WO2024057829A1 - Procédé de broyage d'un polymère à base de cellulose - Google Patents
Procédé de broyage d'un polymère à base de cellulose Download PDFInfo
- Publication number
- WO2024057829A1 WO2024057829A1 PCT/JP2023/029954 JP2023029954W WO2024057829A1 WO 2024057829 A1 WO2024057829 A1 WO 2024057829A1 JP 2023029954 W JP2023029954 W JP 2023029954W WO 2024057829 A1 WO2024057829 A1 WO 2024057829A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cellulose
- pulp
- acid
- roller mill
- polymer
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 64
- 229920003174 cellulose-based polymer Polymers 0.000 title claims abstract description 41
- 239000001913 cellulose Substances 0.000 claims description 136
- 229920002678 cellulose Polymers 0.000 claims description 127
- 229920000642 polymer Polymers 0.000 claims description 47
- 238000010298 pulverizing process Methods 0.000 claims description 45
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 36
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 36
- 150000003839 salts Chemical class 0.000 claims description 27
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 25
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000010980 cellulose Nutrition 0.000 description 125
- 238000011282 treatment Methods 0.000 description 50
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 44
- 239000002245 particle Substances 0.000 description 37
- 239000002994 raw material Substances 0.000 description 37
- 239000007864 aqueous solution Substances 0.000 description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000006467 substitution reaction Methods 0.000 description 17
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000005903 acid hydrolysis reaction Methods 0.000 description 10
- 229920003124 powdered cellulose Polymers 0.000 description 10
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- 229940126062 Compound A Drugs 0.000 description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 9
- 229920002201 Oxidized cellulose Polymers 0.000 description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 229940107304 oxidized cellulose Drugs 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 8
- 238000010411 cooking Methods 0.000 description 8
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000006266 etherification reaction Methods 0.000 description 6
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- -1 nitroxy radicals Chemical class 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
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- 238000002156 mixing Methods 0.000 description 5
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
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- 229920000875 Dissolving pulp Polymers 0.000 description 4
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- 229920001131 Pulp (paper) Polymers 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
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- 239000004020 conductor Substances 0.000 description 4
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
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- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 230000021523 carboxylation Effects 0.000 description 3
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- 239000007772 electrode material Substances 0.000 description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
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- 239000007773 negative electrode material Substances 0.000 description 3
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000004155 Chlorine dioxide Substances 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
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- 239000008103 glucose Substances 0.000 description 2
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- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
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- 150000003944 halohydrins Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009897 hydrogen peroxide bleaching Methods 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005517 mercerization Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-N methyl hydrogen carbonate Chemical group COC(O)=O CXHHBNMLPJOKQD-UHFFFAOYSA-N 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 1
- 229940099402 potassium metaphosphate Drugs 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C15/00—Disintegrating by milling members in the form of rollers or balls co-operating with rings or discs
- B02C15/04—Mills with pressed pendularly-mounted rollers, e.g. spring pressed
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
Definitions
- the present invention relates to a method for pulverizing cellulose polymers.
- cellulose-based polymers such as carboxymethylcellulose are used in various fields for reasons such as high safety, and their use is being considered.
- carboxymethylcellulose or a salt thereof is a product in which a carboxymethyl group is bonded to a part of the hydroxyl group of a glucopyranose monomer that constitutes the cellulose skeleton, or a carboxymethyl group is salt.
- the quality of CMC can be adjusted by adjusting the degree of substitution of carboxymethyl groups, the length of the cellulose skeleton, etc. It is used as a binding agent, binder, water absorbing material, water retaining agent, emulsion stabilizer, etc.
- it since it is derived from natural cellulose, it is an extremely environmentally friendly material that has gradual biodegradability and can be disposed of by incineration, and it is predicted that the applications of CMC will expand in the future.
- Patent Document 1 describes that cellulose fiber is better than carboxymethyl cellulose when used as a binder for adhering the electrode active material of a non-aqueous secondary battery to a current collector, for example.
- the applications of cellulose-based polymers have been limited due to
- An object of the present invention is to provide a method for pulverizing cellulose polymers that can stably produce cellulose polymers having a particle size of less than 50 ⁇ m.
- the present inventors found that the above object could be achieved by performing pulverization under predetermined conditions, and found that the above problems could be solved.
- the present invention it is possible to provide a method for pulverizing a cellulose-based polymer that can stably produce a cellulose-based polymer having a particle size of less than 50 ⁇ m.
- FIG. 1 is a schematic diagram showing an example of a roller mill used in the present invention.
- the method for pulverizing cellulose polymers of the present invention will be explained below.
- the cellulose polymer pulverization method of the present invention is a cellulose polymer pulverization method using a roller mill, wherein the supply rate of the cellulose polymer to the roller mill is 30 to 150 kg/h, and the turntable of the roller mill is The rotation speed is 50 to 500 rpm, and the amount of air supplied to the roller mill is 5 to 50 m 3 /min.
- cellulose polymer In the present invention, as the cellulose-based polymer to be pulverized, any compound derived from cellulose can be used without particular limitation, but it is preferable to use a chemically modified cellulose-based polymer or unmodified pulp.
- Cellulose-based polymers can be obtained using cellulose as a raw material. That is, cellulose that can be used as a cellulose raw material in the present invention is a polysaccharide with a structure in which D-glucopyranose (simply referred to as "glucose residue” or “anhydroglucose”) is linked by ⁇ , 1-4 bonds. means. Cellulose is generally classified into natural cellulose, regenerated cellulose, fine cellulose, microcrystalline cellulose excluding non-crystalline regions, etc. based on its origin, manufacturing method, etc.
- Examples of natural cellulose include bleached pulp or unbleached pulp (bleached wood pulp or unbleached wood pulp); linters, purified linters; cellulose produced by microorganisms such as acetic acid bacteria, and the like.
- the raw material for bleached pulp or unbleached pulp is not particularly limited, and examples thereof include wood, cotton, straw, bamboo, and the like.
- the method for producing bleached pulp or unbleached pulp is not particularly limited, and may be a mechanical method, a chemical method, or a combination of the two in between.
- Examples of bleached pulp or unbleached pulp classified by manufacturing method include mechanical pulp, chemical pulp, groundwood pulp, sulfite pulp, and kraft pulp.
- dissolving pulp may be used in addition to papermaking pulp. Dissolving pulp is a chemically refined pulp that is mainly used after being dissolved in chemicals, and is the main raw material for artificial fibers, cellophane, etc.
- regenerated cellulose examples include those obtained by dissolving cellulose in some kind of solvent such as a cupric ammonia solution, a cellulose xanthate solution, or a morpholine derivative, and respinning the resulting cellulose.
- solvent such as a cupric ammonia solution, a cellulose xanthate solution, or a morpholine derivative
- Fine cellulose is obtained by depolymerizing cellulose materials such as the above-mentioned natural cellulose and regenerated cellulose (for example, acid hydrolysis, alkaline hydrolysis, enzymatic decomposition, blasting treatment, vibrating ball mill treatment, etc.) Examples include those obtained by mechanically processing the above-mentioned cellulose-based materials.
- ⁇ Chemically modified cellulose polymer for example, a cellulose polymer obtained by anion modification or a cellulose polymer obtained by cation modification may be used.
- cellulose-based polymers obtained by anionic modification include carboxylated cellulose (also called oxidized cellulose), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and phosphate-esterified cellulose. may be in the form of a salt. Although the type of salt does not matter, it is preferable to select a suitable salt, such as a metal salt such as a sodium salt or an ammonium salt, depending on the use and purpose. Although there are no particular limitations on the cellulose-based polymer used in the present invention, it is preferable to use carboxymethylcellulose and/or a salt thereof.
- carboxylated cellulose (oxidized cellulose)
- carboxylated cellulose (oxidized cellulose)
- carboxylated cellulose oxidized cellulose
- it can be obtained by carboxylating (oxidizing) a cellulose raw material by a known method.
- the amount of carboxyl groups is 2.4 to 9.3 mmol/g, preferably 3.1 to 8.0 mmol/g, more preferably 3. It is preferable to adjust it to 7 to 6.8 mmol/g.
- a cellulosic raw material is oxidized in water with an oxidizing agent in the presence of an N-oxyl compound and a compound selected from the group consisting of bromides, iodides or mixtures thereof.
- an oxidizing agent in the presence of an N-oxyl compound and a compound selected from the group consisting of bromides, iodides or mixtures thereof.
- the primary hydroxyl group at the C6 position of the glucopyranose ring on the cellulose surface is selectively oxidized, resulting in cellulose fibers having an aldehyde group and a carboxy group (-COOH) or carboxylate group (-COO-) on the surface.
- the concentration of cellulose during the reaction is not particularly limited, but is preferably 5% by mass or less.
- the N-oxyl compound refers to a compound that can generate nitroxy radicals.
- any compound can be used as long as it promotes the desired oxidation reaction. Examples include 2,2,6,6-tetramethylpiperidine-1-oxyradical (TEMPO) and its derivatives (eg, 4-hydroxyTEMPO).
- TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyradical
- 4-hydroxyTEMPO 4-hydroxyTEMPO
- the amount of the N-oxyl compound used is not particularly limited as long as it is a catalytic amount that can oxidize cellulose as a raw material.
- it is preferably 0.01 to 10 mmol, more preferably 0.01 to 1 mmol, and even more preferably 0.05 to 0.5 mmol, per 1 g of bone dry cellulose. Further, it is preferably about 0.1 to 4 mmol/L to the reaction system.
- a bromide is a compound containing bromine, and examples thereof include alkali metal bromides that can be dissociated and ionized in water.
- iodide is a compound containing iodine, and examples thereof include alkali metal iodide.
- the amount of bromide or iodide to be used can be selected within a range that can promote the oxidation reaction.
- the total amount of bromide and iodide is, for example, preferably 0.1 to 100 mmol, more preferably 0.1 to 10 mmol, and even more preferably 0.5 to 5 mmol, per 1 g of bone dry cellulose.
- the oxidizing agent known ones can be used, such as halogen, hypohalous acid, halous acid, perhalogenic acid, salts thereof, halogen oxides, peroxides, and the like.
- sodium hypochlorite is preferred because it is inexpensive and has a low environmental impact.
- the amount of the oxidizing agent used is, for example, preferably 0.5 to 500 mmol, more preferably 0.5 to 50 mmol, even more preferably 1 to 25 mmol, and most preferably 3 to 10 mmol, per 1 g of bone dry cellulose. Further, for example, it is preferably 1 to 40 mol per 1 mol of the N-oxyl compound.
- the reaction temperature is preferably 4 to 40°C, and may be room temperature of about 15 to 30°C.
- carboxy groups are generated in the cellulose, so a decrease in the pH of the reaction solution is observed.
- an alkaline solution such as an aqueous sodium hydroxide solution to maintain the pH of the reaction solution at about 8 to 12, preferably about 10 to 11. Water is preferable as the reaction medium because of ease of handling and the fact that side reactions are less likely to occur.
- the reaction time in the oxidation reaction can be appropriately set according to the degree of progress of oxidation, and is usually about 0.5 to 6 hours, for example about 0.5 to 4 hours.
- the oxidation reaction may be carried out in two stages. For example, by oxidizing the oxidized cellulose obtained by filtration after the completion of the first-stage reaction again under the same or different reaction conditions, the efficiency can be improved without being inhibited by the salt produced as a by-product in the first-stage reaction. Can be oxidized well.
- Another example of the carboxylation (oxidation) method is a method of oxidizing a cellulose raw material by bringing it into contact with a gas containing ozone. This oxidation reaction oxidizes the hydroxyl groups at at least the 2- and 6-positions of the glucopyranose ring and causes decomposition of the cellulose chain.
- the ozone concentration in the ozone-containing gas is preferably 50 to 250 g/m 3 , more preferably 50 to 220 g/m 3 .
- the amount of ozone added to the cellulose raw material is preferably 0.1 to 30 parts by mass, more preferably 5 to 30 parts by mass, when the solid content of the cellulose raw material is 100 parts by mass.
- the ozone treatment temperature is preferably 0 to 50°C, more preferably 20 to 50°C.
- the ozone treatment time is not particularly limited, but is about 1 to 360 minutes, preferably about 30 to 360 minutes. When the ozone treatment conditions are within these ranges, excessive oxidation and decomposition of cellulose can be prevented, resulting in a good yield of oxidized cellulose.
- additional oxidation treatment may be performed using an oxidizing agent.
- the oxidizing agent used in the additional oxidation treatment is not particularly limited, but examples include chlorine-based compounds such as chlorine dioxide and sodium chlorite, oxygen, hydrogen peroxide, persulfuric acid, and peracetic acid.
- the additional oxidation treatment can be performed by dissolving these oxidizing agents in water or a polar organic solvent such as alcohol to prepare an oxidizing agent solution, and immersing the cellulose raw material in the solution.
- the amount of carboxy groups in the oxidized cellulose can be adjusted by controlling the reaction conditions such as the amount of the oxidizing agent added and the reaction time.
- Carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, or hydroxypropyl cellulose which are exemplified above as cellulose-based polymers obtained by anion modification, may be obtained by etherifying cellulose raw materials by a known method, or commercially available products. May be used.
- Carboxymethylcellulose or its salt For example, when obtaining carboxymethylcellulose or a salt thereof (hereinafter sometimes referred to as "CMC"), the method for producing carboxymethylcellulose or a salt thereof is not limited, and any known method for producing carboxymethylcellulose or a salt thereof may be applied. can. That is, after treating cellulose, which is a raw material, with a mercerizing agent (alkali) to prepare mercerized cellulose (alkali cellulose), an etherifying agent is added to cause an etherification reaction to produce carboxymethylcellulose or its salt in the present invention. can be manufactured.
- a mercerizing agent alkali
- any of the above-mentioned celluloses can be used without particular limitation, but those with high cellulose purity are preferred, and it is particularly preferred to use dissolving pulp and linters. By using these, highly pure carboxymethyl cellulose or a salt thereof can be obtained.
- alkali metal hydroxide salts such as sodium hydroxide and potassium hydroxide can be used.
- etherification agent monochloroacetic acid, monochloroacetic acid soda, etc. can be used.
- the molar ratio of the mercerizing agent to the etherifying agent in the general production method of water-soluble carboxymethylcellulose is generally 2.00 to 2.45 when monochloroacetic acid is used as the etherifying agent. .
- the reason for this is that if it is less than 2.00, the etherification reaction may not be carried out sufficiently, resulting in unreacted monochloroacetic acid remaining and being wasted; This is because there is a possibility that a side reaction between an excess of the mercerizing agent and monochloroacetic acid may proceed to produce an alkali metal salt of glycolic acid, which may be uneconomical.
- carboxymethylcellulose or its salt may be used as it is, or after treatment if necessary.
- Commercially available products include, for example, the trade name "Sunrose” (sodium salt of carboxymethyl cellulose) manufactured by Nippon Paper Industries, Ltd.
- carboxymethylcellulose or salt thereof of the present invention has a degree of carboxymethyl substitution per anhydroglucose unit of 0.5 or more, more preferably 0.6 or more. If the degree of carboxymethyl substitution is less than 0.5, the solubility in water may be insufficient.
- anhydroglucose units refer to individual anhydroglucoses (glucose residues) that constitute cellulose.
- the degree of carboxymethyl substitution also referred to as the degree of etherification refers to the proportion of hydroxyl groups (-OH) in glucose residues constituting cellulose that are substituted with carboxymethyl ether groups (-OCH 2 COOH). show. Note that the degree of carboxymethyl substitution may be abbreviated as DS or CM-DS.
- the upper limit of the degree of carboxymethyl substitution per anhydroglucose unit of carboxymethyl cellulose or its salt is preferably 1.2 or less, more preferably 1.0 or less.
- the method for measuring the degree of substitution of carboxymethyl groups is as follows: Weigh approximately 2.0 g of the sample accurately and place it in a 300 mL Erlenmeyer flask with a stopper. Add 100 mL of a solution prepared by adding 100 mL of special grade concentrated nitric acid to 1000 mL of methanol, and shake for 3 hours to convert carboxymethyl cellulose salt (CMC) to H-CMC (hydrogen form carboxymethyl cellulose). Accurately weigh 1.5 to 2.0 g of the bone-dried H-CMC and place it in a 300 mL Erlenmeyer flask with a stopper.
- CMC carboxymethyl cellulose salt
- the CMC used in the present invention may be one type, or a combination of two or more types of CMC having different degrees of etherification, CM-DS, viscosity, molecular weight, etc. Note that the viscosity will be described later.
- the cellulose When using phosphoric acid esterified cellulose as a cellulose-based polymer obtained by anion modification, the cellulose can be prepared by mixing the powder or aqueous solution of phosphoric acid compound A with the cellulose raw material described above, or by adding phosphoric acid to a slurry of the cellulose raw material. It can be obtained by adding an aqueous solution of Compound A.
- Examples of the phosphoric acid compound A include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, polyphosphonic acid, or esters thereof. These may be in the form of salts. Among these, compounds having a phosphoric acid group are preferred because they are low cost and easy to handle. Examples of compounds having a phosphoric acid group include phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium metaphosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, and phosphoric acid.
- Examples include tripotassium acid, potassium pyrophosphate, potassium metaphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium metaphosphate. These can be used alone or in combination of two or more.
- phosphoric acid, a sodium salt of phosphoric acid, a potassium salt of phosphoric acid, and an ammonium salt of phosphoric acid are more preferable from the viewpoint of high efficiency of introducing a phosphoric acid group and easy industrial application.
- Particularly preferred are sodium dihydrogen phosphate and disodium hydrogen phosphate.
- the phosphoric acid compound A in the form of an aqueous solution, since the uniformity of the reaction and the efficiency of introducing phosphoric acid groups are increased.
- the pH of the aqueous solution of the phosphoric acid compound A is preferably 7 or less since this increases the efficiency of introducing phosphoric acid groups, but the pH is preferably 3 to 7 from the viewpoint of suppressing hydrolysis of pulp fibers.
- a phosphoric acid compound A is added to a dispersion of a cellulose raw material having a solid content concentration of 0.1 to 10% by mass with stirring to introduce phosphoric acid groups into the cellulose.
- the amount of phosphoric acid compound A added is preferably 0.2 to 500 parts by mass, more preferably 1 to 400 parts by mass as the amount of phosphorus element. If the proportion of phosphoric acid compound A is equal to or higher than the lower limit, the yield of fine fibrous cellulose can be further improved. However, if the above upper limit is exceeded, the effect of improving the yield reaches a ceiling, which is not preferable from a cost standpoint.
- compound B is not particularly limited, but is preferably a nitrogen-containing compound that exhibits basicity.
- “Basic” herein is defined as the aqueous solution exhibiting a pink to red color in the presence of the phenolphthalein indicator, or the pH of the aqueous solution being greater than 7.
- the basic nitrogen-containing compound used in the present invention is not particularly limited as long as it exhibits the effects of the present invention, but compounds having an amino group are preferred.
- Examples include, but are not limited to, urea, methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, and hexamethylenediamine.
- urea is preferred because it is low cost and easy to handle.
- the amount of compound B added is preferably 2 to 1000 parts by weight, more preferably 100 to 700 parts by weight, based on 100 parts by weight of the solid content of the cellulose raw material.
- the reaction temperature is preferably 0 to 95°C, more preferably 30 to 90°C.
- the reaction time is not particularly limited, but is approximately 1 to 600 minutes, more preferably 30 to 480 minutes.
- cellulose can be prevented from being excessively esterified and easily dissolved, and the yield of phosphoric acid esterified cellulose can be improved.
- After dehydrating the obtained phosphoric acid esterified cellulose suspension it is preferably heat-treated at 100 to 170° C. from the viewpoint of suppressing hydrolysis of cellulose. Further, during heat treatment, it is preferable to heat at 130° C. or lower, preferably 110° C. or lower while water is contained, and after removing water, heat treatment at 100 to 170° C.
- the degree of phosphoric acid group substitution per glucose unit of the phosphoric acid esterified cellulose is preferably 0.001 to 0.40.
- a cationically modified cellulose polymer As the chemically modified cellulose polymer, cellulose obtained by further cationizing the carboxylated cellulose can be used.
- the cationically modified cellulose is produced by adding a cationizing agent such as glycidyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrialkylammonium halide or its halohydrin type to the carboxylated cellulose raw material, and an alkali metal hydroxide as a catalyst. (sodium hydroxide, potassium hydroxide, etc.) in the presence of water or an alcohol having 1 to 4 carbon atoms.
- the degree of cation substitution per glucose unit is preferably 0.02 to 0.50.
- the degree of cation substitution can be adjusted by adjusting the amount of the cationizing agent to be reacted and the composition ratio of water or alcohol having 1 to 4 carbon atoms.
- the viscosity of a 1% by mass aqueous solution of the chemically modified cellulose polymer to be pulverized at 25°C as measured by a B-type viscometer (30 rpm) is preferably 1,000 to 20,000 mPa ⁇ s, or more. It is preferably 1,500 to 15,000 mPa ⁇ s, more preferably 1,500 to 10,000 mPa ⁇ s.
- the viscosity measurement method is as follows: The chemically modified cellulose polymer to be crushed is measured into a 1000 mL glass beaker, dispersed in 900 mL of distilled water, and the solid content is 1% (w/v). Prepare an aqueous dispersion so that The aqueous dispersion is stirred at 25° C. using a stirrer at 600 rpm for 3 hours. Thereafter, according to the method of JIS-Z-8803, using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.), No. Measure the viscosity after 3 minutes with 4 rotors/30 rpm.
- the unmodified pulp is not particularly limited, but it is preferable to use powdered cellulose using unmodified pulp.
- powdered cellulose using unmodified pulp include those obtained by mechanically crushing pulp or acid hydrolyzing it to powder.
- the method for producing powdered cellulose is not particularly limited as long as it is a method for obtaining powdered cellulose from a cellulose raw material, but examples include a method that includes at least a pulverization process, and it is easy to obtain powdered cellulose with few impurities. A method in which an acid hydrolysis treatment is further performed is preferred.
- the cellulose raw materials include those mentioned above, but it is preferable to use pulp, and pulp derived from wood is more preferable.
- pulp derived from wood include pulp derived from broad-leaved trees and pulp derived from coniferous trees.
- Examples of the method for preparing wood-derived pulp include a method including a treatment using a pulping method (cooking method).
- the pulping method dissolves and removes the colored substance lignin, making it possible to obtain pulp with a high degree of whiteness.
- the pulping method (cooking method) include sulfite cooking, kraft cooking, soda quinone cooking, and organosolve cooking, with kraft pulp being preferred from an environmental standpoint.
- Bleaching treatment methods include, for example, chlorine treatment (C), chlorine dioxide bleaching (D), alkaline extraction (E), hypochlorite bleaching (H), Hydrogen peroxide bleaching (P), alkaline hydrogen peroxide treatment stage (Ep), alkaline hydrogen peroxide/oxygen treatment stage (Eop), ozone treatment (Z), chelation treatment (Q), and two or more of these treatments.
- chlorine treatment C
- chlorine dioxide bleaching D
- alkaline extraction E
- hypochlorite bleaching H
- Hydrogen peroxide bleaching P
- alkaline hydrogen peroxide treatment stage Ep
- alkaline hydrogen peroxide/oxygen treatment stage Eop
- ozone treatment Z
- chelation treatment Q
- Examples of combinations (sequences) of two or more processes include D-E/P-D, C/D-E-HD, Z-E-D-PZ/D-Ep-D, and Z/D- Ep-DP, D-Ep-D, D-Ep-DP, D-Ep-PD, Z-Eop-DD, Z/D-Eop-D, Z/D-Eop-D- ED (the "/" in the sequence means that the processes before and after the "/" are performed consecutively without washing).
- Bleaching treatment is not limited to the above example, and may be any commonly used method. Pulp that has undergone bleaching treatment is usually in a fluid state (fluid pulp). The whiteness of the pulp is preferably 80% or more based on ISO 2470.
- the acid used in the acid hydrolysis treatment examples include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid.
- the acid concentration is not particularly limited, but from the viewpoint of maintaining the degree of polymerization and whiteness, it is preferably lower than the acid concentration in the acid hydrolysis treatment for the conventional production of powdered cellulose, more preferably 0.4 to 2.0N, and more preferably 0.5 to 1.5N. If the acid concentration is less than 0.4N, the depolymerization of cellulose by the acid is suppressed and the decrease in the degree of polymerization of cellulose can be reduced, but fine pulverization may be difficult.
- the reaction conditions for the acid hydrolysis treatment are not particularly limited, but the reaction temperature is usually 80 to 100°C, and the reaction time is usually 30 minutes to 3 hours.
- the cellulose raw material Prior to the acid hydrolysis treatment, the cellulose raw material may be pretreated. Examples include slurrying the cellulose raw material (preparation of a dispersion) and adjusting the concentration of the cellulose raw material. The concentration of the cellulose raw material is usually 3 to 10% by weight (based on solid content) based on the dispersion.
- a treatment to increase the pulp density is usually performed before hydrolysis.
- a dehydrator such as a screw press or a belt filter may be used to adjust (concentrate) the cellulose raw material concentration.
- the acid hydrolysis treatment may be performed on a slurry of cellulose raw material, or may be performed on a sheet-shaped cellulose raw material. When the cellulose raw material is a dry sheet of pulp, the acid hydrolysis treatment is usually performed after the pulp is loosened. When loosening the pulp, a crusher such as a roll crusher may be used.
- the neutralization treatment may be performed by adding an alkaline agent.
- the deliquid treatment is usually a solid-liquid separation treatment, and waste acid can be separated from the hydrolyzed product.
- the hydrolyzate may undergo a drying (dehydration) treatment.
- the solid content concentration can be adjusted and the physical properties of the powdered cellulose can be easily controlled.
- the solid content concentration is usually adjusted to 15% or more, preferably 20% or more.
- a flash dryer For drying, it is preferable to use a flash dryer. As a result, regardless of whether the processed material after hydrolysis is a cake-like solid, slurry, solution, etc., it is possible to apply high-speed hot air while dispersing it in the air stream, and also to utilize the depressurizing effect inside the dryer. It can be dried instantly. In addition, since the exposure time to hot air is extremely short, the product temperature can be kept low, making it ideal for drying products that are sensitive to heat or products with low melting points.
- the conditions for drying using the flash dryer are not particularly limited and can be set as appropriate, but an example is as follows.
- the outlet drying temperature is usually 80 to 180°C, preferably 90 to 160°C.
- the amount of air supplied is usually 150 to 350 m 3 /h, preferably 160 to 320 m 3 /h.
- the product is sprayed and instantly dried with hot air to produce granules. Therefore, it is often not suitable for drying solid or semi-solid objects with low moisture content, and the particles are more likely to be exposed to high heat instantaneously than when drying with a flash dryer, which may affect the product. be done.
- the unmodified pulp may be pulverized by mechanically pulverizing the processed material that has undergone the previous step.
- a classification process may be performed simultaneously with the pulverization or after the pulverization.
- the crusher used for the powdering treatment of unmodified pulp can be used without any particular restrictions, but examples include a jaw crusher (manufactured by Makino Co., Ltd.), a pulverizer (manufactured by Hosokawa Micron Co., Ltd.), a super micron mill (manufactured by Hosokawa Micron Co., Ltd.), Tornado mill (manufactured by Nikkiso Co., Ltd.), Jiyu crusher (manufactured by Nara Kikai Seisakusho Co., Ltd.), Turbo mill (manufactured by Freund Sangyo Co., Ltd.), Spar powder mill (manufactured by Nishimura Kikai Seisakusho Co., Ltd.), Blade mill (Nissin Engineering Co., Ltd.) It is preferable to use a supersonic jet mill (manufactured by Nippon Pneumatic Industries Co., Ltd.), or a current jet (manufactured by Nisshin Engineering Co.,
- the conditions for the powdering treatment of the unmodified pulp or the classification treatment performed as necessary can be appropriately set so as to obtain the desired powdered cellose.
- the processing conditions can be adjusted with reference to a calibration curve created from the pulverization conditions (eg, processing time, input amount) and desired physical properties of the powdered cellulose.
- At least one other component for example, an organic component, an inorganic component
- the pulverization treatment together with the acid-hydrolyzed product, if necessary.
- functionality can be imparted to the powdered cellulose or the functionality can be improved.
- the amounts of other components to be blended may be appropriately selected.
- chemical treatment may be performed as necessary.
- any treatment that does not pose a risk of significantly impairing the degree of polymerization of the cellulose raw material can be selected as appropriate.
- the timing of the chemical treatment includes, for example, before the acid hydrolysis treatment and at the same time as the pulverization treatment, but is not particularly limited.
- a roller mill is usually configured with a main shaft that is a vertical rotating shaft, a turntable that is attached to the main shaft and rotates in a substantially horizontal direction when the main shaft rotates, and a turntable that can roll or rotate on the turntable. It has a configuration in which when the turntable rotates, the object to be crushed is crushed by shearing and/or centrifugal force between the roller and the turntable.
- Roller mills can be used without any particular restrictions, but roller mills (manufactured by Kotobuki Giken Co., Ltd.), VX mills (manufactured by Kurimoto Iron Works Co., Ltd.), vertical roller mills (manufactured by Chumble Co., Ltd.), and KVM type roller mills (manufactured by Chumble Co., Ltd.) can be used. (manufactured by Earth Technica), etc.
- the classification method is not particularly limited, but a method using a dry classifier is preferred.
- the dry classification it is preferable to perform airflow classification.
- FIG. 1 is a schematic diagram showing an example of a roller mill that can be used in the present invention.
- the roller mill 2 includes a casing 4, a main shaft 6 provided vertically in the casing 4 and configured to be rotatable by a drive device (not shown), a main shaft 6 attached to the upper end of the main shaft 6 or near the upper end, and arranged substantially horizontally.
- a turntable 8 is provided to be rotatable in a direction
- a support shaft 10 is fixed to the turntable 8 and supports a roller 12
- a support shaft 10 is attached to the support shaft 10 and is configured to be rotatable in a substantially horizontal direction on the turntable 8.
- a roller 12 is provided.
- the casing 4 also includes a raw material supply section 14 that supplies a predetermined amount of cellulose polymer as a material to be crushed onto the turntable 8 by a feeder (not shown), and an air supply section that supplies a predetermined amount of air into the casing 4. 16.
- a rotary shaft 18 provided vertically downward from the top of the housing 4 and configured to be rotatable; a classifier 20 installed at or near the lower end of the rotary shaft 18 and rotatable in a substantially horizontal direction;
- the product recovery section 22 is provided with a bag filter or the like, which recovers the pulverized cellulose polymer (fine powder) classified by the machine 20 and having a particle diameter of a predetermined value or less.
- the turntable 8 has a substantially circular shape when viewed vertically.
- the roller 12 has a wheel or ring shape of a predetermined width. 1 shows two rollers 12, there is no particular limitation on the number of rollers 12, and it is sufficient to have at least one roller, and it is preferable to have two or more rollers. That is, for example, the configuration is not limited to that shown in FIG. 1, and may be a configuration having 3 to 6 rollers 12.
- the material of the turntable 8 and/or the roller 12 is preferably at least one selected from zirconia, alumina, and silicon nitride. Further, grooves may be provided on the upper surface of the turntable 8 and/or at the locations of the rollers 12 that come into contact with the object to be crushed.
- the top surface of the turntable 8 and the roller 12 may be in contact with each other, or the turntable 8 and the roller 12 may be placed between the turntable 8 and the roller 12 within a range that does not impede the pulverizing performance from the viewpoint of quietness etc.
- a configuration may also be adopted in which a predetermined gap is provided.
- the roller 12 may be configured to slide outward from the center of rotation of the turntable (main shaft 6) due to the influence of centrifugal force when the turntable 8 rotates.
- the roller 12 and the inner wall surface of the casing 4 are close to each other, and the object to be crushed can also be pulverized between the roller 12 and the inner wall surface of the casing 4.
- the classifier 20 can adopt a configuration in which blades are attached to the outside of a cage-type classification rotor or a disk, and is attached to the lower part of the rotating shaft 18 provided at the upper part of the housing 4. That is, by rotating the rotary shaft 18 by a drive device (not shown), the classifier 20 is rotated, and the pulverized cellulose-based polymer is classified.
- the classification point may be adjusted by adjusting the rotation speed of the classifier 20.
- the arrows in FIG. 1 indicate the direction of movement of the cellulosic polymer and/or air.
- the rotation of the main shaft 6 is started by a drive device (not shown), and the turntable 8 is rotated as the main shaft 6 rotates. Further, as the turntable 8 rotates, the roller 12 attached to the support shaft 10 also rotates. Further, continuous supply of air from the air supply unit 16 into the housing 4 at a predetermined supply amount is started. Further, the rotation of the rotating shaft 18 is started, and the classifier 20 rotates as the rotating shaft 18 rotates.
- the cellulose-based polymer as a material to be crushed When the cellulose-based polymer as a material to be crushed is supplied from the raw material supply section 14 into the housing 4 , the cellulose-based polymer falls onto the turntable 8 .
- the cellulosic polymer supplied onto the turntable 8 is pulverized between the turntable 8 and the roller 12.
- the cellulose-based polymer is also crushed between the roller 12 and the inner wall surface of the housing 4. .
- the pulverized cellulose-based polymer rises to the upper part of the casing 4 due to the swirling upward airflow caused by the air supplied from the air supply section, and is classified by the classifier 20.
- Cellulose-based polymer fine powder having a particle size less than a predetermined value is collected by the product collection section 22.
- cellulose-based polymers having a particle diameter of a predetermined value or more are bounced downward from the housing 4 by the classifier 20 and subjected to pulverization by the turntable 8 and rollers 12.
- the roller 12 is attached to the support shaft 10 fixed to the turntable 8, but the structure is such that the support shaft is fixed to the casing 4, and the roller 12 is attached to the support shaft fixed to the casing 4. It may also be configured to attach. Further, in this case, pressure may be applied by a spring or hydraulic pressure via the support shaft during crushing.
- the amount of cellulose-based polymer supplied from the raw material supply section 14 into the casing 4 is 30 to 150 kg/h, preferably 40 to 120 kg/h. If the supply amount is too large, a problem arises in that the particle size of the obtained sample becomes large. Furthermore, if the supply amount is too small, problems such as a decrease in productivity and a decrease in the viscosity of the obtained sample will occur.
- the rotation speed of the turntable 8 is 50 to 500 rpm, preferably 70 to 300 rpm. If the rotation speed is too high, a problem arises in that the viscosity of the sample obtained becomes low. Furthermore, if the rotational speed is too low, a problem arises in that the particle size of the obtained sample becomes large.
- the amount of air supplied from the air supply unit 16 into the housing 4 is 5 to 50 m 3 /min, preferably 10 to 40 m 3 /min. If the amount of air supplied is too large, a problem arises in that the viscosity of the sample obtained becomes low. Furthermore, if the amount of air supplied is too small, a problem arises in that the particle size of the sample obtained becomes large.
- the amount of cellulose polymer supplied into the housing 4, the rotation speed of the turntable 8, and the amount of air supplied into the housing 4 are within the above ranges, thereby satisfying the above ranges.
- a cellulose-based polymer having a particle size of 50 ⁇ m or less can be stably produced.
- the particle diameter indicates the maximum particle diameter (D max ) determined by a grain gauge (grind gauge). Specifically, it is the maximum particle diameter (D max ) determined from the dispersity of the linear method measured with a grind gauge in accordance with JIS K5600 and JIS K5400 (1990).
- a chemically modified cellulose polymer when used as the cellulose polymer, 1% by mass of the cellulose polymer measured with a B-type viscometer (30 rpm) at 25°C after pulverization with a roller mill.
- the viscosity of the aqueous solution is preferably 500 to 15,000 mPa ⁇ s, more preferably 800 to 13,000 mPa ⁇ s, and even more preferably 1,000 to 10,000 mPa ⁇ s.
- the viscosity of the cellulose polymer after being pulverized by a roller mill can be measured in the same manner as the method for measuring the viscosity of the cellulose polymer to be pulverized.
- the ratio of mass M to mass m is preferably less than 50 ppm. If it is 50 ppm or more, when a film is formed using a cellulose polymer, appearance defects such as streaks and pinholes may occur in the film, and the quality of products using the film may deteriorate.
- the lower limit of the ratio of the mass M to the mass m is not particularly limited, and the smaller the ratio, the better.
- the cellulose-based polymer to be pulverized may be pre-pulverized.
- an impact mill can be used, although it is not particularly limited.
- Impact mills include Pulperizer (manufactured by Hosokawa Micron Co., Ltd.), Fine Impact Mill (manufactured by Hosokawa Micron Co., Ltd.), Super Micron Mill (manufactured by Hosokawa Micron Co., Ltd.), Sample Mill (manufactured by Seishin Co., Ltd.), and Bantam Mill (manufactured by Seishin Co., Ltd.).
- Examples include Seishin Co., Ltd.), atomizers (Seishin Co., Ltd.), tornado mills (Nikkiso Co., Ltd.), turbo mills (Turbo Kogyo Co., Ltd.), and bevel impactors (Aikawa Tekko Co., Ltd.).
- the use of the pulverized cellulose-based polymer obtained by the cellulose-based polymer pulverization method of the present invention is not particularly limited, and can be applied to various uses.
- thickeners thickeners, gelling agents, sizing agents, food additives, excipients, paint additives, adhesive additives, paper manufacturing additives, abrasives, compounded materials for rubber and plastics, water retention agents, It can be used as a filler, mud water conditioner, filter aid, mud flooding prevention agent, etc.
- the pulverized cellulose polymer obtained by the cellulose polymer pulverization method of the present invention can be used as a binder for the positive electrode and/or negative electrode of a nonaqueous electrolyte secondary battery such as a lithium ion secondary battery.
- the above-mentioned positive electrode and/or negative electrode can be formed by laminating an electrode composition on a current collector by blade coating, bar coating, die coating, etc., and then heating, drying, pressurizing, etc.
- the electrode composition contains an electrode active material, a binder, and other components such as a conductive material as necessary, and as a binder, a pulverized cellulose polymer obtained by the cellulose polymer pulverization method of the present invention is used. Can be used.
- the manufacturing conditions for the electrode composition are not particularly limited, but for example, other components constituting the electrode composition are added to the above-mentioned aqueous solution or dispersion of the pulverized cellulose-based polymer, and if necessary, while stirring. Obtained by mixing.
- the properties of the electrode composition are not particularly limited, and may be any of liquid, paste, and slurry forms.
- the electrode active material in the electrode composition includes a positive electrode active material or a negative electrode active material.
- the positive electrode active material is preferably a LiMe x O y (Me means a transition metal containing at least one of Ni, Co, and Mn. x and y represent arbitrary numbers) type positive electrode active material, LiCoO 2 or the like can be preferably used.
- Examples of negative electrode active materials include graphite materials such as graphite (natural graphite, artificial graphite), coke, and carbon fiber; elements that can form an alloy with lithium (for example, Al, Si, Sn, Ag, Bi , Mg, Zn, In, Ge, Pb, Ti, etc.); a composite of an element capable of forming an alloy with lithium and the compound, and carbon and/or the graphitic material; Nitrides containing nitrides, etc. can be used.
- graphite materials and/or silicon-based compounds are preferable, it is more preferable that graphite and/or silicon-based compounds are included, and it is preferable that at least a silicon-based compound is included.
- a pulverized cellulose polymer obtained by the cellulose polymer pulverization method of the present invention and a rubber binder such as styrene butadiene rubber (SBR) may be used in combination, if necessary.
- the conductive material one that can ensure electrical conductivity of the positive electrode and/or negative electrode can be used.
- the conductive material include one or a mixture of two or more carbon substances such as carbon black, acetylene black, and graphite.
- any electrical conductor that does not cause a fatal chemical change in the constructed battery can be used.
- the current collector for the negative electrode active material stainless steel, nickel, copper, titanium, carbon, copper, or stainless steel whose surface is coated with carbon, nickel, titanium, or silver can be used. Among these, copper or copper alloy is preferred, and copper is more preferred.
- the material for the current collector for the positive electrode include metals such as aluminum and stainless steel, with aluminum being preferred.
- As the shape of the current collector a net, punched metal, foam metal, foil processed into a plate shape, etc. can be used, and foil processed into a plate shape is preferable.
- a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery has a structure in which positive electrodes and negative electrodes are alternately stacked with separators interposed therebetween and wound many times.
- An electrode containing as a binder a pulverized cellulose-based polymer obtained by the cellulose-based polymer pulverization method described above can be used.
- the separator is usually impregnated with a nonaqueous electrolyte.
- each index for carboxymethylcellulose or its salt as a cellulose-based polymer was measured by the following method.
- CM-DS carboxymethyl substitution degree
- H-CMC was wetted with 15 mL of 80% methanol, 100 mL of 0.1N NaOH was added, and the mixture was shaken at room temperature for 3 hours. Excess NaOH was back titrated with 0.1N H 2 SO 4 using phenolphthalein as indicator. CM-DS was calculated using the following equation 1.
- ⁇ Viscosity> A cellulose-based polymer was measured into a 1000 mL glass beaker and dispersed in 900 mL of distilled water to prepare an aqueous dispersion with a solid content of 1% (w/v). The aqueous dispersion was stirred at 25° C. using a stirrer at 600 rpm for 3 hours. Thereafter, according to the method of JIS-Z-8803, using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.), No. The viscosity was measured after 3 minutes using 4 rotors/30 rpm.
- ⁇ Particle size (grain gauge)> The particle size was measured using a grain gauge (grind gauge). Specifically, the maximum particle diameter (D max ) was determined by the dispersity of the linear method measured using a grind gauge in accordance with JIS K5600 and JIS K5400 (1990).
- Example 1 1161 g of isopropyl alcohol and 121 g of sodium hydroxide dissolved in 231 g of water were added to a twin-screw kneader whose rotational speed was adjusted to 100 rpm, and the dry mass of linter pulp (160 g when dried at 100° C. for 60 minutes) was charged. After stirring and mixing at 30°C for 90 minutes to prepare mercerized cellulose, a solution of 124 g of monochloroacetic acid in 142 g of isopropyl alcohol was added, and the mixture was heated to 70°C to carry out a carboxymethylation reaction for 90 minutes.
- CMC1 carboxymethyl cellulose
- the obtained CMC1 was pulverized using a roller mill shown in FIG.
- the amount of CMC 1 supplied into the casing 4 of the roller mill 2 is 120 kg/h
- the rotation speed of the turntable 8 is 150 rpm
- the amount of air supplied into the casing 4 of the roller mill 2 is 20 m 3 /min.
- the viscosity of the 1 mass % aqueous solution of CMC1 after pulverization was 3,300 mPa ⁇ s, and the maximum particle diameter (D max ) determined by a particle gauge was 43 ⁇ m.
- Example 2 Except that the amount of CMC1 supplied into the casing of the roller mill 2 was changed to 40 kg/h, the rotation speed of the turntable 8 was changed to 100 rpm, and the amount of air supplied into the casing 4 of the roller mill 2 was changed to 12 m 3 /min. CMC1 was pulverized in the same manner as in Example 1.
- the viscosity of a 1% by mass aqueous solution of CMC1 after pulverization at 25° C. measured with a B-type viscometer was 3,300 mPa ⁇ s, and the maximum particle diameter (D max ) determined by a particle gauge was 45 ⁇ m.
- Example 3 1201 g of isopropyl alcohol and 101 g of sodium hydroxide dissolved in 255 g of water were added to a twin-screw kneader whose rotation speed was adjusted to 100 rpm, and the dry mass of linter pulp (160 g when dried at 100° C. for 60 minutes) was charged. After stirring and mixing at 30°C for 90 minutes to prepare mercerized cellulose, a solution of 104 g of monochloroacetic acid in 118 g of isopropyl alcohol was added, and the mixture was heated to 70°C to carry out a carboxymethylation reaction for 90 minutes.
- CMC2 carboxymethyl cellulose
- the obtained CMC2 was pulverized using a roller mill shown in FIG.
- the amount of CMC 1 supplied into the casing 4 of the roller mill 2 is 60 kg/h
- the rotation speed of the turntable 8 is 120 rpm
- the amount of air supplied into the casing 4 of the roller mill 2 is 15 m 3 /min.
- the viscosity of the 1 mass % aqueous solution of CMC2 after pulverization was 8,420 mPa ⁇ s, and the maximum particle diameter (D max ) determined by a particle gauge was 37 ⁇ m.
- Example 4 1201 g of isopropyl alcohol and 101 g of sodium hydroxide dissolved in 255 g of water were added to a twin-screw kneader whose rotation speed was adjusted to 100 rpm, and the dry mass of linter pulp (160 g when dried at 100° C. for 60 minutes) was charged. After stirring and mixing at 40° C. for 120 minutes to prepare mercerized cellulose, a solution of 104 g of monochloroacetic acid dissolved in 118 g of isopropyl alcohol was added, and the mixture was heated to 70° C. to carry out a carboxymethylation reaction for 90 minutes.
- CMC3 carboxymethyl cellulose having a maximum particle diameter (D max ) determined by a gauge of more than 100 ⁇ m was obtained.
- the obtained CMC3 was pulverized using a roller mill shown in FIG.
- the amount of CMC 1 supplied into the casing 4 of the roller mill 2 is 85 kg/h
- the rotation speed of the turntable 8 is 200 rpm
- the amount of air supplied into the casing 4 of the roller mill 2 is 27 m 3 /min.
- the viscosity of a 1% by mass aqueous solution of CMC3 after pulverization at 25° C. measured with a B-type viscometer was 8,800 mPa ⁇ s, and the maximum particle diameter (D max ) determined by a particle gauge was 45 ⁇ m.
- roller mill 4... Housing, 8... Turntable, 12... Roller, 14... Raw material supply section, 16... Air supply section, 20... Classifier, 22... Product recovery section
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Abstract
L'invention concerne un procédé de broyage d'un polymère à base de cellulose à l'aide d'un broyeur à rouleaux, la quantité du polymère à base de cellulose fournie au broyeur à rouleaux étant de 30 à 150 kg/h, la vitesse de rotation d'un plateau tournant 8 du broyeur à rouleaux étant de 50 à 500 tr/min, et la quantité d'air fournie au broyeur à rouleaux étant de 5 à 50 m3/min.
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JP2012144651A (ja) * | 2011-01-13 | 2012-08-02 | Oji Paper Co Ltd | 微細繊維状セルロースの製造方法 |
JP2012211340A (ja) * | 2006-08-08 | 2012-11-01 | Shin-Etsu Chemical Co Ltd | 低置換度ヒドロキシプロピルセルロース粉末及び固形製剤 |
JP2013133398A (ja) * | 2011-12-26 | 2013-07-08 | Kao Corp | カルボキシメチルセルロースの製造方法 |
JP2014088538A (ja) * | 2012-10-01 | 2014-05-15 | Nippon Paper Industries Co Ltd | 粉末状セルロース及びその製造方法 |
JP2015183020A (ja) * | 2014-03-20 | 2015-10-22 | 日本製紙株式会社 | 粉末状セルロース |
JP2015183019A (ja) * | 2014-03-20 | 2015-10-22 | 日本製紙株式会社 | 粉末状セルロース |
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- 2023-08-21 WO PCT/JP2023/029954 patent/WO2024057829A1/fr unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2012211340A (ja) * | 2006-08-08 | 2012-11-01 | Shin-Etsu Chemical Co Ltd | 低置換度ヒドロキシプロピルセルロース粉末及び固形製剤 |
JP2012144651A (ja) * | 2011-01-13 | 2012-08-02 | Oji Paper Co Ltd | 微細繊維状セルロースの製造方法 |
JP2013133398A (ja) * | 2011-12-26 | 2013-07-08 | Kao Corp | カルボキシメチルセルロースの製造方法 |
JP2014088538A (ja) * | 2012-10-01 | 2014-05-15 | Nippon Paper Industries Co Ltd | 粉末状セルロース及びその製造方法 |
JP2015183020A (ja) * | 2014-03-20 | 2015-10-22 | 日本製紙株式会社 | 粉末状セルロース |
JP2015183019A (ja) * | 2014-03-20 | 2015-10-22 | 日本製紙株式会社 | 粉末状セルロース |
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