以次臨界流體萃取陰極射線管螢光粉中之稀土金屬釔與銪

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研究生：	柯若昕 Jo-Hsin Ko
論文名稱：	以次臨界流體萃取陰極射線管螢光粉中之稀土金屬釔與銪 Extraction of Yttrium and Europium from CRT Phosphor by Subcritical Water
指導教授：	劉志成 Jhy-Chern Liu
口試委員:	顧洋李奇旺
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2017
畢業學年度：	105
語文別：	英文
論文頁數：	74
中文關鍵詞：	陰極射線管螢光粉、銪、萃取、次臨界流體、釔
外文關鍵詞：	Cathod ray tube phosphor, Europium, Extraction, Subcritical water extraction, Yttrium
相關次數：	點閱：207 下載：7
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上一筆

稀土金屬例如釔(Y)和銪(Eu)被廣泛的應用在電子產品中，在螢光粉的結構上更是不可或缺。但隨著電子產品的生命週期不斷縮短，電子廢棄物的量在這幾年逐漸提高，因此從電子廢棄物中對稀土金屬回收並且再利用，是永續發展中至關重要的一環。此研究主要探討利用次臨界流體從陰極射線管的螢光粉萃取釔跟銪，並與傳統萃取方法比較研究結果。
其中探討酸的種類、濃度與萃取溫度對於反應的影響，研究結果顯示，在硫酸、硝酸和鹽酸的萃取過程中，利用硫酸萃取釔跟銪可以達到最佳的萃取效果。另外此研究也將此三種酸，使用不同的比例混合；結果顯示，混合酸萃取含有硫酸的效果，比沒有硫酸的系統效果好。在次臨界流體萃取純螢光粉中，使用0.5 N 硫酸在100oC下能將所有的釔跟銪萃取出來。比較實驗結果，我們發現相同條件下，廢棄螢光粉比純螢光粉難萃取，這可能是廢棄螢光粉中的雜質優先與酸反應。在傳統萃取方法的動力實驗中，我們利用shrinking core model去模擬萃取的數據，可以推測在傳統萃取反應中，化學反應控制了整個實驗的反應速度。
本研究初步結果顯示，次臨界萃取法需要較少的時間，與使用較低濃度的硫酸，卻得到更好的效果，次臨界萃取法對從螢光粉中萃取釔跟銪是充滿發展潛力的環境友善萃取方法。

Rare earth elements (REEs), such as yttrium (Y) and europium (Eu) are widely used in electronic products, especially as an essential constituent in phosphor. With the life cycle of electronic products becoming shorter, the amount of electronic waste (e-waste) increases continuously in recent years. Therefore, recycling and reuse of REEs from e-waste is critical for sustainable development. The current study investigated Y and Eu extraction from cathode ray tube (CRT) phosphor by subcritical water extraction (SWE) and compared the results with those from conventional extraction.
Effects of acid type, acid concentration, and extraction temperature were examined. Experimental results indicated that extraction efficiency of Y and Eu was the best when using sulfuric acid (H2SO4) compared with hydrochloric acid (HCl) and nitric acid (HNO3). Mixed acids with different ratio were used in SWE. It was found that any mixed acid containing H2SO4 resulted in better extraction efficiency. In SWE of pure phosphor, use of 0.5 N H2SO4 at 100oC could achieve complete Y and Eu leaching. Comparing the results of pure phosphor and waste phosphor, it was found that waste phosphor was more difficult to extract. This might be because the impurities in waste phosphor reacted preferentially with acid over Y2O2S. In the waste phosphor of kinetic study of conventional extraction, shrinking core model fit the results of kinetics well, and it can be inferred that waste phosphor conventional extraction was controlled by chemical reaction.
In this preliminary study, it was observed that SWE required less reaction time at lower acid concentration, yet resulted in better efficiency. SWE is a process full of potential to extract Y and Eu from phosphor.

CONTENTS
摘要    I
ABSTRACT    III
ACKNOWLEDGEMENT    V
CONTENTS    VII
LIST OF FIGURES    IX
LIST OF TABLES    XI
CHAPTER1 INTRODUCTION    1-1
1.1 Background    1-1
1.2 Objectives of study    1-2
CHAPTER2 LITERATURE REVIEW    2-1
2.1 Phosphor    2-1
2.2 Extraction of REEs from phosphor    2-2
2.3 Subcritical water extraction (SWE)    2-3
CHAPTER3 METHODS AND MATERIALS    3-1
3.1 Materials and reagents    3-1
3.2    Instruments    3-2
3.3    Experimental framework and procedures    3-3
3.4 Experimental method    3-4
3.4.1 Subcritical water extraction (SWE)    3-4
3.4.2 Conventional Extraction    3-6
3.4.3 Sample analysis    3-7
CHAPTER4 RESULTS AND DISSCUSSION    4-1
4.1 Characterization of phosphor    4-1
4.1.1 Pure CRT phosphor    4-1
4.1.2 Waste CRT phosphor    4-4
4.2 Result from subcritical water extraction (SWE)    4-11
4.2.1 Effect of acid type    4-12
4.2.2 Effect of acid concentration    4-13
4.3 Result from conventional extraction    4-18
4.3.1 Effect of acid type    4-18
4.3.2 Effect of acid concentration    4-21
4.3.3 Effect of temperature    4-23
4.4 Kinetic study on phosphor leaching    4-26
CHAPTER5 CONCLUSIONS AND RECOMMENDATIONS    5-1
5.1 Conclusions    5-1
5.2 Recommendations    5-3
REFERENCE    R-1
APPENDIX EXPERIMENTAL DATA    A-1

LIST OF FIGURES
Figure3. 1 Experimental scheme of the study    3-3
Figure3. 2 The apparatus of SWE    3-5
Figure 4.1 FESEM image and EDX results of pure phosphor    4-2
Figure 4.2 XRD patterns of pure phosphor    4-3
Figure 4.3 FESEM image and EDX results of waste CRT phosphor (Lin, 2016).    4-7
Figure 4.4 FESEM images and EDX results of waste CRT phosphor in different shape (Lin, 2016).    4-8
Figure 4.5 XRD patterns of original waste CRT phosphor (Lin, 2016).    4-9
Figure 4.6 XRD patterns of waste CRT phosphor after aqua-regia digestion    4-10
Figure 4.7 SWE efficiency using 0.1 N acid at 100oC of pure phosphor    4-14
Figure 4.8 SWE efficiency using 0.1 N mixed acid at 100oC of pure phosphor    4-14
Figure 4.9 SWE efficiency using 0.5 N acid at 100oC of pure phosphor    4-15
Figure 4.10 SWE efficiency using 0.5 N mixed acid at 100oC of pure phosphor    4-15
Figure 4. 11 SWE efficiency using H2SO4 at 100oC of waste phosphor.    4-16
Figure 4. 12 SWE efficiency using H2SO4 at 100oC of waste phosphor of Y and Zn.    4-16
Figure 4.13 XRD patterns of original and residual phosphor    4-17
Figure 4.14 Conventional extraction efficiency of Y from pure phosphor with different pure acid under 25oC.    4-19
Figure 4.15 Conventional extraction efficiency of Eu from pure phosphor with different pure acid under 25oC.    4-19
Figure 4.16 Conventional extraction efficiency of Y from pure phosphor with different concentration of H2SO4 under 25oC.    4-22
Figure 4.17 Conventional extraction efficiency of Eu from pure phosphor with different concentration of H2SO4 under 25oC.    4-22
Figure 4.18 Conventional extraction efficiency of Y from pure phosphor with different temperature with 0.5 N H2SO4    4-24
Figure 4.19 Conventional extraction efficiency of Eu from pure phosphor with different temperature with 0.5 N H2SO4    4-24
Figure 4.20 Conventional extraction efficiency of Y from waste phosphor with different temperature with 0.5 M H2SO4    4-25
Figure 4.21 Conventional extraction efficiency of Eu from waste phosphor with different temperature with 0.5 M H2SO4    4-25
Figure 4.22 Kinetic plot of pure phosphor extraction of Y with 0.5 N H2SO4.    4-29
Figure 4.23 Kinetic plot of pure phosphor extraction of Eu with 0.5 N H2SO4.    4-29

LIST OF TABLES
Table 2.1 Summary of treatment technologies of waste CRT phosphor    2-4
Table 2.2 Summary of treatment technologies of waste fluorescent lamp phosphor    2-5
Table 2.3 Summary of environmental applications of SWE    2-7
Table 4.1 Metal composition of pure phosphor by aqua-regia digestion…………………4-3
Table 4.2 Metal contents in waste CRT phosphor as analyzed by aqua-regia digestion (Lin, 2016).    4-6
Table 4.3 SWE and conventional extraction efficiency with 0.1 N acid of pure phosphor    4-20
Table 4.4 SWE and conventional extraction (25oC) efficiency with 0.5 N H2SO4 of pure phosphor.    4-21
Table 4.5 SWE and conventional extraction efficiency of Y and from waste phosphor using0.5 M H2SO4.    4-23
Table 4.6 Kinetic parameters of waste phosphor of Y acid leaching.    4-27
Table 4.7 Kinetic parameters of waste phosphor of Eu acid leaching.    4-27
Table 4.8 Kinetic parameter of pure phosphor extraction of Y with 0.5 N H2SO4    4-30
Table 4.9 Kinetic parameter of pure phosphor extraction of Eu with 0.5 N H2SO4    4-30
                                

Akinlua, A. and Smith, R. (2010). Subcritical water extraction of trace metals from petroleum source rock. Talanta, 81(4-5), pp.1346-1349.
Ali, A. G., Dejene, B. F., Swart, H. C. (2016). The influence of oxygen partial pressure on material properties of Eu3+-doped Y2O2S thin film deposited by Pulsed Laser Deposition. Physica B: Condensed Matter, 480, pp.174-180.
A. Haghighi Asl and M. Khajenoori (2013). Subcritical Water Extraction, Mass Transfer - Advances in Sustainable Energy and Environment Oriented Numerical Modeling, Dr. Hironori Nakajima (Ed.), InTech, DOI: 10.5772/54993. Available from: https://www.intechopen.com/books/mass-transfer-advances-in-sustainable-energy-and-environment-oriented-numerical-modeling/subcritical-water-extraction
Baldé, C.P., Wang, F., Kuehr, R., Huisman, J. (2015), The global e-waste monitor – 2014, United NationsUniversity, IAS – SCYCLE, Bonn, Germany.
Carr, A., Mammucari, R. and Fooster, N. (2011). A review of subcritical water as a solvent and its utilisation for the processing of hydrophobic organic compounds. Chemical Engineering Journal, 172(1), pp.1-17.
Chen, M. and Ma, L. (2001). Comparison of three aqua regia digestion methods for twenty Florida soils. Soil Science Society of America Journal, 65(2), p.491-499.
De Michelis, I., Ferella, F., Varelli, E. and Vegliò, F. (2011). Treatment of exhaust fluorescent lamps to recover yttrium: Experimental and process analyses. Waste Management, 31(12), pp.2559-2568.
Dexpert-Ghys, J., Regnier, S., Canac, S., Beaudette, T., Guillot, P., Caillier, B., Mauricot, R., Navarro, J., Sekhri, S. (2009). Re-processing CRT phosphors for mercury-free applications. Journal of Luminescence, 129(12), pp.1968-1972.
Dutta, Tanushree., Kim, K.-H., Uchimiya, M., Kwon, E. E., Jeon, B.-H., Deep, A., Yun, S.-T. (2016). Global demand for rare earth resources and strategies for green mining. Environmental Research, 150, pp.182-190.
Guyonnet, D., Planchon, M., Rollat, A., Escalon, V., Tuduri, J., Charles, N., Vaxelaire, S., Dubois, D. and Fargier, H. (2015). Material flow analysis applied to rare earth elements in Europe. Journal of Cleaner Production, 107, pp.215-228.
Han, P., Jiang X., Xu M., Yu F., Jiao B., Guan R., Zhang Q. (2015). Three primary colors upconversion phosphors and combined white upconversion luminscence in Y2O2S matrix. Materials Research Bulletin, 70, pp.658-662.
Herrero, M., Sánchez-Camargo, A. P., Cifuentes, A., Ibáñez, E. (2015). Plants, seaweeds, microalgae and food by-products as natural sources of functional ingredients obtained using pressurized liquid extraction and supercritical fluid extraction. TrAC Trends in Analytical Chemistry, 70, pp.26-38.
Hirajima, T., Bissombolo, A., Sasaki, K., Nakayama, K., Hirai, H., Tsunekawa, M. (2005a). Floatability of rare earth phosphors from waste fluorescent lamps. International Journal of Mineral Processing, 77(4), pp.187-198.
Hirajima, T., Bissombolo, A., Sasaki, K., Nakayama, K., Hirai, H., Tsunekawa, M. (2005b). Feasibility of an efficient recovery of rare earth-activated phosphors from waste fluorescent lamps through dense-medium centrifugation. Separation and Purification Technology, 44(3), pp.197-204.
Hu, A. H., Kuo, C.-H., Huang, L. H., Su, C.-C. (2017). Carbon footprint assessment of recycling technologies for rare earth elements: A case study of recycling yttrium and europium from phosphor. Waste Management, 60, pp.765-774.
Hu, Y., Zhang, P., Li, J. and Chen, D. (2015). Stabilization and separation of heavy metals in incineration fly ash during the hydrothermal treatment process. Journal of Hazardous Materials, 299, pp.149-157.
Huynh, L. H., Tran Nguyen, P. L., Ho, Q. P., Ju, Y.-H. (2012). Catalyst-free fatty acid methyl ester production from wet activated sludge under subcritical water and methanol condition. Bioresource Technology, 123, pp-112-116.
Innocenzi, V., De Michelis, I., Ferella, F., Beolchini, F., Kopacek, B. and Vegliò, F. (2013b). Recovery of yttrium from fluorescent powder of cathode ray tube, CRT: Zn removal by sulphide precipitation. Waste Management, 33(11), pp.2364-2371.
Innocenzi, V., De Michelis, I., Kopacek, B. and Vegliò, F. (2014). Yttrium recovery from primary and secondary sources: A review of main hydrometallurgical processes. Waste Management, 34(7), pp.1237-1250.
Islam, M., Jung, H. and Park, J. (2015). Subcritical water treatment of explosive and heavy metals co-contaminated soil: Removal of the explosive, and immobilization and risk assessment of heavy metals. Journal of Environmental Management, 163, pp.262-269.
Islam, M., Park, J., Shin, M. and Park, H. (2014). Decontamination of PCBs-containing soil using subcritical water extraction process. Chemosphere, 109, pp.28-33.
Jo, Y., Kim, J., Jung, K., Min, S. and Chun, J. (2015). Effect of sub- abs super-critical water treatment on physicochemical properties of porcine skin. Korean Journal for Food Science of Animal Resources, 35(1), pp.35-40.
Jordens, A., Cheng, Y. P., Waters, K. E. (2013). A review of the beneficiation of rare earth element bearing minerals. Minerals Engineering, 41, pp.97-114.
Kirmizakis, P., Tsamoutsoglou, C., Kayan, B. and Kalderis, D. (2014). Subcritical water treatment of landfill leachate: Application of response surface methodology. Journal of Environmental Management, 146, pp.9-15.
Lee, C.-H., Liao, C.-H., Popuri, S. R., Hung, C.-E. (2017). Integrated process development for the recovery of Europium and Yttrium from waste fluorescent powder. Journal of Material Cycles and Waste Management, 19(3), pp.1235-1243.
Levenspiel, O., Chemical reaction engineering, 3rd ed. Times Roman: Bi-Comp Inc., 1972, Ch.25.
Li, H. (2010). Recovery of rare earths from phosphor sludge by acid leaching. Xiyou Jinshu/Chinese Journal of Rare Metals, 34(6), pp.898-904.
Liang, Y., Liu, Y., Lin, R., Guo, D., Liao, C. (2016). Leaching of rare earth elements from waste lamp phosphor mixtures by reduced alkali fusion followed by acid leaching. Hydrometallurgy, 163, pp.99-103.
Liu, H., Zhang, S., Pan, D., Tian, J., Yang, M., Wu, M. and Volinsky, A. (2014). Rare earth elements recycling from waste phosphor by dual hydrochloric acid dissolution. Journal of Hazardous Materials, 272, pp.96-101.
Massari, S. and Ruberti, M. (2013). Rare earth elements as critical raw materials: Focus on international markets and future strategies. Resources Policy, 38(1), pp.36-43.
Meshram, P., Pandey, B. D., Mankhand, T. R. (2015). Leaching of base metals from spent Ni–metal hydride batteries with emphasis on kinetics and characterization. Hydrometallurgy, 158, pp.172-179.
Möller, M., Nilges, P., Harnisch, F. and Schröder, U. (2011). Subcritical water as reaction environment: Fundamentals of hydrothermal biomass transformation. ChemSusChem, 4(5), pp.566-579.
Moss, R., Tzimas, E., Willis, P., Arendorf, J., Thompson, P., Chapman, A., Morley, N., Sims, E., Bryson, R., Peason, J., Tercero-Espinoza, L., Sartorius, C., Ostertag, K. (2013). Critical metals in the path towards the decarbonisation of the EU energy sector. Assessing Rare Metals as Supply-chain Bottlenecks in Low-carbon Energy Technologies, p. 242.
Morales-Muñoz, S., Luque-Garcı́a, J. L., Luque de Castro, M. D. (2004). Pressurised liquid–liquid extraction. An approach to the removal of inorganic non-metal species from used industrial oils. Chemosphere, 56(10), pp.943-947.
Mukherjee, N. (2016). Unusual properties of water: Phase behavior of subcritical and supercritical water. Available from: https://www.linkedin.com/pulse/unusual-properties-water-phase-behavior-subcritical-mukherjee.
Oh, S., Yoon, M., Kim, I., Kim, J. and Bae, W. (2011). Chemical extraction of arsenic from contaminated soil under subcritical conditions. Science of The Total Environment, 409(16), pp.3066-3072.
Pan, X., Peng, L., Chen, W., Wang, J. and Chen, Z. (2013). Recovery of Y and Eu from Waste Phosphors of CRT TVs and the Preparation of Yttrium Europium Oxide. AMM, 295-298, pp.1840-1845.
Plaza, M. and Turner, C. (2015). Pressurized hot water extraction of bioactives. TrAC Trends in Analytical Chemistry, 71, pp.39-54.
Rabah, M. (2008). Recyclables recovery of europium and yttrium metals and some salts from spent fluorescent lamps. Waste Management, 28(2), pp.318-325.
Resende, L. and Morais, C. (2010). Study of the recovery of rare earth elements from computer monitor scraps – Leaching experiments. Minerals Engineering, 23(3), pp.277-280.
Resende, L. V. and C. A. Morais (2015). Process development for the recovery of europium and yttrium from computer monitor screens. Minerals Engineering, 70, pp.217-221.
Shi, W., Liu, C., Ding, D., Lei, Z., Yang, Y., Feng, C. and Zhang, Z. (2013). Immobilization of heavy metals in sewage sludge by using subcritical water technology. Bioresource Technology, 137, pp.18-24.
Shimizu, R., Sawada, K., Enokida, Y. and Yamamoto, I. (2005). Supercritical fluid extraction of rare earth elements from luminescent material in waste fluorescent lamps. The Journal of Supercritical Fluids, 33(3), pp.235-241.
Singh, N., Li, J. and Zeng, X. (2016). Solutions and challenges in recycling waste cathode-ray tubes. Journal of Cleaner Production, 133, pp.188-200.
Song G.,Yuan W., Zhu X., Wang X., Zhang C., Li J., Bai J., Wang J. (2017). Improvement in rare earth element recovery from waste trichromatic phosphors by mechanical activation. Journal of Cleaner Production, 151, pp.361-370.
,
Tavakoli, O. and Yoshida, H. (2008). Application of sub-critical water technology for recovery of heavy metal ions from the wastes of Japanese scallop Patinopecten yessoensis. Science of the Total Environment, 398(1-3), pp.175-184.
Teo, C., Tan, S., Yong, J., Hew, C. and Ong, E. (2010). Pressurized hot water extraction (PHWE). Journal of Chromatography A, 1217(16), pp.2484-2494.
Tian, X., Yin, X., Gong, Y., Wu, Y., Tan, Z., Xu, P. (2016). Characterization, recovery potentiality, and evaluation on recycling major metals from waste cathode-ray tube phosphor powder by using sulphuric acid leaching. Journal of Cleaner Production, 135, pp.1210-1217.
Tunsu, C., Petranikova, M., Ekberg, C., Retegan, T. (2016). A hydrometallurgical process for the recovery of rare earth elements from fluorescent lamp waste fractions. Separation and Purification Technology, 161, pp.172-186.
Wu, Y., Yin, X., Zhang, Q., Wang, W. and Mu, X. (2014). The recycling of rare earths from waste tricolor phosphors in fluorescent lamps: A review of processes and technologies. Resources, Conservation and Recycling, 88, pp.21-31.
Yabalak, E. and Gizir, A.M., (2013). Subcritical and supercritical fluid extraction of heavy metals from sand and sewage sludge. Journal of Serbian Chemical. Society, 78, 1013-1022.
Yoshida, A., Terazono, A., Ballesteros, F. C., Nguyen, D.-Q., Sukandar, S.,Kojima, M.,Sakata, S. (2016). E-waste recycling processes in Indonesia, the Philippines, and Vietnam: A case study of cathode ray tube TVs and monitors. Resources, Conservation and Recycling, 106, pp.48-58.
Yoshida, H., Izhar, S., Nishio, E., Utsumi, Y., Kakimori, N., Feridoun, S. A. (2014). Recovery of indium from TFT and CFg lasses in LCD panel wastes using sub-critical water. Solar Energy Materials & Solar Cells, 125, 14–19
Lin, Y. Y., “Recovery of Yttrium and Europium from waste CRT phosphor by subcritical water extraction,” Master Dissertation of National Taiwan University of Science and Technology, Taiwan Taipei (2016).
Zeng, X., Gong, R., Chen, W.-Q., Li, J. (2016). Uncovering the recycling potential of “new” WEEE in China. Environmental Science & Technology, 50(3), pp.1347-1358.
Zhang, S.G., Yang, M., Liu, H., Pan, D.A., Tian, J.J. (2013). Recovery of waste rare earth fluorescent powders by two steps acid leaching. Rare Metals, 32(6), pp. 609–615

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