Antibiotics Recycling of Tetracycline Hydrochloride from Capsule Waste

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姓名

謝汶蓁(Wen-Chen Hsieh) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

(Antibiotics Recycling of Tetracycline Hydrochloride from Capsule Waste)

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摘要(中)

根據統計，每年台灣丟棄的廢棄藥物至少達193噸以上，而抗生素在其中占了相當大的比例。然而，四環素是世界上第二大類抗生素，也是最常見的獸醫用藥。因此，本研究的目的是從廢棄抗生素膠囊中回收其活性藥物成分(API)鹽酸四環素（TCH）作為案例研究。此研究包括兩個部分：（1）根據國際醫藥法規協和會（ICH）所訂定人類用藥之製程殘留溶劑標準，選擇TCH再結晶之溶劑以及（2）將第一部分的結果延伸至500 ml的攪拌槽規模並混合KINGDOM®和NOVABIOTIC®兩種市售的抗生素膠囊，從其中回收鹽酸四環素。本研究將探討混合、老化時間、老化溫度、反溶劑添加速率以及攪拌速率對製程的影響。在25℃下利用甲醇以300 rpm攪拌1.5 小時固液萃取其中的鹽酸四環素，經0.22 μm聚偏二氟乙烯(PVDF)膜過濾未溶解之物質。再以9.9 毫升/分鐘的速率添加甲基叔丁基醚(MTBE)作為反溶劑，添加後以900 rpm攪拌老化2小時，利用1μm棉絨纖維濾紙過濾蒐集固體。鹽酸四環素的回收率達到73.1％且HPLC純度測定達到99.2％。藥物回收的技術已屈指可數，然而相比之下利用結晶製程回收藥物更是乏人問津。此研究不僅是一個新穎的方法，更具其他優點，例如製程操作簡單且快速也具再現性。最重要的是，其中的活性藥物成分(API)能夠直接被回收而非分解或轉換成其他物質。

摘要(英)

According to the statistics, at least 193 tons of drugs are thrown away in Taiwan every year and antibiotics make up a large proportion. Among them, tetracycline is the second largest class of antibiotics in the world, and the most common veterinary drug. For this reason, the aim of this research is to recycle tetracycline hydrochloride (TCH), one of the antibiotics, from capsule wastes as a case study. Experiments include two parts: (1) solvent screening and selection for recrystallization of purchased TCH according to the International Council for Harmonization of Technical Requirements for Pharmaceuticals for Human Use (ICH) guideline Q3C (R6) on impurities: Guideline for residual solvents, and (2) the results based on the first part were extended to recycle TCH from different brands of capsules (KINGDOM® and NOVABIOTIC®) in a 500 ml stirred tank scale. The effects of mixing, aging time, aging temperature, addition rates, and agitation rates on TCH recycling are studied. Solid-liquid extraction was applied to the capsules in methanol with an agitation rate of 300 rpm for 1.5 hours, and filtration by a 0.22 μm PVDF filter membrane. The addition of antisolvent, MTBE with an addition rate of 9.9 ml/min, with an agitation rate of 900 rpm, and aged for 2 hours at 25℃, then filtered through a 1μm alpha cotton cellulose filter paper to collect the solids. The recovery rates of TCH achieved 73.1%, and the HPLC assay achieved 99.2%. A novel, fast and simple operation, and reproducible recycling processes were carried out in this research. Most importantly, the original pure form of the active pharmaceutical ingredient (API) can be recovered directly instead of decomposing or transforming into some other components.

關鍵字(中)

★ 藥物回收
★ 抗生素
★ 結晶

關鍵字(英)

★ Drug recycling
★ Antibiotic
★ Crystallization

論文目次

摘要 I
Abstract II
Acknowledgments IV
Table of Contents VI
List of Figures X
List of Table XIX
List of Scheme XXII
Chapter 1. Executive Summary 1
1.1 Status of Unused Drugs 1
1.1.1 Situation of Drug Wastes 1
1.1.2 Pollution of Drug Waste 3
1.1.3 Recycling unused drugs 4
1.2 Antibiotics 7
1.2.1 Introduction of antibiotics 7
1.2.2 Introduction of tetracycline hydrochloride 11
1.3 Comparison of Tetracycline Removal 15
1.3.1 Adsorption 18
1.3.2 Photodegradation 24
1.3.3 Membrane Processes 28
1.3.4 Combined Processes 32
1.3.5 Other Processes 36
1.4 Conceptual Framework 40
1.5 References 43
Chapter 2. Materials and Methods 54
2.1 Materials 54
2.1.1 Chemicals 54
2.1.2 Solvents 56
2.2 Experimental Framework 58
2.2.1 Concept of Experiment 58
2.2.2 Solvent Selection 59
2.2.3 Single Crystal Growth 62
2.3 Purchased TCH Recrystallization 63
2.3.1 Mixing and Aging Time Effect 64
2.3.2 Antisolvent Effect 65
2.3.3 Solvent Ratio Effect 66
2.4 Recycled TCH from Capsules 67
2.4.1 Addition Rate Effect 67
2.5 Scale Up recycling TCH from capsules 68
2.5.1 Aging Time Effect 69
2.5.2 Aging Temperature Effect 70
2.5.3 Agitation Rate Effect 71
2.5.4 Addition Rate Effect 72
2.6 Analytical Instruments 73
2.6.1 Fourier Transform Infrared (FT-IR) Spectroscopy 73
2.6.2 Powder X-ray Diffraction (PXRD) 74
2.6.3 Polarized Optical Microscopy (POM) 75
2.6.4 Single Crystal X-ray Diffractometer (SXD) 76
2.6.5 High Performance Liquid Chromatography (HPLC) 77
2.7 References 80
Chapter 3. Results and Discussion 81
3.1 Solvent Selection 81
3.2 Characterization of TCH 85
3.2.1 FTIR Spectrum 85
3.2.2 Powder X-ray Diffraction & Single Crystal X-ray Diffraction 86
3.3 Purchased TCH Recrystallization 89
3.3.1 Mixing and Aging Time Effect 89
3.3.2 Antisolvent Effect 97
3.3.3 Solvent Ratio Effect 98
3.4 Recycled TCH from Capsules in Laboratory Scale 100
3.4.1 Antisolvent Addition Rate Effect 100
3.5 Scale Up Recycling TCH from Capsules 106
3.5.1 Aging Time Effect 106
3.5.2 Aging Temperature Effect 110
3.5.3 Agitation Rate Effect 112
3.5.4 Addition Rate Effect 116
3.6 References 121
Chapter 4. Conclusions and Future Works 123
4.1 Conclusions 123
4.2 Future Works 125
4.3 References 134

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76 Pang, Y. X.; Kong, L. J; Lei, H. Y.; Chen, D. Y.; Yuvaraja, G. Combined microwave-induced and photocatalytic oxidation using zinc ferrite catalyst for eﬃcient degradation of tetracycline hydrochloride in aqueous solution. J. Taiwan. Inst. Chem. Eng. 2018, 93, 397-404.
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79 Ma, Y.; Xiong, H. F.; Zhao, Z. Q.; Yu, Y.; Zhou, D. D.; Dong, S. S.; Model-based evaluation of tetracycline hydrochloride removal and mineralization in an intimately coupled photocatalysis and biodegradation reactor. Chem. Eng. J. 2018, 351, 967-975.
80 Xiong, H. F.; Zou, D. L; Zhou, D. D.; Wang, S. S.; Wang, J. W.; Rittmann, B. E. Enhancing degradation and mineralization of tetracycline using intimately coupled photocatalysis and biodegradation (ICPB). Chem. Eng. J. 2017, 316, 7-14.
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83 Guo, D. G.; Ni, L.; Wang, L.; Shao, L. Separation and determination of tetracycline hydrochloride in real water samples using binary small molecule alcohol‐salt aqueous two‐phase system coupled with high‐performance liquid chromatography. Chirality. 2019, 31(4), 1-11.
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85 Lee, T.; Yeh, K. L.; You, J. X.; Fan, Y. C.; Cheng, Y. S.; Pratama, D. E. Reproducible Crystallization of Sodium Dodecyl Sulfate·1/8 Hydrate by Evaporation, Antisolvent Addition, and Cooling. ACS Omega. 2020, 5(2), 1068-1079.
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Chapter 2.
1 景德鹽酸四環素膠囊Tetracycline HCl Capsules "KINGDOM". https://www.kingnet.com.tw/knNew/medicine/merchandise_single.html?license_id=%E5%85%A7%E8%A1%9B%E8%97%A5%E8%A3%BD%E5%AD%97%E7%AC%AC001542%E8%99%9F (acessed April 9, 2018)
2 Lee, T.; Kuo, C. S.; Chen, Y. H. Solubility, polymorphism, crystallinity, and crystal habit of acetaminophen and ibuprofen: By initial solvent screening. Pharm. Technol. 2006, 30(10), 72-92.
3 ICH guideline Q3C (R6) on impurities: guideline for residual solvents. European Medicines Agency, Science Medicines Health. (accessed August 9, 2019).
4 Sheldrick, G. M. SHELXL-2017, Program for Solution of Crystal Structures, University of Gottingen, Germany, 2017.
5 Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 3-8.
6 https://www.bruker.com/cn/products/x-ray-diffraction-and-elemental-analysis/single-crystal-x-ray-diffraction/d8-quest-eco.html.
7 United States Pharmacopeia and National Formulary (USP 35-NF 30). Tetracycline Hydrochloride. http://usp35.infostar.com.cn/uspnf/pub/data/v35300/usp35nf30s0_m81810.html#usp35nf30s0_m81810

Chapter 3.
1 Lee, T.; Kuo, C. S.; Chen, Y. H. Solubility, polymorphism, crystallinity, and crystal habit of acetaminophen and ibuprofen: By initial solvent screening. Pharm. Technol. 2006, 30(10), 72-92.
2 Benzyl alcohol.
https://en.wikipedia.org/wiki/Benzyl_alcohol (accessed June 22, 2020).
3 Dimethylformamide.
https://en.wikipedia.org/wiki/Dimethylformamide (accessed June 2, 2020).
4 Dimethyl sulfoxide.
https://en.wikipedia.org/wiki/Dimethyl_sulfoxide (accessed May 15, 2020).
5 ICH guideline Q3C (R6) on impurities: guideline for residual solvents. European Medicines Agency, Science Medicines Health. (accessed August 9, 2019)
6 National Center for Biotechnology Information. PubChem Database. Tetracycline hydrochloride.
https://pubchem.ncbi.nlm.nih.gov/compound/Tetracycline-hydrochloride (accessed June 30,
2020).
7 IR Spectroscopy Tutorial: Amines.
http://www.orgchemboulder.com/Spectroscopy/irtutor/aminesir.shtml
8 IR Spectrum Table & Chart.
https://www.sigmaaldrich.com/technical-documents/articles/biology/ir-spectrum-table.html
9 Clegg, W.; Teat, S. J. Tetracycline Hydrochloride: A Synchrotron Microcrystal Study. Acta. Crystallogr. C. 2000, 11(11), 1343-1345.
10 United States Pharmacopeia and National Formulary (USP 35-NF 30). Tetracycline Hydrochloride. http://usp35.infostar.com.cn/uspnf/pub/data/v35300/usp35nf30s0_m81810.html#usp35nf30s0_m81810
11 Mullin, J. W. Crystallization, 4th ed.; Butterworth-Heinemann, 2001.
12 Genck, W. Make The Most of Antisolvent Crystallization. A number of factors can affect solids′ formation.
https://www.chemicalprocessing.com/articles/2010/210/ (accessed November 08, 2010).
13 Brubaker, J. How to Calculate HPLC Resolutions.
https://sciencing.com/calculate-hplc-resolutions-7547102.html (accessed April 30, 2018).
14 Hair, M. L. Hydroxyl groups on silica surface. J Non Cryst Solids. 1975, 19, 299-309.
15 Reverchon, E.; Caputo, G.; Marco, I. D. Role of Phase Behavior and Atomization in the Supercritical Antisolvent Precipitation. Ind. Eng. Chem. Res. 2003, 42(25), 6406-6414.

Chapter 4.
1 Genck, W. Make The Most of Antisolvent Crystallization: A number of factors can affect solids′ formation.
https://www.chemicalprocessing.com/articles/2010/210/ (accessed November 08. 2010).
2 Robbe, C. L.; Jeb, S. T.; Donna, A. P.; Hullahalli, R. P.; Ajaz, S. H. Stability Proﬁles of Drug Products Extended beyond Labeled Expiration Dates. J Pharm Sci. 2006, 95(7), 1549-1560.
3 U.S. Food and Drug Administration. Don’t Be Tempted to Use Expired Medicines. https://www.fda.gov/drugs/special-features/dont-be-tempted-use-expired-medicines (accessed April 01, 2016)
4 Vapor-Liquid Equilibrium Calculator.
http://www.vle-calc.com/phase_diagram.html
5 Cassata, J. R.; Parker, S. J.; Hwan, R. J.; Conkwright, C. J. Extraction of methanol from methyl tertiary butyl ether. E. P. Patent No. 0652199A1, 1994.
6 Chen, Y.; Pan, Z.; Dong, Y. Measurements of Liquid−Liquid Equilibria for Quaternary Mixtures of Water, Methyltert-Butyl Ether, and Diisopropyl Ether with Methanol or Ethanol. Journal of Chemical & Engineering Data. 2005, 50(3), 1047-1051.

指導教授

李度(Tu Lee)

審核日期

2020-7-29

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