COMPARISON OF EXTRACTION METHODS OF LITHIUM AND ITS COMPOUNDS FROM NATURAL RAW MATERIALS

The paper deals with lithium (and its compounds) which is one of the promising materials used in hydrogen energy. Its individual and complex hydrides are used for storing and transporting hydrogen in hydrogen power plants. The paper compares the different methods of lithium extraction from natural raw materials. The main industrial techniques of processing spodumene and other lithium minerals are considered. Since the volumes of these mineral deposits in the world are limited, hydro-mineral raw materials gradually become the main source of lithium. The paper focuses on the analysis of methods for lithium containing hydromineralic raw materials processing. The paper indicates that at the first stage of lithium recovery (the production of its concentrates) there are the most commonly used the galurgical methods of concentrating and isolating lithium from natural brines. However, these methods are only applicable to rich natural lithium brines. Another method (the method of its deposition in the form of sparingly soluble compounds) is danger from the ecological point of view due to the large impact on these brines, and the problems of their further utilization. The sorption methods of lithium extraction, especially from poor in composition of natural and technological solutions, are more promising. In view of complexity of the salt composition of hydro-mineral raw materials, the use of highly selective inorganic ion-exchange materials is the most promising method for recovery of lithium too. In order to complete the general picture of lithium production, the paper analyzes the modern methods for obtaining metallic lithium and various lithium-containing compounds. Moreover, the paper describes the methods of reprocessing lithium carbonate into other compounds, as well as methods for obtaining lithium hydroxide and lithium chloride, and electrochemical and vacuum-thermal methods for obtaining metallic lithium. Furthermore, the methods of lithium refining and the need for processing secondary lithium resources are briefly considered.

1. Kudryavtsev P.G. Lithium In Nature, Application, Methods of Extraction (Review). Journal “Scientific Israel-Technological Advantages”, 2016;18(3):63– 83; ISSN: 1565-1532

2. Khimiya i tekhnologiya redkikh i rasseyannykh elementov, part I. Ed. K.A. Bol'shakov. Moscow, “Vyssh. Shkola” Publ., 1976 (in Russ.).

3. Wietelmann U., Bauer R.J. Lithium and Lithium Compounds. Ullmann's Encyclopedia of Industrial Chemistry, 2000; ISBN 3-527-30673-0. doi:10.1002/14356007.a15_39310.

4. Plyushchev B.E., Stepin B.D. Khimiya i tekhnologiya soyedineniy litiya, rubidiya i tseziya. Leningrad: “Khimiya” Publ., 1970 (in Russ.).

5. Ryabtsev A.D. Gidromineral'noye syr'yo - neischerpayemyy istochnik litiya v XXI veke. Izvestiya Tomskogo politekhnicheskogo universiteta, 2004;307(7)64–70 (in Russ.).

6. Meshram P., Pandey B.D., Mankhand T.R. Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation: A comprehensive review. Hydrometallurgy, 2014;150:192–208.

7. Peiró L.T., Méndez G.V., Ayres R.U.Lithium: Sources, Production, Uses, and Recovery Outlook. JOM, 2013;65(8):986–996. Available on: https://doi.org/10.1007/s11837-013-0666-4 (30.06.17.).

8. Zhang H.Z. et al. Lithium Recovery Techniques from Solid and Liquid Mineral Resources. Advanced Materials Research, 2012;549:528–531; doi: 10.4028/www.scientific.net/AMR.549.528

9. Lanina T.D., Bykov I.Yu. Izvlecheniye litiya iz vysokomineralizovannykh plastovykh vod neftyanykh mestorozhdeniy. Izvestiya Komi NTS UrO RAN, 2010;1(1):69–71 (in Russ.).

10. Nemudryy A.P., Isupov V.P., Kotsupalo N.P. Vzaimodeystviye kristallicheskogo gidroksida alyuminiya s vodnymi rastvorami soley litiya. Izv. SO AN SSSR, 1984;4:47–51 (in Russ.).

11. Kotsupalo N.P. Perspektivy polucheniya soyedineniy litiya iz prirodnykh khloridnykh rassolov. Khimiya v interesakh ustoychivogo razvitiya, 2001;9:243–253 (in Russ.).

12. Isupov V.P., Chupakhina L.E., Boldyrev V.V. Sintez interkalyatsionnykh soyedineniy gidroksida alyuminiya s solyami litiya. DAN RAS, 1993;332(3)330– 332 (in Russ.).

13. Isupov V.P. et al.Vliyaniye razmera chastits i narusheniya reshetki trigidroksida alyuminiya na interkalyatsiyu v nego khlorida litiya. DAN USSR, 1991;316(5):1144–1146 (in Russ.).

14. Isupov V.P., Chupakhina L.E., Kotsupalo N.P.Anionoobmennyy sintez osnovnykh soley alyuminiya i litiya. Izv. SO AN USSR. Ser.khim.nauk, 1989;4:37–40 (in Russ.).

15. Kotsupalo N.P., Menzheres L.T., Mamylova E.V. Sorption Properties of Defective Forms of LiCl∙2Al(OH)3∙mH2O. Russian Journal of Applied Chemistry, 1998;71(10):1750–1755.

16. Isupov V.P., Antsiferova V.V. Senchenko L.H.Fiziko- khimicheskiye svoystva produktov deinterkalyatsii khlorida litiya iz LiCl-2Al(OH)3∙nH2O. Izv. SO AN USSR. Ser.khim.nauk, 1989;3:48–51 (in Russ.).

17. Isupov V.P., Kotsupalo N.P., Nemudryy A.P. Ispol'zovaniye mekhanicheski aktivirovannogo gidroksida alyuminiya v kachestve selektivnogo sorbenta litiya. ZHPKH, 1996;69(7):1385–1387 (in Russ.).

18. Menzheres L.T., Kotsupalo N.P. Granulated LiCl∙2Al(OH)3∙mH2O-based Sorbents and Their Properties. Russian Journal of Applied Chemistry, 1999;72(10):1714–1717.

19. Kim S., Lee J., Kang J.S., Jo K., Kim S., Yung-Eun Sung Y.-E., Yoon J. Lithium recovery from brine using a λ-MnO2 activated carbon hybrid supercapacitor system. Chemosphere, 2015;125:50–56; doi: 10.1016/j.chemosphere.2015.01.024

20. Ji Z.-Yang, Chen Q.-b., Yuan J.-S., Liu J., Yingying Zhao Y.-Y., Feng W.-X. Preliminary study on recovering lithium from high Mg2+/Li+ ratio brines by electrodialysis. Separation and Purification Technology, 2017;172: 168–177. Available on: http://dx.doi.org/10.1016/j.seppur.2016.08.006

21. Ji Z.-Y., Zhao M.-Y., Yuan J.-S., Wang J., Zhou J.-Q., Yin H.-B., Sun B/-Y. Li+ Extraction from Spinel-Type LiMn2O4 in Different Eluents and Li+ Insertion in the Aqueous Phase. Solvent Extraction and Ion Exchange, 2016;34(6):549–557; doi: 10.1080/07366299.2016.1221266

22. Kudryavtsev P. Alkoxides of chemical elements - Promising class of chemical compounds which are raw materials for HI-TECH industries. Journal ”Scientific Israel–Technological Advantages”, 2014;16(2):147–170.

23. Zil'berman M.V., Kalinin N.F., Chentsova T.V., Yelizarova I.A., Antipov M.A., Murav'yev Ye.N.. Sorbtsionnaya tekhnologiya pererabotki prirodnykh rassolov v soyedineniya litiya, rubidiya i tseziya. Khimiya i tekhnologiya neorganicheskikh sorbentov. Mezhvuzovskiy sbornik nauchnykh trudov. Perm': Perm' PI Publ., 1989, pp. 5–9 (in Russ.).

24. Vol'khin V.V., Leont'yeva G.V., Chirkova L.G. Nekotoryye printsipy polucheniya neorganicheskikh ionoobmennikov, selektivnykh k ionam litiya. Neorganicheskiye ionoobmennyye materialy, Iss. 2, Mezhvuzovskiy sbornik. Ed. Academician B.P. Nikol'sky, Izdatel'stvo LGU, Leningrad,1980, pp. 3–9 (in Russ.).

25. A.C. USSR No. 455560. Onorin S.A., Vol'khin V.V. Sposob polucheniya neorganicheskikh ionoobmennikov, 1972 (in Russ.).

26. Patent RF №1811679. Vol'khin V.V., Leont'yeva G.V., Cheraneva L.G., Bakhireva O.I. Sposob desorbtsii litiya s neorganicheskogo ionoobmennika na osnove oksidov margantsa i alyuminiya, 1991 (in Russ.).

27. A.C. USSR № 1160627. Kudryavtsev P.G. Onorin S.A., Vol'khin V.V. Sposob polucheniya neorganicheskogo sorbenta dlya izvlecheniya litiya iz rastvorov, 1983 (in Russ.).

28. A.C. USSR № 1256274. Kudryavtsev P.G. Onorin S.A., Vol'khin V.V., Yakimov V.A. Sposob polucheniya neorganicheskogo sorbenta selektivnogo k litiyu, 1985 (in Russ.).

29. A.C. USSR № 451456. Onorin S.A., Vol'khin V.V., Sostav dlya neorganicheskogo ionoobmennika, 1972 (in Russ.).

30. Senyavin M.M., Krachak A.N., Nikashina V.A. Issledovaniye sorbtsii litiya iz vysokomineralizovannykh rastvorov na razlichnykh tipakh neorganicheskikh ionitov. Khimiya i tekhnologiya neorganicheskikh sorbentov, Mezhvuzovskiy sbornik nauchnykh trudov, Perm', Perm' PI Publ., 1989, pp.10–26 (in Russ.).

31. Bengtsson G.B., Bortun A.I., Strelko V.V. Strontium Binding Properties of Inorganic Adsorbents. Journal of Radioanalytical and Nuclear Chemistry, 1996;204(1):75–82.

32. Kudryavtsev P.G. Onorin S.A., Vol'khin V.V. Neorganicheskiy ionoobmennik ISN-1, selektivnyy k ionam litiya. Izv. VUZ. Tsvetnaya metallurgiya,1977;(3):50–53 (in Russ.).

33. Kudryavtsev P.G., Onorin S.A. Sorbtsiya ionov shchelochnykh metallov gidratirovannoy pyatiokis'yu niobiya. Neorganicheskiye ionoobmenniki (sintez, struktura, svoystva), Mezhvuzovskiy sbornik nauchnykh trudov, 1977;(212):105–108 (in Russ.).

34. Vol'khin V.V., Leont'yeva G.V., Onorin S.A., Khodyashev N.B., Kudryavtsev P.G., Shvetsova T.I. Ionno-sitovyye kationity dlya selektivnoy sorbtsii litiya. Khimiya i tekhnologiya neorganicheskikh sorbentov, Perm', 1980, pp. 67–71 (in Russ.).

35. A.C. USSR № 1274763. Kudryavtsev P.G., Onorin S.A., Vol'khin V.V. Sposob polucheniya neorganicheskogo anionoobmennika, 06.05.1985 (in Russ.).

36. Kudryavtsev P.G., Onorin S.A., Vol'khin V.V. Vybor legiruyushchikh ionov i otsenka ikh vliyaniya na kationoobmennyye svoystva oksigidratnykh sorbentov. Khimiya tverdogo tela, Sverdlovsk, 1983, pp. 67–75 (in Russ.).

37. A.C. USSR № 1160627. Kudryavtsev P.G., Onorin S.A., Vol'khin V.V. Sposob polucheniya neorganicheskogo sorbenta dlya izvlecheniya litiya iz rastvorov, 06.20.1983 (in Russ.).

38. A.C. USSR № 1203739. Kudryavtsev P.G., Onorin S.A., Vol'khin V.V. Sposob polucheniya selektivnogo k litiyu neorganicheskogo sorbenta, 04.13.1984 (in Russ.).

39. A.C. USSR № 1125043. Kudryavtsev P.G., Onorin S.A., Vol'khin V.V. Sposob polucheniya neorganicheskogo anionoobmennika, 07.26.1983 (in Russ.).

40. A.C. USSR № 1256274. Kudryavtsev P.G., Onorin S.A., Vol'khin V.V. Sposob polucheniya neorganicheskogo sorbenta selektivnogo k litiyu, 01.04.1985 (in Russ.).

41. A.C. USSR № 1189497. Kudryavtsev P.G., Onorin S.A., Vol'khin V.V. Sposob polucheniya neorganicheskogo anionoobmennika, 05.03.1984 (in Russ.).

42. Ravnovesiye ionnogo obmena na oksigidratnykh sorbentakh, oslozhnennoye dispersiyey obmennykh tsentrov po konstante obmena. Zhurnal fiicheskoy khimii, 1987;61(3):848–851 (in Russ.).

43. A.S. USSR № 1435280. Kudryavtsev P.G., Onorin S.A. Sposob polucheniya neorganicheskogo anionoobmennika AAT-1, 04.13.1987 (in Russ.).

44. A.S. USSR № 1435281. Kudryavtsev P.G., Onorin S.A., Vol'khin V.V. Sposob polucheniya neorganicheskogo anionoobmennika, 04.13.1987(in Russ.).

45. Kudryavtsev P.G., Onorin S.A., Vol'khin V.V. Sintez i svoystva selektivnykh k litiyu kationoobmennikov na osnove gidratirovannoy pyatiokisi niobiya s legiruyushchimi dobavkami. Khimiya i tekhnologiya neorganicheskikh sorbentov, Mezhvuzovskiy sbornik nauchnykh trudov, PPI, Perm', 1989, pp.140–149 (in Russ.).

46. Kudryavtsev P.G., Onorin S.A., Vol'khin V.V. Vliyaniye termoobrabotki na ionoobmennyye svoystva i stroyeniye materialov, soderzhashchikh gidratirovannyy oksid alyuminiya. Izvestiya VUZ. Tsvetnaya metallurgiya, 1990;3:26–31 (in Russ.).

47. Kudryavtsev P.G., Vol'khin V.V. Zol'-gel' protsessy i nekotoryye yego tekhnologicheskiye prilozheniya. Zol'-gel' protsessy polucheniya neorganicheskikh materialov, Perm', 1991, pp. 3–5 (in Russ.).

48. Kudryavtsev P.G., Onorin S.A., Vol'khin V.V. Strukturoobrazovaniye i ionoobmennyye svoystva smeshannykh oksidov v sisteme Li2O-Fe2O3-Nb2O5. Izvestiya AN USSR ser. Neorganicheskiye materialy, 1991;27(7):1479–1482 (in Russ.).

49. Vol'khin V.V., Leont'yeva G.V., Onorin S.A. Sintez, struktura, svoystva ionnositovogo kationita ISM-1. Izv. AN SSSR. Neorganicheskiye materialy, 1973;9(6):1041–1046 (in Russ.).

50. Zil'berman M. V., Vol'khin V. V. Struktura smeshannogo ferrotsianida medi i sootvetstvuyushchikh yemu produktov molekulyarnoy sorbtsii. ZH. strukturnoy khimii, 1971;12:649–652 (in Russ.).

51. Leont'yeva G.V., Chirkova L.G., Vol'khin V.V. Termicheskoye modifitsirovaniye dvuokisi margantsa kak sorbenta dlya ionov shchelochnozemel'nykh metallov. Zhurnal prikladnoy khimii, 1980;(6):1229– 1233 (in Russ.).

52. Vol'khin V.V., Onorin S.A. Sorbtsionnyye svoystva gidratirovannoy dvuokisi titana i produktov yeye obezvozhivaniya. Izv. AN USSR. Neorganicheskiye materialy, 1976;12(8):1415–1418 (in Russ.).

53. Kalyuzhnyy A.V., Vol'khin V.V., Zil'berman M.V., Kolesova S.A. Red-oks-potentsial smeshannogo ferrotsianida kadmiya i kaliya. Zhurnal prikladnoy khimii, 1977;50(1):201–203 (in Russ.).

54. Kalyuzhnyy A.B., Vol'khin V.V., Milyutin V.V. Ferrotsianidnyye elektronoionoob-menniki dlya sorbtsii rubidiya i tseziya. Tsvetnaya metallurgiya: Izvestiya VUZ. 1980;(1):57 (in Russ.).

55. Kalinin N.F., Vol'khin V.V., Zil'berman M.V. Obmennaya i neobmennaya sorbtsiya malorastvorimymi neorganicheskimi soyedineniyami. Zhurnal prikladnoy khimii, 1979;(3):524–528 (in Russ.).

56. Onorin C.A., Vol'khin V.V., Zil'berman M.B., Khodyashev N.B. Sintez kationitov ISM-1A i IST-1A s povyshennoy obmennoy yemkost'yu. Izv. AN SSSR. Neorgan. materialy, 1978;14(1):150–153 (in Russ.).

57. Vol'khin V.V. Selektivnyye neorganicheskiye sorbenty i ikh primeneniye. Mezhvuz. sb. “Khimiya i tekhnologiya neorganicheskikh sorbentov”, Perm', 1980, pp. 3–19 (in Russ.).

58. A.C. USSR № 735296. Leont'yeva G.V., Vol'khin V.V., Chirkova L.G., Mironova Ye. A., Neorganicheskiy ionoobmennik na osnove smesi okislov margantsa i alyuminiya i sposob yego polucheniya, 1980 (in Russ.).

59. A.C. USSR № 919205. Kozlova G.A., Vol'khin V.V., Zil'berman M.V. Sposob polucheniya kompozitsionnykh ferrotsianidnykh sorbentov, 1981 (in Russ.).

60. Timoshevskiy A.N., Ktalkherman M.G., Yemel'kin V.A., Pozdnyakov B.A., Zamyatin A.P. Vysokotemperaturnoye razlozheniye karbonata litiya pri atmosfernom davlenii. Teplofizika vysokikh temperatur, - 2008;46(3):457–465 (in Russ.).

61. Ktalkherman M.G., Yemel'kin V.A., Pozdnyakov B.A. Polucheniye oksida litiya pri razlozhenii karbonata litiya v potoke teplonositelya. Teoreticheskiye osnovy khimicheskoy tekhnologii, 2009;43(1):93–98 (in Russ.).

62. Kaplan G.Ye., Silina G.F., Ostroushko YU.I. Elektroliz v metallurgii redkikh metallov. Moscow: Metallurgizdat Publ., 1963 (in Russ.).

63. Izgaryshev N.A., Elektrokhimiya tsvetnykh i blagorodnykh metallov. Moscow,1933 (in Russ.).

64. Shamray, F.I. Litiy i yego splavy, AN SSSR, Int obshchey i neorgan. khimii im. N.S. Kurnakova. Mos-cow: AN USSR Publ., 1952 (in Russ.).

65. Ostroushko YU.I., Buchikhin P.I., Alekseyeva V.V. Litiy, yego khimiya i tekhnologiya. Moscow: Atomizdat Publ., 1960 (in Russ.).

66. US patent 4,092,228 / С25С 3/02 / Ross F.J. Electrolytic cell, 30.05.78,

67. Patent №2453639 RF / MPK C25C 3/02, C25C 7/00. Aleksandrov A.B., Valov P.M., Muratov Ye.P., Rozhkov V.V., Tibilov V.S., Shevkunov V.P., Shkuro V.V. Elektrolizer dlya polucheniya metallicheskogo litiya, 10.08.2010, Bul. No. 17 (in Russ.),

68. Kudryavtsev P., Figovsky O. The sol-gel technology of porous composites. Monograph, LAP Lambert Academic Publishing, 2015; ISBN 978-3-659-78529-0.

69. Kudryavtsev P.G., Figovsky O.L. System of storage and hydrogen generation for power propulsion systems and cars. International Scientific Journal for Alternative Energy and Ecology (ISJAEE), 2016;(13-14):46–55; doi: 10.15518/isjaee.2016.13-14.046-055.

70. Belyayev A.I. Fiziko-khimicheskiye osnovy ochistki metallov i poluprovodnikovykh materialov. Moscow: Metallurgiya Publ., 1973 (in Russ.).

71. The certificate for a utility model № 1997 by application № 93015452. Kudryavtsev P.G. The apparatus for producing high-purity metallic scandium. 03.24.1993.

72. Sullivan D.E. Recycled Cell Phones–A Treasure Trove of Valuable Metals. U.S. Geological Survey, Fact Sheet 2006-3097.