JP6256754B2 - Method for producing lithium sulfide - Google Patents
Method for producing lithium sulfide Download PDFInfo
- Publication number
- JP6256754B2 JP6256754B2 JP2014012241A JP2014012241A JP6256754B2 JP 6256754 B2 JP6256754 B2 JP 6256754B2 JP 2014012241 A JP2014012241 A JP 2014012241A JP 2014012241 A JP2014012241 A JP 2014012241A JP 6256754 B2 JP6256754 B2 JP 6256754B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- sulfide
- gas
- reaction
- lithium sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 title claims description 78
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 74
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 55
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 55
- 239000007789 gas Substances 0.000 claims description 46
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 34
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- 238000005096 rolling process Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 27
- 238000004255 ion exchange chromatography Methods 0.000 description 20
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 19
- 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 19
- 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 18
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- -1 naphtha Chemical compound 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910052743 krypton Inorganic materials 0.000 description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229910052754 neon Inorganic materials 0.000 description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052704 radon Inorganic materials 0.000 description 3
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NMZQZAOLJBLJBO-UHFFFAOYSA-N ClP(Cl)Cl.F.F.F.F.F Chemical compound ClP(Cl)Cl.F.F.F.F.F NMZQZAOLJBLJBO-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- CQXADFVORZEARL-UHFFFAOYSA-N Rilmenidine Chemical compound C1CC1C(C1CC1)NC1=NCCO1 CQXADFVORZEARL-UHFFFAOYSA-N 0.000 description 1
- 229910018503 SF6 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000074 antimony hydride Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- FFCZHQLUEDCQKI-UHFFFAOYSA-N diarsenic Chemical compound [As]#[As] FFCZHQLUEDCQKI-UHFFFAOYSA-N 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910000078 germane Inorganic materials 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- HXQGSILMFTUKHI-UHFFFAOYSA-M lithium;sulfanide Chemical compound S[Li] HXQGSILMFTUKHI-UHFFFAOYSA-M 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 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
- 239000007790 solid phase Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical compound [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- QHMQWEPBXSHHLH-UHFFFAOYSA-N sulfur tetrafluoride Chemical compound FS(F)(F)F QHMQWEPBXSHHLH-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910000059 tellane Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、電池用イオン伝導性固体電解質、エンジニアリングプラスチックス、潤滑剤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 method for producing high purity lithium sulfide useful as an intermediate raw material for ion conductive solid electrolytes for batteries, engineering plastics, lubricants and chemicals.
近年、電池用イオン伝導性固体電解質、エンジニアリングプラスチックス、潤滑剤や化学薬品用の中間原料として、高純度の金属硫化物が求められている。中でも硫化リチウムは、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、電池用イオン伝導性固体電解質の原料として用いられている。 In recent years, high-purity metal sulfides are required as intermediate raw materials for ion-conducting solid electrolytes for batteries, engineering plastics, lubricants and chemicals. Among them, lithium sulfide is a white powder having a specific odor, and is used as a raw material for polymerization of polyarylene sulfide resin and a raw material for ion conductive solid electrolyte for batteries.
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、硫酸リチウム、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 from lithium sulfate, lithium hydroxide and lithium carbonate is known.
水酸化リチウムから硫化リチウムを製造する方法としては、固体の水酸化リチウムに硫化水素や硫黄蒸気といったガス状硫黄源を、１３０〜４４５℃以下の温度で反応させる方法（特許文献１）や、水酸化リチウムを水や有機溶媒に溶解し、硫化水素を吹き込んで反応させ水硫化リチウムを得た後、脱硫化水素する方法（特許文献２〜４）が知られている。 As a method for producing lithium sulfide from lithium hydroxide, a method of reacting solid lithium hydroxide with a gaseous sulfur source such as hydrogen sulfide or sulfur vapor at a temperature of 130 to 445 ° C. or lower (Patent Document 1), water A method is known in which lithium oxide is dissolved in water or an organic solvent and hydrogen sulfide is blown into the reaction to obtain lithium hydrosulfide, followed by dehydrogenation (Patent Documents 2 to 4).
また、炭酸リチウムから硫化リチウムを製造する方法としては、６００℃に加熱した炭酸リチウムに硫化水素を反応させる方法（特許文献５）が知られていた。 As a method for producing lithium sulfide from lithium carbonate, a method of reacting hydrogen sulfide with lithium carbonate heated to 600 ° C. has been known (Patent Document 5).
しかしながら、特許文献１、５のように固体の原料に硫化水素ガス等を反応させる方法では、電池材料で求められる高純度の品質の硫化リチウムは得られないという課題があった。また特許文献３、４のように有機溶媒で反応を行う場合は、有機溶媒由来の不純物が硫化リチウムに残存し、これを高純度化するために、大量の有機溶媒を用いて精製を行う必要があった。また、特許文献２のように、水中で反応を行う場合は、多大なエネルギーを使用して水を除去する必要があるなど必ずしも効率の良い方法ではなかった。 However, the method of reacting hydrogen sulfide gas or the like with a solid raw material as in Patent Documents 1 and 5 has a problem that high-purity quality lithium sulfide required for battery materials cannot be obtained. Moreover, when reacting with an organic solvent like patent document 3, 4, the impurity derived from an organic solvent remains in lithium sulfide, and in order to refine this, it is necessary to refine | purify using a lot of organic solvents was there. Moreover, when reacting in water like patent document 2, it was not necessarily an efficient method, such as having to remove water using a lot of energy.
そこで、本発明の目的は、高純度な硫化リチウムを、精製や溶媒の除去をすることなく製造する方法を提供することにある。 Therefore, an object of the present invention is to provide a method for producing high-purity lithium sulfide without purification or solvent removal.
上記目的を達成するに当たり、鋭意検討の結果、炭酸リチウム粒子を運動させた状態で硫化水素を気固反応させることによって、精製や溶媒の除去をすることなく、高純度な硫化リチウムが得られることを見出した。 As a result of diligent studies in achieving the above object, high-purity lithium sulfide can be obtained without purifying or removing the solvent by gas-solid reaction of hydrogen sulfide with the lithium carbonate particles in motion. I found.
本発明の硫化リチウムの製造方法により、不純物の生成が抑制され、高純度の硫化リチウムを得ることができる。すなわち、得られた硫化リチウムに含まれる不純物である亜硫酸塩、硫酸塩、チオ硫酸塩の合計を０．５ｗｔ％以下、更に好ましくは０．３ｗｔ％以下に抑えることができる。高純度の硫化リチウムが得られるため、特に精製等を必要とせず、経済的に有利である。 According to the method for producing lithium sulfide of the present invention, generation of impurities is suppressed, and high-purity lithium sulfide can be obtained. That is, the total of sulfites, sulfates, and thiosulfates, which are impurities contained in the obtained lithium sulfide, can be suppressed to 0.5 wt% or less, more preferably 0.3 wt% or less. Since high-purity lithium sulfide can be obtained, no purification or the like is required, which is economically advantageous.
また、本発明の硫化リチウムの製造方法は、金属炭酸塩の反応速度が速くなる。短時間で反応が終了するため生産性が高くなる。また、低い温度で反応させることができ、エネルギーを節約することができる。また、装置の耐熱性を下げることができ、安価な装置で製造することができる。 Moreover, the method for producing lithium sulfide of the present invention increases the reaction rate of the metal carbonate. Productivity increases because the reaction is completed in a short time. Moreover, it can be made to react at a low temperature and energy can be saved. Further, the heat resistance of the apparatus can be lowered, and the apparatus can be manufactured with an inexpensive apparatus.
本発明の硫化リチウムの製造方法は、固体の炭酸リチウムに気体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、除いた溶媒等の廃液が発生しないため経済的に有利である。 The method for producing lithium sulfide of the present invention is a gas-solid reaction in which a gas is reacted with solid lithium carbonate , and since no solvent is used, there is no need to remove the solvent, and no waste liquid such as a removed solvent is generated. Therefore, it is economically advantageous.
本発明の硫化リチウムの製造方法によれば、得られる硫化リチウムは粉状で生成され、生成する硫化リチウムが、原料の炭酸リチウムの形状をそのまま継承して反応容器から取り出せるので作業性が良い。さらに、反応装置形態に転動層、中でもロータリーキルンを使用した場合、連続的に反応を行うことができ、効率が良い。 According to the method for producing lithium sulfide of the present invention, the obtained lithium sulfide is produced in a powder form, and the produced lithium sulfide inherits the shape of the raw material lithium carbonate as it is and can be taken out from the reaction vessel, so that workability is good. Furthermore, when a rolling bed, especially a rotary kiln is used as the reactor configuration, the reaction can be continuously carried out and the efficiency is good.
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スの原料や、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 chemical .
本発明の硫化リチウムの製造方法を用いて得た硫化リチウムは、高純度であるため、イオン伝導性固体電解質として用いた場合、電気伝導度の高いイオン伝導性固体電解質が得られる。 Since lithium sulfide obtained by using the method for producing lithium sulfide of the present invention has high purity, when used as an ion conductive solid electrolyte, an ion conductive solid electrolyte having high electrical conductivity can be obtained.
以下に、本発明の硫化リチウムの製造方法について詳細に記載する。 Below, the manufacturing method of the lithium sulfide of this invention is described in detail.
本発明の硫化リチウムの製造方法では、炭酸リチウムを運動させた状態で硫化水素と気固反応させる。 In the method for producing lithium sulfide of the present invention, gas-solid reaction with hydrogen sulfide is performed in a state where lithium carbonate is moved.
本発明で用いられる金属炭酸塩は、炭酸リチウムである。 The metal carbonate used in the present invention is lithium carbonate .
炭酸リチウムの平均粒子径は、２２μｍである。 The average particle diameter of the lithium carbonate is 22μ m.
炭酸リチウムの平均粒子径は、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 diameter of lithium carbonate 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炭酸リチウムは、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、炭酸リチウム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 lithium carbonate used in the present invention may be obtained by any method and may be a commercially available product. Usually, lithium carbonate contains a foreign metal and other impurities, but from the viewpoint of suppressing side reactions, lithium carbonate having a purity as high as possible is preferable.
炭酸リチウムは、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。 Lithium carbonate may be dried prior to 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.
炭酸リチウムの乾燥温度は１００℃以上が好ましく、より好ましくは２００℃以上、さらに好ましくは４５０℃から７２５℃である。温度が１００℃以上であれば、十分に、水分が除去され好ましい。 The drying temperature of lithium carbonate is preferably 100 ° C. or higher, more preferably 200 ° C. or higher, and further preferably 450 ° C. to 725 ° C. A temperature of 100 ° C. or higher is preferable because water is sufficiently removed.
炭酸リチウムの乾燥時の雰囲気ガスは、水素や窒素または、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、水素含有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 atmosphere gas for drying lithium carbonate , hydrogen, nitrogen, or a rare gas such as helium, neon, argon, krypton, xenon, or radon is preferably used. Among these, nitrogen and hydrogen-containing nitrogen are preferable because they are inexpensive. Two or more kinds of atmospheric gases at the time of drying may be used.
炭酸リチウムと硫化水素とを反応させる際の温度は、２００℃〜７２５℃が好ましい。より好ましくは３５０〜７００℃である。さらに好ましくは４５０℃〜７００℃である。温度が２００℃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。また、副生する硫黄酸化物含量が少なく好ましい。 As for the temperature at the time of making lithium carbonate and hydrogen sulfide react, 200 to 725 degreeC is preferable. More preferably, it is 350-700 degreeC. More preferably, it is 450 degreeC-700 degreeC. If temperature is 200 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. Moreover, the content of sulfur oxides by-produced is small and preferable.
本発明における炭酸リチウム粒子が運動している状態とは、炭酸リチウム粒子が目視で確認できるマクロな運動をしている状態であって、外部から与えられた力によって、炭酸リチウムの粒子が運動している状態である。力は、重力や、炭酸リチウムを充填した容器へのガスの導入、炭酸リチウム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、炭酸リチウムを静止させ、ガスを流通して反応させる固定層反応は、本発明における炭酸リチウム粒子が運動している状態ではない。 The state in which lithium carbonate particles of the present invention is in motion, a state in which lithium carbonate particles are macroscopic motion can be confirmed visually, by the force given from the outside, particles of lithium carbonate in motion It is in a state. The force is applied by gravity, introduction of gas into a container filled with lithium carbonate , or movement of a container filled with lithium carbonate . Therefore, the micro motion represented by the Brownian motion is not included. For example, lithium carbonate is stationary, fixed bed reaction and reacted with circulated gas is not a state in which lithium carbonate particles of the present invention is in motion.
社団法人化学工学会編、化学工学便覧改訂六版９６０ページ、表１８．４に気固反応装置の主な反応装置形態と応用例が記載されている。本発明における金属炭酸塩粒子が運動している状態は、化学工学便覧改訂六版９６０ページ、表１８．４の固相が「運動」している状態に相当する。 The main reactor configuration and application examples of the gas-solid reactor are described in the Chemical Society of Japan edition, page 960 of the 6th edition of the Chemical Engineering Handbook, Table 18.4. The state in which the metal carbonate particles are in motion in the present invention corresponds to the state in which the solid phase in Table 18.4 is “moving”, page 960 of the Chemical Engineering Handbook 6th revised edition.
本発明における気固反応の反応装置は、移動層、転動層、流動層、気流層のいずれかを有する。 The reaction device for gas-solid reaction in the present invention has any one of a moving bed, a rolling bed, a fluidized bed, and an airflow bed.
本発明における移動層とは、連続的に塔頂から金属炭酸塩粒子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 metal carbonate particles are continuously supplied from the top of the tower, gently lowered, and brought into contact with gas in a 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、金属炭酸塩粒子を充填した容器や格子を運動させることで、金属炭酸塩を転動させ、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 device form in which a metal carbonate is rolled by moving a container or a lattice filled with metal carbonate particles and brought into contact with a gas to react. 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、金属炭酸塩粒子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 metal carbonate particles are suspended and suspended in a gas and brought into contact with the gas to cause a reaction 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.
本発明における気流層とは、比表面積を大きくした金属酸化物を、気体と均一に混合し、両者をほぼ同一速度で反応雰囲気を通過させる反応装置形態である。気流層は、微粉炭燃焼、気相合成、石炭ガス化などに応用されている。 The airflow layer in the present invention is a reactor configuration in which a metal oxide having a large specific surface area is uniformly mixed with a gas and both are passed through the reaction atmosphere at substantially the same speed. The airflow layer is applied to pulverized coal combustion, gas phase synthesis, coal gasification, and the like.
本発明における気固反応の反応装置は、移動層、転動層、流動層、気流層が２種類以上複合させた形態としてもよい。 The gas-solid reaction reactor in the present invention may have a configuration in which two or more kinds of moving bed, rolling layer, fluidized bed, and airflow layer are combined.
本発明における気固反応の反応装置は、転動層を有する反応装置が好ましく、気体の供給速度や炭酸リチウム粒子の運動状態を、炭酸リチウム粒子の比重や粒子径等に左右されること無く自由に設定することができ、かつ連続的に反応を行うことができ、さらには粒子が固着することが無く好ましい。本発明における気固反応の反応装置は、ロータリーキルンがさらに好適に用いられる。炭酸リチウムのロータリーキルンへの仕込量は、炉の容積に対する炭酸リチウムの割合である充填率が２０％以下、より好ましくは１５％以下、さらに好ましくは１２％以下である。充填率が２０％以下であれば、炭酸リチウムを均一に加熱することができ、反応にムラが無く好ましい。 Reactor gas-solid reaction in the present invention is preferably a reaction apparatus having a rolling layer, the motion state of the feed rate and lithium carbonate particles of the gas, without freedom be dependent on the specific gravity and particle diameter of the lithium carbonate particles It is preferable that the reaction can be carried out continuously and the particles do not stick. A rotary kiln is more preferably used for the gas-solid reaction reactor in the present invention. The charging amount of lithium carbonate into the rotary kiln is such that the filling rate, which is the ratio of lithium carbonate to the volume of the furnace, is 20% or less, more preferably 15% or less, and even more preferably 12% or less. If the filling rate is 20% or less, lithium carbonate can be heated uniformly, and there is no unevenness in the reaction, which is preferable.
本発明で用いられる硫化水素は、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。 Hydrogen sulfide used in the present invention is separated and recovered from a gas containing hydrogen sulfide obtained by hydrodesulfurization reaction of fuel oil such as petroleum, or obtained by reacting hydrogen and sulfur vapor in a heating reactor, For example, iron sulfide or sodium sulfide obtained by allowing an inorganic acid to act on it is used.
硫化水素は、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 from a cylinder to the reactor 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.
硫化水素の分圧は、０．１％〜９９％が好ましい。０．１％以上であれば、短時間で反応が進行し、９９％以下であれば、十分な分圧でその他の共存させることができ、反応速度向上、不純物低減といった効果が得られることがある。 The partial pressure of hydrogen sulfide is preferably 0.1% to 99%. If it is 0.1% or more, the reaction proceeds in a short time, and if it is 99% or less, other coexistence can be achieved with a sufficient partial pressure, and effects such as improvement in reaction rate and reduction in impurities can be obtained. is there.
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、得られる金属硫化物中の不純物が少なく好ましい。 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. When the purity of hydrogen sulfide is 80% or more, the reaction is sufficiently completed, and there are few impurities in the resulting metal sulfide.
本発明において、炭酸リチウムに接触させる硫化水素の供給量は、炭酸リチウムの仕込量に対して１モル倍から１５モル倍が好ましく、より好ましくは、１．２モル倍から９モル倍である。１モル倍以上であれば、高純度の炭酸リチウムが得られ、１５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 to be brought into contact with lithium carbonate is preferably 1 to 15 mol times, more preferably 1.2 to 9 mol times with respect to the charged amount of lithium carbonate . If it is 1 mol or more, high purity lithium carbonate can be obtained, and if it is 15 mol or less, the reaction time is short and the loss of hydrogen sulfide is reduced, which is economical.
硫化水素は、適切な分圧になるように不活性ガスと混合し供給しても良い。不活性ガスには、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。硫化水素を不活性ガスに希釈して導入することで、爆発危険性を抑制したり、反応を穏やかに進行させたり、硫化水素が十分に過熱することで熱分解し、発生期状態の水素が生じ、反応を促進したり、不純物の生成を抑制することがあり好ましい。不活性ガスは２種類以上用いても良い。 Hydrogen sulfide may be mixed with an inert gas and supplied so as to have an appropriate partial pressure. As the inert gas, a rare gas such as nitrogen, helium, neon, argon, krypton, xenon, or radon is used. Among these, nitrogen is preferable in terms of cost. By diluting and introducing hydrogen sulfide into an inert gas, the risk of explosion is suppressed, the reaction is allowed to proceed gently, or when hydrogen sulfide is sufficiently heated, it is thermally decomposed, and This is preferable because it may promote the reaction and suppress the generation of impurities. 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では、還元性ガスの存在下、硫化水素と金属炭酸塩を反応させることで、高純度な硫化リチウムが得られることがある。還元性ガスは、例えば一酸化炭素、二酸化硫黄、ホルムアルデヒド、アンモニア、水素などが挙げられる。中でも水素が、安価で高純度な硫化リチウムが得られるため好ましい。 In the method for producing lithium sulfide of the present invention, high-purity lithium sulfide may be obtained by reacting hydrogen sulfide with a metal carbonate in the presence of a reducing gas. Examples of the reducing gas include carbon monoxide, sulfur dioxide, formaldehyde, ammonia, and hydrogen. Of these, hydrogen is preferred because it provides inexpensive and high-purity lithium sulfide .
本発明で用いられる水素は、水の電解、硫化水素の熱分解、メタン、ナフサ、メタノールおよびジメチルエーテルなどの炭化水素原料を、ニッケルを主成分とする触媒上で水蒸気と反応させる水蒸気改質法、一酸化炭素と水を反応させ、生じた水素と二酸化炭素から、ガーボトール法により二酸化炭素を除去する水生ガスシフト反応等の方法で得たものを用いることができる。水素は、ボンベから反応装置へ供給しても良いし、硫化水素を熱分解させ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水素を用いると、反応が速やかに進行し、かつ不純物の生成が抑制され好ましい。 Hydrogen used in the present invention includes water electrolysis, hydrogen sulfide thermal decomposition, a steam reforming method in which a hydrocarbon raw material such as methane, naphtha, methanol and dimethyl ether is reacted with steam on a nickel-based catalyst, Carbon monoxide and water can be reacted and those obtained by a method such as an aquatic gas shift reaction in which carbon dioxide is removed from the generated hydrogen and carbon dioxide by the garbotol method can be used. Hydrogen may be supplied from a cylinder to the reactor, or may be generated in the reaction system by thermally decomposing hydrogen sulfide. It is preferable to use hydrogen in the nascent state generated in the reaction system because the reaction proceeds rapidly and the generation of impurities is suppressed.
本発明で使用する水素の純度は、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。水素の純度が８０％以上であれば、十分に反応が完結し、得られる硫化リチウム中に含まれる不純物が少なくなり好ましい。 The purity of hydrogen used in the present invention is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. A hydrogen purity of 80% or more is preferable because the reaction is sufficiently completed and impurities contained in the obtained lithium sulfide are reduced.
本発明において、金属炭酸塩に接触させる水素の分圧は、０．１％から９９％が好ましく、より好ましくは０．５％から９０％である。０．１％以上であれば反応促進、不純物低減の効果が得られ、９９％以下であれば十分な濃度で硫化水素ガスと共存させられる。 In the present invention, the partial pressure of hydrogen brought into contact with the metal carbonate is preferably 0.1% to 99%, more preferably 0.5% to 90%. If it is 0.1% or more, the effect of promoting the reaction and reducing impurities can be obtained, and if it is 99% or less, it can coexist with hydrogen sulfide gas at a sufficient concentration.
水素は、適切な分圧になるように不活性ガスと混合し供給しても良い。不活性ガスには、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。水素を不活性ガスに希釈して導入することで、爆発危険性を低減したり、反応を穏やかに進行させたり、十分に過熱することで熱分解し、発生期状態の水素が生じ、反応を促進したり、不純物の生成を抑制することがあり好ましい。不活性ガスは２種類以上用いても良い。 Hydrogen may be supplied after being mixed with an inert gas so as to have an appropriate partial pressure. As the inert gas, a rare gas such as nitrogen, helium, neon, argon, krypton, xenon, or radon is used. Among these, nitrogen is preferable in terms of cost. By introducing hydrogen diluted in an inert gas, the risk of explosion is reduced, the reaction is allowed to proceed gently, or when it is sufficiently heated, it undergoes thermal decomposition, producing hydrogen in the nascent state, and reacting. It is preferable because it promotes or suppresses the generation of impurities. 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では、精製や溶媒の除去をすることなく、高純度な硫化リチウムが得られるという目的を達成されうる限り、その他のガスを共存させても良い。その他のガスとは、応温度において気体である物質であって、具体的には、酸素、二酸化炭素、亜酸化窒素、一酸化窒素、二酸化窒素、三フッ化窒素、ホスゲン、アルシン、三酸化二砒素、三塩化二砒素、三フッ化砒素、五フッ化砒素、三塩化ホウ素、三臭化ホウ素、三フッ化ホウ素、ジボラン、四塩化ゲルマニウム、ゲルマン、三塩化リン、三フッ化リン、五フッ化リン、ホスフィン、オキシ塩化リン、アセチレン、スチビン、セレン化水素、四塩化スズ、テルル化水素、四塩化チタン、四塩化ケイ素、トリクロロシラン、ジクロロシラン、四フッ化ケイ素、シラン、六フッ化タングステン、塩素、臭素、塩化水素、フッ化水素、クロロスルホン酸、シアン化水素、四フッ化硫黄、六フッ化硫黄、硫黄蒸気、天然ガス、アクロレイン、メタノール、メチルメルカプタン、ベンゼン、フェノール、塩化メチレン、クロロホルム、四塩化炭素、１，１，１−トリクロロエタン、トリクロロエチレン、テトラクロロエチレン、トリクロロフルオロメタン、トリメチルアミン、フルオロフォルム、プロパン、ヘキサフルオロプロパン、六フッ化エタン、フルオロカーボン類などが挙げられる。その他のガスは、反応系内で発生させても良い。その他のガスは、２種類以上用いても良い。その他のガスの分圧は、０．１％〜９０％が好ましい。０．１％以上であれば、短時間で反応が進行し、９０％以下であれば、十分な分圧で、硫化水素等を共存させることができ、反応速度促進、不純物の低下といった所望の効果が得られる。 In the method for producing lithium sulfide of the present invention, other gas may be allowed to coexist as long as the object of obtaining high-purity lithium sulfide can be achieved without purification and removal of the solvent. The other gas is a substance that is a gas at a temperature, and specifically includes oxygen, carbon dioxide, nitrous oxide, nitric oxide, nitrogen dioxide, nitrogen trifluoride, phosgene, arsine, dioxide trioxide. Arsenic, diarsenic trichloride, arsenic trifluoride, arsenic pentafluoride, boron trichloride, boron tribromide, boron trifluoride, diborane, germanium tetrachloride, germane, phosphorous trichloride, phosphorous trifluoride, pentafluoride Phosphorus chloride, phosphine, phosphorus oxychloride, acetylene, stibine, hydrogen selenide, tin tetrachloride, hydrogen telluride, titanium tetrachloride, silicon tetrachloride, trichlorosilane, dichlorosilane, silicon tetrafluoride, silane, tungsten hexafluoride , Chlorine, bromine, hydrogen chloride, hydrogen fluoride, chlorosulfonic acid, hydrogen cyanide, sulfur tetrafluoride, sulfur hexafluoride, sulfur vapor, natural gas, acrolein, meta , Methyl mercaptan, benzene, phenol, methylene chloride, chloroform, carbon tetrachloride, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene, trichlorofluoromethane, trimethylamine, fluoroform, propane, hexafluoropropane, hexafluoroethane And fluorocarbons. Other gases may be generated in the reaction system. Two or more kinds of other gases may be used. The partial pressure of other gases is preferably 0.1% to 90%. If it is 0.1% or more, the reaction proceeds in a short time, and if it is 90% or less, hydrogen sulfide and the like can coexist with a sufficient partial pressure, and the desired reaction rate acceleration, impurity reduction, etc. An effect is obtained.
本発明の硫化リチウムの製造方法では、二酸化炭素と水が副生する。これら副生物は、反応中に供給される硫化水素、不活性ガス、還元性ガスおよびその他のガスによって、同伴し排出することができる。こうすることで、硫化リチウムと二酸化炭素との副反応を防ぎ、硫化リチウムへの金属炭酸塩の残留を低下させる。また、硫黄酸化物含量も低減し、高純度な硫化リチウムが得られる。 In the method for producing lithium sulfide of the present invention, carbon dioxide and water are by-produced. These by-products can be entrained and discharged by hydrogen sulfide, inert gas, reducing gas and other gases supplied during the reaction. By doing this, side reactions between lithium sulfide and carbon dioxide are prevented, and the residual metal carbonate in lithium sulfide is reduced. In addition, the sulfur oxide content is reduced, and high purity lithium sulfide is obtained.
本発明の硫化リチウムの製造方法では、反応は大気圧下で行っても良いし、高圧下で行っても良い。 In the method for producing lithium sulfide of the present invention, the reaction may be carried out under atmospheric pressure or under high pressure.
得られた硫化リチウムの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。 For the purpose of making the obtained lithium sulfide particles uniform, crushing treatment may be performed. 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 .
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。
Ion chromatography measurement device: ICS-2000 (manufactured by Nippon Dionex)
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
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、１％ホルマリン溶液で１００ｍｌにメスアップした。サンプルは調整後、直ちに測定した。
Flow rate: 1.25 mL / min
Suppressor: ASRS-300 (130 mA / recycle)
Column temperature: 30 ° C
Amount introduced: 25 μL
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 1% formalin solution. Samples were measured immediately after adjustment.
実施例、比較例に記載の転化率とは、イオンクロマトグラフィーにて生成物中の炭酸イオンを定量して、炭酸リチウム換算し、試料全体に対する重量割合を求め、１００から引いた値を示す。 The conversion rate described in Examples and Comparative Examples is a value obtained by quantifying carbonate ions in the product by ion chromatography, converting to lithium carbonate, obtaining a weight ratio with respect to the whole sample, and subtracting from 100.
（参考例１）
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。石英製のインナーケース（容積：５０ｃｍ３）に炭酸リチウム（高純度炭酸リチウム ＰＬＣ−４Ｎ、平均粒子径１００μｍ、嵩密度０．８５ｇ／ｃｍ３、パシフィックリチウム株式会社製）を１．００ｇ充填した。すなわち、炭酸リチウムの充填率は２．３％である。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シリコン栓で密封した。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ガスを５０ｍｌ／ｍｉｎの速度で流しながら、透明石英管を４５分間かけて室温から６２５℃まで加熱した。透明石英管が６２５℃に到達したのを確認した後、硫化水素を２ｍｌ／ｍｉｎの速度で、１５０分間窒素と同伴させながら供給することで、炭酸リチウムと硫化水素とを反応させた。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０．６４ｇ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転化率は７７％、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、硫酸リチウム、チオ硫酸リチウムいずれも０．１ｗｔ％未満であった。
( Reference Example 1)
A rotary kiln for laboratory use (RK-0330, manufactured by Motoyama Co., Ltd.) was used as the rotary kiln. Quartz inner case (volume: 50 cm 3 ) was charged with 1.00 g of lithium carbonate (high purity lithium carbonate PLC-4N, average particle diameter 100 μm, bulk density 0.85 g / cm 3 , Pacific Lithium Co., Ltd.). That is, the filling rate of lithium carbonate is 2.3%. 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 silicon stopper attached to a gas inlet. The transparent quartz tube was rotated at a speed of 5 rpm to move the lithium carbonate. The transparent quartz tube was heated from room temperature to 625 ° C. over 45 minutes while flowing nitrogen gas from the gas inlet at a rate of 50 ml / min. After confirming that the transparent quartz tube reached 625 ° C., hydrogen carbonate was supplied at a rate of 2 ml / min while being accompanied by nitrogen for 150 minutes to react lithium carbonate and hydrogen sulfide. After completion of the reaction, the supply of hydrogen sulfide was stopped and the mixture was cooled to room temperature to obtain 0.64 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 conversion rate of the obtained lithium sulfide was 77%, and the impurity contents measured by ion chromatography were each less than 0.1 wt% for lithium sulfite, lithium sulfate, and lithium thiosulfate.
（参考例２）
参考例１において、反応時間を１５０分からを３００分に、硫化水素の供給量を１．０モル倍／炭酸リチウムから２．０モル倍／炭酸リチウムに変更した以外は、実施例１と同様に合成することで、硫化リチウム０．６２ｇを得た。得られた硫化リチウムの転化率は９１％、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％未満、チオ硫酸リチウム０．１ｗｔ％未満で、合計０．１ｗｔ％であった。
( Reference Example 2)
In Reference Example 1, the reaction time was changed from 150 minutes to 300 minutes, and the supply amount of hydrogen sulfide was changed from 1.0 mole times / lithium carbonate to 2.0 mole times / lithium carbonate, as in Example 1. By synthesis, 0.62 g of lithium sulfide was obtained. The conversion rate of the obtained lithium sulfide was 91%, and the impurity contents measured by ion chromatography were 0.1 wt% lithium sulfite, less than 0.1 wt% lithium sulfate, and less than 0.1 wt% lithium thiosulfate, respectively, and the total content was 0. It was 1 wt%.
（参考例３）
参考例２において、窒素ガスの供給速度を５０ｍｌ／ｍｉｎから２５ｍｌ／ｍｉｎに変更した以外は、参考例２と同様に合成することで、硫化リチウム０．６１ｇを得た。得られた硫化リチウムの転化率は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０．１ｗｔ％、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。
( Reference Example 3)
In Reference Example 2, 0.61 g of lithium sulfide was obtained by synthesizing in the same manner as in Reference Example 2 except that the supply rate of nitrogen gas was changed from 50 ml / min to 25 ml / min. The conversion rate of the obtained lithium sulfide was 99% or more, and the impurity contents measured by ion chromatography were 0.1 wt% lithium sulfite, 0.1 wt% lithium sulfate, and less than 0.1 wt% lithium thiosulfate, respectively. It was 2 wt%.
（参考施例４）
参考例３において、窒素ガスの供給速度を透明石英管の回転速度を５ｒｐｍから１ｒｐｍに変更した以外は、参考例３と同様に合成することで、硫化リチウム０．６０ｇを得た。得られた硫化リチウムの転化率は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０．２ｗｔ％、チオ硫酸リチウム０．１ｗｔ％未満で、合計０．３ｗｔ％であった。
( Reference Example 4)
In Reference Example 3, 0.60 g of lithium sulfide was obtained by synthesizing in the same manner as in Reference Example 3 except that the nitrogen gas supply rate was changed from 5 rpm to 1 rpm. The conversion rate of the obtained lithium sulfide was 99%, and the impurity contents measured by ion chromatography were 0.1 wt% lithium sulfite, 0.2 wt% lithium sulfate, and less than 0.1 wt% lithium thiosulfate, respectively. It was 3 wt%.
（参考例５）
参考例３において、窒素ガスの供給速度を透明石英管の回転速度を５ｒｐｍから１０ｒｐｍに変更した以外は、参考例３と同様に合成することで、硫化リチウム０．５３ｇを得た。得られた硫化リチウムの転化率は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０．２ｗｔ％、チオ硫酸リチウム０．１ｗｔ％未満で、合計０．３ｗｔ％であった。
( Reference Example 5)
In Reference Example 3, 0.53 g of lithium sulfide was obtained by synthesizing in the same manner as in Reference Example 3, except that the nitrogen gas supply rate was changed from 5 rpm to 10 rpm. The conversion rate of the obtained lithium sulfide was 99%, and the impurity contents measured by ion chromatography were 0.1 wt% lithium sulfite, 0.2 wt% lithium sulfate, and less than 0.1 wt% lithium thiosulfate, respectively. It was 3 wt%.
（参考例６）
参考例３において、雰囲気ガスを窒素から３％水素含有窒素に変更した以外は、参考例３と同様に合成することで、硫化リチウム０．６３ｇを得た。得られた硫化リチウムの転化率は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％未満、チオ硫酸リチウム０．１ｗｔ％未満で、合計０．１ｗｔ％であった。
( Reference Example 6)
In Reference Example 3, 0.63 g of lithium sulfide was obtained by synthesizing in the same manner as in Reference Example 3 except that the atmosphere gas was changed from nitrogen to nitrogen containing 3% hydrogen. The conversion rate of the obtained lithium sulfide was 99%, and the impurity contents measured by ion chromatography were 0.1 wt% lithium sulfite, less than 0.1 wt% lithium sulfate, and less than 0.1 wt% lithium thiosulfate, respectively, and the total content was 0. It was 1 wt%.
（参考例７）
参考例３において、炭酸リチウムの仕込み量を１ｇから２ｇに（充填率４．７％）、硫化水素供給量を１．０ｍｏｌ倍／炭酸リチウムから３．０ｍｏｌ倍／炭酸リチウムに、雰囲気ガスの供給速度を２５ｍｌ／ｍｉｎから５ｍｌ／ｍｉｎに、硫化水素の供給速度を２．０ｍｌ／ｍｉｎから１０ｍｌ／ｍｉｎに、反応時間を３００分から１８０分にそれぞれ変更した以外は、参考例３と同様に合成することで、硫化リチウム１．２５ｇを得た。得られた硫化リチウムの転化率は９３％、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。
( Reference Example 7)
In Reference Example 3, the supply amount of lithium carbonate was changed from 1 g to 2 g (filling rate 4.7%), the supply amount of hydrogen sulfide was changed from 1.0 mol times / lithium carbonate to 3.0 mol times / lithium carbonate, and the atmospheric gas was supplied. Synthesis was performed in the same manner as in Reference Example 3 except that the rate was changed from 25 ml / min to 5 ml / min, the supply rate of hydrogen sulfide was changed from 2.0 ml / min to 10 ml / min, and the reaction time was changed from 300 minutes to 180 minutes. As a result, 1.25 g of lithium sulfide was obtained. The conversion rate of the obtained lithium sulfide was 93%, and the impurity contents measured by ion chromatography were 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８）
参考例７において、反応温度を６２５℃から６５０℃に変更した以外は、参考例７と同様に合成することで、硫化リチウム１．０６ｇを得た。得られた硫化リチウムの転化率は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０．１ｗｔ％、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。
( Reference Example 8)
In Reference Example 7, 1.06 g of lithium sulfide was obtained by synthesis in the same manner as in Reference Example 7 except that the reaction temperature was changed from 625 ° C. to 650 ° C. The conversion rate of the obtained lithium sulfide was 99% or more, and the impurity contents measured by ion chromatography were 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９）
参考例８において、炭酸リチウムの平均粒子径を１００μｍから２μｍ（ＵＦ−２００、平均粒子径２μｍ、嵩密度０．４６ｇ／ｃｍ３、パシフィックリチウム株式会社製）に変更した以外は、参考例８と同様に合成した。充填率は８．３％であった。得られた硫化リチウム１．１８ｇ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０．１ｗｔ％、硫酸リチウム０．２ｗｔ％、チオ硫酸リチウム０．１ｗｔ％未満で、合計０．３ｗｔ％であった。
(Reference Example 9 )
Reference Example 8, 2 [mu] m average particle size of lithium carbonate from 100 [mu] m (UF-200, average particle diameter 2 [mu] m, a bulk density of 0.46 g / cm 3, Pacific manufactured lithium Ltd.) was changed to, as in Reference Example 8 It synthesized similarly. The filling rate was 8.3%. The conversion rate of 1.18 g of the obtained lithium sulfide was 99% or more, and the impurity contents measured by ion chromatography were less than 0.1 wt% lithium sulfite, 0.2 wt% lithium sulfate, and less than 0.1 wt% lithium thiosulfate, respectively. The total was 0.3 wt%.
（参考例１０）
参考例８において、インナーケースの容積を５０ｃｍ３から１０２ｃｍ３に、炭酸リチウムの仕込量を２ｇから６ｇに、反応時間を１８０分から５４０分に変更した以外は、参考例８と同様に合成した。充填率は６．９％であった。得られた硫化リチウム３．５２ｇ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０．１ｗｔ％、硫酸リチウム０．２ｗｔ％、チオ硫酸リチウム０．１ｗｔ％未満で、合計０．３ｗｔ％であった。
( Reference Example 10 )
Reference Example 8, in 102cm 3 volume of the inner case from 50 cm 3 to 6g the charged amount of lithium carbonate from 2g, except that the reaction time was changed to 180 minutes to 540 minutes, and in the same manner as in Reference Example 8 Synthesis. The filling rate was 6.9%. The conversion rate of 3.52 g of the obtained lithium sulfide was 99% or more, and the impurity contents measured by ion chromatography were less than 0.1 wt% lithium sulfite, 0.2 wt% lithium sulfate, and less than 0.1 wt% lithium thiosulfate, respectively. The total was 0.3 wt%.
（参考例１１）
参考例８において、インナーケースの容積を５０ｃｍ３から１０２ｃｍ３に、炭酸リチウムの仕込量を２ｇから８ｇに、反応時間を１８０分から７２０分に変更した以外は、参考例８と同様に合成した。得られた硫化リチウム４．７０ｇ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０．１ｗｔ％、チオ硫酸リチウム０．１ｗｔ％未満で、合計０．３ｗｔ％であった。
( Reference Example 11 )
Reference Example 8, in 102cm 3 volume of the inner case from 50 cm 3 to 8g the charged amount of lithium carbonate from 2g, except that the reaction time was changed to 180 minutes to 720 minutes, and in the same manner as in Reference Example 8 Synthesis. The conversion rate of the obtained lithium sulfide 4.70 g was 99% or more, and the impurity contents measured by ion chromatography were less than 0.2 wt% lithium sulfite, 0.1 wt% lithium sulfate, and less than 0.1 wt% lithium thiosulfate, respectively. The total was 0.3 wt%.
（参考例１２）
参考例８において、インナーケースの容積を５０ｃｍ３から１０２ｃｍ３に、炭酸リチウムの仕込量を２ｇから１０ｇに、反応時間を１８０分から９００分に変更した以外は、参考例８と同様に合成した。充填率は１１．５％であった。得られた硫化リチウム５．６５ｇ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０．１ｗｔ％、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。
( Reference Example 12 )
Reference Example 8, in 102cm 3 volume of the inner case from 50 cm 3, the charged amount of lithium carbonate in 10g from 2g, except that the reaction time was changed to 180 minutes to 900 minutes, and in the same manner as in Reference Example 8 Synthesis. The filling rate was 11.5%. The conversion rate of 5.65 g of the obtained lithium sulfide was 99% or more, 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. The total was 0.2 wt%.
（参考例１３）
参考例９において、インナーケースの容積を５０ｃｍ３から１０２ｃｍ３に、炭酸リチウムの仕込み量を２ｇから５ｇへ、雰囲気ガスの流量を５ｍｌ／ｍｉｎから０ｍｌ／ｍｉｎへ、硫化水素の流量を１０ｍｌ／ｍｉｎから１００ｍｌ／ｍｉｎへ、反応時間を１８０分から４５分へそれぞれ変更した以外は、参考例９と同様に合成した。充填率は１０．７％であった。得られた硫化リチウム３．１１ｇの転化率は９９％以上、イオンクロマトｔ％、硫酸リチウム０．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０．２ｗ１ｗｔ％未満、チオ硫酸リチウム０．１ｗｔ％未満で、合計０．２ｗｔ％であった。
(Reference Example 13 )
In Reference Example 9 , the volume of the inner case is changed from 50 cm 3 to 102 cm 3 , the charged amount of lithium carbonate is changed from 2 g to 5 g, the flow rate of the atmospheric gas is changed from 5 ml / min to 0 ml / min, and the flow rate of hydrogen sulfide is 10 ml / min. Was synthesized in the same manner as in Reference Example 9 except that the reaction time was changed from 180 minutes to 100 ml / min and the reaction time was changed from 180 minutes to 45 minutes. The filling rate was 10.7%. The conversion rate of 3.11 g of the obtained lithium sulfide was 99% or more, ion chromatography t%, lithium sulfate 0.1%. The impurity content measured by the graph was less than 0.2 w1 wt% lithium sulfite and less than 0.1 wt% lithium thiosulfate, respectively, for a total of 0.2 wt%.
（参考例１４）
参考例１３において、炭酸リチウムの平均粒子径を２μｍから６μｍ（マイクロナイズドバッテリーグレード、平均粒子径６μｍ、嵩密度０．４９ｇ／ｍ３、 ＦＭＣ Ｌｉｔｈｉｕｍ社製）に変更した以外は、参考例１３と同様に合成した。充填率は１０．０％であった。得られた硫化リチウム３．１８ｇ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０．３ｗｔ％、硫酸リチウム０．１ｗｔ％未満、チオ硫酸リチウム０．１ｗｔ％未満で、合計０．３ｗｔ％であった。
(Reference Example 14 )
Reference Example 13, 6 [mu] m average particle size of lithium carbonate from 2μm was changed to (micronized battery grade, average particle size 6 [mu] m, a bulk density 0.49g / m 3, FMC Lithium Corporation) is Reference Example 13 It synthesized similarly. The filling rate was 10.0%. The conversion rate of 3.18 g of the obtained lithium sulfide was 99% or more, and the impurity content measured by ion chromatography was 0.3 wt% lithium sulfite, less than 0.1 wt% lithium sulfate, and less than 0.1 wt% lithium thiosulfate, respectively. The total was 0.3 wt%.
（実施例１）
参考例１３において、炭酸リチウムの平均粒子径を２μｍから２２μｍ（バッテリーグレード、平均粒子径２２μｍ、嵩密度０．６９ｇ／ｃｍ３、ＦＭＣ Ｌｉｔｈｉｕｍ社製）に変更した以外は、参考例１３と同様に合成した。充填率は７．１％であった。得られた硫化リチウム２．９０ｇ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０．１ｗｔ％未満、チオ硫酸リチウム０．１ｗｔ％未満で、合計０．２ｗｔ％であった。
(Example 1 )
Reference Example 13, 22 .mu.m average particle size of lithium carbonate from 2μm was changed to (battery grade, average particle size 22 .mu.m, a bulk density of 0.69g / cm 3, FMC Lithium Corporation), in the same manner as in Reference Example 13 Synthesized. The filling rate was 7.1%. The conversion rate of 2.90 g of the obtained lithium sulfide was 99% or more, and the impurity contents measured by ion chromatography were 0.2 wt% lithium sulfite, less than 0.1 wt% lithium sulfate, and less than 0.1 wt% lithium thiosulfate, respectively. The total was 0.2 wt%.
（比較例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）を１．０２ｇ充填した。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、窒素を５０ｍｌ／ｍｉｎ導入し、外部加熱により６２５℃まで加熱した。すなわち反応装置形態は固定層である。目視で、炭酸リチウムが運動していないことを確認した。６２５℃になったことを確認した後、硫化水素ガス（ジャパンファインプロダクツ株式会社製）を供給速度２ｍｌ／ｍｉｎで、窒素ガスに同伴させて供給し、雰囲気ガスを流しながら１５０分反応を行った。反応終了後、室温まで冷却することで、白色塊状の硫化リチウム０．６５ｇ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。得られた硫化リチウムの転化率は１００％、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１．５ｗｔ％、硫酸リチウム１．３ｗｔ％、チオ硫酸リチウム０．３ｗｔ％で、合計３．１ｗｔ％であった。
(Comparative 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 1.02 g of lithium) was filled. 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. Nitrogen was introduced at 50 ml / min from the gas supply pipe at the bottom of the reactor and heated to 625 ° C. by external heating. That is, the reactor configuration is a fixed layer. It was visually confirmed that lithium carbonate was not moving. After confirming that the temperature reached 625 ° C., hydrogen sulfide gas (manufactured by Japan Fine Products Co., Ltd.) was supplied along with nitrogen gas at a supply rate of 2 ml / min, and the reaction was carried out for 150 minutes while flowing atmospheric gas. . After completion of the reaction, the mixture was cooled to room temperature to obtain 0.65 g of white lump lithium sulfide. When X-ray diffraction was measured, only the lithium sulfide peak was obtained, and it was confirmed that the product was lithium sulfide. The conversion rate of the obtained lithium sulfide was 100%, and the impurity contents measured by ion chromatography were 1.5 wt% lithium sulfite, 1.3 wt% lithium sulfate, and 0.3 wt% lithium thiosulfate, respectively, for a total of 3.1 wt. %Met.
（比較例２）
比較例１において、雰囲気ガスを窒素から３％水素含有窒素に、雰囲気ガスの供給速度を２５ｍｌ／ｍｉｎに変更することで、硫化リチウム０．６１ｇを得た。得られた硫化リチウムの転化率は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０．４ｗｔ％、硫酸リチウム０．２ｗｔ％、チオ硫酸リチウム０．１ｗｔ％で合計０．７ｗｔ％であった。
(Comparative Example 2)
In Comparative Example 1, 0.61 g of lithium sulfide was obtained by changing the atmosphere gas from nitrogen to nitrogen containing 3% hydrogen and changing the supply rate of the atmosphere gas to 25 ml / min. The conversion rate of the obtained lithium sulfide was 99% or more, and the impurity contents measured by ion chromatography were 0.4 wt% lithium sulfite, 0.2 wt% lithium sulfate, and 0.1 wt% lithium thiosulfate, respectively, for a total of 0.7 wt%. %Met.
（比較例３）
参考例９において、反応装置形態を転動層から比較例１に記載の固定層に変更した以外は、参考例９と同様に合成することで、硫化リチウム１．０８ｇを得た。得られた硫化リチウムの転化率は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０．５ｗｔ％、硫酸リチウム０．４ｗｔ％、チオ硫酸リチウム０．２ｗｔ％で合計１．１ｗｔ％であった。
(Comparative Example 3)
In Reference Example 9 , 1.08 g of lithium sulfide was obtained by synthesizing in the same manner as in Reference Example 9 except that the reactor configuration was changed from the rolling layer to the fixed layer described in Comparative Example 1. The conversion rate of the obtained lithium sulfide was 99% or more, and the impurity contents measured by ion chromatography were 1.1 wt% in total, respectively 0.5 wt% lithium sulfite, 0.4 wt% lithium sulfate, and 0.2 wt% lithium thiosulfate. %Met.
実施例、参考例、比較例の実験条件と、品質の一覧を表２から５にまとめた。 Tables 2 to 5 summarize the experimental conditions of Examples, Reference Examples, and Comparative Examples, and a list of quality.
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