纤维素乙醇废水生物处理技术研究
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摘要
本文研究纤维素乙醇废水治理方法,涉及新能源和环境工程两个行业。针对能源危机,寻找新能源成为人们关注的重点。在所有从植物物质获得的燃料中乙醇尤其受到人们的关注,是来自可再生资源的最有发展前景的液体燃料,但目前生物法生产的乙醇还主要来自糖类和淀粉发酵,面对世界人口的急剧膨胀和粮食短缺,用粮食生产酒精的发展将受到限制。随着全球性能源危机、粮食危机和环境危机的到来,以秸秆为原料的纤维素乙醇引起世界各国的高度重视。由于纤维素乙醇原料秸秆化学结构复杂,纤维素、半纤维素不但被木质素包裹,而且半纤维素共价和木质素结合,纤维素具有高度有序晶体结构,因此必须经过预处理,破坏晶体结构,降低聚合度。预处理采用秸秆粉碎蒸汽爆碎技术,产生的废水中含有部分纤维素、木质素、半纤维等难生物降解物质,生产过程产生的冷凝水含有大量的挥发性酸、糠醛及挥发性酚类物质,是一种危害很大的废水。本文以河南南阳某集团纤维素生产线预处理工段产生滤液为研究对象,进行小试试验、中试试验、并将实验结果工程化,建成处理800t/d污水处理工程,取得以下主要研究成果：
1、采用固定化白腐菌对河南南阳某集团纤维乙醇蒸汽爆破之后板框压滤滤液进行试验,在试验过程中考察pH、停留时间及瘤胃微生物对处理效果影响,为纤维素乙醇处理奠定基础。
2、通过实验选择预处理、生化、深度处理适当工艺。对比气浮、微电解/H2O2、Fenton试剂催化氧化对废水进行预处理。对比厌氧、好氧对废水进行生化处理。通过实验对比,确定采用微电解+厌氧+好氧实验装置对废水进行处理是可行的,且该系统具有较强的抗冲击负荷能力；对废水深度处理进行探索,对比絮凝沉淀、ClO2催化氧化、Fenton试剂催化氧化、Fenton试剂催化氧化+接触氧化的去除效果,Fenton试剂催化氧化后COD去除率为50%左右,废水可生化性提高。
3、对纤维素乙醇废水采用中试处理,研究了中试处理效果及COD负荷、停留时间、pH对处理效果的影响,从而得出最佳运行COD负荷、停留时间、pH,对废水处理工程化提供指导意义。
4、基于前述技术论证及中试研究,对河南某集团纤维乙醇预处理滤液及综合废水采用预处理+UASB+一级好氧反应器+催化氧化、接触氧化复合好氧的处理工艺,建设废水处理工程。对废水处理进行调试,处理系统运行较为稳定,出水达到污水综合排放一级标准,可实现达标排放；在经过一级好氧处理后废水可生化性差,经过Fenton试剂催化氧化后,废水可生化性提高,为后继接触氧化提供条件；催化氧化后再采用接触氧化法可进一步降低废水污染物浓度,实现达标排放。
5、瘤胃微生物可缩短厌氧装置的启动时间,强化厌氧处理效果；白腐真菌可促进好氧菌胶团的形成,提高好氧处理效果。
6、废水污染物浓度较高,处理难度较大,该工程采用较多工段,废水运行费用较高,约3.56元/t。
7、本研究使纤维质原料生产乙醇过程中产生的废水在厌氧处理过程中又可产生燃料沼气,为天然纤维质原料生物量获得全利用奠定基础。
This paper describes the wastewater treatment methods,which is produced in the new energy of cellulosic ethanol production, involving both new energy industry and environmental engineering industry. Because of the energy crisis, the search for new energy sources is becoming the focus of attention. In all the material obtained from plants, particularly, ethanol attracts people's concern, which is the most promising liquid fuel coming from renewable resources, but currently biological production of ethanol primarily from sugar and starch fermentation, facing the rapid expansion of the world's population and food shortages, the development of alcohol produced with grain will be restricted. As the advent of global energy crisis, food crisis and environmental crisis, cellulosic ethanol has drawn worldwide attention. Because of the complexity of the chemical structure of Straw cellulosic ethanol in which cellulose and hemi cellulose not only have been wrapped lignin,but also covalently with cellulose,with highly ordered crystal structure, it must be pretreatmented to damage crystal structure, reduce the degree of polymerization. The steam explosion pre-treatment technology is used. The waste water from Ethanol production contains some cellulose,lignin, hemicelluloses and so on,which is difficult to be degraded.The condensate from Ethanol production contains a large number of volatile acid, furfural and volatile phenols.In the paper, filtrate from Ethanol production pretreatment process is as the object, carryed out small scale testing, pilot testing, and the results have been used to the engineering and the processing 800t/d sewage treatment project was builted,which has achieved the following research results:
(1) In the experiment, we used the immobilized white-rot fungi on the filtrate from cellulosic ethanol steam explosion frame filter press process t. In the course of the experiment, we studyed the treatment effect impact of pH, residence time, and dosing rumen micro-organisms, and the results will help lay the foundation. for cellulosic ethanol processing.
(2) In the experiment, we can select the appropriate technology for pre-processing system, biochemical, in-depth processing. We compared some pretreatment technology, flotation, micro-electrolysis/H2O2, Fenton reagent catalytic oxidation; and compared to anaerobic, aerobic biological treatment of wastewater. Through the experimental comparison, we determined it was feasible which was the use of micro-electrolysis+anaerobic+aerobic experimental device for wastewater treatment, and the system has a strong ability for the impact load;We explored the depth of processing for wastewater, contrasted the removal effect of the coagulation and sedimentation, ClO2 catalytic oxidation, Fenton's reagent oxidation, Fenton's reagent oxidation catalytic oxidation +contact oxidation, after Fenton's reagent oxidation the COD removal is 50%, waste water biodegradability increase.
(3) In the system, we used pilot treatment for wastewater from cellulosic ethanol production, studyed the treatment effect and the impact of treatment effect by COD load, residence time, pH and thus the optimum running COD load, residence time, pH, provide guidance to the wastewater treatment engineering.
(4) This system is based on the aforementioned and technical feasibility studies and research by Nanyang, Henan one Group of cellulosic ethanol and treatment of the filtrate and the comprehensive wastewater using an aerobic pretreatment+UASB+ first aerobic reactor+oxidation+combined aerobic contact oxidation treatment process, and build waste water treatment engineering. During debugging wastewater treatment, the initial trial keep a relatively stable operation, and the effluent wastewater can achieve the discharge standards; in the treated wastewater through an aerobic biodegradability is poor, but when it have the catalytic oxidation of Fenton's reagent, wastewater biodegradability will increased, and provide the conditions for follow-up contact oxidation; contact oxidation after catalytic oxidation can be used to further reduce wastewater pollutant concentrations,the wastewater will achieve discharge standards.
(5) According to microorganism growth picture condition analysis, the result indicated Rumen micro-organisms reduce start time of aerobic and strengthen processing effect; white-rot fungi promote formation of Fungus rubber group and enhance processing effect.
(6) Because of the high concentrations of pollutants in wastewater, handling is difficulty, the project used several steps, and the costs of the wastewater operating are high, about 3.56 yuan/t.
(7) In this paper, wastewater which is produced in the new energy of cellulosic ethanol production product methane in the process of anaerobic and it Settles foundation for natural fiber raw material Biomass for full used.
1、采用固定化白腐菌对河南南阳某集团纤维乙醇蒸汽爆破之后板框压滤滤液进行试验,在试验过程中考察pH、停留时间及瘤胃微生物对处理效果影响,为纤维素乙醇处理奠定基础。
2、通过实验选择预处理、生化、深度处理适当工艺。对比气浮、微电解/H2O2、Fenton试剂催化氧化对废水进行预处理。对比厌氧、好氧对废水进行生化处理。通过实验对比,确定采用微电解+厌氧+好氧实验装置对废水进行处理是可行的,且该系统具有较强的抗冲击负荷能力；对废水深度处理进行探索,对比絮凝沉淀、ClO2催化氧化、Fenton试剂催化氧化、Fenton试剂催化氧化+接触氧化的去除效果,Fenton试剂催化氧化后COD去除率为50%左右,废水可生化性提高。
3、对纤维素乙醇废水采用中试处理,研究了中试处理效果及COD负荷、停留时间、pH对处理效果的影响,从而得出最佳运行COD负荷、停留时间、pH,对废水处理工程化提供指导意义。
4、基于前述技术论证及中试研究,对河南某集团纤维乙醇预处理滤液及综合废水采用预处理+UASB+一级好氧反应器+催化氧化、接触氧化复合好氧的处理工艺,建设废水处理工程。对废水处理进行调试,处理系统运行较为稳定,出水达到污水综合排放一级标准,可实现达标排放；在经过一级好氧处理后废水可生化性差,经过Fenton试剂催化氧化后,废水可生化性提高,为后继接触氧化提供条件；催化氧化后再采用接触氧化法可进一步降低废水污染物浓度,实现达标排放。
5、瘤胃微生物可缩短厌氧装置的启动时间,强化厌氧处理效果；白腐真菌可促进好氧菌胶团的形成,提高好氧处理效果。
6、废水污染物浓度较高,处理难度较大,该工程采用较多工段,废水运行费用较高,约3.56元/t。
7、本研究使纤维质原料生产乙醇过程中产生的废水在厌氧处理过程中又可产生燃料沼气,为天然纤维质原料生物量获得全利用奠定基础。
This paper describes the wastewater treatment methods,which is produced in the new energy of cellulosic ethanol production, involving both new energy industry and environmental engineering industry. Because of the energy crisis, the search for new energy sources is becoming the focus of attention. In all the material obtained from plants, particularly, ethanol attracts people's concern, which is the most promising liquid fuel coming from renewable resources, but currently biological production of ethanol primarily from sugar and starch fermentation, facing the rapid expansion of the world's population and food shortages, the development of alcohol produced with grain will be restricted. As the advent of global energy crisis, food crisis and environmental crisis, cellulosic ethanol has drawn worldwide attention. Because of the complexity of the chemical structure of Straw cellulosic ethanol in which cellulose and hemi cellulose not only have been wrapped lignin,but also covalently with cellulose,with highly ordered crystal structure, it must be pretreatmented to damage crystal structure, reduce the degree of polymerization. The steam explosion pre-treatment technology is used. The waste water from Ethanol production contains some cellulose,lignin, hemicelluloses and so on,which is difficult to be degraded.The condensate from Ethanol production contains a large number of volatile acid, furfural and volatile phenols.In the paper, filtrate from Ethanol production pretreatment process is as the object, carryed out small scale testing, pilot testing, and the results have been used to the engineering and the processing 800t/d sewage treatment project was builted,which has achieved the following research results:
(1) In the experiment, we used the immobilized white-rot fungi on the filtrate from cellulosic ethanol steam explosion frame filter press process t. In the course of the experiment, we studyed the treatment effect impact of pH, residence time, and dosing rumen micro-organisms, and the results will help lay the foundation. for cellulosic ethanol processing.
(2) In the experiment, we can select the appropriate technology for pre-processing system, biochemical, in-depth processing. We compared some pretreatment technology, flotation, micro-electrolysis/H2O2, Fenton reagent catalytic oxidation; and compared to anaerobic, aerobic biological treatment of wastewater. Through the experimental comparison, we determined it was feasible which was the use of micro-electrolysis+anaerobic+aerobic experimental device for wastewater treatment, and the system has a strong ability for the impact load;We explored the depth of processing for wastewater, contrasted the removal effect of the coagulation and sedimentation, ClO2 catalytic oxidation, Fenton's reagent oxidation, Fenton's reagent oxidation catalytic oxidation +contact oxidation, after Fenton's reagent oxidation the COD removal is 50%, waste water biodegradability increase.
(3) In the system, we used pilot treatment for wastewater from cellulosic ethanol production, studyed the treatment effect and the impact of treatment effect by COD load, residence time, pH and thus the optimum running COD load, residence time, pH, provide guidance to the wastewater treatment engineering.
(4) This system is based on the aforementioned and technical feasibility studies and research by Nanyang, Henan one Group of cellulosic ethanol and treatment of the filtrate and the comprehensive wastewater using an aerobic pretreatment+UASB+ first aerobic reactor+oxidation+combined aerobic contact oxidation treatment process, and build waste water treatment engineering. During debugging wastewater treatment, the initial trial keep a relatively stable operation, and the effluent wastewater can achieve the discharge standards; in the treated wastewater through an aerobic biodegradability is poor, but when it have the catalytic oxidation of Fenton's reagent, wastewater biodegradability will increased, and provide the conditions for follow-up contact oxidation; contact oxidation after catalytic oxidation can be used to further reduce wastewater pollutant concentrations,the wastewater will achieve discharge standards.
(5) According to microorganism growth picture condition analysis, the result indicated Rumen micro-organisms reduce start time of aerobic and strengthen processing effect; white-rot fungi promote formation of Fungus rubber group and enhance processing effect.
(6) Because of the high concentrations of pollutants in wastewater, handling is difficulty, the project used several steps, and the costs of the wastewater operating are high, about 3.56 yuan/t.
(7) In this paper, wastewater which is produced in the new energy of cellulosic ethanol production product methane in the process of anaerobic and it Settles foundation for natural fiber raw material Biomass for full used.
引文
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