JP2006289248A - Material for removing nitrogen oxide - Google Patents
Material for removing nitrogen oxide Download PDFInfo
- Publication number
- JP2006289248A JP2006289248A JP2005112613A JP2005112613A JP2006289248A JP 2006289248 A JP2006289248 A JP 2006289248A JP 2005112613 A JP2005112613 A JP 2005112613A JP 2005112613 A JP2005112613 A JP 2005112613A JP 2006289248 A JP2006289248 A JP 2006289248A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- manganese oxide
- porous
- manganese
- porous body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 239000000463 material Substances 0.000 title claims abstract description 49
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 148
- 239000011148 porous material Substances 0.000 claims abstract description 135
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 238000000746 purification Methods 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229920001410 Microfiber Polymers 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 230000002776 aggregation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 239000004113 Sepiolite Substances 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 238000005054 agglomeration Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 235000019355 sepiolite Nutrition 0.000 claims description 4
- 229910052624 sepiolite Inorganic materials 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 238000000151 deposition Methods 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 description 51
- 239000004094 surface-active agent Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 27
- 229920001451 polypropylene glycol Polymers 0.000 description 23
- 239000007864 aqueous solution Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000002243 precursor Substances 0.000 description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 14
- 150000002696 manganese Chemical class 0.000 description 13
- 229910052748 manganese Inorganic materials 0.000 description 13
- 239000011572 manganese Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002131 composite material Substances 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000007772 electroless plating Methods 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 238000010306 acid treatment Methods 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 235000013162 Cocos nucifera Nutrition 0.000 description 5
- 244000060011 Cocos nucifera Species 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920000428 triblock copolymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- -1 Halide salts Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000002301 combined effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229920000359 diblock copolymer Polymers 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical class [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-O benzylaminium Chemical compound [NH3+]CC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-O 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、窒素酸化物浄化材料に関し、より詳しくは、メソ孔領域又はそれより小さい中心細孔直径を有する多孔体を用いた窒素酸化物浄化材料に関する。 The present invention relates to a nitrogen oxide purification material, and more particularly to a nitrogen oxide purification material using a porous body having a mesopore region or a smaller central pore diameter.
近年、窒素酸化物（ＮＯｘ）による環境汚染が問題となってきている。このようなＮＯｘは空気中に様々な形で存在していると言われているが、その大部分はＮＯとＮＯ２である。このようなＮＯ２は水やアルカリに容易に溶けるため吸収、除去し易い。これに対して、ＮＯは水に殆ど溶けず、更には活性炭やシリカゲル等の非常に吸着活性の大きいものであっても極一部でしか吸着されないという問題を有している。 In recent years, environmental pollution due to nitrogen oxides (NO x ) has become a problem. Such NO x is said to be present in various forms in the air, most of which are NO and NO 2. Since such NO 2 is easily dissolved in water and alkali, it is easy to absorb and remove. On the other hand, NO has a problem that it hardly dissolves in water, and even if it has a very large adsorption activity such as activated carbon or silica gel, it is adsorbed only in a very small part.
このような一酸化窒素吸着除去を目的とした窒素酸化物浄化技術としては、特開平５−１２３５３３号公報（特許文献１）において、予備荷電部と集塵極板とからなる電気集塵部と、前記電気集塵部の後段に設けられた窒素酸化物除去フィルタとからなる窒素酸化物除去装置が開示されており、オゾンを利用して窒素酸化物（ＮＯｘ）を除去することが記載されている。しかしながら、特許文献１に記載の窒素酸化物除去装置においては、オゾン発生器とＮＯの酸化に使用されなかった余剰オゾンの後処理装置が必要となり、コスト高となっていた。また、人が余剰オゾンに曝される可能性もあり、生活環境で使用するには安全上問題があった。なお、オゾンは有害物質（発がん性物質）として人の健康を損なうおそれがあるとして日本産業衛生学会ではオゾンの許容濃度を０．１ｐｐｍ以下と定めている。 As such a nitrogen oxide purification technique for the purpose of removing and removing nitrogen monoxide, as disclosed in Japanese Patent Laid-Open No. 5-123533 (Patent Document 1), an electric dust collecting portion comprising a precharged portion and a dust collecting electrode plate; , A nitrogen oxide removing device comprising a nitrogen oxide removing filter provided at a subsequent stage of the electric dust collecting unit is disclosed, and it is described that nitrogen oxide (NO x ) is removed using ozone. ing. However, the nitrogen oxide removing device described in Patent Document 1 requires an ozone generator and a surplus ozone post-treatment device that has not been used for oxidation of NO, resulting in high costs. In addition, there is a possibility that humans may be exposed to surplus ozone, and there has been a safety problem when used in a living environment. Note that ozone is a harmful substance (carcinogenic substance) and may harm human health. The Japan Society for Occupational Health sets the allowable concentration of ozone to 0.1 ppm or less.
また、特開平４−２９３５４２号公報（特許文献２）においては、ハニカム状に成型された活性炭成型体と、このハニカム状活性炭成型体に担持されたＫＭｎＯ４等の酸化剤とを有するＮＯ吸着体が開示されている。しかしながら、ＫＭｎＯ４等の酸化剤を担持した特許文献２に記載のＮＯ吸着体においては、その酸化活性と比表面積が不足するため、十分なＮＯｘ除去性能を得ることが困難であった。 Further, in Japanese Patent Laid-Open No. 4-293542 (Patent Document 2), an NO adsorbent having an activated carbon molded body formed into a honeycomb shape and an oxidizing agent such as KMnO 4 supported on the honeycomb activated carbon molded body. Is disclosed. However, in the NO adsorbent described in Patent Document 2 carrying an oxidant such as KMnO 4 , it is difficult to obtain sufficient NO x removal performance because its oxidation activity and specific surface area are insufficient.
さらに、特開昭４９−１２９６９５号公報（特許文献３）においては、二酸化マンガン（ＭｎＯ２）を触媒として用い、ＮＯをＮＯ２に酸化した後に、ＮＯ２を吸着除去する方法が記載されている。しかしながら、特許文献３に記載の方法においては、ＭｎＯ２によるＮＯの酸化反応に１５０〜３５０℃の高温が必要であったため、経済的ではなく、更には生活環境における使用に適さないという問題点があった。 Further, JP-A-49-129695 (Patent Document 3) describes a method of adsorbing and removing NO 2 after oxidizing NO to NO 2 using manganese dioxide (MnO 2 ) as a catalyst. . However, in the method described in Patent Document 3, a high temperature of 150 to 350 ° C. is necessary for the oxidation reaction of NO with MnO 2 , which is not economical and is not suitable for use in a living environment. there were.
また、特開２００３−２２１２０９号公報（特許文献４）においては、３次元チャンネル構造である３Ｄ−Ｃｕｂｉｃ Ｆｍ３ｍ構造を有する金属酸化物からなるメソ多孔体が開示されている。しかしながら、Ｆｍ３ｍ構造を有する金属酸化物からなるメソ多孔体であっても、現実には細孔径の拡大に限界があり、ＮＯｘの拡散速度は必ずしも十分なものではなかった。
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、ＮＯｘを細孔内に速やかに拡散させることができ、しかも優れた吸着能及び触媒能を発揮して室温においてもＮＯを酸化できるとともにＮＯ２に対する高い吸着能を発揮して効率よく且つ確実にＮＯｘを除去することを可能とする窒素酸化物浄化材料を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and can rapidly diffuse NO x into the pores, exhibit excellent adsorption ability and catalytic ability, and can be NO even at room temperature. An object of the present invention is to provide a nitrogen oxide purification material capable of oxidizing NOx and exhibiting a high adsorption capacity for NO 2 and capable of efficiently and reliably removing NO x .
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、窒素酸化物浄化材料に酸化マンガンの超微細繊維が凝集して中心細孔直径１〜２０ｎｍの二次細孔が形成されている酸化マンガン多孔体と、多孔材料に金属を担持させた金属担持多孔材料とを用いることにより、驚くべきことにＮＯｘの除去性能が相乗的に向上して前記目的が達成されることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have aggregated ultrafine manganese oxide fibers on the nitrogen oxide purification material to form secondary pores having a central pore diameter of 1 to 20 nm. By using the porous manganese oxide and the metal-supported porous material in which a metal is supported on the porous material, it is surprising that the NO x removal performance is synergistically improved and the object is achieved. The headline and the present invention were completed.
すなわち、本発明の窒素酸化物浄化材料は、酸化マンガンの超微細繊維が凝集して中心細孔直径１〜２０ｎｍの二次細孔が形成されている酸化マンガン多孔体と、多孔材料に金属を担持させた金属担持多孔材料とからなることを特徴とするものである。 That is, the nitrogen oxide purifying material of the present invention comprises a manganese oxide porous body in which secondary fine pores having a central pore diameter of 1 to 20 nm are formed by agglomeration of manganese oxide ultrafine fibers, and a metal in the porous material. It is characterized by comprising a supported metal-supporting porous material.
上記本発明の窒素酸化物浄化材料としては、前記酸化マンガン多孔体の含有量が１０〜９０質量％であることが好ましく、また、前記酸化マンガン多孔体としては、その結晶相
がγ−ＭｎＯ２であり、且つ、その比表面積が１５０ｍ２／ｇ以上であることが好ましい。更に、上記本発明の窒素酸化物浄化材料としては、前記金属がニッケルであることが好ましく、また、前記多孔材料が、活性炭、シリカゲル、ゼオライト、セピオライト、アルミナ及びセリアからなる群から選択される少なくとも１種であることが好ましい。
The nitrogen oxide purifying material of the present invention, the preferably the amount of manganese oxide porous body is 10 to 90 mass%, also, as the manganese oxide porous body, the crystal phase gamma-MnO 2 It is preferable that the specific surface area is 150 m 2 / g or more. Further, as the nitrogen oxide purification material of the present invention, the metal is preferably nickel, and the porous material is at least selected from the group consisting of activated carbon, silica gel, zeolite, sepiolite, alumina, and ceria. One type is preferable.
なお、本発明の窒素酸化物浄化材料によって、ＮＯｘを細孔内に速やかに拡散させることができ、しかも優れた吸着能及び触媒能を発揮して室温においてもＮＯを酸化できるとともにＮＯ２に対する高い吸着能を発揮して効率よく且つ確実にＮＯｘを除去することが可能となる理由は必ずしも定かではないが、本発明者らは以下のように推察する。すなわち、本発明にかかる酸化マンガン多孔体は超微細繊維凝集多孔体という構造を有しているため、細孔内にＮＯｘを拡散させる際における拡散抵抗が非常に小さくなる。また細孔径、比表面積及び細孔容積が大きいため、ＮＯｘの吸着速度及び酸化反応速度を向上させることが可能となり、室温においても効率よく酸化することが可能となる。一方、本発明にかかる金属担持多孔材料においては、多孔材料が有するマイクロ孔の物理吸着作用によって気中の希薄な窒素酸化物を吸着、濃縮することが可能となる。また、濃縮されたそれらの窒素酸化物を外表面に担持された金属（活性成分）で遂次化学的に捕捉することが可能となる。このように、物理吸着作用及び化学吸着作用の複合効果により気中に含有される低濃度の窒素酸化物を効果的に吸着除去することが可能となる。そして、このような酸化マンガン多孔体と金属担持多孔材料とを近接した状態で混合することで、室温における吸着及び酸化が困難なＮＯを酸化マンガン多孔体によって効率的に酸化してより吸着が容易なＮＯ２とした後、近接して存在する金属担持多孔材料が、発生したＮＯ２を物理吸着作用及び化学吸着作用によってより効果的に吸着するため、ＮＯｘを吸着、除去する効果が相乗的に向上するものと本発明者らは推察する。 Depending nitrogen oxide purification material of the present invention, with respect to NO 2 with the NO x can be quickly diffused in the pores, yet capable of oxidizing NO even at room temperature to exhibit excellent adsorption ability and catalytic ability The reason why it is possible to efficiently and reliably remove NO x by exhibiting high adsorption ability is not necessarily clear, but the present inventors speculate as follows. That is, manganese oxide porous body according to the present invention because it has a structure that ultrafine fibers aggregate porous body, diffusion resistance at the time of diffusing NO x in the pores is very small. Further, since the pore diameter, specific surface area, and pore volume are large, it is possible to improve the NO x adsorption rate and oxidation reaction rate, and it is possible to efficiently oxidize even at room temperature. On the other hand, in the metal-supporting porous material according to the present invention, it is possible to adsorb and concentrate dilute nitrogen oxides in the air by the physical adsorption action of the micropores of the porous material. In addition, the concentrated nitrogen oxides can be sequentially chemically captured by the metal (active component) supported on the outer surface. Thus, the low concentration nitrogen oxide contained in the air can be effectively adsorbed and removed by the combined effect of the physical adsorption action and the chemical adsorption action. And by mixing such a manganese oxide porous material and a metal-supporting porous material in close proximity, NO, which is difficult to adsorb and oxidize at room temperature, is efficiently oxidized by the manganese oxide porous material, making adsorption easier. after a such NO 2, metal loading porous material present in proximity, in order to adsorb more efficiently the generated NO 2 by physical adsorption and chemical adsorption, adsorption of NO x, the effect of removing synergistic The present inventors speculate that this is improved.
本発明によれば、ＮＯｘを細孔内に速やかに拡散させることができ、しかも優れた吸着能及び触媒能を発揮して室温においてもＮＯを酸化できるとともにＮＯ２に対する高い吸着能を発揮して効率よく且つ確実にＮＯｘを除去することを可能とする窒素酸化物浄化材料を提供することが可能となる。 According to the present invention, NO x can be rapidly diffused into the pores, and excellent adsorption ability and catalytic ability can be exhibited to oxidize NO even at room temperature and to exhibit high adsorption ability for NO 2 . Therefore, it is possible to provide a nitrogen oxide purification material that can efficiently and reliably remove NO x .
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
本発明の窒素酸化物浄化材料は、酸化マンガンの超微細繊維が凝集して中心細孔直径１〜２０ｎｍの二次細孔が形成されている酸化マンガン多孔体と、多孔材料に金属を担持させた金属担持多孔材料とからなることを特徴とするものである。 The nitrogen oxide purification material of the present invention comprises a manganese oxide porous body in which secondary fine pores having a central pore diameter of 1 to 20 nm are formed by aggregation of ultrafine manganese oxide fibers, and a metal supported on the porous material. And a metal-supporting porous material.
（酸化マンガン多孔体）
先ず、本発明にかかる酸化マンガン多孔体について説明する。本発明にかかる酸化マンガン多孔体は、酸化マンガンの超微細繊維が凝集して中心細孔直径１〜２０ｎｍの二次細孔が形成されているものである。このような酸化マンガン多孔体は、ＮＯの酸化材として作用するものである。すなわち、本発明にかかる酸化マンガン多孔体は超微細繊維凝集多孔体という構造を有しているため、細孔内にＮＯｘを拡散させる際における拡散抵抗が非常に小さいものとなり、また細孔径、比表面積及び細孔容積が大きいため吸着速度及び反応速度を向上させることが可能となり、室温においても効率よくＮＯを酸化することが可能となる。
(Porous manganese oxide)
First, the manganese oxide porous body according to the present invention will be described. The manganese oxide porous body according to the present invention is one in which ultrafine fibers of manganese oxide are aggregated to form secondary pores having a central pore diameter of 1 to 20 nm. Such a manganese oxide porous body acts as an oxidizing agent for NO. That is, manganese oxide porous body according to the present invention because it has a structure that ultrafine fibers aggregate porous body, it is assumed diffusion resistance at the time of diffusing NO x in the pores are very small, also the pore diameter, Since the specific surface area and pore volume are large, the adsorption rate and reaction rate can be improved, and NO can be efficiently oxidized even at room temperature.
本発明にかかる酸化マンガン多孔体は、酸化マンガンの超微細繊維が凝集してなるものであり、このような超微細繊維としては、１〜５ｎｍ（より好ましくは２〜４ｎｍ）の平均直径、２０ｎｍ以上（より好ましくは２０〜１００ｎｍ）の平均長さ、及び４以上（より好ましくは１０〜３０）の平均アスペクト比を有するものであることが好ましい。前記超微細繊維の平均直径が上記下限未満では超微細繊維が密に凝集して細孔径が低下して吸着物質等の拡散速度が低下する傾向にあり、他方、上記上限を超えると比表面積及び細孔容積が低下して吸着特性や触媒活性が低下してしまう傾向にある。また、前記超微細繊維の平均長さ及び平均アスペクト比が上記下限未満では、超微細繊維の凝集が不十分となり、比表面積及び細孔容積が低下して吸着特性や触媒活性が低下してしまう傾向にある。 The porous manganese oxide according to the present invention is formed by agglomeration of ultrafine fibers of manganese oxide. As such ultrafine fibers, an average diameter of 1 to 5 nm (more preferably 2 to 4 nm), 20 nm. It is preferable to have an average length of (more preferably 20 to 100 nm) and an average aspect ratio of 4 or more (more preferably 10 to 30). If the average diameter of the ultrafine fibers is less than the above lower limit, the ultrafine fibers are densely aggregated and the pore diameter tends to decrease, and the diffusion rate of the adsorbed material and the like tends to decrease. There is a tendency that the pore volume decreases and the adsorption characteristics and catalytic activity decrease. In addition, if the average length and average aspect ratio of the ultrafine fibers are less than the above lower limit, the aggregation of the ultrafine fibers becomes insufficient, the specific surface area and the pore volume decrease, and the adsorption characteristics and catalytic activity decrease. There is a tendency.
本発明にかかる酸化マンガン多孔体は、酸化マンガンの超微細繊維からなり、いわゆるメソ孔領域又はそれより小さい中心細孔直径の二次細孔を有するものであり、その中心細孔直径は１〜２０ｎｍであり、より好ましくは２〜１０ｎｍである。本発明にかかる酸化マンガン多孔体において、中心細孔直径が１ｎｍ未満の場合は、吸着物質や反応基質が細孔内に十分な速度で拡散せず、十分な吸着特性や触媒活性が発揮されない。他方、中心細孔直径が２０ｎｍを超える場合は、比表面積及び細孔容積が低下して、吸着特性や触媒活性が低下してしまう。 The manganese oxide porous body according to the present invention is composed of ultrafine fibers of manganese oxide, and has a so-called mesopore region or a secondary pore having a smaller central pore diameter. It is 20 nm, More preferably, it is 2-10 nm. In the manganese oxide porous body according to the present invention, when the central pore diameter is less than 1 nm, the adsorbing substance and the reaction substrate do not diffuse at a sufficient rate in the pores, and sufficient adsorption characteristics and catalytic activity are not exhibited. On the other hand, when the central pore diameter exceeds 20 nm, the specific surface area and pore volume are reduced, and the adsorption characteristics and catalytic activity are reduced.
前記中心細孔直径とは、細孔容積（Ｖ）を細孔直径（Ｄ）で微分した値（ｄＶ／ｄＤ）を細孔直径（Ｄ）に対してプロットした曲線（細孔径分布曲線）の最大ピークにおける細孔直径である。なお、細孔径分布曲線は、次に述べる方法により求めることができる。すなわち、酸化マンガン多孔体を液体窒素温度（−１９６℃）に冷却して窒素ガスを導入し、定容量法あるいは重量法によりその吸着量を求め、次いで、導入する窒素ガスの圧力を徐々に増加させ、各平衡圧に対する窒素ガスの吸着量をプロットし、吸着等温線を得る。この吸着等温線を用い、Ｃｒａｎｓｔｏｎ−Ｉｎｋｌａｙ法、Ｐｏｌｌｉｍｏｒｅ−Ｈｅａｌ法、ＢＪＨ法等の計算法により細孔径分布曲線を求めることができる。 The central pore diameter is a curve (pore diameter distribution curve) in which a value (dV / dD) obtained by differentiating the pore volume (V) with respect to the pore diameter (D) is plotted against the pore diameter (D). It is the pore diameter at the maximum peak. The pore size distribution curve can be obtained by the method described below. That is, the manganese oxide porous body is cooled to liquid nitrogen temperature (−196 ° C.), nitrogen gas is introduced, the adsorption amount is obtained by a constant volume method or a gravimetric method, and then the pressure of the introduced nitrogen gas is gradually increased. Then, the adsorption amount of nitrogen gas with respect to each equilibrium pressure is plotted, and an adsorption isotherm is obtained. Using this adsorption isotherm, a pore size distribution curve can be obtained by a calculation method such as Cranston-Inklay method, Pollimore-Heal method, BJH method or the like.
このような本発明にかかる酸化マンガン多孔体においては、細孔径分布曲線における中心細孔直径の±４０％の範囲に全細孔容積の２５％以上が含まれることが好ましい。ここで、「細孔径分布曲線における最大ピークを示す細孔直径の±４０％の範囲に全細孔容積の２５％以上が含まれる」とは、例えば、中心細孔直径が３．００ｎｍである場合、この３．００ｎｍの±４０％、すなわち１．８０〜４．２０ｎｍの範囲にある細孔の容積の合計が、全細孔容積の２５％以上を占めていることを意味する。 In such a manganese oxide porous body according to the present invention, it is preferable that 25% or more of the total pore volume is included in a range of ± 40% of the center pore diameter in the pore diameter distribution curve. Here, “the range of ± 40% of the pore diameter showing the maximum peak in the pore diameter distribution curve includes 25% or more of the total pore volume” means, for example, that the central pore diameter is 3.00 nm. In this case, this means that the total volume of pores in the range of ± 40% of 3.00 nm, that is, 1.80 to 4.20 nm occupies 25% or more of the total pore volume.
また、本発明にかかる酸化マンガン多孔体の比表面積については特に制限はないが、１５０ｍ２／ｇ以上であることが好ましく、１５０〜５００ｍ２／ｇであることが好ましい。比表面積は、吸着等温線からＢＥＴ等温吸着式を用いてＢＥＴ比表面積として算出することができる。さらに、本発明にかかる酸化マンガン多孔体の細孔容積についても特に制限はないが、０．０５〜１．０ｍＬ／ｇであることが好ましい。本発明にかかる酸化マンガン多孔体の比表面積及び細孔容積が上記下限未満では、吸着特性や触媒活性が低下してしまう傾向にあり、他方、上記上限を超えると、酸化マンガン多孔体の強度が低下してしまう傾向にある。 No particular limitation is imposed on the specific surface area of manganese oxide porous body according to the present invention, preferably at 150 meters 2 / g or more, preferably a 150~500m 2 / g. The specific surface area can be calculated as a BET specific surface area from the adsorption isotherm using the BET isotherm adsorption equation. Further, the pore volume of the manganese oxide porous body according to the present invention is not particularly limited, but is preferably 0.05 to 1.0 mL / g. If the specific surface area and the pore volume of the porous manganese oxide according to the present invention are less than the above lower limit, the adsorption characteristics and catalytic activity tend to be reduced. On the other hand, if the upper limit is exceeded, the strength of the porous manganese oxide is increased. It tends to decrease.
本発明にかかる酸化マンガン多孔体の結晶相がγ−ＭｎＯ２であることが好ましい。このように結晶相をγ−ＭｎＯ２とすることで、本発明にかかる酸化マンガン多孔体がより高い触媒能を発揮することができる。また、本発明にかかる酸化マンガン多孔体としては、吸着能や触媒能をより向上させるという観点から、結晶相がγ−ＭｎＯ２であるとともに比表面積が１５０ｍ２／ｇ以上であることがより好ましい。すなわち、本発明にかかる酸化マンガン多孔体のフレームワーク（骨格）をより高い触媒能を発揮できるγ−ＭｎＯ２とし、且つより高い吸着能を発揮できる１５０ｍ２／ｇ以上という大きな比表面積とすることで、本発明にかかる酸化マンガン多孔体により高度な吸着性能や触媒性能を発揮させることが可能となる。 The crystal phase of the porous manganese oxide according to the present invention is preferably γ-MnO 2 . Thus the crystalline phase by a γ-MnO 2, can be manganese oxide porous body according to the present invention exhibits a higher catalytic activity. As the manganese oxide porous body according to the present invention, from the viewpoint of further improving the adsorption ability and catalytic activity, and more preferably a specific surface area together with the crystalline phase is a gamma-MnO 2 is 150 meters 2 / g or more . That is, the framework (skeleton) of the porous manganese oxide according to the present invention is γ-MnO 2 capable of exhibiting higher catalytic ability and a large specific surface area of 150 m 2 / g or more capable of exhibiting higher adsorption ability. Thus, the manganese oxide porous body according to the present invention can exhibit high adsorption performance and catalytic performance.
本発明にかかる酸化マンガン多孔体の形状は特に限定されず、支持膜、自立膜、透明膜、配向膜、球状や繊維状のもの、更には、粉末、顆粒及びμｍサイズの明瞭な形態をもつ粒子等の粉体等を挙げることができるが、金属担持多孔材料と近接した状態で混合状態とすることが可能であるという観点から、その形状を粉体とすることが好ましい。このような粉体形状の酸化マンガン多孔体を用いる場合においては、その粉体の粒径は特に制限されないが、金属担持多孔材料とより近接した状態で混合状態とすることが可能であるという観点から、平均粒径を０．１〜５０μｍ程度とすることが好ましい。 The shape of the porous manganese oxide according to the present invention is not particularly limited, and has a clear form of a support film, a self-supporting film, a transparent film, an alignment film, a spherical shape or a fibrous shape, and powder, granules, and μm size. Although powders such as particles can be mentioned, it is preferable to make the shape powder from the viewpoint that it can be mixed with the metal-supporting porous material. In the case of using such a powder-shaped manganese oxide porous body, the particle size of the powder is not particularly limited, but it is possible to make a mixed state in a state closer to the metal-supporting porous material. Therefore, the average particle size is preferably about 0.1 to 50 μm.
以下において、本発明にかかる酸化マンガン多孔体を製造するための好適な製造方法について説明する。 Below, the suitable manufacturing method for manufacturing the manganese oxide porous body concerning this invention is demonstrated.
本発明にかかる酸化マンガン多孔体を製造する方法においては、先ず、マンガン塩と界面活性剤とを含有する水溶液中でマンガンのゾルを加水分解及び縮合反応せしめ、マンガンと前記界面活性剤とからなる有機／無機複合体を生成せしめる（第一の工程）。 In the method for producing a manganese oxide porous body according to the present invention, first, a sol of manganese is hydrolyzed and condensed in an aqueous solution containing a manganese salt and a surfactant, and consists of manganese and the surfactant. An organic / inorganic composite is formed (first step).
このような製造方法において原料として用いられる前記マンガン塩としては、マンガンの硝酸塩、硫酸塩、ハロゲン化物（塩化物、弗化物等）、酢酸塩等が挙げられ、中でも水等の溶媒に対する溶解度が大きいことと安価であるという観点からマンガンの硝酸塩又はハロゲン化物が好ましい。なお、上記金属塩は、単独で用いることもできるが、２種類以上を組み合わせて用いることも可能である。 Examples of the manganese salt used as a raw material in such a production method include manganese nitrates, sulfates, halides (chlorides, fluorides, etc.), acetates, etc., among which the solubility in water and other solvents is high. In view of the fact that it is inexpensive, manganese nitrate or halide is preferred. In addition, although the said metal salt can also be used independently, it can also be used in combination of 2 or more types.
前記界面活性剤としては、特に限定されるものではなく、陽イオン性、陰イオン性、非イオン性のうちのいずれであってもよく、具体的には、アルキルトリメチルアンモニウム、アルキルトリエチルアンモニウム、ジアルキルジメチルアンモニウム、ベンジルアンモニウム等のハロゲン化物塩あるいは水酸化物；脂肪酸塩、アルキルスルホン酸塩、アルキルリン酸塩、ポリエチレンオキサイド系非イオン性界面活性剤、一級アルキルアミン等が挙げられる。これらの界面活性剤は、単独で又は二種以上混合して用いられる。 The surfactant is not particularly limited, and may be any of cationic, anionic and nonionic. Specifically, alkyltrimethylammonium, alkyltriethylammonium, dialkyl Halide salts or hydroxides such as dimethylammonium and benzylammonium; fatty acid salts, alkylsulfonates, alkylphosphates, polyethylene oxide nonionic surfactants, primary alkylamines and the like. These surfactants may be used alone or in combination of two or more.
また、上記の界面活性剤のうち、ポリエチレンオキサイド系非イオン性界面活性剤としては、疎水性成分として炭化水素基、親水性部分としてポリエチレンオキサイドをそれぞれ有するポリエチレンオキサイド系非イオン性界面活性剤等が挙げられる。このような界面活性剤としては、例えば、一般式ＣｎＨ２ｎ＋１（ＯＣＨ２ＣＨ２）ｍＯＨで表され、ｎが１０〜３０、ｍが１〜３０であるものが好適に使用できる。また、このような界面活性剤としては、オレイン酸、ラウリン酸、ステアリン酸、パルミチン酸等の脂肪酸とソルビタンとのエステル、あるいはこれらのエステルにポリエチレンオキサイドが付加した化合物を用いることもできる。 Among the above surfactants, polyethylene oxide nonionic surfactants include, for example, polyethylene oxide nonionic surfactants each having a hydrocarbon group as a hydrophobic component and polyethylene oxide as a hydrophilic portion. Can be mentioned. Such surfactants, for example, the general formula C n H 2n + 1 (OCH 2 CH 2) expressed in m OH, n is 10 to 30, m can be preferably used those which are 1 to 30. As such a surfactant, an ester of a fatty acid such as oleic acid, lauric acid, stearic acid, palmitic acid and sorbitan, or a compound obtained by adding polyethylene oxide to these esters can also be used.
さらに、このような界面活性剤としては、トリブロックコポリマー型のポリアルキレンオキサイドを用いることもできる。このような界面活性剤としては、ポリエチレンオキサイド（ＥＯ）とポリプロピレンオキサイド（ＰＯ）からなり、一般式（ＥＯ）ｘ（ＰＯ）ｙ（ＥＯ）ｘで表されるものが挙げられる。ｘ、ｙはそれぞれＥＯ、ＰＯの繰り返し数を表すが、ｘは５〜１１０、ｙは１５〜７０であることが好ましく、ｘは１３〜１０６、ｙは２９〜７０であることがより好ましい。上記のトリブロックコポリマーとしては、（ＥＯ）１９（ＰＯ）２９（ＥＯ）１９、（ＥＯ）１３（ＰＯ）７０（ＥＯ）１３、（ＥＯ）５（ＰＯ）７０（ＥＯ）５、（ＥＯ）１３（ＰＯ）３０（ＥＯ）１３、（ＥＯ）２０（ＰＯ）３０（ＥＯ）２０、（ＥＯ）２６（ＰＯ）３９（ＥＯ）２６、（ＥＯ）１７（ＰＯ）５６（ＥＯ）１７、（ＥＯ）１７（ＰＯ）５８（ＥＯ）１７、（ＥＯ）２０（ＰＯ）７０（ＥＯ）２０、（ＥＯ）８０（ＰＯ）３０（ＥＯ）８０、（ＥＯ）１０６（ＰＯ）７０（ＥＯ）１０６、（ＥＯ）１００（ＰＯ）３９（ＥＯ）１００、（ＥＯ）１９（ＰＯ）３３（ＥＯ）１９、（ＥＯ）２６（ＰＯ）３６（ＥＯ）２６が挙げられる。これらのトリブロックコポリマーはＢＡＳＦ社、アルドリッチ社等から入手可能であり、また、小規模製造レベルで所望のｘ値とｙ値を有するトリブロックコポリマーを得ることができる。 Further, as such a surfactant, a triblock copolymer type polyalkylene oxide may be used. Examples of such surfactants include those composed of polyethylene oxide (EO) and polypropylene oxide (PO) and represented by the general formula (EO) x (PO) y (EO) x . x and y represent the number of repetitions of EO and PO, respectively, x is preferably 5 to 110, y is preferably 15 to 70, x is preferably 13 to 106, and y is more preferably 29 to 70. Examples of the triblock copolymer include (EO) 19 (PO) 29 (EO) 19 , (EO) 13 (PO) 70 (EO) 13 , (EO) 5 (PO) 70 (EO) 5 , (EO). 13 (PO) 30 (EO) 13 , (EO) 20 (PO) 30 (EO) 20 , (EO) 26 (PO) 39 (EO) 26 , (EO) 17 (PO) 56 (EO) 17 , ( EO) 17 (PO) 58 (EO) 17 , (EO) 20 (PO) 70 (EO) 20 , (EO) 80 (PO) 30 (EO) 80 , (EO) 106 (PO) 70 (EO) 106 , (EO) 100 (PO) 39 (EO) 100 , (EO) 19 (PO) 33 (EO) 19 , (EO) 26 (PO) 36 (EO) 26 . These triblock copolymers are available from BASF, Aldrich, etc., and triblock copolymers having desired x and y values can be obtained at a small scale production level.
また、エチレンジアミンの２個の窒素原子にそれぞれ２本のポリエチレンオキサイド（ＥＯ）鎖−ポリプロピレンオキサイド（ＰＯ）鎖が結合したスターダイブロックコポリマーも使用することができる。このようなスターダイブロックコポリマーとしては、一般式（（ＥＯ）ｘ（ＰＯ）ｙ）２ＮＣＨ２ＣＨ２Ｎ（（ＰＯ）ｙ（ＥＯ）ｘ）２で表されるものが挙げられる。ここでｘ、ｙはそれぞれＥＯ、ＰＯの繰り返し数を表すが、ｘは５〜１１０、ｙは１５〜７０であることが好ましく、ｘは１３〜１０６、ｙは２９〜７０であることがより好ましい。 Also, a star diblock copolymer in which two polyethylene oxide (EO) chains-polypropylene oxide (PO) chains are bonded to two nitrogen atoms of ethylenediamine can be used. Examples of such star diblock copolymers include those represented by the general formula ((EO) x (PO) y ) 2 NCH 2 CH 2 N ((PO) y (EO) x ) 2 . Here, x and y represent the number of repetitions of EO and PO, respectively, x is preferably 5 to 110, y is preferably 15 to 70, x is 13 to 106, and y is 29 to 70. preferable.
このような界面活性剤の中では、結晶性の高い繊維状の酸化マンガンがより得られ易いという観点から、アルキルトリメチルアンモニウム［ＣｐＨ２ｐ＋１Ｎ（ＣＨ３）３］の塩（好ましくはハロゲン化物塩）を用いることが好ましい。また、その場合は、アルキルトリメチルアンモニウム中のアルキル基の炭素数は１２〜２０であることがより好ましい。このようなものとしては、塩化オクタデシルトリメチルアンモニウム、塩化セチルトリメチルアンモニウム、塩化テトラデシルトリメチルアンモニウム、塩化ドデシルトリメチルアンモニウム、臭化オクタデシルトリメチルアンモニウム、臭化セチルトリメチルアンモニウム、臭化テトラデシルトリメチルアンモニウム、臭化ドデシルトリメチルアンモニウム等が挙げられる。 Among such surfactants, a salt (preferably a halide) of alkyltrimethylammonium [C p H 2p + 1 N (CH 3 ) 3 ] from the viewpoint that fiber-like manganese oxide having high crystallinity is more easily obtained. Salt) is preferably used. In that case, the alkyl group in the alkyltrimethylammonium preferably has 12 to 20 carbon atoms. These include octadecyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, dodecyl bromide. And trimethylammonium.
また、第一の工程において、前記マンガン塩と前記界面活性剤とを含有する水溶液中で前記マンガンのゾルを析出せしめて加水分解及び縮合反応せしめる方法は特に制限されないが、水又は水と有機溶媒との混合溶媒を溶媒として使用し、塩基の存在下で前記マンガンのゾルを析出せしめて加水分解及び縮合反応せしめることが好ましい。ここで好適に用いられる有機溶媒としてはアルコール、アセトン等が挙げられ、混合溶媒とする場合の有機溶媒の含有量は５〜５０重量％程度であることが好ましい。また、ゾルを析出せしめるために使用される塩基としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化カルシウム、水酸化アンモニウム等が挙げられ、溶液のｐＨは７〜１１、より好ましくは８〜９の弱塩基性であることが好ましい。 In the first step, the method for depositing the manganese sol in an aqueous solution containing the manganese salt and the surfactant to cause hydrolysis and condensation reaction is not particularly limited, but water or water and an organic solvent. It is preferable that the manganese sol is precipitated in the presence of a base to cause hydrolysis and condensation reaction. Examples of the organic solvent suitably used here include alcohol, acetone and the like, and the content of the organic solvent in the mixed solvent is preferably about 5 to 50% by weight. Examples of the base used for precipitating the sol include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, ammonium hydroxide, and the pH of the solution is 7 to 11, more preferably It is preferably 8 to 9 weakly basic.
このような第一の工程における前記マンガン塩の含有量は、１０〜２５０ｇ／Ｌ程度であることが好ましい。マンガン塩の含有量が前記下限未満では酸化マンガンの超微細繊維の形成が不完全となる傾向にあり、他方、前記上限を超えると非多孔性の塊状の析出物が生成する割合が増大する傾向にある。また、第一の工程における前記界面活性剤の濃度は５０〜５００ｇ／Ｌ程度であることが好ましい。界面活性剤の濃度が前記下限未満では細孔の形成が不完全となる傾向にあり、他方、前記上限を超えると未反応で溶液中に残留する界面活性剤の量が増大して細孔の均一性が低下する傾向にある。さらに、第一の工程における前記マンガン塩と前記界面活性剤との比率（モル比）は、０．１：１〜１：１の範囲であることが好ましい。前記マンガン塩の比率が前記下限未満では、マンガン塩に対する界面活性剤の量が過度に多くなり、未反応の界面活性剤が増大して細孔の均一性が低下する傾向にあり、他方、前記上限を超えると、マンガン塩に対する界面活性剤の量が過度に少なくなり、細孔の形成が不完全となる傾向にある。 The manganese salt content in the first step is preferably about 10 to 250 g / L. If the content of manganese salt is less than the lower limit, the formation of ultrafine manganese oxide fibers tends to be incomplete. On the other hand, if the content exceeds the upper limit, the proportion of non-porous massive precipitates tends to increase. It is in. Moreover, it is preferable that the density | concentration of the said surfactant in a 1st process is about 50-500 g / L. If the concentration of the surfactant is less than the lower limit, pore formation tends to be incomplete, whereas if the upper limit is exceeded, the amount of unreacted surfactant remaining in the solution increases, resulting in pore formation. Uniformity tends to decrease. Furthermore, the ratio (molar ratio) between the manganese salt and the surfactant in the first step is preferably in the range of 0.1: 1 to 1: 1. When the ratio of the manganese salt is less than the lower limit, the amount of the surfactant relative to the manganese salt is excessively increased, and the unreacted surfactant tends to increase and the uniformity of the pores tends to decrease. When the upper limit is exceeded, the amount of the surfactant with respect to the manganese salt becomes excessively small, and the pore formation tends to be incomplete.
また、上記第一の工程における諸条件（温度、時間、等）は特に制限されず、用いるマンガン塩や界面活性剤等に応じて適宜選択されるが、一般的には２０〜９０℃程度の温度で８〜１００時間程度の時間、前記マンガン塩と前記界面活性剤とを含有する水溶液中で前記マンガンのゾルを加水分解及び縮合反応せしめ、熟成させることが好ましい。この温度が上記下限未満では加水分解が十分に促進されない傾向にあり、他方、上記上限を超えると耐圧性に優れた反応容器が必要になりコスト高となる傾向にある。また、この時間が上記下限未満では加水分解が十分に促進されない傾向にあり、他方、上記上限を超えると加水分解は飽和に達し、無意味な時間を費やすこととなる傾向にある。 In addition, the conditions (temperature, time, etc.) in the first step are not particularly limited and are appropriately selected according to the manganese salt, surfactant, etc. to be used, but generally about 20 to 90 ° C. Preferably, the manganese sol is hydrolyzed and condensed in an aqueous solution containing the manganese salt and the surfactant for about 8 to 100 hours at a temperature and aged. If this temperature is less than the above lower limit, hydrolysis tends not to be promoted sufficiently. On the other hand, if it exceeds the above upper limit, a reaction vessel having excellent pressure resistance is required and the cost tends to increase. On the other hand, if this time is less than the above lower limit, hydrolysis tends not to be sufficiently promoted. On the other hand, if the upper limit is exceeded, hydrolysis reaches saturation, and there is a tendency to spend meaningless time.
このように、本発明にかかる酸化マンガン多孔体を製造する方法においては、先ず、マンガン塩と界面活性剤とを含有する水溶液中で前記マンガンのゾルを加水分解及び縮合反応せしめるが、（i）予めマンガン塩を含有する水溶液中に塩基を添加してマンガンのゾルを生成させておき、そこに界面活性剤を添加してマンガンのゾルを加水分解及び縮合反応せしめる方法であっても、（ii）マンガン塩と界面活性剤と塩基とを含有する水溶液中でマンガンのゾルを生成せしめると共に加水分解及び縮合反応せしめる方法であってもよい。 Thus, in the method for producing a porous manganese oxide according to the present invention, first, the manganese sol is hydrolyzed and condensed in an aqueous solution containing a manganese salt and a surfactant. Even in a method in which a base is added to an aqueous solution containing a manganese salt in advance to form a manganese sol, and a surfactant is added thereto to cause hydrolysis and condensation reaction of the manganese sol. ) A method in which a manganese sol is produced in an aqueous solution containing a manganese salt, a surfactant and a base, and a hydrolysis and condensation reaction is performed.
いずれの方法であっても、テンプレートとしての前記界面活性剤はミセルを形成し、その界面活性剤のミセルは規則正しく配列し、界面活性剤の周囲に前記マンガンのゾルが集合することによって有機／無機複合体のゲルが生成される。そして、前記マンガンのゾルの加水分解及び縮合反応が促進して熟成され、三次元的に配列された界面活性剤とその周囲に形成された酸化マンガンとからなる有機／無機複合体が生成される。このような有機／無機複合体は、通常沈殿として水溶液中に沈殿するので、得られた有機／無機複合体をろ過、洗浄、乾燥して以下の第二の工程に供することが好ましい。 In any method, the surfactant as a template forms micelles, the micelles of the surfactant are regularly arranged, and the manganese sol collects around the surfactant to form organic / inorganic. A composite gel is produced. Then, the hydrolysis and condensation reaction of the manganese sol is accelerated and ripened to produce an organic / inorganic composite composed of a three-dimensionally arranged surfactant and manganese oxide formed around the surfactant. . Since such an organic / inorganic composite is usually precipitated in an aqueous solution as a precipitate, the obtained organic / inorganic composite is preferably filtered, washed and dried and then subjected to the following second step.
次に、本発明にかかる酸化マンガン多孔体を製造する方法においては、前記第一の工程において得られた有機／無機複合体から界面活性剤を除去して多孔体前駆体を得る（第二の工程）。 Next, in the method for producing a manganese oxide porous body according to the present invention, a surfactant is removed from the organic / inorganic composite obtained in the first step to obtain a porous body precursor (second Process).
このように界面活性剤を除去する方法としては、例えば、（i）界面活性剤に対する溶解度が高い溶媒（例えば、メタノール、エタノール、アセトン、水）中に前記有機／無機複合体を浸漬して界面活性剤を除去する方法、（ii）前記有機／無機複合体を空気中又は不活性ガス中において４００〜７００℃で４〜６時間焼成して界面活性剤を除去する方法を挙げることができる。このような第二の工程によって、前記有機／無機複合体において界面活性剤（界面活性剤イオン）が存在していた部位に空孔や歪みが形成され、粒子状の多孔体前駆体が得られる。 As a method for removing the surfactant in this way, for example, (i) the organic / inorganic composite is immersed in a solvent (for example, methanol, ethanol, acetone, water) having a high solubility in the surfactant. Examples thereof include a method for removing the activator, and (ii) a method for removing the surfactant by baking the organic / inorganic composite in air or an inert gas at 400 to 700 ° C. for 4 to 6 hours. By such a second step, pores and strains are formed at the site where the surfactant (surfactant ion) was present in the organic / inorganic composite, and a particulate porous precursor is obtained. .
次に、本発明にかかる酸化マンガン多孔体を製造する方法においては、前記第二の工程において得られた多孔体前駆体を、ｐＫａが２．５以下である酸の５ｍｏｌ／Ｌ以上の濃度の水溶液を用いて酸処理し、酸化マンガンの超微細繊維が凝集して中心細孔直径１〜２０ｎｍの二次細孔が形成されている多孔体を得る（第三の工程）。 Next, in the method for producing a manganese oxide porous body according to the present invention, the porous body precursor obtained in the second step has a concentration of 5 mol / L or more of an acid having a pKa of 2.5 or less. Acid treatment is performed using an aqueous solution to obtain a porous body in which ultrafine fibers of manganese oxide are aggregated to form secondary pores having a central pore diameter of 1 to 20 nm (third step).
本発明にかかる第三の工程において使用する酸は、ｐＫａが２．５以下（より好ましくは−３〜２．２）のものであり、硫酸、硝酸、塩酸、燐酸等の無機酸、並びにベンゼンスルホン酸、ナフタレンスルホン酸等の有機酸が挙げられる。ｐＫａが２．５を超える酸では、超微細繊維への改質が不十分となり、吸着特性や触媒活性が十分に向上した多孔体が得られない。また、本発明にかかる第三の工程において使用する水溶液は、前記酸の５ｍｏｌ／Ｌ以上（より好ましくは５〜２０ｍｏｌ／Ｌ）の濃度の水溶液である。前記酸を用いた場合であっても、その濃度が５ｍｏｌ／Ｌ未満では、超微細繊維への改質が不十分となり、吸着特性や触媒活性が十分に向上した多孔体が得られない。 The acid used in the third step according to the present invention has a pKa of 2.5 or less (more preferably -3 to 2.2), an inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and benzene. Examples thereof include organic acids such as sulfonic acid and naphthalenesulfonic acid. If the acid has a pKa of more than 2.5, the modification to ultrafine fibers becomes insufficient, and a porous body with sufficiently improved adsorption characteristics and catalytic activity cannot be obtained. The aqueous solution used in the third step according to the present invention is an aqueous solution having a concentration of 5 mol / L or more (more preferably 5 to 20 mol / L) of the acid. Even when the acid is used, if the concentration is less than 5 mol / L, the modification to ultrafine fibers becomes insufficient, and a porous body with sufficiently improved adsorption characteristics and catalytic activity cannot be obtained.
また、上記第三の工程における諸条件（温度、時間、等）は特に制限されず、適用する酸化マンガンや酸等に応じて適宜選択されるが、一般的には２０〜１００℃程度の温度で３０分〜１０時間程度の時間、前記多孔体前駆体に対して前記酸水溶液を用いて酸処理を施すことが好ましい。この温度が上記下限未満では超微細繊維への改質が不十分となり、吸着特性や触媒活性が十分に向上した多孔体が得られない傾向にあり、他方、上記上限を超えると耐酸性に優れた反応容器が必要となりコスト高となる傾向にある。また、この時間が上記下限未満では超微細繊維への改質が不十分となり、吸着特性や触媒活性が十分に向上した多孔体が得られない傾向にあり、他方、上記上限を超えると改質は飽和に達し、無意味な時間を費やすこととなる傾向にある。 Further, various conditions (temperature, time, etc.) in the third step are not particularly limited and are appropriately selected according to the applied manganese oxide, acid, etc., but generally a temperature of about 20-100 ° C. It is preferable that the porous body precursor is subjected to an acid treatment using the acid aqueous solution for a time of about 30 minutes to 10 hours. If this temperature is less than the above lower limit, the modification to ultrafine fibers becomes insufficient, and there is a tendency that a porous body having sufficiently improved adsorption characteristics and catalytic activity is not obtained. On the other hand, if the upper limit is exceeded, the acid resistance is excellent. The reaction container tends to be expensive. Also, if this time is less than the above lower limit, the modification to ultrafine fibers becomes insufficient, and there is a tendency that a porous body having sufficiently improved adsorption characteristics and catalytic activity tends not to be obtained. Tends to reach saturation and spend meaningless time.
このような第三の工程によって、前記粒子状の多孔体前駆体が酸と反応することによって超微細繊維へと改質され、その超微細繊維の凝集により中心細孔直径１〜２０ｎｍの二次細孔が形成されて本発明にかかる酸化マンガン多孔体が得られる。 By such a third step, the particulate porous precursor is modified to ultrafine fibers by reacting with an acid, and the secondary fine particles having a central pore diameter of 1 to 20 nm are formed by aggregation of the ultrafine fibers. Fine pores are formed to obtain the manganese oxide porous body according to the present invention.
なお、上記の酸処理の後、安全性等の観点から、得られた多孔体を十分に水洗して酸をきれいに洗い流すことが好ましい。 In addition, after said acid treatment, it is preferable from a viewpoint of safety | security etc. to wash the obtained porous body fully with water, and to wash away an acid cleanly.
（金属担持多孔材料）
次に、本発明にかかる金属担持多孔材料について説明する。本発明にかかる金属担持多孔材料は、多孔材料に金属を担持させたものである。このような金属担持多孔材料は、NO２の吸収材として作用するものである。すなわち、前記金属担持多孔材料においては、前記多孔材料のマイクロ孔の物理吸着作用によって気中の希薄な窒素酸化物を吸着、濃縮することが可能となると同時に、濃縮されたそれらの酸化物を外表面に担持された金属（活性成分）で遂次化学的に捕捉することが可能となる。このように、本発明にかかる金属担持多孔材料においては、物理吸着作用及び化学吸着作用の複合効果により気中に含有される低濃度の窒素酸化物を効果的に吸着除去することが可能となる。
(Metal-supported porous material)
Next, the metal-supporting porous material according to the present invention will be described. The metal-supporting porous material according to the present invention is obtained by supporting a metal on a porous material. Such a metal-supporting porous material acts as an NO 2 absorbent. That is, in the metal-supporting porous material, it is possible to adsorb and concentrate dilute nitrogen oxides in the air by the physical adsorption action of the micropores of the porous material, and at the same time remove the concentrated oxides. It becomes possible to sequentially capture chemically with the metal (active component) supported on the surface. As described above, in the metal-supported porous material according to the present invention, it is possible to effectively adsorb and remove low-concentration nitrogen oxides contained in the air by the combined effect of physical adsorption and chemical adsorption. .
前記多孔材料としては、活性炭、チタニア、セピオライト、ゼオライト、シリカゲル、アルミナ、セリア、セリア-ジルコニア複合酸化物等が挙げられる。このような多孔材料の中でも、より高い吸着能を発揮できるという観点から、活性炭、シリカゲル、ゼオライト、セピオライト、アルミナ及びセリアからなる群から選択される少なくとも１種を用いることが好ましい。また、このような多孔材料は、１種を単独で、若しくは２種以上を混合して用いることができる。 Examples of the porous material include activated carbon, titania, sepiolite, zeolite, silica gel, alumina, ceria, ceria-zirconia composite oxide, and the like. Among such porous materials, it is preferable to use at least one selected from the group consisting of activated carbon, silica gel, zeolite, sepiolite, alumina, and ceria from the viewpoint that higher adsorption ability can be exhibited. Moreover, such a porous material can be used individually by 1 type or in mixture of 2 or more types.
また、前記金属としては、例えば無電解めっき法により金属担持多孔材料を調整する場合には、無電解めっき法により前記多孔材料に担持させることが容易な金属種であるという観点から、白金（Ｐｔ）、ルテニウム（Ｒｕ）、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）、銀（Ａｇ）、金（Ａｕ）、オスミウム（Ｏｓ）、銅（Ｃｕ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、鉄（Ｆｅ）、スズ（Ｓｎ）等が好ましい。また、このような金属の中でも、ＮＯ２との反応性が高く吸着能をより向上させることができるという観点からＮｉを用いることが特に好ましい。このような金属は単独で、若しくは２種以上の混合物や合金として使用することができる。また、前記金属を無電解めっき法により前記多孔材料に担持させる場合には、金属間の電位差を利用して異種金属を積層化させて使用することもできる。更に、前記金属を無電解めっき法により前記多孔材料に担持させた後に、前記金属を薬剤及び熱処理等により酸化させて金属酸化物として使用することもできる。なお、無電解めっき法により担持可能な金属種について、以下において電位とｐHとの関係における各金属の析出曲線のグラフを示す図１に基づいて説明する。 In addition, as the metal, for example, when preparing a metal-supporting porous material by an electroless plating method, platinum (Pt) is used from the viewpoint that it is a metal species that can be easily supported on the porous material by an electroless plating method. ), Ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), gold (Au), osmium (Os), copper (Cu), cobalt (Co), nickel (Ni), iron (Fe) ), Tin (Sn) and the like are preferable. Among these metals, it is particularly preferable to use Ni from the viewpoint that the reactivity with NO 2 is high and the adsorption ability can be further improved. Such metals can be used alone or as a mixture or alloy of two or more. Further, when the metal is supported on the porous material by an electroless plating method, different metals can be laminated using a potential difference between the metals. Furthermore, after the metal is supported on the porous material by an electroless plating method, the metal can be oxidized by a chemical agent, heat treatment or the like and used as a metal oxide. The metal species that can be supported by the electroless plating method will be described below with reference to FIG. 1 showing a graph of the precipitation curve of each metal in the relationship between potential and pH.
図１には、各金属固有の析出曲線が示されている。また、各金属は析出曲線より低い電位においては金属イオンの状態が安定であり、他方、析出曲線より高い電位においては金属の状態が安定である。ここで、無電解めっき法において金属を析出させる駆動力は、還元剤の酸化還元電位と析出金属の還元電位との差によって与えられるものである。従って、水素の発生電位曲線よりも高い析出曲線で示されるＡｕ、Ｐｔ、Ａｇ等の貴金属は金属として析出しやすく、次いでＣｕ、Ｎｉ、Ｃｏ等が析出しやすいと言える。一方、水素の発生電位曲線より低い析出曲線で示される亜鉛（Ｚｎ）等の卑金属においては金属イオンを還元剤で還元する際、金属の析出反応よりも水素発生反応の方が優先して起きるので、金属として析出させるのは困難と考えられる。従って、無電解めっき法により前記多孔材料に担持させるのに好適な金属種としては、図１に示す金属の析出曲線が水素の発生電位曲線の近傍及びそれ以上の電位に位置するＰｔ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ａｕ、Ｏｓ、Ｃｕ、Ｃｏ、Ｎｉ、Ｆｅ、Ｓｎ等が挙げられる。 FIG. 1 shows a deposition curve specific to each metal. Each metal has a stable metal ion state at a potential lower than the precipitation curve, while the metal state is stable at a potential higher than the precipitation curve. Here, the driving force for depositing metal in the electroless plating method is given by the difference between the redox potential of the reducing agent and the reduction potential of the deposited metal. Accordingly, it can be said that noble metals such as Au, Pt, and Ag, which are indicated by a precipitation curve higher than the hydrogen generation potential curve, are likely to precipitate as metals, and then Cu, Ni, Co, and the like are likely to precipitate. On the other hand, in the case of a base metal such as zinc (Zn) shown by a precipitation curve lower than the hydrogen generation potential curve, when the metal ion is reduced with a reducing agent, the hydrogen generation reaction takes precedence over the metal precipitation reaction. It is considered difficult to deposit as a metal. Accordingly, as a metal species suitable for supporting the porous material by electroless plating, the metal deposition curve shown in FIG. 1 is located near or above the hydrogen generation potential curve, such as Pt, Ru, Rh, Pd, Ag, Au, Os, Cu, Co, Ni, Fe, Sn, etc. are mentioned.
また、本発明にかかる金属担持多孔材料の比表面積については特に制限はないが、１００〜１０００ｍ２／ｇ程度であることが好ましい。さらに、本発明にかかる金属担持多孔材料の細孔容積についても特に制限はないが、０．１〜１ｍｌ／ｇであることが好ましい。本発明にかかる金属担持多孔材料の比表面積及び細孔容積が上記下限未満では、吸着特性が低下してしまう傾向にあり、他方、上記上限を超えると、嵩比重が小さくなり例えば触媒層への単位容積当りの充填量が少なくなる傾向にある。 Moreover, there is no restriction | limiting in particular about the specific surface area of the metal carrying | support porous material concerning this invention, However, It is preferable that it is about 100-1000 m < 2 > / g. Further, the pore volume of the metal-supporting porous material according to the present invention is not particularly limited, but is preferably 0.1 to 1 ml / g. If the specific surface area and the pore volume of the metal-supporting porous material according to the present invention are less than the above lower limit, the adsorption characteristics tend to be reduced. On the other hand, if the upper limit is exceeded, the bulk specific gravity becomes small, for example, to the catalyst layer. The filling amount per unit volume tends to decrease.
また、本発明にかかる金属担持多孔材料の形状は特に限定されず、支持膜、自立膜、透明膜、配向膜、球状や繊維状のもの、更には、粉末、顆粒及びμｍサイズの明瞭な形態をもつ粒子等の粉体等を挙げることができるが、前記酸化マンガン多孔体と近接した状態で混合状態とすることが可能であるという観点から、その形状を粉体とすることが好ましい。このような粉体形状の金属担持多孔材料を用いる場合においては、その粉体の粒径は特に制限されないが、酸化マンガン多孔体とより近接した状態で混合状態とすることが可能であるという観点から、平均粒径を０．１〜５０μｍ程度とすることが好ましい。 In addition, the shape of the metal-supporting porous material according to the present invention is not particularly limited, and is a support film, a self-supporting film, a transparent film, an alignment film, a spherical shape or a fibrous shape, and further, a powder, a granule, and a clear form of μm size From the viewpoint that it can be mixed in a state close to the porous manganese oxide, the shape is preferably powder. In the case of using such a powder-shaped metal-supporting porous material, the particle size of the powder is not particularly limited, but it is possible to make a mixed state in a state closer to the manganese oxide porous body. Therefore, the average particle size is preferably about 0.1 to 50 μm.
また、本発明にかかる金属担持多孔材料を製造する方法としては特に制限されず、前記多孔材料に前記金属を担持させることが可能な公知の方法を適宜選択して採用することができ、例えば、無電解めっき法により製造する方法が挙げられる。 Further, the method for producing the metal-supporting porous material according to the present invention is not particularly limited, and a known method capable of supporting the metal on the porous material can be appropriately selected and employed. The method of manufacturing by an electroless plating method is mentioned.
（窒素酸化物浄化材料）
本発明の窒素酸化物浄化材料は、酸化マンガンの超微細繊維が凝集して中心細孔直径１〜２０ｎｍの二次細孔が形成されている前記酸化マンガン多孔体と、多孔材料に金属を担持させた前記金属担持多孔材料とからなることを特徴とするものである。このような窒素酸化物浄化材料によって、ＮＯｘを細孔内に速やかに拡散させ、しかも優れた吸着能及び触媒能を発揮して室温においてもＮＯを酸化できるとともにＮＯ２に対する高い吸着能を発揮して効率よく且つ確実にＮＯｘを除去することが可能となる。
(Nitrogen oxide purification material)
The nitrogen oxide purification material of the present invention comprises the manganese oxide porous body in which secondary fine pores having a central pore diameter of 1 to 20 nm are formed by agglomeration of manganese oxide ultrafine fibers, and a metal supported on the porous material And the metal-supported porous material. Such nitrogen oxide purification material, NO x rapidly diffuse into the pores and exhibits a high adsorption capacity for NO 2 addition with capable of oxidizing NO even at room temperature to exhibit excellent adsorption ability and catalytic ability Thus, NO x can be efficiently and reliably removed.
このような窒素酸化物浄化材料における前記酸化マンガン多孔体の含有量としては、窒素酸化物浄化材料中に１０〜９０質量％であることが好ましく、４０〜８０質量％であることがより好ましい。このような酸化マンガン多孔体の含有量が前記下限未満では、得られる窒素酸化物浄化材料のＮＯを酸化する性能が低下する傾向にあり、他方、前記上限を超えると、前記金属担持多孔材料の含有量が少なくなるため窒素酸化物浄化材料のＮＯ２を吸着、除去する性能が低下する傾向にある。 As content of the said manganese oxide porous body in such a nitrogen oxide purification material, it is preferable that it is 10-90 mass% in a nitrogen oxide purification material, and it is more preferable that it is 40-80 mass%. When the content of such a manganese oxide porous material is less than the lower limit, the performance of oxidizing NO of the obtained nitrogen oxide purification material tends to be reduced. On the other hand, when the content exceeds the upper limit, the metal-supporting porous material Since the content is reduced, the performance of adsorbing and removing NO 2 of the nitrogen oxide purification material tends to decrease.
本発明の窒素酸化物浄化材料としては、前記酸化マンガン多孔体と前記金属担持多孔材料とを混ぜただけのものでもよいが、前記酸化マンガン多孔体と前記金属担持多孔材料とを混ぜたものを所定の形状に成形して使用してもよい。このような成形する手段としては特に制限されないが、押出成形、打錠成形、転動造粒、圧縮成形、ＣＩＰ等を好適に採用することができる。また、その形状は、使用する箇所及び方法に応じて決めることができ、例えば円柱状、破砕状、球状、ハニカム状、凹凸状、波板状等が挙げられる。 The nitrogen oxide purification material of the present invention may be a mixture of the manganese oxide porous body and the metal-supporting porous material, but a mixture of the manganese oxide porous body and the metal-supporting porous material. You may use it shape | molded in a defined shape. Such a molding means is not particularly limited, and extrusion molding, tableting molding, rolling granulation, compression molding, CIP and the like can be suitably employed. Moreover, the shape can be determined according to the location and method to be used, and examples thereof include a columnar shape, a crushed shape, a spherical shape, a honeycomb shape, an uneven shape, and a corrugated shape.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.
［合成例１：多孔体前駆体］
塩化マンガン（ＭｎＣｌ２）１１．９ｇを水５０ｍＬに溶解した。また、水酸化ナトリウム（ＮａＯＨ）２．４ｇを水５０ｍＬに溶解した。次いで、上記ＭｎＣｌ２水溶液中に上記ＮａＯＨ水溶液を攪拌下で滴下し、溶液中にマンガンのゾルを生成させた。
[Synthesis Example 1: Porous body precursor]
11.9 g of manganese chloride (MnCl 2 ) was dissolved in 50 mL of water. Moreover, 2.4 g of sodium hydroxide (NaOH) was dissolved in 50 mL of water. Next, the NaOH aqueous solution was dropped into the MnCl 2 aqueous solution with stirring to form a manganese sol in the solution.
一方、臭化セチルトリメチルアンモニウム（ＣＴＡＢ）６６．７ｇを水１５０ｍＬに溶解した。このとき、水温を３５℃に保ちながら攪拌下でＣＴＡＢを少量ずつ加え、溶解させた。 On the other hand, 66.7 g of cetyltrimethylammonium bromide (CTAB) was dissolved in 150 mL of water. At this time, CTAB was added little by little with stirring while keeping the water temperature at 35 ° C., and dissolved.
次に、上記マンガンのゾルを生成させた溶液を７５℃に昇温し、そこに上記ＣＴＡＢ水溶液を少量ずつ加え、ＣＴＡＢ水溶液を全量加えた後に温度を７５℃に保ちつつ１時間攪拌した。その後、得られた混合溶液を７５℃に設定した恒温槽に入れ、４８時間熟成させた。４８時間経過後、沈殿が生成した混合溶液を恒温槽から取り出し、吸引ろ過を行い、固形分を室温で２４時間乾燥した。更に、その固形分を６０℃に設定された乾燥機中で６時間乾燥させることにより、有機／無機複合体を得た。 Next, the temperature of the solution in which the manganese sol was formed was raised to 75 ° C., and the CTAB aqueous solution was added little by little, and after adding the entire amount of the CTAB aqueous solution, the solution was stirred for 1 hour while maintaining the temperature at 75 ° C. Then, the obtained mixed solution was put into a thermostat set at 75 ° C. and aged for 48 hours. After 48 hours, the mixed solution in which the precipitate was generated was taken out from the thermostatic bath, suction filtered, and the solid content was dried at room temperature for 24 hours. Further, the solid content was dried in a drier set at 60 ° C. for 6 hours to obtain an organic / inorganic composite.
次いで、得られた有機/無機複合体を乳鉢を用いて粉末状とし、これを電気炉にて昇温速度２℃／分で５００℃まで昇温し、その温度で４時間焼成してＣＴＡＢを除去することにより、酸化マンガンからなる粒子状の多孔体前駆体を得た。得られた多孔体前駆体の透過型電子顕微鏡（ＴＥＭ）写真を図２に示す。また、得られた多孔体前駆体の比表面積及び細孔容積を表１に示す。 Next, the obtained organic / inorganic composite is powdered using a mortar, and this is heated to 500 ° C. at a heating rate of 2 ° C./min in an electric furnace, and calcined at that temperature for 4 hours to obtain CTAB. By removing, a particulate porous precursor made of manganese oxide was obtained. A transmission electron microscope (TEM) photograph of the obtained porous precursor is shown in FIG. Table 1 shows the specific surface area and pore volume of the obtained porous precursor.
［合成例２：酸化マンガン多孔体］
合成例１で得られた多孔体前駆体に対して更に以下の酸処理を施して酸化マンガン多孔体を製造した。すなわち、前記粒子状の多孔体前駆体５ｇを１０ｍｏｌ／Ｌ硫酸１００ｍＬ中に分散させ、２５℃で２時間攪拌して反応させた。次いで、得られた固形分をろ過し、水洗をした後、乾燥させることにより、酸化マンガンの超微細繊維が凝集して二次細孔を形成した酸化マンガン多孔体を得た。得られた酸化マンガン多孔体の透過型電子顕微鏡（ＴＥＭ）写真を図３に示す。また、得られた酸化マンガン多孔体の比表面積及び細孔容積を表１に示し、合成例１で得られた多孔体前駆体及び合成例２で得られた酸化マンガン多孔体の細孔分布曲線のグラフを図４に示す。
[Synthesis Example 2: Manganese oxide porous body]
The porous body precursor obtained in Synthesis Example 1 was further subjected to the following acid treatment to produce a manganese oxide porous body. That is, 5 g of the particulate porous precursor was dispersed in 100 mL of 10 mol / L sulfuric acid and stirred at 25 ° C. for 2 hours for reaction. Subsequently, the obtained solid content was filtered, washed with water, and dried to obtain a manganese oxide porous body in which ultrafine fibers of manganese oxide aggregated to form secondary pores. A transmission electron microscope (TEM) photograph of the obtained manganese oxide porous material is shown in FIG. The specific surface area and the pore volume of the obtained manganese oxide porous material are shown in Table 1, and the pore distribution curve of the porous material precursor obtained in Synthesis Example 1 and the manganese oxide porous material obtained in Synthesis Example 2 This graph is shown in FIG.
［合成例３：金属担持多孔材料］
先ず、金属塩として塩化パラジウム(II)１６２ｍｇをイオン交換水１Ｌに溶解させて溶液を得た。次いで、強く撹拌しながら１ｗｔ％ｎ−ドデシルベンゼンスルホン酸ナトリウム水溶液１０ｍＬを前記溶液に加え、さらに０．１５ｗｔ％水素化ほう素ナトリウム水溶液５０ｍＬを加えることにより、パラジウムコロイドを調製した。このパラジウムコロイド１Ｌに多孔材料として粉末状のヤシ殻活性炭（キャタラー社製、製品名：ＢＦＧ）６．５ｇを加え、３時間隔拌した後、濾過、水洗、乾燥をさせてパラジウムコロイド粒子が吸着担持されたヤシ殻活性炭粉末を得た。
[Synthesis Example 3: Metal-supporting porous material]
First, 162 mg of palladium (II) chloride as a metal salt was dissolved in 1 L of ion-exchanged water to obtain a solution. Next, 10 mL of a 1 wt% sodium n-dodecylbenzenesulfonate aqueous solution was added to the solution with vigorous stirring, and 50 mL of a 0.15 wt% sodium borohydride aqueous solution was further added to prepare a palladium colloid. 6.5 g of powdered coconut shell activated carbon (product name: BFG, manufactured by Cataler Co., Ltd.) is added as a porous material to 1 L of this palladium colloid, stirred for 3 hours, filtered, washed with water and dried to adsorb palladium colloid particles. A supported coconut shell activated carbon powder was obtained.
次に、水１Ｌに対し、塩化ニッケル３０ｇ、次亜リン酸ナトリウム１０ｇ及び酢酸ナトリウム１０ｇを加えて溶解してｐＨ５．７のニッケル化学めっき液を調製した。このようにして得られたニッケル化学めっき液に先のパラジウムで活性化したヤシ殻活性炭粉末を９０℃の温度条件下において１時間浸漬した後、濾過、水洗、乾燥をさせてヤシ殻活性炭粉末の外表面にのみニッケルが担持された金属担持多孔材料を得た。なお、このようにして得られた金属担持多孔材料中のニッケルの担持量は２４．８ｗｔ％であった。 Next, 30 g of nickel chloride, 10 g of sodium hypophosphite, and 10 g of sodium acetate were added to 1 L of water and dissolved to prepare a nickel chemical plating solution having a pH of 5.7. After immersing the coconut shell activated carbon powder activated with palladium in the nickel chemical plating solution thus obtained for 1 hour at a temperature of 90 ° C., the coconut shell activated carbon powder is filtered, washed and dried. A metal-supporting porous material having nickel supported only on the outer surface was obtained. The amount of nickel supported in the metal-supported porous material thus obtained was 24.8 wt%.
（実施例１）
合成例２で得られた酸化マンガン多孔体と、合成例３で得られた金属担持多孔材料とを質量比で、酸化マンガン多孔体：金属担持多孔材料＝３：１となるようにして配合して本発明の窒素酸化物浄化材料を得た。
Example 1
The manganese oxide porous material obtained in Synthesis Example 2 and the metal-supported porous material obtained in Synthesis Example 3 were blended in a mass ratio such that manganese oxide porous material: metal-supported porous material = 3: 1. Thus, the nitrogen oxide purification material of the present invention was obtained.
（比較例１）
合成例１で得られた多孔体前駆体をそのまま比較対象としての窒素酸化物浄化材料とした。
(Comparative Example 1)
The porous body precursor obtained in Synthesis Example 1 was directly used as a nitrogen oxide purification material for comparison.
（比較例２）
過マンガン酸カリウム担持活性炭を比較対象としての窒素酸化物浄化材料とした。すなわち、先ず、過マンガン酸カリウム１ｇをイオン交換水１０ｍＬに溶解して過マンガン酸カリウム溶液を得た。次に、ヤシ殻活性炭（キャタラー社製、製品名：ＢＦＧ）１０ｇをビーカーに測り取り、これに過マンガン酸カリウム溶液を含浸させた後、乾燥させることにより過マンガン酸カリウムが担持された活性炭（過マンガン酸カリウム担持活性炭）を製造して比較対象としての窒素酸化物浄化材料を得た。
(Comparative Example 2)
Potassium permanganate-supported activated carbon was used as a nitrogen oxide purification material for comparison. That is, first, 1 g of potassium permanganate was dissolved in 10 mL of ion exchange water to obtain a potassium permanganate solution. Next, 10 g of coconut shell activated carbon (manufactured by Cataler, product name: BFG) is measured in a beaker, impregnated with a potassium permanganate solution, and then dried to activate activated carbon on which potassium permanganate is supported ( Nitrogen oxide purification material as a comparative object was obtained by manufacturing potassium permanganate-supported activated carbon).
（比較例３）
合成例２で得られた酸化マンガン多孔体をそのまま比較対象としての窒素酸化物浄化材料とした。
(Comparative Example 3)
The manganese oxide porous material obtained in Synthesis Example 2 was directly used as a nitrogen oxide purification material for comparison.
（比較例４）
合成例３で得られた金属担持多孔材料をそのまま比較対象としての窒素酸化物浄化材料とした。
(Comparative Example 4)
The metal-supported porous material obtained in Synthesis Example 3 was directly used as a nitrogen oxide purification material for comparison.
窒素酸化物浄化材料の評価
＜ＮＯの酸化性能及びＮＯｘの除去性能の評価＞
実施例１及び比較例１〜２で得られた窒素酸化物浄化材料について、以下の手順に従って吸着性能を評価した。すなわち、先ず、実施例１及び比較例１〜２で得られた窒素酸化物浄化材料をそれぞれ０．１ｇずつ、１００ｐｐｍのＮＯを含む空気５リットルを封入したガス非透過性の袋に入れて密封し、それぞれの袋を２５℃の温度条件で一定に保った恒温槽内に静置した。そして、２４時間経過後に各袋内のＮＯｘ濃度及びＮＯ２濃度をそれぞれガス検知管で測定した。このような測定により得られたＮＯｘ濃度及びＮＯ２濃度を用いて、ＮＯの酸化性能を表す尺度であるＮＯ２／ＮＯｘの比と、ＮＯｘの除去性能を表す尺度であるＮＯｘ除去率とを求めた。得られた結果を表２に示す。
Evaluation of nitrogen oxide purification material <Evaluation of removal performance of the oxidation performance and NO x of the NO>
About the nitrogen oxide purification material obtained in Example 1 and Comparative Examples 1-2, adsorption | suction performance was evaluated in accordance with the following procedures. That is, first, 0.1 g of each of the nitrogen oxide purification materials obtained in Example 1 and Comparative Examples 1 and 2 was sealed in a gas-impermeable bag containing 5 liters of air containing 100 ppm NO. And each bag was left still in the thermostat kept constant at 25 degreeC temperature conditions. Then, to measure the concentration of NO x and NO 2 concentration in each bag after a lapse of 24 hours at each gas detector tube. Using the NO x concentration and NO 2 concentration obtained by such measurement, the NO 2 / NO x ratio, which is a measure representing NO oxidation performance, and NO x removal, which is a measure representing NO x removal performance. We asked for rate. The obtained results are shown in Table 2.
表２に示す結果からも明らかなように、実施例１で得られた本発明の窒素酸化物浄化材料は、比較例１及び２で得られた比較対象としての窒素酸化物浄化材料に比べて、ＮＯの酸化性能及びＮＯｘ除去性能が共に優れていることがわかる。 As is clear from the results shown in Table 2, the nitrogen oxide purification material of the present invention obtained in Example 1 was compared with the nitrogen oxide purification material as a comparison object obtained in Comparative Examples 1 and 2. It can be seen that both NO oxidation performance and NO x removal performance are excellent.
＜ＮＯｘの除去性能の評価＞
実施例１及び比較例３〜４で得られた窒素酸化物浄化材料のＮＯｘガス吸着等温線を測定した。すなわち、先ず、実施例１及び比較例３〜４で得られた窒素酸化物浄化材料をそれぞれ０．１ｇずつ、１００、２００及び８００ｐｐｍのＮＯを含む空気５Ｌをそれぞれ封入したガス非透過性の袋に入れて密封し、それぞれの袋を２５℃の温度条件で一定に保った恒温槽内に静置した。そして、２４時間経過後に袋内のＮＯｘ濃度をガス検知管で測定し、袋に窒素酸化物浄化材料を入れないで同様に測定したブランク濃度との差に基づいてＮＯｘ吸着量を求めた。このようにして得られたＮＯｘ吸着量に基づいてＮＯｘ残留（平衡）濃度とＮＯｘ吸着量の関係（吸着等温線）をプロットした。得られた結果を図５に示す。
<Evaluation of NO x removal performance>
Was measured NO x sorption isotherms of nitrogen oxide purification material obtained in Example 1 and Comparative Examples 3-4. That is, first, 0.1 g of the nitrogen oxide purification material obtained in Example 1 and Comparative Examples 3 to 4, respectively, and a gas-impermeable bag in which 5 L of air containing 100, 200, and 800 ppm of NO was respectively enclosed. Each bag was placed in a thermostatic bath kept constant under a temperature condition of 25 ° C. Then, after 24 hours, the NO x concentration in the bag was measured with a gas detector tube, and the NO x adsorption amount was determined based on the difference from the blank concentration measured in the same manner without putting the nitrogen oxide purification material into the bag. . Based on the NO x adsorption amount thus obtained, the relationship between the NO x residual (equilibrium) concentration and the NO x adsorption amount (adsorption isotherm) was plotted. The obtained results are shown in FIG.
図５に示す結果からも明らかなように、実施例１で得られた本発明の窒素酸化物浄化材料は、比較例３及び４で得られた比較対象としての窒素酸化物浄化材料に比べて、ＮＯｘの除去性能が著しく優れていることが分かった。このことから、窒素酸化物浄化材料に酸化マンガン多孔体と金属担持多孔体とを含有させることで、相乗的にＮＯｘの除去性能が向上することが確認された。 As is clear from the results shown in FIG. 5, the nitrogen oxide purification material of the present invention obtained in Example 1 is compared with the nitrogen oxide purification material as a comparison object obtained in Comparative Examples 3 and 4. The NO x removal performance was found to be remarkably excellent. Therefore, by the nitrogen oxide purification material contains a manganese oxide porous body and the metal bearing porous body, it was confirmed that synergistically improved removal performance NO x.
以上説明したように、本発明によれば、ＮＯｘを細孔内に速やかに拡散させることができ、しかも優れた吸着能及び触媒能を発揮して室温においてもＮＯを酸化できるとともにＮＯ２に対する高い吸着能を発揮して効率よく且つ確実にＮＯｘを除去することを可能とする窒素酸化物浄化材料を提供することが可能となる。 As described above, according to the present invention, with respect to NO 2 with the NO x can be rapidly diffused into the pores, yet capable of oxidizing NO even at room temperature to exhibit excellent adsorption ability and catalytic ability It is possible to provide a nitrogen oxide purification material that exhibits a high adsorbing ability and can efficiently and reliably remove NO x .
したがって、本発明の窒素酸化物浄化材料は、ＮＯｘの除去性能に優れるため、環境汚染物質であるＮＯｘを除去するための各種材料やＮＯｘ除去システムに用いる素材等として非常に有用である。 Accordingly, the nitrogen oxide purification material of the present invention is excellent in removal performance of NO x, it is very useful as a material and the like used in various materials and NO x removal system for removing NO x which is an environmental pollutant .
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| CN114939407A (en) * | 2022-07-06 | 2022-08-26 | 四川大学 | Method for synthesizing loose porous manganese oxide and composite oxide thereof |
| CN116943638A (en) * | 2023-08-07 | 2023-10-27 | 陕西积健环保科技有限公司 | Flue gas denitration catalyst and preparation method thereof |
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