WO2022202757A1 - 三酸化モリブデン粉体及びその製造方法 - Google Patents
三酸化モリブデン粉体及びその製造方法 Download PDFInfo
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- WO2022202757A1 WO2022202757A1 PCT/JP2022/012990 JP2022012990W WO2022202757A1 WO 2022202757 A1 WO2022202757 A1 WO 2022202757A1 JP 2022012990 W JP2022012990 W JP 2022012990W WO 2022202757 A1 WO2022202757 A1 WO 2022202757A1
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- molybdenum trioxide
- molybdenum
- trioxide powder
- powder
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 title claims abstract description 361
- 239000000843 powder Substances 0.000 title claims abstract description 112
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000013078 crystal Substances 0.000 claims abstract description 106
- 239000011164 primary particle Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002296 dynamic light scattering Methods 0.000 claims abstract description 9
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 46
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 46
- 239000002243 precursor Substances 0.000 claims description 42
- 238000001816 cooling Methods 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 39
- 238000002441 X-ray diffraction Methods 0.000 claims description 24
- 150000002736 metal compounds Chemical class 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 6
- 238000004876 x-ray fluorescence Methods 0.000 claims description 5
- 238000004438 BET method Methods 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 238000010304 firing Methods 0.000 description 36
- 239000002245 particle Substances 0.000 description 29
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 239000011593 sulfur Substances 0.000 description 15
- 229910052717 sulfur Inorganic materials 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 13
- 238000007664 blowing Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 238000010586 diagram Methods 0.000 description 10
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 10
- 230000009257 reactivity Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229920003196 poly(1,3-dioxolane) Polymers 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 229910025794 LaB6 Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000007806 chemical reaction intermediate Substances 0.000 description 4
- 229910052961 molybdenite Inorganic materials 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000012916 structural analysis Methods 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000005078 molybdenum compound Substances 0.000 description 3
- 150000002752 molybdenum compounds Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEFUJGURFLOFAN-UHFFFAOYSA-N 1,3-dichloro-5-isocyanatobenzene Chemical compound ClC1=CC(Cl)=CC(N=C=O)=C1 XEFUJGURFLOFAN-UHFFFAOYSA-N 0.000 description 2
- 238000005169 Debye-Scherrer Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- -1 aluminum compound Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241001168730 Simo Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MYBBIWKGJMUBDF-UHFFFAOYSA-N [O-2].[Li+].[Mo+4] Chemical compound [O-2].[Li+].[Mo+4] MYBBIWKGJMUBDF-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RCMWGBKVFBTLCW-UHFFFAOYSA-N barium(2+);dioxido(dioxo)molybdenum Chemical compound [Ba+2].[O-][Mo]([O-])(=O)=O RCMWGBKVFBTLCW-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- IKUPISAYGBGQDT-UHFFFAOYSA-N copper;dioxido(dioxo)molybdenum Chemical compound [Cu+2].[O-][Mo]([O-])(=O)=O IKUPISAYGBGQDT-UHFFFAOYSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- AGNOBAWAZFBMMI-UHFFFAOYSA-N dicesium dioxido(dioxo)molybdenum Chemical compound [Cs+].[Cs+].[O-][Mo]([O-])(=O)=O AGNOBAWAZFBMMI-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 150000003748 yttrium compounds Chemical class 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Definitions
- the present invention relates to molybdenum trioxide powder and a method for producing the same.
- This application claims priority based on Japanese Patent Application No. 2021-050489 filed in Japan on March 24, 2021, the content of which is incorporated herein.
- Patent Document 1 discloses an apparatus for producing a metal oxide by a flux evaporation method and a method for producing the metal oxide.
- a molybdenum compound is used as a flux, powdered molybdenum trioxide is be recovered.
- Patent Document 2 discloses a method for producing a nanocrystalline molybdenum mixed oxide and the use of the molybdenum mixed oxide as a catalyst for chemical conversion.
- molybdenum trioxide powder When molybdenum trioxide powder is used as a precursor of molybdenum sulfide, commercially available molybdenum trioxide powder has poor sulfidation reactivity. In addition, molybdenum trioxide with a higher purity can obtain molybdenum sulfide with a higher purity, and if the purity is lower, sulfide derived from impurities may be generated. Generally, sulfides other than molybdenum sulfide have poor stability and are easily decomposed by acid or water to generate highly toxic hydrogen sulfide. Therefore, from the viewpoint of storage stability (generation of hydrogen sulfide), extremely high purity is required.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a molybdenum trioxide powder suitable as a precursor of molybdenum sulfide, and a method for producing the same.
- the present invention includes the following aspects. (1) It contains an aggregate of primary particles containing a crystal structure of molybdenum trioxide, the crystal structure includes ⁇ -crystals having an average crystallite size of 50 nm or less, and the number of primary particles obtained by a dynamic light scattering method. A molybdenum trioxide powder having a median diameter D50 of 2000 nm or less. (2) The trioxide according to (1) above, wherein the content of MoO3 measured by X-ray fluorescence (XRF) is 99.5% by mass or more relative to the total weight of the molybdenum trioxide powder. Molybdenum powder.
- XRF X-ray fluorescence
- a method for producing molybdenum oxide powder (9) calcining a raw material mixture comprising a molybdenum oxide precursor compound and a metal compound other than said molybdenum oxide precursor compound to vaporize said molybdenum oxide precursor compound to form molybdenum trioxide vapor; , The method for producing molybdenum trioxide powder according to the above (8), wherein the ratio of the metal compound to 100% by mass of the raw material mixture is 95% by mass or less in terms of oxide.
- molybdenum trioxide powder suitable as a precursor of molybdenum sulfide and a method for producing the same.
- FIG. 1 is a schematic diagram showing an example of an apparatus used for producing molybdenum trioxide particles, which is a raw material for molybdenum sulfide particles.
- FIG. 2A shows the measured XRD profile of Example 1, the uppermost alpha crystal peak position diagram, and the lower (middle) ⁇ crystal peak position diagram.
- FIG. 2B is the XRD profile of Comparative Example 1, and the upper part is an ⁇ -crystal peak position diagram.
- 3A is an analysis diagram of crystallite size and diffraction intensity in Example 1.
- FIG. 3B is an analysis diagram of the crystallite size and diffraction intensity of Comparative Example 1.
- FIG. 1 is a schematic diagram showing an example of an apparatus used for producing molybdenum trioxide particles, which is a raw material for molybdenum sulfide particles.
- FIG. 2A shows the measured XRD profile of Example 1, the uppermost alpha crystal peak position diagram, and the lower (middle) ⁇ crystal peak position
- the molybdenum trioxide powder of the present embodiment contains an aggregate of primary particles containing a crystal structure of molybdenum trioxide, the crystal structure contains ⁇ -crystals having an average crystallite size of 50 nm or less, and dynamic light scattering
- the median diameter D50 of the primary particles determined by law is 2000 nm or less.
- the molybdenum trioxide powder of the present embodiment has a median diameter D50 of 2000 nm or less of the primary particles determined by a dynamic light scattering method, and is composed of an aggregate of primary particles containing a crystal structure of molybdenum trioxide. Further, the crystal structure includes ⁇ -crystals having an average crystallite size of 50 nm or less. Therefore, the molybdenum trioxide powder of the present embodiment has better reactivity with sulfur than the conventional molybdenum trioxide powder.
- the median diameter D50 of the primary particles determined by the dynamic light scattering method is preferably 10 nm or more and 2000 nm or less, more preferably 10 nm or more and 500 nm or less, and still more preferably 10 nm. 200 nm or less.
- the median diameter D50 of the primary particles of the molybdenum trioxide powder is calculated from the volume-based cumulative particle size distribution measured using, for example, a dynamic light scattering particle size distribution analyzer.
- the average particle size of the primary particles of the molybdenum trioxide powder is obtained by photographing the molybdenum trioxide powder with a transmission electron microscope (TEM) or a scanning electron microscope (SEM) and obtaining a two-dimensional image of the For the smallest unit particles (i.e., primary particles) that make up the aggregates of the When the short Feret diameter) is measured and the average value is defined as the primary particle size, it means the average value of the primary particle sizes of 50 randomly selected primary particles.
- TEM transmission electron microscope
- SEM scanning electron microscope
- the average crystallite size of ⁇ -crystals contained in the crystal structure of molybdenum trioxide is preferably 5 nm or more and 50 nm or less, more preferably 5 nm or more and 45 nm or less, still more preferably 10 nm or more and 40 nm or less, Especially preferably, it is 10 nm or more and 35 nm or less.
- the average crystallite size of the ⁇ -crystals is within the above preferred range, the reactivity of the molybdenum trioxide powder with sulfur tends to be better.
- the content ratio of MoO3 measured by X-ray fluorescence (XRF) with respect to the total mass of the molybdenum trioxide powder of the present embodiment is preferably 99.5% by mass or more with respect to the total detected peak intensity, It is more preferably 99.7% by mass or more, and still more preferably 99.9% by mass or more.
- the molybdenum trioxide powder of the present embodiment is subjected to a sulfidation reaction so that high-purity sulfides derived from impurities are not generated. It is easy to obtain molybdenum sulfide with good Therefore, the molybdenum trioxide powder of the present embodiment can be suitably used as a precursor of molybdenum sulfide.
- the reactivity of molybdenum trioxide powder with sulfur is determined, for example, by mixing 1.00 g of molybdenum trioxide powder to be evaluated with 1.57 g of sulfur and firing the mixture at 400° C. for 4 hours in a nitrogen atmosphere. , can be evaluated by determining the conversion of the resulting black powder to MoS2 .
- the conversion to MoS 2 can be determined by the RIR (Reference Intensity Ratio) method from the profile obtained by X-ray diffraction (XRD) measurement of this black powder.
- R C (%) ( IA / KA )/( ⁇ (IB/ KB )) ⁇ 100 (1)
- values listed in the ICSD database can be used, and integrated powder X-ray analysis software (Rigaku, PDXL Version 2) can be used for analysis.
- the specific surface area is preferably 10 m 2 /g or more, more preferably 20 m 2 /g or more, because the reactivity with sulfur is improved. , 30 m 2 /g or more.
- it is preferably 100 m 2 /g or less, may be 90 m 2 /g or less, or may be 80 m 2 /g or less, because it facilitates production. good.
- the crystal structure of molybdenum trioxide may further include ⁇ crystals with an average crystallite size of 50 nm or less.
- the crystal structure of molybdenum trioxide includes ⁇ crystals and ⁇ crystals, the reactivity of molybdenum trioxide powder with sulfur tends to be better.
- the average crystallite size of the ⁇ crystals included in the crystal structure of molybdenum trioxide is preferably 5 nm or more and 50 nm or less, more preferably 5 nm or more and 45 nm or less, still more preferably 10 nm or more and 40 nm or less, Especially preferably, it is 10 nm or more and 30 nm or less.
- the average crystallite size of the ⁇ -crystals is within the above preferable range, the reactivity of the molybdenum trioxide powder with sulfur tends to be better.
- the ⁇ crystal structure of molybdenum trioxide is due to the presence of the peak of the (021) plane of the ⁇ crystal of MoO3 (2 ⁇ : around 27.32°_No.166363 (Inorganic Crystal Structure Database, ICSD)) , can be verified.
- the ⁇ crystal structure is attributed to the (011) plane of the ⁇ crystal of MoO 3 in a profile obtained from powder X-ray diffraction (XRD) using Cu—K ⁇ rays as an X-ray source, (2 ⁇ : 23. It can be confirmed by the presence of a peak near 01°, No. 86426 (Inorganic Crystal Structure Database, ICSD)).
- the molybdenum trioxide powder of the present embodiment has a peak intensity attributed to the (011) plane of the ⁇ crystal of MoO 3 in the profile obtained from powder X-ray diffraction (XRD) using Cu-K ⁇ rays as the X-ray source.
- the ratio ( ⁇ (011) / ⁇ (021)) to the peak intensity attributed to the (021) plane of the ⁇ crystal of MoO 3 is preferably 0.1 or more, more preferably 0.2 or more. Preferably, it is more preferably 0.4 or more.
- the ratio ( ⁇ (011)/ ⁇ (021)) is preferably 10.0 or less.
- the peak intensity attributed to the (011) plane of the ⁇ crystal of MoO 3 and the peak intensity attributed to the (021) plane of the ⁇ crystal of MoO 3 read the maximum intensity of the peak, respectively, and the ratio ( ⁇ (011 )/ ⁇ (021)).
- the ratio ( ⁇ (011)/ ⁇ (021)) is preferably 0.1 to 10.0, more preferably 0.2 to 10.0. More preferably, it is particularly preferably 0.4 to 10.0.
- the content of ⁇ crystals in the molybdenum trioxide powder of the present embodiment is not particularly limited, but may be 20% or more, 50% or more, or 70% or more. It may be 80% or more, or it may be 100%.
- the content of ⁇ -crystals of MoO 3 can be determined from the obtained profile data by the RIR (Reference Intensity Ratio) method.
- MoO 3 ⁇ -crystal content (%) (I A /K A )/((I A /K A )+(I B /K B )) ⁇ 100 (2)
- RIR values values listed in the ICSD database can be used, and integrated powder X-ray analysis software (manufactured by Rigaku, PDXL Version 2) can be used for analysis.
- the shape of the primary particles in a two-dimensional image taken with a transmission electron microscope (TEM) is visually observed or photographed, and is particulate, spherical, plate-like (sheet-like). ), needle-like, string-like, or ribbon-like, and combinations of these shapes may be included.
- the shape of the primary particles of the molybdenum trioxide powder may be ribbon-like or sheet-like having a nano-order thickness.
- the ⁇ crystal structure of molybdenum trioxide can also be confirmed by the presence of peaks at wavenumbers 773, 848 cm ⁇ 1 and 905 cm ⁇ 1 in the Raman spectrum obtained from Raman spectroscopy.
- the ⁇ crystal structure of molybdenum trioxide can be confirmed by the presence of peaks at wavenumbers of 663, 816 cm ⁇ 1 and 991 cm ⁇ 1 .
- the molybdenum trioxide powder of the present embodiment is useful as a raw material for molybdenum sulfide (MoS 2 ) because it has good reactivity with sulfur. Moreover, since the molybdenum trioxide powder of the present embodiment can be made highly pure, it can be applied in industrial grade. Further, the molybdenum trioxide powder of the present embodiment is expected to be applied to various catalyst applications.
- MoS 2 molybdenum sulfide
- the method for producing molybdenum trioxide powder of this embodiment is the method for producing molybdenum trioxide powder of the above embodiment, wherein a molybdenum oxide precursor compound is vaporized to form molybdenum trioxide vapor, and the Including cooling the molybdenum oxide vapor.
- a raw material mixture containing a molybdenum oxide precursor compound and a metal compound other than the molybdenum oxide precursor compound is fired to vaporize the molybdenum oxide precursor compound.
- the ratio of the metal compound to 100% by mass of the raw material mixture is preferably 70% by mass or less in terms of oxide.
- the method for producing molybdenum trioxide powder according to the present embodiment can be suitably carried out using the production apparatus 1 shown in FIG.
- FIG. 1 is a schematic diagram of an example of an apparatus used for producing molybdenum trioxide powder according to the present embodiment.
- a production apparatus 1 includes a firing furnace 2 for firing a molybdenum oxide precursor compound or the raw material mixture to vaporize the molybdenum oxide precursor compound, and a firing furnace 2 connected to the molybdenum trioxide vaporized by the firing. It has a cross-shaped cooling pipe 3 for pulverizing steam and a recovery device 4 as a recovery means for recovering the molybdenum trioxide powder pulverized in the cooling pipe 3 . At this time, the firing furnace 2 and the cooling pipe 3 are connected through an exhaust port 5 .
- the cooling pipe 3 is provided with an opening adjusting damper 6 for an outside air intake (not shown) at the left end, and an observation window 7 at the upper end.
- the collection machine 4 is connected to an exhaust device 8 as a first air blowing means. When the exhaust device 8 exhausts the air, the collector 4 and the cooling pipe 3 are sucked, and outside air is blown to the cooling pipe 3 from the opening adjustment damper 6 of the cooling pipe 3 . That is, the cooling pipe 3 is passively blown with air by the exhaust device 8 having a suction function.
- the manufacturing apparatus 1 may have an external cooling device 9, which makes it possible to arbitrarily control the cooling conditions of the molybdenum trioxide vapor generated from the kiln 2.
- the molybdenum oxide precursor compound is not particularly limited as long as it is a precursor compound for forming the molybdenum trioxide powder of the present invention.
- molybdenum oxide precursor compounds may be used alone or in combination of two or more.
- the form of the molybdenum oxide precursor compound is not particularly limited.
- it may be in the form of powder such as molybdenum trioxide, or may be in the form of liquid such as aqueous solution of ammonium molybdate.
- it is in the form of powder, which is easy to handle and energy efficient.
- molybdenum oxide precursor compound it is preferable to use commercially available ⁇ -crystalline molybdenum trioxide. Further, when ammonium molybdate is used as the molybdenum oxide precursor compound, it is converted to thermodynamically stable molybdenum trioxide by firing, so the molybdenum oxide precursor compound to be vaporized is the molybdenum trioxide. .
- molybdenum oxide precursor compounds it is preferable to include molybdenum trioxide from the viewpoint of easy control of the purity of the molybdenum trioxide powder to be obtained, the average particle size of the primary particles, and the crystal structure.
- Molybdenum trioxide vapor can also be formed by firing a raw material mixture containing a molybdenum oxide precursor compound and a metal compound other than the molybdenum oxide precursor compound.
- Metal compounds other than the molybdenum oxide precursor compound are not particularly limited, but are aluminum compounds, silicon compounds, titanium compounds, magnesium compounds, sodium compounds, potassium compounds, zirconium compounds, yttrium compounds, zinc compounds, copper compounds, and iron compounds. etc. Among these, aluminum compounds, silicon compounds, titanium compounds, and magnesium compounds are preferably used.
- a molybdenum oxide precursor compound and a metal compound other than the molybdenum oxide precursor compound may sometimes form an intermediate. It can be vaporized in the form
- the metal compound other than the molybdenum oxide precursor compound among these, it is preferable to use an aluminum compound in order to prevent damage to the firing furnace. It is also possible not to use a metal compound other than the body compound.
- Aluminum compounds include aluminum chloride, aluminum sulfate, basic aluminum acetate, aluminum hydroxide, boehmite, pseudoboehmite, transitional aluminum oxides ( ⁇ -aluminum oxide, ⁇ -aluminum oxide, ⁇ -aluminum oxide, etc.), Examples include ⁇ -aluminum oxide and mixed oxide aluminum having two or more crystal phases.
- the content of the molybdenum oxide precursor compound with respect to 100% by mass of the raw material mixture is 5% by mass to 5% by mass. It is preferably 100% by mass, may be 10% by mass to 100% by mass, and may be 20% by mass to 100% by mass.
- the firing temperature varies depending on the molybdenum oxide precursor compound, the metal compound, and the desired molybdenum trioxide powder used, but it is usually preferable to set the temperature at which the intermediates can be decomposed.
- the temperature is preferably 500° C. to 1500° C. , 600°C to 1550°C, more preferably 700°C to 1600°C.
- the firing time is also not particularly limited, and can be, for example, 1 minute or more, 1 minute to 30 hours, 10 minutes to 25 hours, or 100 minutes to 20 hours. can be done.
- the heating rate varies depending on the properties of the molybdenum oxide precursor compound used, the metal compound, and the desired molybdenum trioxide powder, but from the viewpoint of production efficiency, it is 0.1 to 100° C./min. more preferably 1 to 50°C/min, even more preferably 2 to 10°C/min.
- the internal pressure in the firing furnace is not particularly limited, and may be a positive pressure or a reduced pressure. It is preferably done in A specific degree of reduced pressure is preferably -5000 to -10 Pa, more preferably -2000 to -20 Pa, and even more preferably -1000 to -50 Pa.
- a specific degree of reduced pressure is preferably -5000 to -10 Pa, more preferably -2000 to -20 Pa, and even more preferably -1000 to -50 Pa.
- the degree of pressure reduction is -5000 Pa or more, the high airtightness and mechanical strength of the firing furnace are not required excessively, and the manufacturing cost can be reduced, which is preferable.
- the degree of pressure reduction is -10 Pa or less, clogging of the molybdenum oxide precursor compound at the discharge port of the firing furnace can be prevented, which is preferable.
- the temperature of the gas to be blown is preferably 5 to 500°C, more preferably 10 to 100°C.
- the blowing speed of the gas is preferably 1 to 500 L/min, more preferably 10 to 200 L/min, with respect to the effective volume of the firing furnace of 100 L.
- the temperature of the vaporized molybdenum trioxide vapor varies depending on the type of molybdenum oxide precursor compound used, it is preferably 200 to 2000°C, more preferably 400 to 1500°C. If the vaporized molybdenum trioxide vapor has a temperature of 2000° C. or less, it tends to be easily pulverized by blowing outside air (0 to 100° C.) in a cooling pipe.
- the discharge rate of molybdenum trioxide vapor discharged from the firing furnace depends on the amount of the molybdenum oxide precursor compound used, the amount of the metal compound, the temperature of the firing furnace, the blowing of gas into the firing furnace, and the diameter of the firing furnace exhaust port. can be controlled by
- the discharge rate of molybdenum trioxide vapor from the kiln to the cooling pipes is preferably 0.001 to 100 g/min, more preferably 0.1 to 50 g/min, although it depends on the cooling capacity of the cooling pipes. more preferred.
- the content of molybdenum trioxide vapor contained in the gas discharged from the firing furnace is preferably 0.01 to 1000 mg/L, more preferably 1 to 500 mg/L.
- the molybdenum trioxide vapor is then cooled and pulverized. Cooling of the molybdenum trioxide vapor is performed by lowering the temperature of the cooling pipe.
- the cooling means includes cooling by blowing gas into the cooling pipe, cooling by a cooling mechanism provided in the cooling pipe, and cooling by an external cooling device, as described above.
- the cooling temperature (the temperature of the cooling pipe) is not particularly limited, but is preferably -100 to 600°C, more preferably -50 to 400°C.
- the cooling rate of the molybdenum trioxide vapor is not particularly limited, it is preferably 100 to 100000°C/s, more preferably 1000 to 50000°C/s. There is a tendency that the higher the cooling rate of the molybdenum trioxide vapor, the smaller the particle size and the larger the specific surface area of the molybdenum trioxide powder.
- the temperature of the blown gas is preferably -100 to 300°C, more preferably -50 to 100°C.
- the blowing speed of the gas is preferably 0.1 to 20 m 3 /min, more preferably 1 to 10 m 3 /min.
- a gas blowing speed of 0.1 m 3 /min or more is preferable because a high cooling speed can be achieved and clogging of the cooling pipes can be prevented.
- the gas blowing speed is 20 m 3 /min or less, the expensive first blowing means (exhaust fan, etc.) becomes unnecessary, which is preferable because the manufacturing cost can be reduced.
- the powder obtained by cooling the molybdenum trioxide vapor is transported to and recovered by a recovery machine.
- the powder obtained by cooling the molybdenum trioxide vapor may be fired again at a temperature of 100°C to 500°C.
- the molybdenum trioxide powder obtained by the method for producing molybdenum trioxide powder of the present embodiment may be fired again at a temperature of 100°C to 500°C.
- the firing temperature for the second firing may be 120°C to 450°C or 140°C to 400°C.
- the firing time for the second firing may be, for example, 1 minute to 4 hours, 10 minutes to 5 hours, or 100 minutes to 6 hours.
- the molybdenum trioxide powder obtained by the method for producing molybdenum trioxide powder of the present embodiment is allowed to stand for 1 day to 2 weeks under conditions of an atmospheric temperature of 5° C. to 200° C. and a humidity of 50% to 95%.
- the ⁇ crystal structure in the molybdenum trioxide powder disappears, the ratio ( ⁇ (011)/ ⁇ (021)) becomes 0, and the crystal structure is all ⁇ crystals (100%).
- Molybdenum oxide is obtained.
- the ambient temperature is 5° C. to 5° C. It may be 200°C, or 15°C to 100°C.
- Humidity may be between 50% and 95% and may be between 70% and 95%.
- the leaving time may be 1 day to 2 weeks, or 1 day to 1 week.
- molybdenum trioxide powder that is entirely ⁇ crystals (100%) can be obtained.
- the solution is similarly prepared, and a particle diameter in the range of 0.015 to 500 ⁇ m is measured using a laser diffraction particle size distribution analyzer (SALD-7000 manufactured by Shimadzu Corporation). The distribution was measured and the median diameter D50 was calculated.
- SALD-7000 laser diffraction particle size distribution analyzer
- the molybdenum trioxide particles constituting the molybdenum trioxide powder are dispersed in ethanol, and are observed under a transmission electron microscope (TEM, JEM1400, manufactured by JEOL). Confirm the shape, measure its major axis (Feret diameter of the longest part observed) and minor axis (short Feret diameter in the direction perpendicular to the Feret diameter of the longest part), and calculate the average value It was obtained as a primary particle size.
- a similar operation was performed on 50 randomly selected primary particles, and the average particle size of the primary particles was calculated from the average value of the primary particle sizes of the primary particles. In particular, particles larger than 1 micron were also photographed with a scanning electron microscope (SEM) to obtain an average primary particle size as a reference value.
- SEM scanning electron microscope
- Molybdenum trioxide particles constituting the molybdenum trioxide powder are dispersed in ethanol, and a transmission electron microscope (TEM, JEM1400 manufactured by JEOL) is used to examine the shape of individual particles or the minimum unit constituting aggregates on a two-dimensional image. confirmed.
- TEM transmission electron microscope
- R C (%) ( IA / KA )/( ⁇ (IB/ KB )) ⁇ 100 (1)
- the RIR values used were values listed in the ICSD database, and the analysis was performed using an integrated powder X-ray analysis software (PDXL Version 2 manufactured by Rigaku). Conversion to MoS 2 was evaluated according to the following criteria. A: Conversion rate of 95% or more B: Conversion rate of less than 95%
- Molybdenum trioxide was produced using a RHK simulator (manufactured by Noritake Co., Ltd.) as a firing furnace and a VF-5N dust collector (manufactured by Amano Co., Ltd.) as a dust collector.
- a RHK simulator manufactured by Noritake Co., Ltd.
- VF-5N dust collector manufactured by Amano Co., Ltd.
- 1.5 kg of aluminum hydroxide manufactured by Nippon Light Metal Co., Ltd.
- 1 kg of molybdenum trioxide manufactured by Nippon Muki Co., Ltd.
- outside air (blowing speed: 150 L/min, outside air temperature: 25° C.) was introduced from the side and bottom surfaces of the firing furnace. After the molybdenum trioxide evaporated in the furnace, it was cooled in the vicinity of the dust collector and precipitated as particles, so molybdenum trioxide (1) was recovered by the dust collector.
- the recovered molybdenum trioxide (1) had a primary particle median diameter D50 of 87.8 nm as determined by dynamic light scattering, and the particle shape observed by TEM was ribbon or particulate. It was confirmed by fluorescent X-ray measurement that the purity of molybdenum trioxide (1) (content ratio of MoO 3 ) was 99.9% by mass.
- the content of ⁇ -crystals of MoO 3 can be determined from the obtained profile data by the RIR (Reference Intensity Ratio) method.
- MoO 3 ⁇ -crystal content (%) (I A /K A )/((I A /K A )+(I B /K B )) ⁇ 100 (2)
- RIR values values listed in the ICSD database can be used, and integrated powder X-ray analysis software (manufactured by Rigaku, PDXL Version 2) can be used for analysis.
- the content of ⁇ -crystals of MoO 3 obtained from equation (2) was 30%.
- Example 2 Molybdenum trioxide fired in the same manner as in Example 1 above was stored at 95% humidity and 50°C for 5 days. %) of molybdenum trioxide (2) could be recovered.
- the average crystallite size of the ⁇ -crystals was 20.4 nm. It was confirmed by fluorescent X-ray measurement that the purity of molybdenum trioxide (2) (content ratio of MoO 3 ) was 99.9% by mass. Further, molybdenum sulfide was obtained in the same manner as in Example 1 except that molybdenum trioxide (1) was replaced with molybdenum trioxide (2). As a result of structural analysis of the black powder obtained by XRD, it was confirmed that the conversion to MoS 2 was 99.9% and the reaction with sulfur occurred rapidly.
- Example 3 Molybdenum trioxide calcined in the same manner as in Example 1 above was heat-treated at 355° C. for 3 hours, and then the particles grew into ribbons or large particles, yielding molybdenum trioxide (3) that was all ⁇ crystals (100%). was able to retrieve it. The average crystallite size of the ⁇ -crystals was 27.6 nm. Molybdenum sulfide was obtained in the same manner as in Example 1, except that molybdenum trioxide (1) was replaced with molybdenum trioxide (3). As a result of structural analysis of the black powder obtained by XRD, it was confirmed that the conversion to MoS 2 was 99.9% and the reaction with sulfur occurred rapidly.
- molybdenum trioxide (1′) was subjected to crystal structure analysis by XRD in the same manner as in Example 1, and all molybdenum trioxide (1′) had an ⁇ crystal structure.
- the average crystallite size of ⁇ -crystals of molybdenum trioxide (1′) was 57.0 nm. It was confirmed by fluorescent X-ray measurement that the purity of molybdenum trioxide (1′) (content ratio of MoO 3 ) was 99.9% by mass.
- FIG. 2A shows the XRD profile of Example 1, the ⁇ crystal peak position map on the top, and the ⁇ crystal peak position map on the bottom (middle).
- FIG. 2B is the XRD profile of Comparative Example 1, and the upper part is an ⁇ -crystal peak position diagram.
- FIG. 3A is an analysis diagram of crystallite size and diffraction intensity in Example 1.
- FIG. 3B is an analysis diagram of the crystallite size and diffraction intensity of Comparative Example 1.
- FIG. 3A is an analysis diagram of crystallite size and diffraction intensity in Example 1.
- FIG. 3B is an analysis diagram of the crystallite size and diffraction intensity of Comparative Example 1.
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Abstract
Description
本願は、2021年3月24日に日本に出願された、特願2021-050489号に基づき優先権主張し、その内容をここに援用する。
(1)三酸化モリブデンの結晶構造を含む一次粒子の集合体を含有し、前記結晶構造は、平均結晶子サイズが50nm以下のα結晶を含み、動的光散乱法により求められる前記一次粒子のメディアン径D50が2000nm以下である、三酸化モリブデン粉体。
(2)蛍光X線(XRF)で測定されるMoO3の含有割合が、前記三酸化モリブデン粉体の総重量に対して99.5質量%以上である、前記(1)に記載の三酸化モリブデン粉体。
(3)BET法で測定される比表面積が10m2/g以上である、前記(1)又は(2)に記載の三酸化モリブデン粉体。
(4)前記結晶構造は、更に、平均結晶子サイズが50nm以下のβ結晶を含む、前記(1)~(3)のいずれか一つに記載の三酸化モリブデン粉体。
(5)X線源としてCu-Kα線を用いた粉末X線回折(XRD)から得られるプロファイルにおいて、MoO3のβ結晶の(011)面に帰属するピーク強度の、MoO3のα結晶の(021)面に帰属するピーク強度に対する比(β(011)/α(021))が0.1以上である、前記(4)に記載の三酸化モリブデン粉体。
(6)X線源としてCu-Kα線を用いた粉末X線回折(XRD)から得られるスペクトルにおいて、MoO3のβ結晶の(011)面に帰属するピーク強度の、MoO3のα結晶の(021)面に帰属するピーク強度に対する比(β(011)/α(021))が10.0以下である、前記(5)に記載の三酸化モリブデン粉体。
(7)前記一次粒子の形状が、ナノオーダーの厚みを有するリボン状またはシート状である、前記(1)~(6)のいずれか一つに記載の三酸化モリブデン粉体。
(8)酸化モリブデン前駆体化合物を気化させて、三酸化モリブデン蒸気を形成し、前記三酸化モリブデン蒸気を冷却することを含む、前記(1)~(7)のいずれか一つに記載の三酸化モリブデン粉体の製造方法。
(9)酸化モリブデン前駆体化合物、及び、前記酸化モリブデン前駆体化合物以外の金属化合物を含む原料混合物を焼成し、前記酸化モリブデン前駆体化合物を気化させて、三酸化モリブデン蒸気を形成することを含み、前記原料混合物100質量%に対する、前記金属化合物の割合が、酸化物換算で95質量%以下である、前記(8)に記載の三酸化モリブデン粉体の製造方法。
本実施形態の三酸化モリブデン粉体は、三酸化モリブデンの結晶構造を含む一次粒子の集合体を含有し、前記結晶構造は、平均結晶子サイズが50nm以下のα結晶を含み、動的光散乱法により求められる前記一次粒子のメディアン径D50が2000nm以下である。
一次粒子のメディアン径D50が上記の好ましい範囲内であると、三酸化モリブデン粉体の硫黄との反応性がより良好となりやすい。三酸化モリブデン粉体の一次粒子のメディアン径D50は、例えば動的光散乱式粒子径分布測定装置を用いて測定された体積基準の累積粒度分布から算出される。
α結晶の平均結晶子サイズが上記の好ましい範囲内であると、三酸化モリブデン粉体の硫黄との反応性がより良好となりやすい。
MoO3の含有割合が上記の好ましい範囲内であると、本実施形態の三酸化モリブデン粉体を硫化反応させることで、高純度な、不純物由来の硫化物が生成するおそれがない、保存安定性の良好な硫化モリブデンを得やすい。したがって、本実施形態の三酸化モリブデン粉体は、硫化モリブデンの前駆体として好適に用いることができる。
MoS2への転化率は、この黒色粉末をX線回折(XRD)測定することにより得られるプロファイルから、RIR(参照強度比)法により求めることができる。硫化モリブデン(MoS2)のRIR値KAおよび硫化モリブデン(MoS2)の(002)面または(003)面に帰属される、2θ=14.4°±0.5°付近のピークの積分強度IA、並びに、各酸化モリブデン(原料であるMoO3、および反応中間体であるMo9O25、Mo4O11、MoO2など)のRIR値KBおよび各酸化モリブデン(原料であるMoO3、および反応中間体であるMo9O25、Mo4O11、MoO2など)の最強線ピークの積分強度IBを用いて、次の式(1)からMoS2への転化率RCを求めることができる。
RC(%)=(IA/KA)/(Σ(IB/KB))×100 ・・・(1)
ここで、RIR値は、ICSDデータベースに記載されている値をそれぞれ用いることができ、解析には、統合粉末X線解析ソフトウェア(Rigaku社、PDXL Version 2)を用いることができる。
β結晶の平均結晶子サイズが上記の好ましい範囲内であると、三酸化モリブデン粉体の硫黄との反応性がより良好となりやすい。
本実施形態の三酸化モリブデン粒子において、前記比(β(011)/α(021))は、10.0以下であることが好ましい。
MoO3のα結晶の含有率(%) =(IA/KA)/((IA/KA)+(IB/KB))×100 ・・・(2)
ここで、RIR値は、ICSDデータベースに記載されている値をそれぞれ用いることができ、解析には、統合粉末X線解析ソフトウェア(Rigaku社製、PDXL Version 2)を用いることができる。
本実施形態の三酸化モリブデン粉体の製造方法は、前記実施形態の三酸化モリブデン粉体の製造方法であって、酸化モリブデン前駆体化合物を気化させて、三酸化モリブデン蒸気を形成し、前記三酸化モリブデン蒸気を冷却することを含む。
三酸化モリブデン蒸気の冷却は、冷却配管を低温にすることにより行われる。この際、冷却手段としては、上述のように冷却配管中への気体の送風による冷却、冷却配管が有する冷却機構による冷却、外部冷却装置による冷却等が挙げられる。
本実施形態の三酸化モリブデン粉体の製造方法で得られた三酸化モリブデン粉体を放置して結晶構造が全てα結晶(100%)である三酸化モリブデンが得る場合、雰囲気温度は5℃~200℃であってもよく、15℃~100℃であってもよい。湿度は、50%~95%であってもよく、70%~95%であってもよい。放置時間は、1日~2週間であってもよく、1日~1週間であってもよい。
エタノール10ccに三酸化モリブデン粉末0.1gを添加し、氷浴中で4時間超音波処理を施した後、さらにエタノールで、動的光散乱式粒子径分布測定装置(MicrotracBEL製Nanotrac WaveII)の測定可能範囲の濃度に適宜調整し、測定サンプルを得た。この測定サンプルを用い、動的光散乱式粒子径分布測定装置(MicrotracBEL製Nanotrac WaveII)により、粒径0.0001~10μmの範囲の粒子径分布を測定し、メディアン径D50を算出した。ただし、メディアン径D50が10μmを超えるものについては、同様に溶液を調整し、レーザ回折式粒度分布測定装置(島津製作所製 SALD-7000)により、粒径0.015~500μmの範囲の粒子径分布を測定し、メディアン径D50を算出した。
各実施例で得られたモリブデン化合物の試料を0.5mm深さの測定試料用ホルダーに充填し、それを広角X線回折(XRD)装置(リガク社製 UltimaIV、光学系は入射側は平行ビーム法+シンチレーションカウンター検出器、回転ステージを使用)にセットし、Cu/Kα線、40kV/40mA、スキャンスピード0.3°/min、ステップ0.02°、走査範囲10°以上70°以下の条件で測定を行った。
リガク社製XRDプロファイル解析ソフト(PDXL Version 2)を適用し、標準物質としてLaB6(NIST SRM660c LaB6 Standard Powder)にてXRD装置定数を確定し、Scherrer法(Scherrer定数K=0.94を使用)を用いて結晶子サイズを評価した。
三酸化モリブデン粉体を構成する三酸化モリブデン粒子を、エタノールに分散させ、透過型電子顕微鏡(TEM、JEOL社製JEM1400)二次元画像上の単独粒子、または凝集体を構成する最小単位の形状を確認した。
蛍光X線分析装置PrimusIV(株式会社リガク製)を用い、回収した三酸化モリブデン粉体の試料約70mgをろ紙にとり、PPフィルムをかぶせて組成分析を行った。XRF分析結果により求められるモリブデン量を、三酸化モリブデン粉体100質量%に対する三酸化モリブデン換算(質量%)により求めた。
三酸化モリブデン粉体又は硫化モリブデン粉体の試料について、比表面積計(マイクロトラックベル製、BELSORP-mini)にて測定し、BET法による窒素ガスの吸着量から測定された試料1g当たりの表面積を、比表面積(m2/g)として算出した。
評価対象の三酸化モリブデン粉体1.00gと、硫黄1.57gとを混合し、窒素雰囲気下、400℃で4時間焼成を行い、得られた黒色粉末をX線回折(XRD)測定した。次に、RIR(参照強度比)法により、硫化モリブデン(MoS2)のRIR値KAおよび硫化モリブデン(MoS2)の(002)面または(003)面に帰属される、2θ=14.4°±0.5°付近のピークの積分強度IA、並びに、各酸化モリブデン(原料であるMoO3、および反応中間体であるMo9O25、Mo4O11、MoO2など)のRIR値KBおよび各酸化モリブデン(原料であるMoO3、および反応中間体であるMo9O25、Mo4O11、MoO2など)の最強線ピークの積分強度IBを用いて、次の式(1)からMoS2への転化率RCを求めた。
RC(%)=(IA/KA)/(Σ(IB/KB))×100 ・・・(1)
ここで、RIR値は、ICSDデータベースに記載されている値をそれぞれ用い、解析には、統合粉末X線解析ソフトウェア(Rigaku社製 PDXL Version 2)を用いて行った。
MoS2への転化率は、以下の基準にしたがって評価した。
A:転化率95%以上
B:転化率95%未満
焼成炉としてRHKシミュレーター(株式会社ノリタケカンパニーリミテド製)を、集塵機としてはVF-5N集塵機(アマノ株式会社製)を用いて三酸化モリブデンの製造を行った。
水酸化アルミニウム(日本軽金属株式会社製)1.5kgと、三酸化モリブデン(日本無機株式会社製)1kgと、を混合し、次いでサヤに仕込み、温度1100℃で10時間焼成した。焼成中、焼成炉の側面および下面から外気(送風速度:150L/min、外気温度:25℃)を導入した。三酸化モリブデンは炉内で蒸発後、集塵機付近で冷却され粒子として析出するため、集塵機により三酸化モリブデン(1)を回収した。
MoO3のα結晶の含有率(%) =(IA/KA)/((IA/KA)+(IB/KB))×100 ・・・(2)
ここで、RIR値は、ICSDデータベースに記載されている値をそれぞれ用いることができ、解析には、統合粉末X線解析ソフトウェア(Rigaku社製、PDXL Version 2)を用いることができる。式(2)より求めたMoO3のα結晶の含有率は30%であった。
上記の実施例1と同じ手法で焼成した三酸化モリブデンを湿度95%、50℃、5日保管後、粒子がリボン又は針状(長さ1~2μm)に成長し、全てがα結晶(100%)である三酸化モリブデン(2)を回収することができた。そのα結晶の平均結晶子サイズは20.4nmであった。蛍光X線測定にて、三酸化モリブデン(2)の純度(MoO3の含有割合)は99.9質量%であることが確認できた。
また、三酸化モリブデン(1)に替えて三酸化モリブデン(2)を用いた以外は実施例1と同様にして硫化モリブデンを得た。XRDにて得られた黒色粉末の構造解析を行った結果、MoS2への転化率が99.9%であり、硫黄との反応が速やかに起こることが確認できた。
上記の実施例1と同じ手法で焼成した三酸化モリブデンを355℃3時間加熱処理後、粒子がリボンまたは大きい粒子に成長し、全てがα結晶(100%)である三酸化モリブデン(3)を回収することができた。そのα結晶の平均結晶子サイズは27.6nmであった。
また、三酸化モリブデン(1)に替えて三酸化モリブデン(3)を用いた以外は実施例1と同様にして硫化モリブデンを得た。XRDにて得られた黒色粉末の構造解析を行った結果、MoS2への転化率が99.9%であり、硫黄との反応が速やかに起こることが確認できた。
市販のマイクロサイズの三酸化モリブデン(1’)(日本無機化学社製、Lot番号は00501-C)1.00g(6.94mmol)と、硫黄(関東化学製、粉末)1.56g(48.6mmol)とを混合し、高温管状炉(山田電機株式会社製、TSS型)を用いて、窒素雰囲気下、400℃で4時間焼成を行い、黒色粉末1.13gを得た。XRDにてこの黒色粉末の構造解析を行った結果、MoS2、MoO2、MoO3の混合物であり、硫黄との反応性が低い事が確認された。
また、三酸化モリブデン(1’)について、実施例1と同様にXRDによる結晶構造解析を行ったところ、三酸化モリブデン(1’)は全てα結晶構造であった。また、実施例1と同様に結晶子サイズを評価したところ、三酸化モリブデン(1’)のα結晶の平均結晶子サイズは57.0nmであった。蛍光X線測定にて、三酸化モリブデン(1’)の純度(MoO3の含有割合)は99.9質量%であることが確認できた。
2 焼成炉
3 冷却配管
4 回収機
5 排気口
6 開度調整ダンパー
7 観察窓
8 排風装置
9 外部冷却装置
Claims (9)
- 三酸化モリブデンの結晶構造を含む一次粒子の集合体を含有し、
前記結晶構造は、平均結晶子サイズが50nm以下のα結晶を含み、
動的光散乱法により求められる前記一次粒子のメディアン径D50が2000nm以下である、三酸化モリブデン粉体。 - 蛍光X線(XRF)で測定されるMoO3の含有割合が、前記三酸化モリブデン粉体の総重量に対して99.5質量%以上である、請求項1に記載の三酸化モリブデン粉体。
- BET法で測定される比表面積が10m2/g以上である、請求項1又は2に記載の三酸化モリブデン粉体。
- 前記結晶構造は、更に、平均結晶子サイズが50nm以下のβ結晶を含む、請求項1~3のいずれか一項に記載の三酸化モリブデン粉体。
- X線源としてCu-Kα線を用いた粉末X線回折(XRD)から得られるプロファイルにおいて、MoO3のβ結晶の(011)面に帰属するピーク強度の、MoO3のα結晶の(021)面に帰属するピーク強度に対する比(β(011)/α(021))が0.1以上である、請求項4に記載の三酸化モリブデン粉体。
- X線源としてCu-Kα線を用いた粉末X線回折(XRD)から得られるスペクトルにおいて、MoO3のβ結晶の(011)面に帰属するピーク強度の、MoO3のα結晶の(021)面に帰属するピーク強度に対する比(β(011)/α(021))が10.0以下である、請求項5に記載の三酸化モリブデン粉体。
- 前記一次粒子の形状が、リボン状またはシート状である、請求項1~6のいずれか一項に記載の三酸化モリブデン粉体。
- 酸化モリブデン前駆体化合物を気化させて、三酸化モリブデン蒸気を形成し、
前記三酸化モリブデン蒸気を冷却することを含む、
請求項1~7のいずれか一項に記載の三酸化モリブデン粉体の製造方法。 - 酸化モリブデン前駆体化合物、及び、前記酸化モリブデン前駆体化合物以外の金属化合物を含む原料混合物を焼成し、前記酸化モリブデン前駆体化合物を気化させて、三酸化モリブデン蒸気を形成することを含み、
前記原料混合物100質量%に対する、前記金属化合物の割合が、酸化物換算で95質量%以下である、請求項8に記載の三酸化モリブデン粉体の製造方法。
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