常数K_b=13.77 gCOD/(L_(溶液)·d)。另外,通过研究高温厌氧消化过程中甲烷产率的动力学关系,得到甲烷最大产率常数M_(max)=18.11L_(gas)/(L_(溶液)·d);甲烷产率系数M_b=49.31 gCOD/(L_(溶液)·d)。这些动力学研究成果,对厌氧消化反应器的设计及运行具有重要的理论意义。
考虑到牛粪废水经高温厌氧消化后有机物含量仍然较高,本文采用自制的SBR反应器对厌氧消化液做进一步处理,重点研究了普通絮状活性污泥的培养、颗粒污泥的培养、两种污泥对污染物去除能力的对比、SBR絮状污泥处理过程中各参数对处理效果的影响以及SBR工艺处理高温厌氧消化液的动力学行为。结果表明:当高温厌氧消化液的COD在0.5～1.6 g/L之间变化时,SBR反应器表现出较强的抗负荷冲击能力;两种污泥对厌氧消化液中污染物去除能力都比较高,其中采用颗粒污泥进行处理,SBR出水悬浮物含量较低,且对COD、总氮(TKN)的去除略优于絮状活性污泥;另外,结合SBR絮状活性污泥处理厌氧消化液实际情况,建立了SBR反应器中COD降解的动力学方程。
最后,针对SBR处理出水仍有较多细小纤维素等悬浮物的特点,本文采用化学絮凝方法,对SBR净化水进行二级处理,旨在降低废水色度、悬浮物含量以及有机物浓度等。实验考察了絮凝剂种类、絮凝剂用量、搅拌速度、絮凝沉淀时间等因素对废水处理效果的影响,得出较佳的絮凝条件,即:采用聚合氯化铝作为絮凝剂、絮凝剂浓度1.5g/L、搅拌速度120r/min、慢速搅拌时间2.5min、沉淀时间20min。在此条件下,处理水的COD浓度低于400mg/L、悬浮物含量144mg/L、色度为48。
本文利用高温厌氧消化并结合SBR-絮凝法对经过预处理的牛粪废水进行处理,既获得了可再生能源-甲烷,又使废水达到了理想的处理效果,处理出水COD、色度、悬浮物等指标可以达到国家规定的畜禽养殖业污染物排放标准(GB18596-2001),为处理类似的畜禽粪便废水及再生能源的回收提供了新的组合工艺及理论依据。
The pollution of the dejection wastewater discharged from breed farms become severely and needed to be solved urgently in China. Based on the characters of the wastewater, the technology of thermophillic anaerobic digestion-SBR-flocculation was studied to treat them in this paper. Not only the reproducible energy was obtained but also the environmental pollutions were treated, it has important social and economic benefits.
The thermophilic anaerobic digestion of cow manure wastewater was the kernel part of this paper. In order to make the biochemistry reaction running smoothly and quickly, the inocula used in the experiments were selected and cultivated firstly, and the effects of the inocula's species, the cultivating conditions etc on the process of the wastewater thermophilic anaerobic digestion were discussed. Results showed that the anaerobic digestion reaction inoculated with the inocula cultivated with mixed sludge start up more quickly, biogas production more steady and last longer than that of the anaerobic digestion inoculated with inocula domesticated with single sludge, and the pH was more steady, COD removal efficiency higher too.
On the basis of the effects of inocula on the biochemistry's reaction, the selected incula was adopted and the effects of temperature, COD concentration and trace elements were studied. Results indicated that the temperature has greater impact on the system's operation. The biogas production, the percentage of methane in the biogas (63%) and the COD removal efficiency (57%) of thermophilic anaerobic digestion were higher than that of room temperature.
There wre some effects of COD concentration on the biogas production. With the increasing of COD concentration, total biogas production increased, while the biogas produced by per-unit quality of COD was decreased. The addition of trace elements had little effect on the lower COD concentration wastewater, but it could improve the treatment efficiency of higher COD wastewater. The appropriate quantity of Fe~(2+), Mg~(2+) or Ni~(2+) was about 0.5 mmol/L to the higher COD wastewater.
Combined with the results of thermophilic anaerobic digestion of cow manure wastewater, a kinetics equation based on the Stover-Kincannon model was obtained with the maximum reaction rate constant U_(max) as 13.18 gCOD/(L_(溶液)·d) and the saturation constant K_b as 13.77 gCOD/(L_(溶液)·d). In the same way, the maximum constant of methane production rate (M_(max)=18.11 L_(gas)/(L_(溶液)·d)) and coefficient of methane yield (M_b= 49.31 gCOD/(L_(溶液)·d)) were obtained too by studying the dynamics of the methane production rate. These research results have very important theoretical significance on the design and operations of anaerobic digestion reactor.
The concentration of COD, suspended substance were still higher than that of the discharge standard after the wastewater was treated by thermophilic anaerobic digestion and the SBR made by ourselves was used to treat them furthermore. The cultivation of popular active sludge and granular sludge, the COD removal efficiency of the two types sludge, the factors that affect the disposal efficiency of popular active sludge and the SBR kinetics were studied in this stage. Results showed that the SBR have a certain ability to resist the impact of organic loading rate when the COD concentration ranged from 0.5 g/L to 1.6 g/L. Both of the two types sludge have high removal efficiencies on organic compounds of the wastewater. The difference between them was that the suspended substance was lower, the removal efficiencies of COD and TKN a little higher of the water treated by granular sludge than that of treated by popular active sludge. In addition to that, the kinetics equation of SBR was established based on the actual situation of treating the effluent of the cow manure wastewater treated by the method of thermophilic anaerobic digestion.
Because the water treated by SBR still contained lots of celluloses and other tiny suspended substances, a process of flocculation as the secondary treatment was adopted to decrease the color, the suspended substances and the organic compounds concentration. The effects of the coagulant categories, dosage of coagulant, stirring speed, stirring time and settlement time were investigated, and the better flocculation conditions were obtained as coagulant dosage 1.5 g/L, stirring speed 120 r/min, stirring time 2.5 min and settlement time 20 min. After being treated under these conditions, COD concentration lower than 400 mg/L, suspended substance about 144 mg/L and the color about 50.
Not only the reproducible energy was obtained but also the ideal treatment effects of cow manure wastewater were obtained by the process of thermophilic anaerobic digestion combined with SBR and flocculation. The COD, suspended substances and color all met the discharge standard of water pollutants for farm breeds (GB18596-2001) after being treated by this method. A new integrated technology and theoretical basis were provided for the treatment of the similar wastewater.
引文
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