Kavurma ve asit liçi yöntemi ile Emet kolemanit zenginleştirme tesisi katı atık killerinden lityum kazanımı

Abstract

Bu çalışmada, Emet konsantratör tesisi katı atık killeri kullanılmıştır. Karakterizasyon testlerinden elde edilen veriler ile 0.5 mm tane boyutu altında kalan, 1942-2035 ppm aralığında Li tenörlü numune fraksiyonu ile çalışmaya karar verilmiştir. Kil numunesi ile tuz karışımları, farklı oranlarda harmanlanarak; ilk aşamada tuz türü ve oranının, ikinci aşamada kavurma süresi ve sıcaklığının liçe etkisi ölçülmüştür. Kavurma çalışmasında kullanılan parametrelerin etkinliği, lityum ekstraksiyon çalışmaları ile değerlendirilmiştir. Çalışmanın üçüncü aşaması olan liç uygulamasında ise, H2SO4 konsantrasyonu ve liç süresi dikkate alınarak çalışma tamamlanmıştır. Gerçekleştirilen işlemlerle öncelikle, Numune/tuz karışım oranı 1/1, tuzların ise kendi arasında NaCl (0.6)-CaCl2 (0.4) oranlarında harmanlanmasıyla elde edilen karışımın; 900 °C sıcaklıkta 1 sa. kavrulması sonucu %77.26 Li kavurma verimi elde edilmiştir. Daha sonra, kavrulmuş malzemenin 0.4M H2SO4 varlığında 1 sa. liç işlemine tabi tutulması ile liç verimi %89.61 Li olarak tespit edilmiştir.

Keywords

• Bor
• Kavurma
• Saponit
• Espey
• Hisarcık

Recovery of lithium from solid waste clays of Emet colemanite beneficiation plant by roasting and acid leaching method

Abstract

In this study, solid waste clays from the Emet Concentrator Plant were used. With the data obtained from the characterization tests, it was decided to work with the sample fraction with a Li grade in the range of 1942-2035 ppm, which is below 0.5 mm grain size. Clay samples and salt mixtures are blended at different rates. In the first stage, the leaching effect of salt type and ratio was investigated, and in the second stage, the roasting time and temperature were investigated. The effectiveness of the parameters used in the roasting study was evaluated by lithium extraction studies. In the third phase of the study, leaching, the study was completed by considering the H2SO4 concentration and leaching time. With the processes carried out, first of all, the mixture obtained by blending the sample/salt mixture ratio of 1/1 and between the salts in the ratios of NaCl (0.6)-CaCl2 (0.4); Result of roasting at 900 °C for 1 hour, a roasting efficiency of 77.26% Li was obtained. Then, by leaching the roasted material in the presence of 0.4M H2SO4 for 1 hour, the leaching efficiency was determined to be 89.61% Li.

Keywords

• Boron
• Roasting
• Saponite
• Espey
• Hisarcık

References

1. [1] Eti Maden “Türkiye’nin Yükselen Değeri: Bor”. https://www.etimaden.gov.tr/turkiyede-bor (21.01.2022).
2. [2] Çolak M, Helvacı C, Maggetti M. “Saponite from the emet colemanite mines, Kutahya, Turkey”. Clays and Clay Minerals, 48(4), 409-423, 2000.
3. [3] Ertan B, Erdoğan Y. “Emet-Espey bölgesindeki borlu killerde eser element tayini”. Dumlupınar Üniversitesi Fen Bilimleri Enstitüsü Dergisi, 33, 22-27, 2014.
4. [4] Akgök YZ, Şahiner M. “Dünya'da ve Türkiye'de Lityum”. Fizibilite Etütleri Daire Başkanlığı, Maden Tetkik Arama, Ankara, Türkiye, 25, 2017.
5. [5] Lee WJ, Yoon SJ, Chon CM, Heo CH, Lee GJ, Lee BH, Cicek M. “Lithium extraction from smectitic clay occurring in lithium-bearing boron deposits in Turkey”. Journal of the Mineralogical Society of Korea, 29(4), 167-177, 2016.
6. [6] Şensöz H, Sayın ZE, Savaş M, Erdoğan Y. “Emet bor üretim tesisleri atıklarının lityum içeriğinin incelenmesi”. Afyon Kocatepe Üniversitesi Fen ve Mühendislik Bilimleri Dergisi, 21-6, 1460-1469, 2021.
7. [7] Mordoğan H, Helvacı C. “Bor yataklarındaki killer ile bazı güncel göl sularındaki lityumun varlığı ve dağılımı”. Geosound Yerbilimleri, 25, 185-195, 1994.
8. [8] Erdoğan Y, Aksu M, Demirbaş A, Abalı Y. “Analyses of boronic ores and sludges and solubilities of boron minerals in CO2-saturated water”. Resources, Conservation and Recycling, 24(3-4), 275-283, 1998.

9. [9] Helvacı C, Mordogan H, Çolak M, Gündogan I. “Presence and distribution of lithium in borate deposits and some recent lake waters of west-central Turkey”. International Geology Review, 46(2), 177-190, 2004.
10. [10] Helvacı C. “Lityum ve lityum minerallerinin kaynakları, yatakların dağılımı ve ekonomik önemi”. 71. Türkiye Jeoloji Kurultayı, Buca, İzmir, 23-27 Nisan 2018.
11. [11] Han B, Tao W, Chen Y, Li H. “Double-sided laser beam welded T-joints for aluminum-lithium alloy aircraft fuselage panels: Effects of filler elements on microstructure and mechanical properties”. Optics & Laser Technology, 93, 99-108, 2017.
12. [12] Hu L, Zhan L, Shen R, Liu Z, Ma Z, Liu J, Yang Y. “Effects of uniaxial creep ageing on the mechanical properties and micro precipitates of Al-Li-S4 alloy”. Materials Science and Engineering: A, 688, 272-279, 2017.
13. [13] Yong Y. Ramachandaramurthy VK, Tan KM, Mithulananthan N. “A review on the state-of-the-art technologies of electric vehicle, its impacts and prospects”. Renewable and Sustainable Energy Reviews, 49, 365-385, 2015.
14. [14] Opitz A, Badami P, Shen L, Vignarooban K, Kannan AM. “Can Li-Ion batteries be the panacea for automotive applications?”. Renewable and Sustainable Energy Reviews, 68, 685-692, 2017.
15. [15] Polat BD, Keleş Ö. “Lityum iyon pil teknolojisi”. Metalürji Dergisi, 162, 42-48, 2012.
16. [16] Swain B. “Recovery and recycling of lithium: A review”. Separation and Purification Technology, 172, 388-403, 2017.
17. [17] Hover VC, Walter LM, Peacor DR, Martini AM. “Mg-smectite authigenesis in a marine evaporative environment, Salina Ometepec, Baja California”. Clays and Clay Minerals, 47(3), 252-268, 1999.
18. [18] Shao H, Pinnavaia TJ. “Synthesis and properties of nanoparticle forms saponite clay, cancrinite zeolite and phase mixtures thereof”. Microporous and Mesoporous Materials, 133(1-3), 10-17, 2010.
19. [19] Tarasevich YI, Polyakov VE, Ivanova ZG, Trifonova MY. “The composition, structure and thermal stability of hydrates of exchange cations of saponite”. Journal of Water Chemistry and Technology, 33(4), 224-229, 2011.
20. [20] Polyakov VE, Tarasevich YI. “Ion exchange equilibria involving uncharged cations on saponite”. Journal of Water Chemistry and Technology, 34, 18-27, 2012.
21. [21] Vogels RJMJ, Kloprogge JT, Geus JW. “Synthesis and characterization of saponite clays”. American Mineralogist, 90(5-6), 931-944, 2005.
22. [22] López-Galindo A, Viseras C, Cerezo P. “Compositional, technical and safety specifications of clays to be used as pharmaceutical and cosmetic products”. Applied Clay Science, 36(1-3), 51-63, 2007.
23. [23] Carretero MI, Pozo M. “Clay and non-clay minerals in the pharmaceutical industry: Part I. Excipients and medical applications”. Applied Clay Science, 46(1), 73-80, 2009.
24. [24] Donauerová A, Bujdák J, Smolinská M, Bujdáková H. “Photophysical and antibacterial properties of complex systems based on smectite, a cationic surfactant and methylene blue”. Journal of Photochemistry and Photobiology B: Biology, 151, 135-141, 2015.
25. [25] Meshram P, Pandey BD, Mankhand TR. “Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation: A comprehensive review”. Hydrometallurgy, 150, 192-208, 2014.
26. [26] Mordoğan H, Helvacı C, Malayoğlu U. “Bor yatakları killeri ve güncel göllerdeki lityum varlığı ve değerlendirme olanakları”. Endüstriyel Hammaddeler Sempozyumu, İzmir, Türkiye, 21-22 Nisan 1995.
27. [27] Vieceli N, Nogueira CA, Pereira MF, Dias APS, Durão FO, Guimarães C, Margarido F. “Effects of mechanical activation on lithium extraction from a lepidolite ore concentrate”. Minerals Engineering, 102, 1-14, 2017.
28. [28] Vieceli N, Nogueira CA, Pereira MF, Durão FO, Guimarães C, Margarido F. “Recovery of lithium carbonate by acid digestion and hydrometallurgical processing from mechanically activated lepidolite”. Hydrometallurgy, 175, 1-10, 2018.
29. [29] Yan Q, Li X, Wang Z, Wu X, Guo H, Hu Q, Peng W, Wang J. “Extraction of valuable metals from lepidolite.” Hydrometallurgy, 117, 116-118, 2012(a).
30. [30] Yan Q, Li X, Wang Z, Wu X, Wang J, Guo H, Hu Q, Peng W. “Extraction of lithium from lepidolite by sulfation roasting and water leaching”. International Journal of Mineral Processing, 110-111, 1-5, 2012(b).
31. [31] Salakjani NK, Singh P, Nikoloski AN. “Production of lithium-A literature review part 1: Pretreatment of spodumene”. Mineral Processing and Extractive Metallurgy Review, 41(5), 335-348, 2020.
32. [32] Ertan B. “Klorlama kavurma işlemi ile bor killerindeki değerli metallerin ekstraksiyonu”. Pamukkale Üniversitesi Mühendislik Bilimleri Dergisi, 26(7), 1267-1272, 2020.
33. [33] Sayın ZE, Altay T. “Emet-Hisarcık (Kütahya) Bölgesi Kilinin Mineralojik Ve Jeokimyasal Özelliklerinin Belirlenmesi ve Kolemanit Zenginleştirmesine Etkisinin İncelenmesi”. Maden Mühendisliği Bölümü, Afyon Kocatepe Üniversitesi, Afyon, Türkiye, Bilimsel Rapor, Proje No: 18.KARİYER.179, 2021.
34. [34] Salakjani NK, Singh P, Nikoloski AN. “Acid roasting of spodumene: Microwave vs. conventional heating”. Minerals Engineering, 138, 161-167, 2019.
35. [35] Tian Q, Chen B, Chen Y, Ma I, Shi X. “Roasting and leaching behaviour of spodumene in sulfuric acid process”. Chinese Journal of Rare Metals, 35, 118-123, 2011.
36. [36] Peltosaari O, Tanskanen P, Heikkinen EP, Fabritius T. “α→γ→β-phase transformation of spodumene with hybrid microwave and conventional furnaces”. Minerals Engineering, 82, 54-60, 2015.
37. [37] Salakjani NK, Singh P, Nikoloski AN. “Mineralogical transformations of spodumene concentrate from Greenbushes, Western Australia. Part 1: conventional heating”. Minerals Engineering, 98, 71-79, 2016.
38. [38] Hofmeister AM, Pertermann M. “Thermal diffusivity of clinopyroxenes at elevated temperature”. European Journal of Mineralogy, 20(4), 537-549, 2008.
39. [39] Fraas F, Ralston OC. “Beneficiation of spodumene by decrepitation”. US Department of the Interior, Bureau of Mines, Washington, USA, 3336, 1937.
40. [40] Peltosaari O, Tanskanen P, Hautala S, Heikkinen EP, Fabritius T. “Mechanical enrichment of converted spodumene by selective sieving”. Minerals Engineering, 98, 30-39, 2016.
41. [41] Yan QX, Li XH, Wang ZX, Wang JX, Guo HJ, Hu Q, Peng WJ, Wu XF. “Extraction of lithium from lepidolite using chlorination roasting-water leaching process”. Transactions of Nonferrous Metals Society of China, 22(7), 1753-1759, 2012.
42. [42] Meshram P, Pandey BD, Mankhand TR. “Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation: A comprehensive review”. Hydrometallurgy, 150, 192-208, 2014.
43. [43] Lien RH. “Recovery of lithium from a montmorillonite-type clay”. Bureau of Mines, Report of Investigations RI 8967, 1985.
44. [44] Akyıldız S, Çolak M. “Kırka (Eskişehir) boraks madeni killerinin ve işletme atıklarının lityum içeriği açısından değerlendirilmesi”. 9. Uluslararası Endüstriyel Hammaddeler Sempozyumu, İzmir, Türkiye, 14-15 Mayıs 2015.
45. [45] Wietelmann U, Bauer RJ. “Lithium and lithium compounds”. Ullmann's Encyclopedia of Industrial Chemistry, Vol. 20. WILEY-VCH Verlag GmbH & Co, Weinheim, Germany, 2003.
46. [46] Kamiensiki CW, McDonald DP, Stark MW, Papcun JR. Lithium and Lithium Compounds. Editors: Othmer K. Kirk-Othmer Encyclopedia of Chemical Technology, 1-40, New Jersey, USA, John Wiley and Sons, 2004.
47. [47] Garrett DE. Handbook of Lithium and Natural Calcium Chloride. California, USA, Elsevier Academic Press, 2004.
48. [48] Sitando O, Crouse PL. “Processing of a Zimbabwean petalite to obtain lithium carbonate”. International Journal of Mineral Processing, 102, 45-50, 2012.
49. [49] Kesler TL. Lithium raw materials. Editors: Gillson JL, Industrial Minerals and Rocks, 521-531, Newyork, USA, Seely W. Mudd Series, 1960.