臺灣博碩士論文加值系統

臺灣南部某彩色濾光片業者之製程廢水，因廠內現有之薄膜生物反應槽（Membrane Bioreactor，MBR）具有系統操作不穩定，如去除效率變差、槽體水面大量泡沫溢出、薄膜壓差變大、生物膜附著於膜面較難去除等問題，造成回收水比率下降，無法達成工廠節水目標。故本研究規劃設計小型MBR反應槽，搭配二種市售不同型式的薄膜（膜旺能源公司生產之聚偏二氟乙烯 Polyvinylidene Difluoride，PVDF中空纖維膜，簡稱HF薄膜及日本KUBOTA公司生產之氯化聚氯乙烯 Chlorinated Polyvinyl Chloride，CPVC平板膜，簡稱FS薄膜），採沉浸式設計，進行該廠製程回收水MBR系統模擬操作，實驗控制參數設定2組水力停留時間（HRT = 14 – 18及21 – 26 小時）及4組污泥停留時間（SRT = 20、25、30天及未排泥）進行交互實驗，每組實驗時間設定20天，溶氧控制在4 – 6.5 mg/L，食微比控制於0.05 – 0.15 kg TOC/ kg MLSS.d間，並定期採樣分析pH、導電度、溶氧(DO)、總有機碳(TOC)、活性污泥濃度(MLSS)，並量測常規透膜通量比例(NPF)及透膜壓差(TMP)，以找出最佳操作參數並提升回收水的品質與比例。
利用前導實驗結果調整正式實驗設計，採用FS薄膜及HF薄膜同時操作，添加營養劑並於反應槽底2側增加氣泡條。研究結果顯示，FS薄膜適合於HRT = 21 – 26 h條件下操作，可達高TOC去除及高透膜通量。HRT = 14 – 18 h條件下操作，透膜通量及TOC去除率較低。HF薄膜適合於HRT = 14 – 18 h條件下操作，可達高透膜通量，但TOC去除率較差。HRT = 21 – 26 h條件下操作，透膜通量較低，但TOC去除率較高。實驗發現進流水pH與導電度對透膜通量及TOC處理效率幾無影響。各組實驗活性污泥微生物相符合中低負荷情況，各組未有太大改變。業者系統於停產對活性污泥處理效能有影響，會造成TOC去除率下降，須留意食微比控制。
綜合而論，實驗條件HRT = 21 – 26 h，以TMP、NPF、TOC去除率及MLSS濃度而言，實驗組FS薄膜及HF薄膜之操作效果均優於業者系統，故業者系統不論選用何種薄膜種類，HRT = 21 – 26 h 應為適當之操作條件。說明實驗條件HRT = 14 – 18 h，FS薄膜及HF薄膜之操作效果較業者系統差，但實際原因為業者水力停留時間運作於HRT = 36 ± 8.1 h，但本研究發現HRT = 14 – 18 h，未排泥條件下，活性污泥濃度MLSS > 1,060 mg/L，TOC去除率可達90%以上，代表低HRT操作條件下，需足夠的活性污泥(微生物)，方可達到良好TOC去除效率。以薄膜選擇來看，業者系統運作不需使用膜孔徑較小的薄膜進行廢水處理，可選擇膜孔徑較大薄膜進行工程設計。

The process wastewater of a color filter manufactory in southern Taiwan is unstable due to the system operation in the existing membrane bioreactor (MBR). Problems such as poor removal efficiency, large foam overflow on the water surface of the tank, and transmembrane pressure high, biofilms attached to the membrane surface are difficult to remove and may result in a decrease in the ratio of recycle water. These may lead to the failure in achieving the water saving goals.
Therefore, this study plans to design a small MBR reaction tank with two types of different membranes. (Polyvinylidene Difluoride, PVDF hollow fiber membrane produced by Taiwan King Membrane Co., Ltd, and Chlorinated Polyvinyl Chloride, CPVC flat sheet produced by Japan Kubota Co., Ltd.). A submerged design for simulated operation of the recycle MBR system was created and the experimental control parameters had 2 sets of hydraulic retention time (HRT = 14 – 18 and 21 – 26 hr) and 4 groups of sludge retention time (SRT = 20, 25, 30 days, and no discharge). The time of each experiment was set for 20 days and the dissolved oxygen was controlled at 4 – 6 mg/L. The F/M ratio is controlled between 0.05 – 0.15 kg TOC / kg MLSS.d and the pH, conductivity, dissolved oxygen (DO), total organic carbon (TOC) and activated sludge concentration (MLSS) were periodically sampled and measured, furthermore, the normalized permeate flux (NPF) and transmembrane pressure (TMP) were also measured to find the best operating parameters for improving the quality and proportion of recycle water.
The formal experimental design was adjusted by using the results of the lead experiment; the FS membrane and the HF membrane were simultaneously operated; the nutrient was added and the bubble strip was added on the bottom side of the reaction tank. The results show that the FS membrane is suitable for operation under HRT = 21 – 26 h conditions, achieving high TOC removal and high permeate flux. Operating at HRT = 14 – 18 h, the permeate flux and TOC removal rate are low. The HF membrane which is suitable for operation at HRT = 14 – 18 h can achieve high permeate flux but the TOC removal rate is poor. Operating at HRT = 21 – 26 h, the membrane flux is low but the TOC removal rate is higher. It was found that the pH and conductivity of the feed water had little effect on the permeate flux and TOC treatment efficiency. The microorganism in the experimentally activated sludge in each group was in accordance with the medium and low load conditions; each group did not change. The stop of production line has an effect on the efficiency of the activated sludge treatment which will result in a decrease in the TOC removal and attention should be paid to the food-to- microorganism ratio control.
In general speaking, the experimental conditions HRT = 21 – 26 h, in terms of TMP, NPF, TOC removal rate and MLSS concentration, the operating effects of the experimental group FS membrane and HF membrane are better than the system. Regardless of what system is adopted, the type of membrane, HRT = 21 – 26 h, should be the proper operating conditions. This has explained that in the experimental conditions HRT = 14 – 18 h, the operation effect of FS membrane and HF membrane is worse than that of the operator system but the actual reason is that the system operates at HRT = 36 ± 8.1 h. However, this study has also found that HRT = 14 – 18 h under the condition of SRT no discharge, the activated sludge concentration indicates MLSS > 1,060 mg/L and the TOC removal rate can reach over 90%. This result has suggested that under the low HRT operating conditions, sufficient activated sludge (microorganism) is needed to achieve good TOC removal effectiveness. In terms of membrane selection, the operation of the system does not require the use of membrane with a small pore size for wastewater treatment and the membrane with a larger pore size of membrane can be selected for engineering design.

摘要 I
Abstract III
誌謝 VI
目錄 VII
表目錄 IX
圖目錄 X
第一章 前言 1
1.1 研究緣起 1
1.2 研究目的 2
第二章 文獻回顧 3
2.1 MBR的型式與分類 3
2.2 MBR在廢水處理的應用 5
2.3 MBR的積垢分類與控制 6
2.4 MBR的關鍵操作因子 11
2.5 彩色濾光片製程廢水特性說明 17
2.6 彩色濾光片業者現行MBR配置與操作方式 18
第三章 實驗材料及方法 21
3.1 研究流程圖 21
3.2 實驗材料及設計 22
3.3 實驗方法 29
3.3.1 前導實驗測試 29
3.3.2 MBR實驗步驟 32
3.4 實驗儀器及分析方法 35
第四章 結果與討論 38
4.1 前導實驗 38
4.1.1 前導實驗結果 38
4.1.2 前導實驗小結 48
4.2 水力停留時間與污泥停留時間對MBR操作效能的影響 49
4.2.1 水力停留時間與污泥停留時間對MBR操作實驗結果 49
4.2.2 水力停留時間與污泥停留時間對MBR操作影響小結 65
4.3 薄膜積垢狀況及污泥微生物相觀察 67
4.3.1 薄膜積垢狀況觀察 67
4.3.2 活性污泥微生物相觀察 72
4.3.3 薄膜積垢狀況及污泥微生物相觀察小結 75
4.4 MBR實驗與業者系統效能比較 75
4.4.1 MBR實驗與業者系統效能比較說明 75
4.4.2 實驗與業者系統效能比較小結 86
第五章 結論與建議 87
5.1 實驗結論 87
5.2 實驗建議 88
參考文獻 89

1. Al-Halbouni, D., Traber, J., Lyko, S., Wintgens, T., Melin, T., Tacke, D., Janot, A., Dott, W. and Hollender, J. (2008). "Correlation of EPS content in activated sludge at different sludge retention times with membrane fouling phenomena." Water Research 42(6): 1475-1488.

2. Arabi, S. and Nakhla, G. (2009). "Impact of magnesium on membrane fouling in membrane bioreactors." Separation and Purification Technology 67(3): 319-325.

3. Azami, H., Sarrafzadeh, M. H. and Mehrnia, M. R. (2011). "Fouling in membrane bioreactors with various concentrations of dead cells." Desalination 278(1): 373-380.

4. Babatsouli, P., Palogos, I., Michalodimitraki, E., Costa, C. and Kalogerakis, N. (2014). "Evaluation of a MBR pilot treating industrial wastewater with a high COD/N ratio." Journal of Chemical Technology & Biotechnology 90(1): 26-33.

5. Bennett, A. (2005). "Membranes in industry: facilitating reuse of wastewater." Filtration & Separation 42(8): 28-30.

6. Braak, E., Alliet, M., Schetrite, S. and Albasi, C. (2011). "Aeration and hydrodynamics in submerged membrane bioreactors." Journal of Membrane Science 379(1): 1-18.

7. Chang, I.-S., Le Clech, P., Jefferson, B. and Judd, S. (2002). "Membrane fouling in membrane bioreactors for wastewater treatment." Journal of Environmental Engineering 128(11): 1018-1029.

8. Chen, W., Liu, J. and Xie, F. (2012). "Identification of the moderate SRT for reliable operation in MBR." Desalination 286: 263-267.

9. De Temmerman, L., Maere, T., Temmink, H., Zwijnenburg, A. and Nopens, I. (2014). "Salt stress in a membrane bioreactor: Dynamics of sludge properties, membrane fouling and remediation through powdered activated carbon dosing." Water Research 63: 112-124.

10. De Temmerman, L., Maere, T., Temmink, H., Zwijnenburg, A. and Nopens, I. (2015). "The effect of fine bubble aeration intensity on membrane bioreactor sludge characteristics and fouling." Water Research 76: 99-109.

11. Deng, L., Guo, W., Ngo, H. H., Zhang, J., Liang, S., Xia, S., Zhang, Z. and Li, J. (2014). "A comparison study on membrane fouling in a sponge-submerged membrane bioreactor and a conventional membrane bioreactor." Bioresource Technology 165: 69-74.

12. Dizge, N., Koseoglu-Imer, D. Y., Karagunduz, A. and Keskinler, B. (2011). "Effects of cationic polyelectrolyte on filterability and fouling reduction of submerged membrane bioreactor (MBR)." Journal of Membrane Science 377(1): 175-181.

13. Duan, L., Song, Y., Yu, H., Xia, S. and Hermanowicz, S. W. (2014). "The effect of solids retention times on the characterization of extracellular polymeric substances and soluble microbial products in a submerged membrane bioreactor." Bioresource Technology 163: 395-398.

14. Fallah, N., Bonakdarpour, B., Nasernejad, B. and Alavi Moghadam, M. R. (2010). "Long-term operation of submerged membrane bioreactor (MBR) for the treatment of synthetic wastewater containing styrene as volatile organic compound (VOC): Effect of hydraulic retention time (HRT)." Journal of Hazardous Materials 178(1): 718-724.

15. Fan, F. and Zhou, H. (2007). "Interrelated effects of aeration and mixed liquor fractions on membrane fouling for submerged membrane bioreactor processes in wastewater treatment." Environmental Science & Technology 41(7): 2523-2528.

16. Faust, L., Temmink, H., Zwijnenburg, A., Kemperman, A. J. B. and Rijnaarts, H. H. M. (2014). "Effect of dissolved oxygen concentration on the bioflocculation process in high loaded MBRs." Water Research 66: 199-207.

17. Feng, S., Zhang, N., Liu, H., Du, X., Liu, Y. and Lin, H. (2012). "The effect of COD/N ratio on process performance and membrane fouling in a submerged bioreactor." Desalination 285: 232-238.

18. Gao, D.-W., Fu, Y., Tao, Y., Li, X.-X., Xing, M., Gao, X.-H. and Ren, N.-Q. (2011). "Linking microbial community structure to membrane biofouling associated with varying dissolved oxygen concentrations." Bioresource Technology 102(10): 5626-5633.

19. Gao, D.-W., Wen, Z.-D., Li, B. and Liang, H. (2013). "Membrane fouling related to microbial community and extracellular polymeric substances at different temperatures." Bioresource Technology 143: 172-177.

20. Goswami, L., Vinoth Kumar, R., Borah, S. N., Arul Manikandan, N., Pakshirajan, K. and Pugazhenthi, G. (2018). "Membrane bioreactor and integrated membrane bioreactor systems for micropollutant removal from wastewater: A review." Journal of Water Process Engineering 26: 314-328.

21. Guo, W., Ngo, H.-H. and Li, J. (2012). "A mini-review on membrane fouling." Bioresource Technology 122: 27-34.

22. Hong, H., Zhang, M., He, Y., Chen, J. and Lin, H. (2014). "Fouling mechanisms of gel layer in a submerged membrane bioreactor." Bioresource Technology 166: 295-302.

23. Ivnitsky, H., Katz, I., Minz, D., Shimoni, E., Chen, Y., Tarchitzky, J., Semiat, R. and Dosoretz, C. G. (2005). "Characterization of membrane biofouling in nanofiltration processes of wastewater treatment." Desalination 185(1): 255-268.

24. Jamal Khan, S., Visvanathan, C. and Jegatheesan, V. (2012). "Effect of powdered activated carbon (PAC) and cationic polymer on biofouling mitigation in hybrid MBRs." Bioresource Technology 113: 165-168.

25. Jang, D., Hwang, Y., Shin, H. and Lee, W. (2013). "Effects of salinity on the characteristics of biomass and membrane fouling in membrane bioreactors." Bioresource Technology 141: 50-56.

26. Jin, L., Ong, S. L. and Ng, H. Y. (2013). "Fouling control mechanism by suspended biofilm carriers addition in submerged ceramic membrane bioreactors." Journal of Membrane Science 427: 250-258.

27. Jin, Y.-L., Lee, W.-N., Lee, C.-H., Chang, I.-S., Huang, X. and Swaminathan, T. (2006). "Effect of DO concentration on biofilm structure and membrane filterability in submerged membrane bioreactor." Water Research 40(15): 2829-2836.

28. Judd, S. (2010). The MBR book: principles and applications of membrane bioreactors for water and wastewater treatment, Elsevier.

29. Keskes, S., Hmaied, F., Gannoun, H., Bouallagui, H., Godon, J. J. and Hamdi, M. (2012). "Performance of a submerged membrane bioreactor for the aerobic treatment of abattoir wastewater." Bioresource Technology 103(1): 28-34.

30. Khan, S. J. and Visvanathan, C. (2008). "Influence of mechanical mixing intensity on a biofilm structure and permeability in a membrane bioreactor." Desalination 231(1): 253-267.

31. Kornboonraksa, T. and Lee, S. H. (2009). "Factors affecting the performance of membrane bioreactor for piggery wastewater treatment." Bioresource Technology 100(12): 2926-2932.

32. Lay, W. C. L., Liu, Y. and Fane, A. G. (2010). "Impacts of salinity on the performance of high retention membrane bioreactors for water reclamation: A review." Water Research 44(1): 21-40.

33. Liu, Y., Liu, Z., Zhang, A., Chen, Y. and Wang, X. (2012). "The role of EPS concentration on membrane fouling control: Comparison analysis of hybrid membrane bioreactor and conventional membrane bioreactor." Desalination 305: 38-43.

34. Lousada-Ferreira, M., Geilvoet, S., Moreau, A., Atasoy, E., Krzeminski, P., van Nieuwenhuijzen, A. and van der Graaf, J. (2010). "MLSS concentration: Still a poorly understood parameter in MBR filterability." Desalination 250(2): 618-622.

35. Luo, Y., Guo, W., Ngo, H. H., Nghiem, L. D., Hai, F. I., Zhang, J., Liang, S. and Wang, X. C. (2014). "A review on the occurrence of micropollutants in the aquatic environment and their fate and removal during wastewater treatment." Science of The Total Environment 473-474: 619-641.

36. Meng, F., Chae, S.-R., Drews, A., Kraume, M., Shin, H.-S. and Yang, F. (2009). "Recent advances in membrane bioreactors (MBRs): Membrane fouling and membrane material." Water Research 43(6): 1489-1512.

37. Meng, F., Shi, B., Yang, F. and Zhang, H. (2007). "Effect of hydraulic retention time on membrane fouling and biomass characteristics in submerged membrane bioreactors." Bioprocess and Biosystems Engineering 30(5): 359-367.

38. Nguyen, T. T., Ngo, H. H., Guo, W., Li, J. and Listowski, A. (2012). "Effects of Sludge Concentrations and Different Sponge Configurations on the Performance of a Sponge-Submerged Membrane Bioreactor." Applied Biochemistry and Biotechnology 167(6): 1678-1687.

39. Nielsen, P. H. and Jahn, A. (1999). Extraction of EPS. Microbial Extracellular Polymeric Substances, Springer: 49-72.

40. Nittami, T., Tokunaga, H., Satoh, A., Takeda, M. and Matsumoto, K. (2014). "Influence of surface hydrophilicity on polytetrafluoroethylene flat sheet membrane fouling in a submerged membrane bioreactor using two activated sludges with different characteristics." Journal of Membrane Science 463: 183-189.

41. Pearce, G. (2007). "Introduction to membranes: Fouling control." Filtration & Separation 44(6): 30-32.

42. Ramesh, A., Lee, D., Wang, M., Hsu, J., Juang, R., Hwang, K., Liu, J. and Tseng, S. (2006). "Biofouling in membrane bioreactor." Separation Science and Technology 41(7): 1345-1370.

43. Rezaei, M. and Mehrnia, M. R. (2014). "The influence of zeolite (clinoptilolite) on the performance of a hybrid membrane bioreactor." Bioresource Technology 158: 25-31.

44. Rosenberger, S., Evenblij, H., te Poele, S., Wintgens, T. and Laabs, C. (2005). "The importance of liquid phase analyses to understand fouling in membrane assisted activated sludge processes—six case studies of different European research groups." Journal of Membrane Science 263(1): 113-126.

45. Rosenberger, S. and Kraume, M. (2002). "Filterability of activated sludge in membrane bioreactors." Desalination 146(1): 373-379.

46. Shen, L.-g., Lei, Q., Chen, J.-R., Hong, H.-C., He, Y.-M. and Lin, H.-J. (2015). "Membrane fouling in a submerged membrane bioreactor: Impacts of floc size." Chemical Engineering Journal 269: 328-334.

47. Skouteris, G., Saroj, D., Melidis, P., Hai, F. I. and Ouki, S. (2015). "The effect of activated carbon addition on membrane bioreactor processes for wastewater treatment and reclamation – A critical review." Bioresource Technology 185: 399-410.

48. Sonune, A. and Ghate, R. (2004). "Developments in wastewater treatment methods." Desalination 167: 55-63.

49. Sponza, D. T. (2002). "Extracellular polymer substances and physicochemical properties of flocs in steady and unsteady-state activated sludge systems." Process Biochemistry 37(9): 983-998.

50. Sullivan, F. and Europe, F. S. (2007). "Membrane filtration technologies tackle water reuse and purification." Membrane Technology(1): 9-11.

51. Sun, F.-Y., Wang, X.-M. and Li, X.-Y. (2008). "Visualisation and characterisation of biopolymer clusters in a submerged membrane bioreactor." Journal of Membrane Science 325(2): 691-697.

52. Tian, Y., Chen, L., Zhang, S., Cao, C. and Zhang, S. (2011). "Correlating membrane fouling with sludge characteristics in membrane bioreactors: An especial interest in EPS and sludge morphology analysis." Bioresource Technology 102(19): 8820-8827.

53. Tian, Y. and Su, X. (2012). "Relation between the stability of activated sludge flocs and membrane fouling in MBR: Under different SRTs." Bioresource Technology 118: 477-482.

54. van den Brink, P., Satpradit, O.-A., van Bentem, A., Zwijnenburg, A., Temmink, H. and van Loosdrecht, M. (2011). "Effect of temperature shocks on membrane fouling in membrane bioreactors." Water Research 45(15): 4491-4500.

55. Van den Broeck, R., Van Dierdonck, J., Nijskens, P., Dotremont, C., Krzeminski, P., van der Graaf, J. H. J. M., van Lier, J. B., Van Impe, J. F. M. and Smets, I. Y. (2012). "The influence of solids retention time on activated sludge bioflocculation and membrane fouling in a membrane bioreactor (MBR)." Journal of Membrane Science 401-402: 48-55.

56. van der Marel, P., Zwijnenburg, A., Kemperman, A., Wessling, M., Temmink, H. and van der Meer, W. (2010). "Influence of membrane properties on fouling in submerged membrane bioreactors." Journal of Membrane Science 348(1): 66-74.

57. Wang, Q., Wang, Z., Wu, Z., Ma, J. and Jiang, Z. (2012). "Insights into membrane fouling of submerged membrane bioreactors by characterizing different fouling layers formed on membrane surfaces." Chemical Engineering Journal 179: 169-177.

58. Wang, X.-M. and Li, X.-Y. (2008). "Accumulation of biopolymer clusters in a submerged membrane bioreactor and its effect on membrane fouling." Water Research 42(4): 855-862.

59. Wang, Z., Chu, J., Song, Y., Cui, Y., Zhang, H., Zhao, X., Li, Z. and Yao, J. (2009). "Influence of operating conditions on the efficiency of domestic wastewater treatment in membrane bioreactors." Desalination 245(1): 73-81.

60. Wang, Z., Ma, J., Tang, C. Y., Kimura, K., Wang, Q. and Han, X. (2014). "Membrane cleaning in membrane bioreactors: A review." Journal of Membrane Science 468: 276-307.

61. Wu, B., Yi, S. and Fane, A. G. (2011). "Microbial behaviors involved in cake fouling in membrane bioreactors under different solids retention times." Bioresource Technology 102(3): 2511-2516.

62. Wu, B., Yi, S. and Fane, A. G. (2011). "Microbial community developments and biomass characteristics in membrane bioreactors under different organic loadings." Bioresource Technology 102(13): 6808-6814.

63. Wu, B., Yi, S. and Fane, A. G. (2012). "Effect of substrate composition (C/N/P ratio) on microbial community and membrane fouling tendency of biomass in membrane bioreactors." Separation Science and Technology 47(3): 440-445.

64. Wu, J. and Huang, X. (2009). "Effect of mixed liquor properties on fouling propensity in membrane bioreactors." Journal of Membrane Science 342(1): 88-96.

65. Wu, S. C. and Lee, C. M. (2011). "Correlation between fouling propensity of soluble extracellular polymeric substances and sludge metabolic activity altered by different starvation conditions." Bioresource Technology 102(9): 5375-5380.

66. Xia, S., Li, J., He, S., Xie, K., Wang, X., Zhang, Y., Duan, L. and Zhang, Z. (2010). "The effect of organic loading on bacterial community composition of membrane biofilms in a submerged polyvinyl chloride membrane bioreactor." Bioresource Technology 101(17): 6601-6609.

67. Yang, X.-L., Song, H.-L., Lu, J.-L., Fu, D.-F. and Cheng, B. (2010). "Influence of diatomite addition on membrane fouling and performance in a submerged membrane bioreactor." Bioresource Technology 101(23): 9178-9184.

68. Yigit, N. O., Harman, I., Civelekoglu, G., Koseoglu, H., Cicek, N. and Kitis, M. (2008). "Membrane fouling in a pilot-scale submerged membrane bioreactor operated under various conditions." Desalination 231(1): 124-132.

69. Zhang, K., Choi, H., Dionysiou, D. D., Sorial, G. A. and Oerther, D. B. (2006). "Identifying pioneer bacterial species responsible for biofouling membrane bioreactors." Environmental Microbiology 8(3): 433-440.

70. Zhang, M., Liao, B.-q., Zhou, X., He, Y., Hong, H., Lin, H. and Chen, J. (2015). "Effects of hydrophilicity/hydrophobicity of membrane on membrane fouling in a submerged membrane bioreactor." Bioresource Technology 175: 59-67.

71. 江誠憲 (2008). 不同鹼度物質對薄膜生物反應槽中硝化作用之影響. 碩士, 嘉南藥理科技大學.