四氢呋喃废水的吹脱处理及厌氧特性研究
摘要
四氢呋喃是一种低沸点、易挥发、与水混溶的含氧五元环有毒有机物。一般易在生产四氢呋喃均聚醚、合成激素药等过程中造成水污染。本课题进行了空气吹脱处理四氢呋喃废水的可行性研究，同时也进行了四氢呋喃的厌氧生物可降解性、四氢呋喃对厌氧活性污泥的产甲烷毒性和驯化性的厌氧静态实验研究。吹脱实验中，对选取的影响吹脱的四个主要因素和每个因素的四个水平值进行了正交组合，以废水中COD的去除率来间接表示废水的处理效果。结果表明，影响四氢呋喃吹脱的主次因素依次为温度→时间→风强→废水浓度。单因素影响吹脱实验结果表明其它影响因素一定时(q=0.5m~3／h，t=30min)时对于COD=600mg／l和COD=1100mg／l的两种浓度废水，温度在20℃、30、40℃、50℃、60℃下，COD去除率分别可达44％、60％、85％、94％、98％左右，所以温度对吹脱影响较大，且在30℃范围内去除效果最明显；T=30℃，q=0.5m~3／h，不同的吹脱时间下，和T=30℃，t=30min，不同的风强下对上述两种浓度废水的吹脱实验结果表明延长吹脱时间比增大风强对THF去除效果好，风强控制在0.5 m~3／h时，气泡密度、直径适中，吹脱时间达到60min后，THF去除率可达85％～90％左右；其它因素一定时进水浓度对COD去除率影响很小；从与四氢呋喃结构相似的四氢糠醇和糠醛废水吹脱实验比较中可知，四氢糠醇的去除率几乎为零，糠醛去除率也很低。厌氧静态实验结果表明四氢呋喃是一种难降解物(COD_(BD)／COD=6.29％)，当THF废水浓度高达约1700mg／l时，厌氧活性污泥的产甲烷活性50％被抑制，但去除毒物只加入乙酸基质后活性能得到一定的恢复；当去除第一次投加的四氢呋喃后再次加入与前次相同量的该毒物后，污泥产生了诱导酶，得到了一定的驯化。
Tetrahydrofuran (THF) has low boiling point and is volatile. And it can mix with water easily. Because THF is a toxic organism it can usually pollute the water during generating PTMEG and hormone. The research was about studying on the feasibility of blowing off THF from the wastewater. At the same time we also studied the biodegradability and toxicity to anaerobic sludge during generating methane of THF and reclamation of sludge under anaerobic condition. In the air stripping experiment we analyzed the factors concerned, such as temperature, the flow of gas, the time of blow and the concentration of THE wastewater, and we gave each factor four different values and made them up orthogonally. The result indicated that temperature was the most important factor that influences the blow-off method among the four factors, time was the second, the third was flow of gas, and the last was inflow concentration. In order to analyze the influence of single factor we made a test to two different concentration wastewater
(COD=600mg/l, COD=1100mg/l). And the result from the test showed that under the same flow of gas (0.5m3/h) and the blowing-off time (30min) condition the removal ratio of COD can reach 44%, 60%, 85%, 94%and 98% respectively at 20℃, 30℃, 40℃, 50℃, 60℃. Then we carried out the experiment on the above two different concentration wastewater in two different conditions, one of which was at 30℃, the flow of 0.5m3/h and different blowing-off time, the other at 30癈, 30min and different flow of gas. We found that when the gas-water ratio was identical increasing time could more improve the removal ratio than raising the flow of gas. And the concentration of wastewater had little influence on blowing-off removal of THF. In comparison with THF, it was difficult to remove tetrahydrofurfuryl alcohol and
furfural whose structures were similar with THF by air stripping method. After analyzing the CODbd/COD (6.29%) value in anaerobic static test we knew that THF exhibited bad biodegradability. And when the THF wastewater concentration reached 1700mg/l high the sludge activity of 50% declined. But when THF was removed from the tested water and only acetic acid substrate was added to the water the part of anaerobic sludge activity was recovered., and when the same THF capacity as the first time was added continually after removing the form noxious substance the sludge was induced., so the biological degradation of anaerobic sludge was enhanced.
Tetrahydrofuran (THF) has low boiling point and is volatile. And it can mix with water easily. Because THF is a toxic organism it can usually pollute the water during generating PTMEG and hormone. The research was about studying on the feasibility of blowing off THF from the wastewater. At the same time we also studied the biodegradability and toxicity to anaerobic sludge during generating methane of THF and reclamation of sludge under anaerobic condition. In the air stripping experiment we analyzed the factors concerned, such as temperature, the flow of gas, the time of blow and the concentration of THE wastewater, and we gave each factor four different values and made them up orthogonally. The result indicated that temperature was the most important factor that influences the blow-off method among the four factors, time was the second, the third was flow of gas, and the last was inflow concentration. In order to analyze the influence of single factor we made a test to two different concentration wastewater
(COD=600mg/l, COD=1100mg/l). And the result from the test showed that under the same flow of gas (0.5m3/h) and the blowing-off time (30min) condition the removal ratio of COD can reach 44%, 60%, 85%, 94%and 98% respectively at 20℃, 30℃, 40℃, 50℃, 60℃. Then we carried out the experiment on the above two different concentration wastewater in two different conditions, one of which was at 30℃, the flow of 0.5m3/h and different blowing-off time, the other at 30癈, 30min and different flow of gas. We found that when the gas-water ratio was identical increasing time could more improve the removal ratio than raising the flow of gas. And the concentration of wastewater had little influence on blowing-off removal of THF. In comparison with THF, it was difficult to remove tetrahydrofurfuryl alcohol and
furfural whose structures were similar with THF by air stripping method. After analyzing the CODbd/COD (6.29%) value in anaerobic static test we knew that THF exhibited bad biodegradability. And when the THF wastewater concentration reached 1700mg/l high the sludge activity of 50% declined. But when THF was removed from the tested water and only acetic acid substrate was added to the water the part of anaerobic sludge activity was recovered., and when the same THF capacity as the first time was added continually after removing the form noxious substance the sludge was induced., so the biological degradation of anaerobic sludge was enhanced.
引文
1．杨振生．萃取精馏法分离四氢呋喃—水的概念设计．天津化工，1008-1267(2002)01-0012-03
2．李新贵，黄美荣，林刚，杨溥臣分离有机物水溶液的渗透汽化与汽化渗透膜．水处理技术，1994：20(1)：1-9
3．边才苗，陈彤，李钧敏．四氢呋喃降解细菌质粒的检出及菌株的生长特性．环境科学研究，2003：16(3)44-46
4．[苏]格鲁什科著，耿玉兰译．工业废水中有害有机化合物手册．1982
5．[美]R．W罗森伯格．物理化学原理．人民教育出版社，1981
6．高羽飞．水处理试验设计与分析．西安建筑科技大学，1998
7．白新桂．数据分析与试验优化设计．北京：清华大学出版社，1986
8．Miller, D.G., "Estimating Vapor Pressures—a Comparision of Epuations."Ind.Eng.Chem.,56,46(March 1964)
9．Fishtine,S.H.,"Reliable Latent heats of Vaporization, "Ind.Eng.Chem.,55,47(June 1963)
10．朱长乐，朱才拴，刘茉娥．化学工程手册，18卷，薄膜过程．化工出版社，北京，1987
11．W.T.莱曼，W.F.雷尔，D.H.罗森布拉特．化学性质估算方法手册．化学工业出版社，1991
12．王连生．有机污染物化学(上、下)．科学出版社，1990
13．李建．涂料和粘胶剂中有毒物质及其检测技术．中国计划出版社，2002
14．李新贵，黄美荣，林刚，杨溥臣．分离有机物水溶液的渗透汽化与汽化渗透膜．水处理技术，1994：20(1)：1-9
15. Anaerobic Lab Work.in:Int.Course on Anaeerobic Wastewater Treanmeant. The Netherlands: WAU,1992
16．唐森本，王欢畅，葛碧洲，朱晓云．环境有机污染化学．冶金工业出版社，1995
17．冯晓西，乌锡康．精细化工废水治理技术．化学工业出版社，2000
18．中国化工防治污染技术协会．化工废水处理技术．化学工业出版社，2000
19．汤鸿霄，钱易，文湘华．水体颗粒物和难降解有机物的特性与控制技术原理(下卷)．中国环境科学出版社，2000
20．今湘灿．有机化合物污染化学．有毒有机物污染化学．清华大学出版社，1990
21．国家环境保护局有毒化学品管理办公室，化工部北京化工研究院环境保护研究所．
化学品毒性法规环境数据手册．中国环境科学出版社，1992
22．南京大学化学系．物理化学词典．科学出版社，1988
23．夏北成．环境污染物生物降解．2002
24．张希功．四氢呋喃技术进展与生产现状．化工生产与技术，2002：9(2)：18-20
25．何志成，张炳辉，梁立新，林善良．从四氢呋喃、乙醇、水三元混合物系中分离四氢呋喃的研究．沈阳化工，1995：30-32
26．郑仙珏．四氢呋喃的回收提纯．环境科学与技术，1997：3：14-16
27．高庆然，路明义．吹脱对含油类污染物地下水处理效果的研究．齐鲁石油化工，2001：29(1)：17-20
28．刘俊良，马孟光．氰化物吹脱回收试验研究．哈尔滨建筑大学学报，1998：31(3)：50-56
29．吴方同，苏秋霞，孟了，李武，金同轨．吹脱法去除城市垃圾填埋场渗滤液中的氨氮，给水排水，2001：27(6)：20-24
30．席建，张庆鸿．吹脱-臭氧化处理气田水．天然气工业，1994：14：(2)74-76
31．杨昌竹，刘君华，崔维成．传质原理．西安建筑科技大学．1992
32．张希衡．废水厌氧生物处理工程．中国环境科学出版社，1996
33. Satoshi Fukuzaki et al..Appl. Environ. Microbial., 1990,56(3):719
34. Hatginger OP.The Handbook of Environmental chemistry.New York:1990:24-32
35．贺延龄．废水的厌氧生物处理．中国轻工业出版社，1998
36．丁忠浩．有机废水处理技术及应用．化学工业出版社．2002
37．蔡宝立，高才昌．降解性质粒的前景与应用微生物学通报．1987，14(4)：180-
38. Kistiakovskii,Vl.a., "Latent Heat of Voporization," J,Russ.Phys.Chem.Sac.,53,I,256-64(1921)
39．罗固源．水污染物化控制原理与技术．化学工业出版社，2003
2．李新贵，黄美荣，林刚，杨溥臣分离有机物水溶液的渗透汽化与汽化渗透膜．水处理技术，1994：20(1)：1-9
3．边才苗，陈彤，李钧敏．四氢呋喃降解细菌质粒的检出及菌株的生长特性．环境科学研究，2003：16(3)44-46
4．[苏]格鲁什科著，耿玉兰译．工业废水中有害有机化合物手册．1982
5．[美]R．W罗森伯格．物理化学原理．人民教育出版社，1981
6．高羽飞．水处理试验设计与分析．西安建筑科技大学，1998
7．白新桂．数据分析与试验优化设计．北京：清华大学出版社，1986
8．Miller, D.G., "Estimating Vapor Pressures—a Comparision of Epuations."Ind.Eng.Chem.,56,46(March 1964)
9．Fishtine,S.H.,"Reliable Latent heats of Vaporization, "Ind.Eng.Chem.,55,47(June 1963)
10．朱长乐，朱才拴，刘茉娥．化学工程手册，18卷，薄膜过程．化工出版社，北京，1987
11．W.T.莱曼，W.F.雷尔，D.H.罗森布拉特．化学性质估算方法手册．化学工业出版社，1991
12．王连生．有机污染物化学(上、下)．科学出版社，1990
13．李建．涂料和粘胶剂中有毒物质及其检测技术．中国计划出版社，2002
14．李新贵，黄美荣，林刚，杨溥臣．分离有机物水溶液的渗透汽化与汽化渗透膜．水处理技术，1994：20(1)：1-9
15. Anaerobic Lab Work.in:Int.Course on Anaeerobic Wastewater Treanmeant. The Netherlands: WAU,1992
16．唐森本，王欢畅，葛碧洲，朱晓云．环境有机污染化学．冶金工业出版社，1995
17．冯晓西，乌锡康．精细化工废水治理技术．化学工业出版社，2000
18．中国化工防治污染技术协会．化工废水处理技术．化学工业出版社，2000
19．汤鸿霄，钱易，文湘华．水体颗粒物和难降解有机物的特性与控制技术原理(下卷)．中国环境科学出版社，2000
20．今湘灿．有机化合物污染化学．有毒有机物污染化学．清华大学出版社，1990
21．国家环境保护局有毒化学品管理办公室，化工部北京化工研究院环境保护研究所．
化学品毒性法规环境数据手册．中国环境科学出版社，1992
22．南京大学化学系．物理化学词典．科学出版社，1988
23．夏北成．环境污染物生物降解．2002
24．张希功．四氢呋喃技术进展与生产现状．化工生产与技术，2002：9(2)：18-20
25．何志成，张炳辉，梁立新，林善良．从四氢呋喃、乙醇、水三元混合物系中分离四氢呋喃的研究．沈阳化工，1995：30-32
26．郑仙珏．四氢呋喃的回收提纯．环境科学与技术，1997：3：14-16
27．高庆然，路明义．吹脱对含油类污染物地下水处理效果的研究．齐鲁石油化工，2001：29(1)：17-20
28．刘俊良，马孟光．氰化物吹脱回收试验研究．哈尔滨建筑大学学报，1998：31(3)：50-56
29．吴方同，苏秋霞，孟了，李武，金同轨．吹脱法去除城市垃圾填埋场渗滤液中的氨氮，给水排水，2001：27(6)：20-24
30．席建，张庆鸿．吹脱-臭氧化处理气田水．天然气工业，1994：14：(2)74-76
31．杨昌竹，刘君华，崔维成．传质原理．西安建筑科技大学．1992
32．张希衡．废水厌氧生物处理工程．中国环境科学出版社，1996
33. Satoshi Fukuzaki et al..Appl. Environ. Microbial., 1990,56(3):719
34. Hatginger OP.The Handbook of Environmental chemistry.New York:1990:24-32
35．贺延龄．废水的厌氧生物处理．中国轻工业出版社，1998
36．丁忠浩．有机废水处理技术及应用．化学工业出版社．2002
37．蔡宝立，高才昌．降解性质粒的前景与应用微生物学通报．1987，14(4)：180-
38. Kistiakovskii,Vl.a., "Latent Heat of Voporization," J,Russ.Phys.Chem.Sac.,53,I,256-64(1921)
39．罗固源．水污染物化控制原理与技术．化学工业出版社，2003