臭氧氧化对奶牛场沼液中磷形态转化的影响
|
摘要
为了提高沼液磷的回收效果,研究了曝气种类和曝气条件对奶牛场沼液磷形态转化的影响。结果表明:在参考曝气条件下,与氮气和空气相比,臭氧能更大程度地降低颗粒态磷和交换态磷含量,并大幅度提升溶解性正磷酸盐含量。臭氧曝气的优选条件为沼液初始pH值为6、臭氧发生量为10 g·h~(-1)、氧化时间为60 min,曝气后沼液中溶解性正磷酸盐浓度提高了76.12%,溶解性正磷酸盐占总磷比例提升20.75%。臭氧氧化可以促进颗粒态磷和交换态磷向溶解性正磷酸盐转化,从而促进沼液磷的回收。
With the rapid development of large-scale livestock and poultry breeding, outputs of biogas slurry are increasing. However, most large-scale farms are located in the suburbs of cities, so it is difficult to find sufficient farmland to absorb the biogas slurry. Moreover, thereis a large amount of phosphorus in biogas slurry, and its direct discharge may lead to eutrophication of water bodies. Phosphorus is an ex?tremely scarce and non-renewable resource, and the recovery of phosphorus from biogas slurry can effectively alleviate the combined prob?lems of phosphorus resource shortage and phosphorus pollution aggravation, which is closely related to the content of dissolved orthophos?phate in biogas slurry. In order to increase the content of dissolved orthophosphate, phosphorus species and contents in biogas slurry from adairy farm in Banan District, Chongqing, were determined. The effects of the initial pH of biogas slurry, aeration type, ozone amount, andoxidation time on the speciation transformation of phosphorus were studied. It was found that the ratio of dissolved orthophosphate to totalphosphorus in the initial biogas slurry was 26.29%, and that of particulate and exchangeable phosphorus was 37.76%, indicating that partic?ulate and exchangeable phosphorus have the potential to be transformed into dissolved orthophosphate. Compared with nitrogen and air,ozone oxidation could lead to larger decreases in particulate and exchangeable phosphorus contents and could greatly enhance the contentof dissolved orthophosphate under reference aeration conditions. The optimal conditions for ozone aeration were also obtained; i.e., an ini?tial pH of biogas slurry was 6, an ozone amount of 10 g·h~(-1), and an oxidation time of 60 min. After ozone aeration, the concentration of dis?solved orthophosphate in biogas slurry increased to 76.12%, and the ratio of dissolved orthophosphate to total phosphorus improved to20.75%. Ozone oxidation can promote the transformation of particulate and exchangeable phosphorus into dissolved orthophosphate, thus promoting the recovery of phosphorus from biogas slurry.
With the rapid development of large-scale livestock and poultry breeding, outputs of biogas slurry are increasing. However, most large-scale farms are located in the suburbs of cities, so it is difficult to find sufficient farmland to absorb the biogas slurry. Moreover, thereis a large amount of phosphorus in biogas slurry, and its direct discharge may lead to eutrophication of water bodies. Phosphorus is an ex?tremely scarce and non-renewable resource, and the recovery of phosphorus from biogas slurry can effectively alleviate the combined prob?lems of phosphorus resource shortage and phosphorus pollution aggravation, which is closely related to the content of dissolved orthophos?phate in biogas slurry. In order to increase the content of dissolved orthophosphate, phosphorus species and contents in biogas slurry from adairy farm in Banan District, Chongqing, were determined. The effects of the initial pH of biogas slurry, aeration type, ozone amount, andoxidation time on the speciation transformation of phosphorus were studied. It was found that the ratio of dissolved orthophosphate to totalphosphorus in the initial biogas slurry was 26.29%, and that of particulate and exchangeable phosphorus was 37.76%, indicating that partic?ulate and exchangeable phosphorus have the potential to be transformed into dissolved orthophosphate. Compared with nitrogen and air,ozone oxidation could lead to larger decreases in particulate and exchangeable phosphorus contents and could greatly enhance the contentof dissolved orthophosphate under reference aeration conditions. The optimal conditions for ozone aeration were also obtained; i.e., an ini?tial pH of biogas slurry was 6, an ozone amount of 10 g·h~(-1), and an oxidation time of 60 min. After ozone aeration, the concentration of dis?solved orthophosphate in biogas slurry increased to 76.12%, and the ratio of dissolved orthophosphate to total phosphorus improved to20.75%. Ozone oxidation can promote the transformation of particulate and exchangeable phosphorus into dissolved orthophosphate, thus promoting the recovery of phosphorus from biogas slurry.
引文
[1]甘寿文,徐兆波,黄武.大型沼气工程生态应用关键技术研究[J].中国生态农业学报,2008,16(5):1293-1297.GAN Shou-wen,XU Zhao-bo,HUANG Wu.Key technology for ecological application of large-scale biogas project[J].Chinese Journal of Eco-Agriculture,2008,16(5):1293-1297.
[2]Niyungeko C,Liang X Q,Liu C L,et al.Effect of biogas slurry application rate on colloidal phosphorus leaching in paddy soil:A column study[J].Geoderma,2018,325:117-124.
[3]靳红梅,常志州,叶小梅,等.江苏省大型沼气工程沼液理化特性分析[J].农业工程学报,2011,27(1):291-296.JIN Hong-mei,CHANG Zhi-zhou,YE Xiao-mei,et al.Physical and chemical characteristics of anaerobically digested slurry from largescale biogas project in Jiangsu Province[J].Transactions of the CSAE,2011,27(1):291-296.
[4]Yuan Z W,Pan X,Chen T M,et al.Evaluating environmental impacts of pig slurry treatment technologies with a life-cycle perspective[J].Journal of Cleaner Production,2018,188:840-850.
[5]韩敏,刘克锋,王顺利,等.沼液的概念、成分和再利用途径及风险[J].农学学报,2014,4(10):54-57.HAN Min,LIU Ke-feng,WANG Shun-li,et al.Definition,ingredient,approaches and risks for reuse in biogas slurry[J].Journal of Agriculture,2014,4(10):54-57.
[6]徐冯迪,高扬,董文渊,等.我国南方红壤区氮磷湿沉降对森林流域氮磷输出及水质的影响[J].生态学报,2016,36(20):6409-6419.XU Feng-di,GAO Yang,DONG Wen-yuan,et al.Impact of atmospheric nitrogen and phosphorus wet deposition on nitrogen and phosphorus export and associated water quality:A case study of forest watershed in the red soil area,southern China[J].Acta Ecologica Sinica,2016,36(20):6409-6419.
[7]Von Horn J,Sartorius C.Impact of supply and demand on the price development of phosphate(fertilizer)[C]//The Proceedings of the International Conference on Nutrient Recovery from Wastewater Streams,London,W A Publishing,2009:45-54.
[8]Roberts T L,Stewart W M.Inorganic phosphorus and potassium production and reserves[J].Better Crops,2002,86(2):6-7.
[9]郝晓地,衣兰凯,王崇臣,等.磷回收技术的研发现状及发展趋势[J].环境科学学报,2010,30(5):897-907.HAO Xiao-di,YI Lan-kai,WANG Chong-chen,et al.Situation and prospects of phosphorus recovery techniques[J].Acta Scientiae Circumstantiae,2010,30(5):897-907.
[10]李洪刚,陈玉成,肖广全,等.鸟粪石结晶法处理牛场沼液过程中磷形态转化[J].农业工程学报,2016,32(3):228-233.LI Hong-gang,CHEN Yu-cheng,XIAO Guang-quan,et al.Phosphorous transformation during cattle farm biogas slurry treatment using struvite crystallization[J].Transactions of the CSAE,2016,32(3):228-233.
[11]He X M,Zhang T,Ren H Q,et al.Phosphorus recovery from biogas slurry by ultrasound/H2O2 digestion coupled with HFO/biochar adsorption process[J].Waste Management,2017,60:219-229.
[12]魏祥甲,王兰,乔瑞平,等.O3/H2O2深度氧化处理石化废水的研究[J].工业用水与废水,2014,45(6):23-27.WEI Xiang-jia,WANG Lan,QIAO Rui-ping,et al.Study on advanced treatment of petrochemical wastewater by O3-H2O2 combined oxidation[J].Industrial Water&Wastewater,2014,45(6):23-27.
[13]彭人勇,邱晓.O3-H2O2氧化法处理印染废水[J].化工环保,2013,33(4):308-311.PENG Ren-yong,QIU Xiao.Treatment of dyeing wastewater by O3-H2O2 oxidation process[J].Environmental Protection of Chemical Industry,2013,33(4):308-311.
[14]吕凯,季文芳,韩萍芳,等.超声、臭氧处理石化污水厂剩余活性污泥研究[J].环境工程学报,2009,3(5):907-910.LüKai,JI Wen-fang,HAN Ping-fang,et al.Study on petrochemical excess activated sludge treatment by ultrasonic and ozone[J].Chinese Journal of Environmental Engineering,2009,3(5):907-910.
[15]Liu Z Q,Tu J L,Wang Q,et al.Catalytic ozonation of diethyl phthalate in aqueous solution using graphite supported zinc oxide[J].Separation and Purification Technology,2018,200:51-58.
[16]Komiyama T,Ito T,Saigusa M.Measurement of the maximum amount of water-extractable phosphorus in animal manure compost by continuous and sequential water extraction[J].Soil Science and Plant Nutrition,2014,60(2):196-207.
[17]刘素美,张经.沉积物中磷的化学提取分析方法[J].海洋科学,2001,25(1):22-25.LIU Su-mei,ZHANG Jing.Chemical extraction and analysis of phosphorus in sediments[J].Marine Science,2001,25(1):22-25.
[18]李悦,乌大年,薛永先.沉积物中不同形态磷提取方法的改进及其环境地球化学意义[J].海洋环境科学,1998,17(1):15-20.LI Yue,WU Da-nian,XUE Yong-xian.The improvement of phosphorus extraction method in sediments and its environmental geochemical significance[J].Marine Environmental Science,1998,17(1):15-20.
[19]国家环境保护总局.水和废水监测分析方法[M].4版.北京:中国环境科学出版社,2002.State Environmental Protection Administration.Methods for monitoring and analysis of water and wastewater[M].4th Edition.Beijing:China Environmental Science Press,2002.
[20]Chang S C J M L.Fraction of soil phosphorus[J].Soil Science,1957,84(2):133-144.
[21]冯磊.三峡库区澎溪河流域消落带土壤磷赋存形态及吸附特性研究[D].重庆:重庆大学,2017.FENG Lei.Study on the morphology and adsorption characteristics of soil phosphorus in Pengxi River basin in the Three Gorges Reservoir area[D].Chongqing:Chongqing University,2017.
[22]付广青,靳红梅,叶小梅,等.猪和奶牛粪污厌氧发酵中固相磷形态变化分析[J].生态与农村环境学报,2014,30(2):239-245.FU Guang-qing,JIN Hong-mei,YE Xiao-mei,et al.Variation in forms of solids phase phosphorus in pig and dairy cow manures under anaerobic digestion[J].Journal of Ecology and Rural Environment,2014,30(2):239-245.
[23]马利民,张明,滕衍行,等.三峡库区消落区周期性干湿交替环境对土壤磷释放的影响[J].环境科学,2008,29(4):1035-1039.MA Li-min,ZHANG Ming,TENG Yan-hang,et al.Characteristics of phosphorous release from soil in periodic alternately waterlogged and drained environments at WFZ of the Three Gorges Reservoir[J].Environmental Science,2008,29(4):1035-1039.
[24]许春雪,袁建,王亚平,等.沉积物中磷的赋存形态及磷形态顺序提取分析方法[J].岩矿测试,2011,30(6):785-794.XU Chun-xue,YUAN Jian,WANG Ya-ping,et al.Speciation and release mechanism of phosphorus in sediments and analysis methods for sequential extraction[J].Rock and Mineral Analysis,2011,30(6):785-794.
[25]Singh S K,Moody C M,Townsend T G.Ozonation pretreatment for stabilized landfill leachate high-pressure membrane treatment[J].Desalination,2014,344:163-170.
[26]Scandelai A P J,Cardozo F L,Martins D C C,et al.Combined processes of ozonation and supercritical water oxidation for landfill leachate degradation[J].Waste Management,2018,77:466-476.
[27]Wu J J,Park S-h,Hengemuehle S M,et al.The effect of storage and ozonation on the physical,chemical,and biological characteristics of swine manure slurries[J].Ozone:Science&Engineering,1998,20(1):35-50.
[28]Hao X D,Wang C C,Lan L,et al.Struvite formation,analytical methods and effects of pH and Ca2+[J].Water Science&Technology,2008,58(8):1687-1692.
[2]Niyungeko C,Liang X Q,Liu C L,et al.Effect of biogas slurry application rate on colloidal phosphorus leaching in paddy soil:A column study[J].Geoderma,2018,325:117-124.
[3]靳红梅,常志州,叶小梅,等.江苏省大型沼气工程沼液理化特性分析[J].农业工程学报,2011,27(1):291-296.JIN Hong-mei,CHANG Zhi-zhou,YE Xiao-mei,et al.Physical and chemical characteristics of anaerobically digested slurry from largescale biogas project in Jiangsu Province[J].Transactions of the CSAE,2011,27(1):291-296.
[4]Yuan Z W,Pan X,Chen T M,et al.Evaluating environmental impacts of pig slurry treatment technologies with a life-cycle perspective[J].Journal of Cleaner Production,2018,188:840-850.
[5]韩敏,刘克锋,王顺利,等.沼液的概念、成分和再利用途径及风险[J].农学学报,2014,4(10):54-57.HAN Min,LIU Ke-feng,WANG Shun-li,et al.Definition,ingredient,approaches and risks for reuse in biogas slurry[J].Journal of Agriculture,2014,4(10):54-57.
[6]徐冯迪,高扬,董文渊,等.我国南方红壤区氮磷湿沉降对森林流域氮磷输出及水质的影响[J].生态学报,2016,36(20):6409-6419.XU Feng-di,GAO Yang,DONG Wen-yuan,et al.Impact of atmospheric nitrogen and phosphorus wet deposition on nitrogen and phosphorus export and associated water quality:A case study of forest watershed in the red soil area,southern China[J].Acta Ecologica Sinica,2016,36(20):6409-6419.
[7]Von Horn J,Sartorius C.Impact of supply and demand on the price development of phosphate(fertilizer)[C]//The Proceedings of the International Conference on Nutrient Recovery from Wastewater Streams,London,W A Publishing,2009:45-54.
[8]Roberts T L,Stewart W M.Inorganic phosphorus and potassium production and reserves[J].Better Crops,2002,86(2):6-7.
[9]郝晓地,衣兰凯,王崇臣,等.磷回收技术的研发现状及发展趋势[J].环境科学学报,2010,30(5):897-907.HAO Xiao-di,YI Lan-kai,WANG Chong-chen,et al.Situation and prospects of phosphorus recovery techniques[J].Acta Scientiae Circumstantiae,2010,30(5):897-907.
[10]李洪刚,陈玉成,肖广全,等.鸟粪石结晶法处理牛场沼液过程中磷形态转化[J].农业工程学报,2016,32(3):228-233.LI Hong-gang,CHEN Yu-cheng,XIAO Guang-quan,et al.Phosphorous transformation during cattle farm biogas slurry treatment using struvite crystallization[J].Transactions of the CSAE,2016,32(3):228-233.
[11]He X M,Zhang T,Ren H Q,et al.Phosphorus recovery from biogas slurry by ultrasound/H2O2 digestion coupled with HFO/biochar adsorption process[J].Waste Management,2017,60:219-229.
[12]魏祥甲,王兰,乔瑞平,等.O3/H2O2深度氧化处理石化废水的研究[J].工业用水与废水,2014,45(6):23-27.WEI Xiang-jia,WANG Lan,QIAO Rui-ping,et al.Study on advanced treatment of petrochemical wastewater by O3-H2O2 combined oxidation[J].Industrial Water&Wastewater,2014,45(6):23-27.
[13]彭人勇,邱晓.O3-H2O2氧化法处理印染废水[J].化工环保,2013,33(4):308-311.PENG Ren-yong,QIU Xiao.Treatment of dyeing wastewater by O3-H2O2 oxidation process[J].Environmental Protection of Chemical Industry,2013,33(4):308-311.
[14]吕凯,季文芳,韩萍芳,等.超声、臭氧处理石化污水厂剩余活性污泥研究[J].环境工程学报,2009,3(5):907-910.LüKai,JI Wen-fang,HAN Ping-fang,et al.Study on petrochemical excess activated sludge treatment by ultrasonic and ozone[J].Chinese Journal of Environmental Engineering,2009,3(5):907-910.
[15]Liu Z Q,Tu J L,Wang Q,et al.Catalytic ozonation of diethyl phthalate in aqueous solution using graphite supported zinc oxide[J].Separation and Purification Technology,2018,200:51-58.
[16]Komiyama T,Ito T,Saigusa M.Measurement of the maximum amount of water-extractable phosphorus in animal manure compost by continuous and sequential water extraction[J].Soil Science and Plant Nutrition,2014,60(2):196-207.
[17]刘素美,张经.沉积物中磷的化学提取分析方法[J].海洋科学,2001,25(1):22-25.LIU Su-mei,ZHANG Jing.Chemical extraction and analysis of phosphorus in sediments[J].Marine Science,2001,25(1):22-25.
[18]李悦,乌大年,薛永先.沉积物中不同形态磷提取方法的改进及其环境地球化学意义[J].海洋环境科学,1998,17(1):15-20.LI Yue,WU Da-nian,XUE Yong-xian.The improvement of phosphorus extraction method in sediments and its environmental geochemical significance[J].Marine Environmental Science,1998,17(1):15-20.
[19]国家环境保护总局.水和废水监测分析方法[M].4版.北京:中国环境科学出版社,2002.State Environmental Protection Administration.Methods for monitoring and analysis of water and wastewater[M].4th Edition.Beijing:China Environmental Science Press,2002.
[20]Chang S C J M L.Fraction of soil phosphorus[J].Soil Science,1957,84(2):133-144.
[21]冯磊.三峡库区澎溪河流域消落带土壤磷赋存形态及吸附特性研究[D].重庆:重庆大学,2017.FENG Lei.Study on the morphology and adsorption characteristics of soil phosphorus in Pengxi River basin in the Three Gorges Reservoir area[D].Chongqing:Chongqing University,2017.
[22]付广青,靳红梅,叶小梅,等.猪和奶牛粪污厌氧发酵中固相磷形态变化分析[J].生态与农村环境学报,2014,30(2):239-245.FU Guang-qing,JIN Hong-mei,YE Xiao-mei,et al.Variation in forms of solids phase phosphorus in pig and dairy cow manures under anaerobic digestion[J].Journal of Ecology and Rural Environment,2014,30(2):239-245.
[23]马利民,张明,滕衍行,等.三峡库区消落区周期性干湿交替环境对土壤磷释放的影响[J].环境科学,2008,29(4):1035-1039.MA Li-min,ZHANG Ming,TENG Yan-hang,et al.Characteristics of phosphorous release from soil in periodic alternately waterlogged and drained environments at WFZ of the Three Gorges Reservoir[J].Environmental Science,2008,29(4):1035-1039.
[24]许春雪,袁建,王亚平,等.沉积物中磷的赋存形态及磷形态顺序提取分析方法[J].岩矿测试,2011,30(6):785-794.XU Chun-xue,YUAN Jian,WANG Ya-ping,et al.Speciation and release mechanism of phosphorus in sediments and analysis methods for sequential extraction[J].Rock and Mineral Analysis,2011,30(6):785-794.
[25]Singh S K,Moody C M,Townsend T G.Ozonation pretreatment for stabilized landfill leachate high-pressure membrane treatment[J].Desalination,2014,344:163-170.
[26]Scandelai A P J,Cardozo F L,Martins D C C,et al.Combined processes of ozonation and supercritical water oxidation for landfill leachate degradation[J].Waste Management,2018,77:466-476.
[27]Wu J J,Park S-h,Hengemuehle S M,et al.The effect of storage and ozonation on the physical,chemical,and biological characteristics of swine manure slurries[J].Ozone:Science&Engineering,1998,20(1):35-50.
[28]Hao X D,Wang C C,Lan L,et al.Struvite formation,analytical methods and effects of pH and Ca2+[J].Water Science&Technology,2008,58(8):1687-1692.