JP6300014B2 - Method for producing lithium sulfide - Google Patents
Method for producing lithium sulfide Download PDFInfo
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- JP6300014B2 JP6300014B2 JP2014051479A JP2014051479A JP6300014B2 JP 6300014 B2 JP6300014 B2 JP 6300014B2 JP 2014051479 A JP2014051479 A JP 2014051479A JP 2014051479 A JP2014051479 A JP 2014051479A JP 6300014 B2 JP6300014 B2 JP 6300014B2
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- lithium
- sulfide
- solid
- lithium sulfide
- gas
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- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 title claims description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 229910052744 lithium Inorganic materials 0.000 claims description 58
- 239000007787 solid Substances 0.000 claims description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 28
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 27
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 26
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 26
- 239000000919 ceramic Substances 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000005096 rolling process Methods 0.000 claims description 5
- 230000019086 sulfide ion homeostasis Effects 0.000 claims 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 21
- 239000002245 particle Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 239000012535 impurity Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000007790 solid phase Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012085 test solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 3
- GMKDNCQTOAHUQG-UHFFFAOYSA-L dilithium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=S GMKDNCQTOAHUQG-UHFFFAOYSA-L 0.000 description 3
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 229910001055 inconels 600 Inorganic materials 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 238000004255 ion exchange chromatography Methods 0.000 description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229910052863 mullite Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- 229910018091 Li 2 S Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- HXQGSILMFTUKHI-UHFFFAOYSA-M lithium;sulfanide Chemical compound S[Li] HXQGSILMFTUKHI-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052704 radon Inorganic materials 0.000 description 2
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000030614 Urania Species 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021344 molybdenum silicide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- -1 respectively Chemical compound 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229940006280 thiosulfate ion Drugs 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Secondary Cells (AREA)
Description
本発明は、硫化リチウムの製造方法に関し、特に、エンジニアリングプラスチック、潤滑剤、電池用リチウムイオン導電性固体電解質や化学薬品用の中間原料として有用な、高純度な硫化リチウムの製造方法に関する。 The present invention relates to a process for the preparation of lithium sulfide, in particular, engineering plastics, lubricants, useful as an intermediate material for a lithium ion conductive solid electrolyte and chemicals for batteries, a method for producing a high-purity lithium sulfide.
硫化リチウムは、特有の臭気のある白色粉末であり、ポリアリーレンスルフィド樹脂の重合用原料や、電池用リチウムイオン導電性固体電解質の原料として用いられている。近年、エンジニアリングプラスチック、潤滑剤、電池用リチウムイオン導電性固体電解質や化学薬品用の中間原料として、高純度の硫化リチウムが求められている。 Lithium sulfide is a white powder with a specific odor and is used as a raw material for polymerization of polyarylene sulfide resin and a raw material for lithium ion conductive solid electrolyte for batteries. In recent years, high-purity lithium sulfide has been demanded as an intermediate material for engineering plastics, lubricants, lithium ion conductive solid electrolytes for batteries and chemicals.
硫化リチウムは、その潮解性により、天然鉱産物としては産出しないため、他のリチウム化合物から合成して得られる。従来は、主に水酸化リチウムおよび炭酸リチウムから製造する方法が知られている。 Lithium sulfide is not produced as a natural mineral product due to its deliquescent nature, and is thus synthesized by synthesis from other lithium compounds. Conventionally, a method of producing mainly from lithium hydroxide and lithium carbonate is known.
また、その反応は、水酸化リチウムや炭酸リチウムといった固体のリチウム源を水や有機溶媒に溶解し、気体の硫黄源と反応させる気液反応と、固体のリチウム源と気体の硫黄源と反応させる気固反応が用いられる。気固反応は、合成後、多大なエネルギーを用いて水や溶媒を留去する必要が無く、留去した溶媒等の廃棄物も生じないため、クリーンで経済的にも有利な方法である。 Also, the reaction involves dissolving a solid lithium source such as lithium hydroxide or lithium carbonate in water or an organic solvent and reacting with a gaseous sulfur source, and reacting with a solid lithium source and a gaseous sulfur source. A gas-solid reaction is used. The gas-solid reaction is a clean and economically advantageous method because it is not necessary to distill off water and the solvent using a great deal of energy after the synthesis and no waste such as the distilled solvent is produced.
気固反応で硫化リチウムを得る装置としては、内径１５ｍｍ、長さ２００ｍｍの硬質ガラス管の中央部に直径０．５ｍｍの孔を多数開けたステンレス製多孔板を取り付けた流動層反応装置（特許文献１参照）や、アルミナ製の筒型反応器に、固体のリチウム源をのせたアルミナ製燃焼ボートを挿入する固定層反応装置（特許文献２参照）、内径３４ｃｍ、長さ６６ｃｍのガラス製レトルトを用いたロータリーキルン（特許文献３参照）が知られていた。 As an apparatus for obtaining lithium sulfide by gas-solid reaction, a fluidized bed reaction apparatus in which a stainless perforated plate having a large number of holes of 0.5 mm in diameter is attached to a central portion of a hard glass tube having an inner diameter of 15 mm and a length of 200 mm (Patent Document) 1), or a fixed bed reactor (see Patent Document 2) in which an alumina combustion boat on which a solid lithium source is placed is inserted into an alumina cylindrical reactor, a glass retort having an inner diameter of 34 cm and a length of 66 cm. The rotary kiln used (see Patent Document 3) was known.
しかしながら、気体の硫黄源に硫化水素を用い、さらに装置の材質に金属を用いると、その反応温度が１３０〜７００℃と極めて高温であるため、硫化水素が装置を腐蝕してしまい、材質の強度が落ちたり、腐蝕した金属が硫化リチウムに混入したりすることがあり、実質用いることができなかった。さらに、装置の材質にガラスや低純度のアルミナを用いた場合、ガラスやアルミナが劣化したり、微量のけい素化合物が硫化リチウム中に混入したりすることがあり、必ずしも満足できる品質の硫化リチウムが得られなかった。
そこで、本発明の目的は、精製や溶媒の除去をすることなく硫化リチウムが得られ、かつ装置が腐蝕したり、不純物が混入しないため高純度な硫化リチウムが得られる、硫化リチウムの製造方法を提供することにある。 An object of the present invention include lithium sulfide obtained without removal of the purification and solvent and equipment or corrosion, because the impurities are not mixed with high-purity lithium sulfide obtained, the production method of vulcanization lithium Is to provide.
上記目的を達成するに当たり、鋭意検討の結果、固体のリチウム源と接する加熱部がセラミックスであり、固体のリチウム源を運動させる機構を具備し、ガスの供給口と排出口とを有する硫化リチウムの製造装置は、過酷な反応条件においても装置が腐蝕することが無いことを見出した。 In achieving the above object, as a result of intensive studies, the heating part that is in contact with the solid lithium source is ceramics, and has a mechanism for moving the solid lithium source, and has a gas supply port and a gas discharge port. The manufacturing apparatus has found that the apparatus does not corrode even under severe reaction conditions.
本発明の硫化リチウムの製造方法に用いられる製造装置は、固体のリチウム源と接する加熱部にセラミックスを用いているため、装置が腐蝕することがない。装置が腐蝕しないため、長期間使用することができ経済的に有利である。 Since the manufacturing apparatus used in the method for manufacturing lithium sulfide according to the present invention uses ceramics for the heating portion in contact with the solid lithium source, the apparatus does not corrode. Since the apparatus does not corrode, it can be used for a long time, which is economically advantageous.
さらに、固体のリチウム源を運動させる機構を具備しているため、均一に反応させることができ、品質にムラを生じることが無く、また、粉末のリチウム源を用いた場合、粒子が塊状になることを防ぎ、粉末状の硫化リチウムが得られるため、取扱い易い。なかでもロータリーキルンを用いた場合、連続的に固体のリチウム源を供給し、かつ得られた硫化リチウムを排出することができ効率が良い。 Furthermore, since a mechanism for moving the solid lithium source is provided, the reaction can be performed uniformly, there is no unevenness in quality, and particles are agglomerated when a powder lithium source is used. This is easy to handle because it prevents powdered lithium sulfide. In particular, when a rotary kiln is used, a solid lithium source can be continuously supplied and the obtained lithium sulfide can be discharged, which is efficient.
加えて、ガスの供給口と排出口を有するため、原料である硫化水素を供給することができ、かつ反応によって生じた副生物を速やかに除去することができる。 In addition, since the gas supply port and the discharge port are provided, hydrogen sulfide as a raw material can be supplied, and by-products generated by the reaction can be quickly removed.
本発明の硫化リチウムの製造方法により得られた硫化リチウムは、装置由来の不純物の混入が無く高純度である。 The lithium sulfide obtained by the method for producing lithium sulfide of the present invention has a high purity with no mixing of impurities derived from the apparatus.
本発明の硫化リチウムの製造方法は、固体のリチウム源に硫化水素を反応させる気固反応であり、溶媒を使用しないため、脱溶剤をする必要が無く、また、除いた溶媒等の廃棄物が発生しないため経済的に有利である。 The method for producing lithium sulfide according to the present invention is a gas-solid reaction in which hydrogen sulfide is reacted with a solid lithium source, and since no solvent is used, there is no need to remove the solvent, and there is no waste such as the removed solvent. Since it does not occur, it is economically advantageous.
本発明の硫化リチウムの製造方法を用いて得られた硫化リチウムは、エンジニアリングプラスチックの原料や、電池用のイオン伝導性固体電解質、潤滑剤、化学薬品の中間原料としても好適に用いることができる。 Lithium sulfide obtained by the production method of lithium sulfide of the invention can be raw materials and engineering plastics, ion-conductive solid electrolytes for batteries, lubricants, be suitably used as an intermediate material for chemicals.
本発明の硫化リチウムの製造方法を用いて得られた硫化リチウムは、高純度であるため、リチウムイオン導電性固体電解質として用いた場合、イオン導電性の高い固体電解質が得られる。 Lithium sulfide obtained by the production method of lithium sulfide of the present invention are the high purity, when used as a lithium ion conductive solid electrolyte, ionic conductivity higher solid electrolyte is obtained.
以下に、硫化リチウムの製造方法について詳細に記載する。 The following describes in detail a method for manufacturing the cured lithium.
本発明の硫化リチウムの製造方法に用いられる製造装置は、固体のリチウム源に接する加熱部にセラミックスを用いる。本発明におけるセラミックスは、成形、焼成などの工程をへて得られる非金属無機材料であって、具体的には、アルミナ、サファイア、ベリリア、マグネシア、ジルコニア、チタニア、フォルステライト、コーディエライト、トリア、ウラニア、サイアロン、炭化ケイ素、炭化チタン、炭化ジルコニウム、窒化ホウ素、窒化アルミニウム、窒化ケイ素、ケイ化モリブデンなどが用いられる。中でもアルミナが好ましく、特に好ましくは純度９９％以上のアルミナが好ましい。アルミナであれば、装置に腐食が無く、アルミナ中の不純物が硫化リチウムに混入せず好ましい。 The manufacturing apparatus used in the method for manufacturing lithium sulfide according to the present invention uses ceramics for a heating unit in contact with a solid lithium source. The ceramic in the present invention is a non-metallic inorganic material obtained through steps such as molding and firing, and specifically, alumina, sapphire, beryllia, magnesia, zirconia, titania, forsterite, cordierite, tria. Urania, sialon, silicon carbide, titanium carbide, zirconium carbide, boron nitride, aluminum nitride, silicon nitride, molybdenum silicide and the like are used. Of these, alumina is preferable, and alumina having a purity of 99% or more is particularly preferable. Alumina is preferable because there is no corrosion in the apparatus and impurities in the alumina do not enter lithium sulfide.
本発明の硫化リチウムの製造方法に用いられる製造装置は、装置の腐蝕や、装置からの不純物の混入を防ぐために、固体のリチウム源と接する加熱部にセラミックスを用いれば良く、固体のリチウム源と接する加熱部以外の部分は、他の素材との複合材料を用いても良い。固体のリチウム源と接する加熱部以外の部分に用いる素材は、例えば、セラミックス層、充填層、鋼層の三層からなる複合材料、金属にセラミックスを溶射した複合材料、セラミックスと高純度セラミックス層とからなる複合材料などである。セラミックスと他の部材との複合材料を用いた場合、セラミックス単独の材料を用いた場合に比べ、一般的に機械的強度が補強され、比較的大型の装置を設計することが可能となり好ましい。 The manufacturing apparatus used in the method for manufacturing lithium sulfide according to the present invention may use ceramics in the heating part in contact with the solid lithium source in order to prevent corrosion of the apparatus and mixing of impurities from the apparatus. A composite material with other materials may be used for the portion other than the heating portion that comes into contact. The material used for the part other than the heating part in contact with the solid lithium source is, for example, a composite material composed of three layers of a ceramic layer, a filler layer, and a steel layer, a composite material obtained by spraying ceramics on a metal, a ceramic and a high-purity ceramic layer A composite material made of When a composite material of ceramics and other members is used, mechanical strength is generally reinforced as compared with the case of using a ceramic material alone, which is preferable because a relatively large apparatus can be designed.
本発明の硫化リチウムの製造方法に用いられる製造装置は、固体のリチウム源を運動させる機構を具備する。本発明における固体のリチウム源を運動させる機構とは、固体のリチウム源が目視で確認できるマクロな運動をさせる機構であって、外部から与えられた力によって、固体のリチウム源の粒子を運動させる機構である。力は、重力や、固体のリチウム源を充填した容器へのガスの導入、固体のリチウム源を充填した容器の運動によって与えられる。従って、ブラウン運動に代表されるミクロな運動は含まない。例えば、固体のリチウム源を静止させ、ガスを流通して反応させる固定層反応は、本発明における固体のリチウム源を運動させる機構を具備していない。 The production apparatus used in the method for producing lithium sulfide of the present invention includes a mechanism for moving a solid lithium source. The mechanism for moving the solid lithium source in the present invention is a mechanism for causing the solid lithium source to move macroscopically so that the solid lithium source can be visually confirmed, and the solid lithium source particles are moved by an externally applied force. Mechanism. The force is applied by gravity, introduction of gas into a container filled with a solid lithium source, or movement of a container filled with a solid lithium source. Therefore, the micro motion represented by the Brownian motion is not included. For example, the fixed bed reaction in which a solid lithium source is made to stand still and gas is circulated to react does not have a mechanism for moving the solid lithium source in the present invention.
本発明における固体のリチウム源を運動させる機構を具備した反応装置形態としては、好ましくは、移動層、転動層、流動層が用いられる。 As the reaction apparatus having a mechanism for moving the solid lithium source in the present invention, a moving bed, a rolling bed, and a fluidized bed are preferably used.
本発明における移動層とは、連続的に塔頂から固体のリチウム源を供給し緩やかに降下させ、向流または並流で気体を接触させて反応する反応装置形態である。装置としては、立型移動層、十字流式縦型移動層などが挙げられる。立型移動層は、金属精錬、セメント製造、石炭ガス化などに、十字流式縦型移動層は排ガス処理にそれぞれ応用されている。 The moving bed in the present invention is a form of a reaction apparatus in which a solid lithium source is continuously supplied from the top of the tower, slowly lowered, and brought into contact with a gas in countercurrent or cocurrent flow to react. Examples of the apparatus include a vertical moving bed and a cross-flow vertical moving bed. The vertical moving bed is applied to metal refining, cement production, coal gasification, etc., and the cross-flow vertical moving bed is applied to exhaust gas treatment.
本発明における転動層とは、固体のリチウム源を充填した容器や格子を運動させることで、固体のリチウム源を転動させ、気体と接触させて反応する反応装置形態である。装置としては、摺動グレート、ロータリーキルンなどが挙げられる。摺動グレートおよびロータリーキルンは、セメント製造、金属精錬、熱分解などにそれぞれ応用されている。 The rolling layer in the present invention is a reaction apparatus form in which a solid lithium source is rolled and brought into contact with a gas by moving a container or lattice filled with the solid lithium source. Examples of the apparatus include a sliding grate and a rotary kiln. Sliding grate and rotary kiln are applied to cement production, metal refining, thermal decomposition, etc., respectively.
本発明における流動層とは、上向きに気体を噴出させることによって、固体のリチウム源を気体中に懸濁浮遊させた状態で、気体と接触させて反応させる反応装置形態である。固体粒子に働く気体の力と重力とがつりあい、全体が均一な流体のように挙動する。反応装置としては、気泡流動層、噴流層、高速流動層などが挙げられる。気泡流動層は、石炭燃焼、ごみ処理、粒子合成、熱分解に、噴流層は、コーティング、粒子合成などに応用されている。 The fluidized bed in the present invention is a reaction device form in which a solid lithium source is suspended and suspended in a gas to be brought into contact with the gas and reacted by ejecting the gas upward. The gas force acting on the solid particles balances with gravity, and the whole behaves like a uniform fluid. Examples of the reaction apparatus include a bubble fluidized bed, a spouted bed, and a high-speed fluidized bed. The bubbling fluidized bed is applied to coal combustion, waste treatment, particle synthesis, and thermal decomposition, and the spouted bed is applied to coating, particle synthesis, and the like.
固体のリチウム源を運動させる機構を具備した反応装置形態は、より好ましくは、好ましくは転動層、流動層である。さらに、転動層がロータリーキルンであると、連続的に製造することが可能であり、より好ましい。 More preferably, the reaction apparatus having a mechanism for moving a solid lithium source is a rolling bed or a fluidized bed. Further, it is more preferable that the rolling layer is a rotary kiln because it can be continuously produced.
固体のリチウム源を運動させる機構を具備した反応装置形態および装置は、例えば、社団法人化学工学会編、化学工学便覧改訂六版の９５９ページから９６４ページに記載されている。 A reactor configuration and apparatus equipped with a mechanism for moving a solid lithium source is described, for example, on pages 959 to 964 of the Chemical Engineering Handbook, Revised Sixth Edition, edited by the Japan Society for Chemical Engineering.
本発明の硫化リチウムの製造方法に用いられる製造装置において、固体のリチウム源は、室温で固体のリチウムおよびその化合物であり、具体的には、炭酸リチウムである。炭酸リチウムは取扱いが容易である。 In the manufacturing apparatus used in the production process of lithium sulfide of the present invention, a solid lithium source is lithium and its compounds are solid at room temperature, specifically, a lithium carbonated. Lithium carbonate acid is easy to handle.
固体のリチウム源の平均粒子径は、０．１μｍ〜１ｍｍが好ましく、より好ましくは、１μｍ〜５００μｍ、さらに好ましくは、１０μｍ〜１５０μｍである。平均粒子径が０．１μｍ以上であれば、表面積が大きいため反応速度が大きく好ましい。また、１ｍｍ以下であれば、嵩密度が大きいため、装置に一度に多くの固体のリチウム源を仕込むことができ、生産性が高く好ましい。また、雰囲気ガスと随伴し、装置外に飛散することなく好ましい。 The average particle size of the solid lithium source is preferably 0.1 μm to 1 mm, more preferably 1 μm to 500 μm, and still more preferably 10 μm to 150 μm. If the average particle size is 0.1 μm or more, the surface area is large and the reaction rate is high. Moreover, if it is 1 mm or less, since a bulk density is large, many solid lithium sources can be charged to an apparatus at once, and productivity is preferable. Further, it is preferable without being scattered outside the apparatus accompanying the atmospheric gas.
固体のリチウム源の平均粒子径は、例えば、レーザー回折・散乱法による体積粒度分布測定により求めることができる。装置にはマイクロトラック（型式：ＨＲＡ、日機装（株）製）などを用いることができる。 The average particle size of the solid lithium source can be determined, for example, by volume particle size distribution measurement by a laser diffraction / scattering method. A microtrack (model: HRA, manufactured by Nikkiso Co., Ltd.) or the like can be used as the apparatus.
本発明で用いられる固体のリチウム源は、いかなる方法により得られたものであってもよく、市販品であっても良い。通常、固体のリチウム源は異種金属やその他の不純物を含有するが、副反応を抑える観点から、できる限り高純度のものが好ましい。 The solid lithium source used in the present invention may be obtained by any method and may be a commercially available product. Usually, the solid lithium source contains a foreign metal and other impurities, but from the viewpoint of suppressing side reactions, a solid lithium source is preferable.
固体のリチウム源は、硫化水素との反応に先立って乾燥を行っても良い。乾燥を行うと、得られる硫化リチウムが塊状化することなく、また水硫化物の副生が抑制され好ましい。乾燥の終点は、雰囲気ガスの露天を計測することで行うことができる。 The solid lithium source may be dried prior to the reaction with hydrogen sulfide. Drying is preferable because the resulting lithium sulfide does not agglomerate and the by-product of hydrosulfide is suppressed. The end point of drying can be performed by measuring the outdoor atmosphere gas.
固形のリチウム源として炭酸リチウムを使用する。炭酸リチウムの乾燥温度は４５０℃以上が好ましく、より好ましくは５００℃〜７２３℃である。温度が４５０℃以上であれば、十分に水分が除去され好ましい。７２３℃未満であれば炭酸リチウムが溶融せず、粉末状を維持でき取り扱い易いため好ましい。 Lithium carbonate is used as a solid lithium source . The drying temperature of lithium carbonate is preferably 450 ° C. or higher, more preferably 500 ° C. to 723 ° C. If the temperature is 450 ° C. or higher, moisture is sufficiently removed, which is preferable. If it is less than 723 degreeC, since lithium carbonate does not melt | dissolve and a powder form can be maintained and it is easy to handle, it is preferable.
乾燥時の雰囲気ガスは、窒素または、ヘリウム、ネオン、アルゴン、クリプトン、キセノン、ラドン等の希ガスが好適に用いられる。中でも窒素は安価であり好ましい。乾燥時の雰囲気ガスは２種類以上用いても良い。 As the atmospheric gas during drying, nitrogen or a rare gas such as helium, neon, argon, krypton, xenon, or radon is preferably used. Among them, nitrogen is preferable because it is inexpensive. Two or more kinds of atmospheric gases at the time of drying may be used.
本発明で用いられる硫化水素としては、例えば、石油などの燃料油の水素化脱硫反応により得られる硫化水素を含むガスから分離・回収したものや、水素と硫黄蒸気とを加熱反応炉で反応させたもの、硫化鉄、硫化ナトリウムに無機酸を作用させたものなどが用いられる。中でも、石油などの燃料油の水素化脱硫反応により得られる硫化水素ガスは、本来廃棄処分されるガスであり、廃物利用の観点から好ましい。 Examples of the hydrogen sulfide used in the present invention include those separated and recovered from a gas containing hydrogen sulfide obtained by hydrodesulfurization reaction of fuel oil such as petroleum, or a reaction between hydrogen and sulfur vapor in a heating reactor. And those obtained by allowing an inorganic acid to act on iron sulfide or sodium sulfide. Among these, hydrogen sulfide gas obtained by hydrodesulfurization reaction of fuel oil such as petroleum is a gas that is originally discarded, and is preferable from the viewpoint of waste utilization.
硫化水素は、パイプラインやボンベから反応装置へ供給しても良いし、反応系内で発生させても良い。反応系内で発生させた発生期状態の硫化水素を用いると、反応が速やかに進行し好ましい。 Hydrogen sulfide may be supplied to the reaction apparatus from a pipeline or a cylinder, or may be generated in the reaction system. The use of nascent hydrogen sulfide generated in the reaction system is preferable because the reaction proceeds rapidly.
本発明で使用する硫化水素の純度は、８０％以上が好ましく、より好ましくは９０％以上、さらに好ましくは９５％以上である。硫化水素の純度が８０％以上であると、十分に反応が完結し、得られる硫化リチウムの純度が高くなり好ましい。 The purity of hydrogen sulfide used in the present invention is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. It is preferable that the purity of hydrogen sulfide is 80% or more because the reaction is sufficiently completed and the purity of the obtained lithium sulfide is increased.
本発明において、固体のリチウム源に接触させる硫化水素の供給量は、固体リチウム源の仕込量に対して１モル倍から１２モル倍が好ましく、より好ましくは、１モル倍から９モル倍である。１モル倍以上であれば、高純度の金属硫化物が得られ、１２モル倍以下であれば、反応時間が短く、かつ硫化水素のロスが少なくなり経済的である。 In the present invention, the supply amount of hydrogen sulfide brought into contact with the solid lithium source is preferably 1 to 12 moles, more preferably 1 to 9 moles, relative to the charged amount of the solid lithium source. . If it is 1 mol or more, a high-purity metal sulfide can be obtained, and if it is 12 mol or less, the reaction time is short and the loss of hydrogen sulfide is reduced, which is economical.
固形のリチウム源として炭酸リチウムを使用する。炭酸リチウムを硫化水素を反応させる際の温度は、４５０℃〜７２３℃が好ましい。より好ましくは５００〜７００℃である。さらに好ましくは５５０℃〜７００℃である。温度が４５０℃以上であれば、十分に反応が進行し、７２５℃以下であれば、原料の炭酸リチウムが融解し、粒子が固着することが無く好ましい。 Lithium carbonate is used as a solid lithium source . The temperature during the reaction of hydrogen sulfide to lithium carbonate is preferably 450 ℃ ~723 ℃. More preferably, it is 500-700 degreeC. More preferably, it is 550 degreeC-700 degreeC. If temperature is 450 degreeC or more, reaction will fully advance, and if it is 725 degrees C or less, lithium carbonate of a raw material will melt | dissolve and a particle | grain will not adhere, and it is preferable.
本発明では、不活性ガスは、好ましくは、窒素やヘリウム、ネオン、アルゴン、クリプトン、キセノン、ラドン等の希ガスが用いられる。中でも窒素が、コストの面で好ましい。不活性ガスは２種類以上用いても良い。 In the present invention, the inert gas is preferably a rare gas such as nitrogen, helium, neon, argon, krypton, xenon, or radon. Among these, nitrogen is preferable in terms of cost. Two or more kinds of inert gases may be used.
本発明の硫化リチウムの製造方法に用いられる製造装置は、ガスの供給口と排出口を有する。ガスの供給口は、硫化水素や雰囲気ガスが通過することができ、固体のリチウム源およびその加熱部に硫化水素や雰囲気ガスが安定的に供給できる口である。ガスの排出口は、未反応の硫化水素、雰囲気ガスおよび副生物を、固形のリチウム源と接する加熱部から排出できる口である。固形のリチウム源に水酸化リチウムを用いた場合、硫化水素との反応は次式で示され、
２ＬｉＯＨ ＋ Ｈ２Ｓ → Ｌｉ２Ｓ ＋ ２Ｈ２Ｏ
副生物として水が生じる。水は、水蒸気となっているが、得られた硫化リチウムと反応して、水酸化リチウムや水硫化リチウムを生じることがある。これを防ぐために、ガスの供給口から、連続的に硫化水素や不活性ガスを供給することで、ガスの排出口から水蒸気となった水を排出すると、高純度な硫化リチウムが得られ好ましい。さらに、固形のリチウム源として、水酸化リチウム一水塩を用いる場合は、ガスの供給口から雰囲気ガスを供給しながら、水酸化リチウム一水塩を加熱することで、排出口から水蒸気となった結晶水を除去することができる。また、固形のリチウム源に炭酸リチウムを用いた場合、硫化水素との反応は、次式で示され、
Ｌｉ２ＣＯ３ ＋ Ｈ２Ｓ → Ｌｉ２Ｓ ＋ ＣＯ２ ＋ Ｈ２Ｏ
副生物として水と炭酸ガスが生じる。水は水蒸気となっているが、得られた硫化リチウムと反応して、水酸化リチウム、水硫化リチウムおよび炭酸リチウムを生じることがある。これを防ぐために、ガスの供給口から、連続的に硫化水素や不活性ガスを供給することで、ガスの排出口から水蒸気となった水や炭酸ガスを排出すると、高純度な硫化リチウムが得られ好ましい。
The production apparatus used in the method for producing lithium sulfide of the present invention has a gas supply port and a discharge port. The gas supply port is a port through which hydrogen sulfide and atmospheric gas can pass, and hydrogen sulfide and atmospheric gas can be stably supplied to the solid lithium source and its heating part. The gas discharge port is a port through which unreacted hydrogen sulfide, atmospheric gas, and by-products can be discharged from the heating unit in contact with the solid lithium source. When lithium hydroxide is used as the solid lithium source, the reaction with hydrogen sulfide is represented by the following formula:
2LiOH + H 2 S → Li 2 S + 2H 2 O
Water is produced as a by-product. Although water is water vapor, it may react with the obtained lithium sulfide to produce lithium hydroxide or lithium hydrosulfide. In order to prevent this, it is preferable to supply hydrogen sulfide or an inert gas continuously from the gas supply port to discharge water that has become water vapor from the gas discharge port, because high-purity lithium sulfide is obtained. Further, when lithium hydroxide monohydrate is used as a solid lithium source, the lithium hydroxide monohydrate is heated while supplying atmospheric gas from the gas supply port, and becomes steam from the discharge port. Crystallized water can be removed. When lithium carbonate is used as the solid lithium source, the reaction with hydrogen sulfide is represented by the following formula:
Li 2 CO 3 + H 2 S → Li 2 S + CO 2 + H 2 O
Water and carbon dioxide are produced as by-products. Although water is water vapor, it may react with the obtained lithium sulfide to produce lithium hydroxide, lithium hydrosulfide and lithium carbonate. To prevent this, high-purity lithium sulfide can be obtained by continuously supplying hydrogen sulfide or inert gas from the gas supply port and discharging water or carbon dioxide gas that has become water vapor from the gas discharge port. It is preferable.
本発明の硫化リチウムの製造方法で製造された硫化リチウムは、粒子を均一化させる目的で、破砕処理を行っても良い。破砕処理に用いる装置は、一般的な装置を用いることができる。具体的には、ビーズミル、ボールミル、高速回転式ミル、ジェットミル等である。破砕処理によって得られる粒子の粒度は、０．１μｍ〜１ｍｍが好ましく、より好ましくは、１μｍ〜１００μｍである。 Lithium sulfide A manufactured by the manufacturing method of the lithium sulfide of the present invention, for the purpose of equalizing the particle may be subjected to crushing. A general apparatus can be used for the apparatus used for the crushing treatment. Specifically, a bead mill, a ball mill, a high-speed rotary mill, a jet mill, and the like. The particle size of the particles obtained by the crushing treatment is preferably 0.1 μm to 1 mm, more preferably 1 μm to 100 μm.
本発明の硫化リチウムの製造方法で製造された硫化リチウムは、得られる硫化リチウムに装置由来の不純物が混入しないため、高純度な硫化リチウムが得られる。特に、好ましくは、硫化リチウムの中のＳｉ含量が２００ｐｐｍ未満に、よりに好ましくは、１００ｐｐｍ未満、さらに好ましくは、５０ｐｐｍ未満に抑えられる。Ｓｉ含量が２００ｐｐｍ未満の硫化リチウムは、精製等を必要とせず、経済的に有利である。本発明において、硫化リチウムの中のＳｉ含量は、ＩＣＰ−ＡＥＳ法により測定される。 Lithium sulfide A manufactured by the manufacturing method of the lithium sulfide of the present invention, since the impurities from device to lithium sulfide obtained is not mixed, high-purity lithium sulfide can be obtained. In particular, the Si content in lithium sulfide is preferably suppressed to less than 200 ppm, more preferably less than 100 ppm, and even more preferably less than 50 ppm. Lithium sulfide having a Si content of less than 200 ppm does not require purification and is economically advantageous. In the present invention, the Si content in lithium sulfide is measured by the ICP-AES method.
以下、実施例により具体的に説明する。なお、各例において得られる硫化リチウムの分析値は、次の方法により測定した。 Hereinafter, specific examples will be described. The analytical value of lithium sulfide obtained in each example was measured by the following method.
イオンクロマトグラフィーによる硫黄酸化物含量測定
装置：ＩＣＳ−２０００（日本ダイオネクス（株）製）
カラム：IonPac AG-11-HC / IonPac AS11-HC
溶離液：下記のＫＯＨグラジエントを用いた
Measurement of sulfur oxide content by ion chromatography Device: ICS-2000 (manufactured by Nippon Dionex Co., Ltd.)
Column: IonPac AG-11-HC / IonPac AS11-HC
Eluent: The following KOH gradient was used.
流量：１．２５ｍＬ／ｍｉｎ
サプレッサ：ＡＳＲＳ−３００（１３０ｍＡ／リサイクル）
カラム温度：３０℃
導入量：２５μＬ 。
Flow rate: 1.25 mL / min
Suppressor: ASRS-300 (130 mA / recycle)
Column temperature: 30 ° C
Introduced volume: 25 μL.
測定方法
３７％ホルマリン液を超純水で５％に希釈後、超音波洗浄機とアスピレーターを用いて１０分間脱気することで、５％ホルマリン水溶液を得た。サンプル約０．１ｇを精秤し、５％ホルマリン溶液で１００ｍｌにメスアップして供試液とした。供試液は調整後、直ちに測定した。得られたチャートから、供試液中の亜硫酸イオン、硫酸イオンおよびチオ硫酸イオンを絶対検量線法にて定量し、リチウム塩換算して、それぞれ亜硫酸リチウム、硫酸リチウムおよびチオ硫酸リチウムを求め硫黄酸化物含量とした。
Measurement method A 37% formalin solution was diluted to 5% with ultrapure water, and then degassed for 10 minutes using an ultrasonic cleaner and an aspirator to obtain a 5% formalin aqueous solution. About 0.1 g of the sample was precisely weighed and made up to 100 ml with a 5% formalin solution to prepare a test solution. The test solution was measured immediately after adjustment. From the obtained chart, sulfite ion, sulfate ion and thiosulfate ion in the test solution were quantified by the absolute calibration curve method, and converted to lithium salt to obtain lithium sulfite, lithium sulfate and lithium thiosulfate, respectively, and sulfur oxide The content.
金属含量測定
金属含量測定には、ＩＣＰ−ＭＳ法およびＩＣＰ−ＡＥＳ法を用いた。不活性ガス雰囲気下で硫化リチウムを採取し、硝酸に溶解した後に定容とし、供試液とした。供試液について、Ａｌ、Ｂ、Ｂａ、Ｃａ、Ｆｅ、Ｋ、Ｍｇ、Ｎａ、Ｒｂ、ＶおよびＺｎをＩＣＰ−ＭＳで、ＳｉをＩＣＰ−ＡＥＳで定量した。
Metal content measurement ICP-MS method and ICP-AES method were used for metal content measurement. Lithium sulfide was collected under an inert gas atmosphere, dissolved in nitric acid, adjusted to a constant volume, and used as a test solution. For the test solution, Al, B, Ba, Ca, Fe, K, Mg, Na, Rb, V and Zn were quantified by ICP-MS, and Si was quantified by ICP-AES.
（実施例１）
内径２１ｍｍ、長さ５００ｍｍの石英ガラス管の中央部に、直径２ｍｍの孔を９箇所あけた目皿を取り付けた反応器に、ガラスウールを詰め、炭酸リチウム（高純度炭酸リチウム ＰＬＣ−４Ｎ，パシフィックリチウム株式会社製、平均粒子径１００μｍ）を２．０２ｇ充填した。さらに、縦２５ｍｍ、横１２ｍｍ、厚さ７ｍｍに成形した純度９９．８％のアルミナ製試験片（ＳＳＡ−Ｓ、株式会社ニッカトー製）を炭酸リチウムに半分浸漬するように設置した。反応器の上部と下部には、ガスの供給管・排気管が取り付けられており、また、熱電対が目皿付近まで到達するように保護管が取り付けられている。反応器下部のガス供給管から、窒素ガスを供給速度２５ｍｌ／ｍｉｎで導入しながら、外部加熱により６５０℃まで加熱した。６５０℃になったことを確認した後、硫化水素ガス（純度９９．９９％、住友精化株式会社製）を供給速度１０ｍｌ／ｍｉｎ、窒素ガスを供給速度５ｍｌ／ｍｉｎでそれぞれ供給しながら、３時間反応を行った。反応終了後、室温まで冷却後、試験片の外観を目視で確認した。試験前後の試験片を図５，６に示す。試験片の炭酸リチウムに埋没していた部分（以下、固相部）と、試験片の炭酸リチウムに埋没していなかった部分（以下、気相部）に、腐蝕を示す変形や変色が見られなかった。得られた硫化リチウムにも、着色は見られず白色塊状の硫化リチウム１．５９ｇを得た。Ｘ線回折を測定したところ、硫化リチウムのピークのみが得られ、生成物が硫化リチウムであることを確認した。
Example 1
Glass wool was filled into a reactor in which a center plate of a quartz glass tube having an inner diameter of 21 mm and a length of 500 mm was attached with a plate having nine holes with a diameter of 2 mm, and lithium carbonate (high purity lithium carbonate PLC-4N, Pacific 2.02 g of Lithium Co., Ltd. average particle size 100 μm) was filled. Furthermore, an alumina test piece (SSA-S, manufactured by Nikkato Co., Ltd.) having a purity of 99.8% and molded into a length of 25 mm, a width of 12 mm, and a thickness of 7 mm was placed so as to be half immersed in lithium carbonate. A gas supply pipe and an exhaust pipe are attached to the upper and lower parts of the reactor, and protective tubes are attached so that the thermocouple reaches the vicinity of the eye plate. While introducing nitrogen gas from the gas supply pipe at the lower part of the reactor at a supply rate of 25 ml / min, it was heated to 650 ° C. by external heating. After confirming that the temperature reached 650 ° C., while supplying hydrogen sulfide gas (purity 99.99%, manufactured by Sumitomo Seika Co., Ltd.) at a supply rate of 10 ml / min and nitrogen gas at a supply rate of 5 ml / min, 3 Time reaction was performed. After completion of the reaction, after cooling to room temperature, the appearance of the test piece was visually confirmed. The test pieces before and after the test are shown in FIGS. Deformation and discoloration showing corrosion are observed in the part of the test piece embedded in lithium carbonate (hereinafter, solid phase part) and the part of the test piece not embedded in lithium carbonate (hereinafter, gas phase part). There wasn't. The obtained lithium sulfide was not colored, and 1.59 g of white lump lithium sulfide was obtained. When X-ray diffraction was measured, only the lithium sulfide peak was obtained, and it was confirmed that the product was lithium sulfide.
（比較例１）
実施例１において、試験片に縦２５ｍｍ、横１１ｍｍ、厚さ４ｍｍに成形したムライト製試験片（ＫＭ、株式会社ニッカトー製）に変更した以外は、実施例１と同様に行った。試験前後の試験片を図７，８に示す。試験片の外観を目視で確認したところ、気相部は、青色の斑点が一面に生じた。また、固相部は褐色の斑点と薄褐色の変色が一面に生じ、気相部、固相部ともに腐蝕していた。模様に変色し腐蝕が確認された。また、得られた硫化リチウムにも薄褐色の着色が確認された。
(Comparative Example 1)
In Example 1, it carried out similarly to Example 1 except having changed into the test piece made from mullite (KM, product made from Nikkato Co., Ltd.) shape | molded by 25 mm in length, 11 mm in width, and 4 mm in thickness in the test piece. The test pieces before and after the test are shown in FIGS. When the appearance of the test piece was visually confirmed, blue spots were generated on the entire surface of the gas phase. Further, the solid phase portion had brown spots and light brown discoloration all over, and both the gas phase portion and the solid phase portion were corroded. The pattern was discolored and corrosion was confirmed. Further, light brown coloring was also confirmed in the obtained lithium sulfide.
（比較例２）
実施例１において、試験片に縦２５ｍｍ、横１２ｍｍ、厚さ２ｍｍに成形したＳＵＳ３１６製試験片に変更した以外は、実施例１と同様に行った。試験前後の試験片を図９，１０に示す。試験片の外観を目視で確認したところ、気相部は、梨地様の凹凸が生じ、その一部が剥離した。また、固相部は全面薄褐色に変色し、気相部、固相部ともに腐蝕していた。また、得られた硫化リチウムには褐色の着色が確認された。
(Comparative Example 2)
In Example 1, it carried out like Example 1 except having changed into the test piece made from SUS316 shape | molded by 25 mm in length, 12 mm in width, and thickness 2mm in the test piece. The test pieces before and after the test are shown in FIGS. When the appearance of the test piece was visually confirmed, a satin-like unevenness was generated in the gas phase portion, and a part thereof peeled off. In addition, the solid phase portion turned completely light brown, and both the gas phase portion and the solid phase portion were corroded. Moreover, brown coloring was confirmed in the obtained lithium sulfide.
（比較例３）
実施例１において、試験片に縦２５ｍｍ、横１３ｍｍ、厚さ３ｍｍに成形したハステロイＣ／Ｃ２７６製試験片に変更した以外は、実施例１と同様に行った。試験前後の試験片を図１１，１２に示す。試験片の外観を目視で確認したところ、気相部は、梨地様の凹凸が生じ、褐色に変色した。また、固相部も全面褐色に変色し、気相部、固相部ともに腐蝕していた。またその腐食により、気相部に打刻してあったアラビア数字の２の文字は、判読できなくなった。加えて、得られた硫化リチウムには褐色の着色が確認された。
(Comparative Example 3)
In Example 1, it carried out similarly to Example 1 except having changed into the test piece made from Hastelloy C / C276 shape | molded by 25 mm in length, 13 mm in width, and thickness 3mm in the test piece. The test pieces before and after the test are shown in FIGS. When the appearance of the test piece was visually confirmed, a satin-like unevenness occurred in the gas phase portion, and the color changed to brown. In addition, the solid phase portion was completely brown and the gas phase portion and the solid phase portion were both corroded. Also, due to the corrosion, the Arabic numeral 2 that was engraved in the gas phase became unreadable. In addition, brown coloring was confirmed in the obtained lithium sulfide.
（比較例４）
実施例１において、試験片に縦２５ｍｍ、横１３ｍｍ、厚さ３ｍｍに成形したインコネル６００製試験片に変更した以外は、実施例１と同様に行った。試験前後の試験片を図１３，１４に示す。試験片の外観を目視で確認したところ、気相部は、梨地様の凹凸が生じ、褐色に変色した。また、固相部も全面褐色に変色し、気相部、固相部ともに腐蝕していた。またその腐食により、気相部に打刻してあったアラビア数字の６の文字は、ほぼ判読できなくなった。加えて、得られた硫化リチウムには褐色の着色が確認された。
(Comparative Example 4)
In Example 1, it carried out similarly to Example 1 except having changed into the test piece made from Inconel 600 shape | molded by 25 mm in length, 13 mm in width, and thickness 3mm in the test piece. The test pieces before and after the test are shown in FIGS. When the appearance of the test piece was visually confirmed, a satin-like unevenness occurred in the gas phase portion, and the color changed to brown. In addition, the solid phase portion was completely brown and the gas phase portion and the solid phase portion were both corroded. Also, due to the corrosion, the Arabic numeral 6 that was engraved in the gas phase became almost unreadable. In addition, brown coloring was confirmed in the obtained lithium sulfide.
（実施例２）
材質にセラミックスである９９．８％アルミナ（ＳＳＡ−Ｓ、株式会社ニッカトー社製）を用い、図１，２に記載のインナーケースを作製した。
(Example 2)
The inner case shown in FIGS. 1 and 2 was produced using 99.8% alumina (SSA-S, manufactured by Nikkato Corporation) as a material.
ロータリーキルンにはラボ用ロータリーキルン（ＲＫ−０３３０、株式会社モトヤマ製）を用いた。セラミックス製のインナーケースに炭酸リチウム（高純度炭酸リチウム ＰＬＣ−４Ｎ，パシフィックリチウム株式会社製、平均粒子径１００μｍ）を１０ｇ充填した。インナーケースをラボ用ロータリーキルンの透明石英管にセットし、透明石英管の両端をガス導入部の付属したブチルゴム栓で密封した。透明石英管を５ｒｐｍの速度で回転させ、炭酸リチウムを運動させた。ガス導入部から窒素を５ｍｌ／ｍｉｎの速度で流しながら、セラミックス製インナーケースを６０分間かけて室温から６５０℃まで加熱した。セラミックス製インナーケースが６５０℃に到達したのを確認した後、硫化水素を１０ｍｌ／ｍｉｎの速度で供給することで、炭酸リチウムと硫化水素とを１５時間反応させた。すなわち硫化水素は、炭酸リチウムに対して３当量供給した。反応終了後、硫化水素の供給を止め、室温まで冷却することで、白色粉末状の硫化リチウム６．４２ｇを得た。Ｘ線回折を測定したところ、硫化リチウムのピークが得られ、生成物が硫化リチウムであることを確認した。得られた硫化リチウムの品質は、表２に記載した。 A rotary kiln for laboratory use (RK-0330, manufactured by Motoyama Co., Ltd.) was used as the rotary kiln. 10 g of lithium carbonate (high purity lithium carbonate PLC-4N, manufactured by Pacific Lithium Co., Ltd., average particle size 100 μm) was filled in the ceramic inner case. The inner case was set in a transparent quartz tube of a laboratory rotary kiln, and both ends of the transparent quartz tube were sealed with a butyl rubber stopper attached to a gas inlet. The transparent quartz tube was rotated at a speed of 5 rpm to move the lithium carbonate. The ceramic inner case was heated from room temperature to 650 ° C. over 60 minutes while flowing nitrogen from the gas inlet at a rate of 5 ml / min. After confirming that the ceramic inner case reached 650 ° C., hydrogen carbonate was supplied at a rate of 10 ml / min to react lithium carbonate and hydrogen sulfide for 15 hours. That is, 3 equivalents of hydrogen sulfide were supplied to lithium carbonate. After completion of the reaction, the supply of hydrogen sulfide was stopped and the mixture was cooled to room temperature to obtain 6.42 g of white powdery lithium sulfide. When X-ray diffraction was measured, a peak of lithium sulfide was obtained, and it was confirmed that the product was lithium sulfide. The quality of the obtained lithium sulfide is shown in Table 2.
炭酸リチウムから硫化リチウムへの転化率は９９％以上、イオンクロマトグラフィーで測定した不純物含量は、それぞれ亜硫酸リチウム０．２ｗｔ％、硫酸リチウム０．２ｗｔ％、チオ硫酸リチウム０．１ｗｔ％未満で、合計０．４ｗｔ％未満であった。 The conversion rate from lithium carbonate to lithium sulfide is 99% or more, and the impurity content measured by ion chromatography is less than 0.2 wt% lithium sulfite, 0.2 wt% lithium sulfate, and less than 0.1 wt% lithium thiosulfate, respectively. It was less than 0.4 wt%.
（比較例５）
実施例２において、インナーケースに石英製インナーケースに変更した以外は、実施例２と同様に行うことで、白色粉末状の硫化リチウム５．６５ｇを得た。Ｘ線回折を測定したところ、硫化リチウムのピークが得られ、生成物が硫化リチウムであることを確認した。得られた硫化リチウムの品質は、表２に記載した。
(Comparative Example 5)
In Example 2, 5.65 g of white powdery lithium sulfide was obtained in the same manner as in Example 2 except that the inner case was changed to a quartz inner case. When X-ray diffraction was measured, a peak of lithium sulfide was obtained, and it was confirmed that the product was lithium sulfide. The quality of the obtained lithium sulfide is shown in Table 2.
炭酸リチウムから硫化リチウムへの転化率は９９％、イオンクロマトグラフィーで測定した不純物含量は、それぞれ亜硫酸リチウム０．１ｗｔ％、硫酸リチウム０．１ｗｔ％、チオ硫酸リチウム０．１ｗｔ％未満で、合計０．２ｗｔ％であった。 The conversion rate from lithium carbonate to lithium sulfide was 99%, and the impurity contents measured by ion chromatography were less than 0.1 wt% lithium sulfite, 0.1 wt% lithium sulfate, and less than 0.1 wt% lithium thiosulfate, respectively. It was 2 wt%.
（参考例１）
実施例２において、炭酸リチウムを水酸化リチウムに、仕込量を１０ｇから２ｇに、反応温度を６５０℃から４００℃に、硫化水素の供給量を炭酸リチウムに対して３当量から水酸化リチウムに対して２当量に変更したほかは、実施例２と同様に行うことで、白色粉末状の硫化リチウム３．８４ｇを得た。Ｘ線回折を測定したところ、硫化リチウムのピークが得られ、生成物が硫化リチウムであることを確認した。得られた硫化リチウムの品質を表２に示した。
( Reference Example 1 )
In Example 2, lithium carbonate was added to lithium hydroxide, the charge was changed from 10 g to 2 g, the reaction temperature was changed from 650 ° C. to 400 ° C., and the supply amount of hydrogen sulfide was changed from 3 equivalents to lithium carbonate to lithium hydroxide. Except for changing to 2 equivalents, 3.84 g of white powdery lithium sulfide was obtained in the same manner as in Example 2. When X-ray diffraction was measured, a peak of lithium sulfide was obtained, and it was confirmed that the product was lithium sulfide. The quality of the obtained lithium sulfide is shown in Table 2.
比較例５で得られた硫化リチウム中には、Ｓｉが３００ｐｐｍ含まれていたのに対し、実施例では、Ｓｉは１０ｐｐｍ未満に低減し、セラミックス製のインナーケースを用いることで、不純物の混入が抑制された。 In the lithium sulfide obtained in Comparative Example 5, 300 ppm of Si was contained, whereas in the example, Si was reduced to less than 10 ppm. By using the ceramic inner case, impurities were mixed. Suppressed.
１：原料
２：インナーケース
３：熱伝対
４：炉
５：炉芯管
６：ロータリージョイント
７：制御ボックス
1: Raw material 2: Inner case 3: Thermocouple 4: Furnace 5: Furnace core tube 6: Rotary joint 7: Control box
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| JP6508673B2 (en) * | 2015-02-16 | 2019-05-08 | 古河機械金属株式会社 | Method of producing lithium sulfide |
| JP7014496B2 (en) * | 2016-06-14 | 2022-02-01 | 出光興産株式会社 | Lithium sulfide and its manufacturing method |
| JP7294795B2 (en) * | 2017-11-17 | 2023-06-20 | 出光興産株式会社 | Lithium sulfide powder and method for producing the same |
| JP6715985B2 (en) * | 2019-03-27 | 2020-07-01 | 古河機械金属株式会社 | Method for producing lithium sulfide |
| JP6837531B2 (en) * | 2019-10-30 | 2021-03-03 | 古河機械金属株式会社 | Lithium sulfide manufacturing equipment |
| CN118201872A (en) * | 2021-11-22 | 2024-06-14 | 三井金属矿业株式会社 | Lithium sulfide, method for producing same, and method for producing sulfide solid electrolyte |
| KR102680726B1 (en) * | 2021-12-09 | 2024-07-03 | 주식회사 레이크테크놀로지 | Apparatus for manufacturing lithium sulfide |
| WO2024034534A1 (en) * | 2022-08-10 | 2024-02-15 | Ａｇｃ株式会社 | Method for purifying hydrogen sulfide and method for producing lithium sulfide |
| WO2024034533A1 (en) * | 2022-08-10 | 2024-02-15 | Ａｇｃ株式会社 | Hydrogen sulfide purification method and lithium sulfide production method |
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