WO2011125504A1 - 活性炭及びその用途 - Google Patents
活性炭及びその用途 Download PDFInfo
- Publication number
- WO2011125504A1 WO2011125504A1 PCT/JP2011/057081 JP2011057081W WO2011125504A1 WO 2011125504 A1 WO2011125504 A1 WO 2011125504A1 JP 2011057081 W JP2011057081 W JP 2011057081W WO 2011125504 A1 WO2011125504 A1 WO 2011125504A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- activated carbon
- mass
- content
- catalyst
- nitrogen
- Prior art date
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 483
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 153
- 239000003054 catalyst Substances 0.000 claims abstract description 109
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 75
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 claims abstract description 54
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000001301 oxygen Substances 0.000 claims abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 47
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 43
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 150000002978 peroxides Chemical class 0.000 claims abstract description 35
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000000524 functional group Chemical group 0.000 claims abstract description 26
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001179 sorption measurement Methods 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims description 43
- 229910052717 sulfur Inorganic materials 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 23
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims 5
- 239000002253 acid Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 32
- 238000007254 oxidation reaction Methods 0.000 abstract description 28
- 230000003647 oxidation Effects 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- -1 hydrogen peroxide) Chemical class 0.000 abstract description 6
- 239000005864 Sulphur Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 68
- 230000004913 activation Effects 0.000 description 58
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 54
- 239000002994 raw material Substances 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 239000007789 gas Substances 0.000 description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 description 27
- 239000001569 carbon dioxide Substances 0.000 description 27
- 238000000197 pyrolysis Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 18
- 238000003763 carbonization Methods 0.000 description 17
- 239000000460 chlorine Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 15
- 229910052801 chlorine Inorganic materials 0.000 description 15
- 230000000704 physical effect Effects 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 11
- 239000002802 bituminous coal Substances 0.000 description 11
- 239000003610 charcoal Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 239000003575 carbonaceous material Substances 0.000 description 10
- 239000003245 coal Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 235000013162 Cocos nucifera Nutrition 0.000 description 8
- 244000060011 Cocos nucifera Species 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 229920002239 polyacrylonitrile Polymers 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 6
- 239000003830 anthracite Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- FNZYUTOJOHLTMX-UHFFFAOYSA-N ClN.ClN Chemical compound ClN.ClN FNZYUTOJOHLTMX-UHFFFAOYSA-N 0.000 description 3
- 229910002089 NOx Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- WQDWFCGISCUJEK-UHFFFAOYSA-N [Cl].ClN Chemical compound [Cl].ClN WQDWFCGISCUJEK-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229960003753 nitric oxide Drugs 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- QEHKBHWEUPXBCW-UHFFFAOYSA-N nitrogen trichloride Chemical compound ClN(Cl)Cl QEHKBHWEUPXBCW-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 231100000676 disease causative agent Toxicity 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HDNHWROHHSBKJG-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol Chemical compound O=C.OCC1=CC=CO1 HDNHWROHHSBKJG-UHFFFAOYSA-N 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 208000007475 hemolytic anemia Diseases 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002678 semianthracite Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003476 subbituminous coal Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
Definitions
- the present invention relates to activated carbon effective as a catalyst (oxidation reaction catalyst, decomposition catalyst, etc.) in organic synthesis and the like, and an application utilizing the catalytic activity of this activated carbon. More particularly, the present invention relates to activated carbon (eg, N-phosphonomethyliminodiacetic acid to N-phosphonomethyl) useful as, for example, a decomposition catalyst (or oxidation catalyst) for peroxide and / or chloramine (chloroamine).
- an activated carbon catalyst capable of maintaining the hydrogen peroxide decomposition function in an aqueous solution and maintaining the performance continuously, and its use (eg, production method of N-phosphonomethylglycine, removal of chloramine) Method).
- activated carbon itself acts as a catalyst.
- activated carbon is known to be useful for various oxidation reactions including oxidation of hydrogen sulfide and SO 2 .
- Activated carbon has been observed to affect such reactions, activated carbon as a catalyst affects only the reaction rate, and activated carbon itself is hardly altered by the reaction.
- Activated carbon produced from raw materials rich in nitrogen effectively catalyzes in specific reactions such as decomposition of hydrogen peroxide, compared with activated carbon produced from raw materials low in nitrogen.
- a nitrogen-containing compound such as ammonia at a high temperature
- the catalytic function of the activated carbon is enhanced.
- activated carbon having a high catalytic activity has been produced by carbonizing a nitrogen-rich substance such as polyacrylonitrile and polyamide at a low temperature or a high temperature and activating (activating) the carbonized material. In either case, the activated carbon is produced by heat treatment at a temperature exceeding 700 ° C. It is also known that it is advantageous to oxidize activated carbon produced from raw materials with low nitrogen content before or during exposure to nitrogen-containing compounds.
- JP-A-60-246328 Patent Document 1
- an activated carbon catalyst from which oxides have been removed from the surface is used and reacted in the presence of oxygen or an oxygen-containing gas, and N-phosphonomethyliminodiacetic acid is used.
- the production of N-phosphonomethylglycine is disclosed.
- the activated carbon catalyst is a method in which carbon is exposed to an oxidizing agent (such as nitric acid) and thermally decomposed in an oxygen-free atmosphere at 800 to 1200 ° C., while an air stream of ammonia and oxygen-containing gas is passed over the carbon. It is also described that it is obtained by a thermal decomposition method at 1200 ° C. In the method of treating a carbon material with this chemical, as described above, it is necessary to use a hazardous chemical that is toxic, and a large amount of toxic and dangerous by-products are produced.
- Patent Document 2 discloses a catalytically active carbonaceous char that rapidly decomposes hydrogen peroxide in an aqueous solution.
- This reference describes the carbonaceous char by oxidation of bituminous coal or bituminous coal-like substance.
- the raw material is oxidized at low temperature, exposed to nitrogen-containing compounds such as urea, heated at high temperature in an inert atmosphere, calcined or activated at high temperature in steam and / or carbon dioxide, The production of carbonaceous char by cooling in an inert atmosphere is described.
- nitrogen-containing compounds such as urea
- Patent Document 3 discloses a method for synthesizing N-phosphonomethylglycine from N-phosphonomethyliminodiacetic acid in the presence of water, hydrogen peroxide and activated carbon.
- the literature describes that commercially available activated carbon can be used and that it can be reused many times.
- the activated carbon has not been optimized, the catalytic activity of the activated carbon is low, and the catalytic activity is greatly reduced by recycling. Further, since no optimization index is shown for the catalytic activity of activated carbon, the influence of the activated carbon catalyst on the method for producing N-phosphonomethylglycine is unknown.
- Patent Document 4 discloses that a catalyst for hydrogen peroxide decomposition is a raw material of protein or polyacrylonitrile fibrous activated carbon, 1 to 5% by weight of nitrogen, 3 to 30% by weight of oxygen, carbon Activated carbon is disclosed that contains 40-95% by weight, has an average pore radius of 15-30 mm, and has at least 50% by volume of perforated mesopores per total volume. Examples in this document describe activated carbon with 2.1 to 4.1 wt% nitrogen and 7.6 to 22.8 wt% nitrogen, and comparative examples with 0.5 wt% nitrogen and 5.6 oxygen. A weight percent of activated carbon is described. However, these activated carbons still have insufficient catalytic activity for decomposing hydrogen peroxide, and the activity may be reduced by repeated use.
- Chloroamine low concentration of chloramine (chloroamine) is used as a substitute for chlorine for disinfection of tap water.
- Chloramine includes monochloroamine (monochloramine), dichloroamine, and trichloroamine. Monochloramine is more stable than chlorine and does not volatilize. In addition, halomethanes are not generated even in the presence of methane. For this reason, the use of chloramine (particularly monochloramine) is increasing. In recent years, however, many researchers have recognized monochloramine as a causative agent of organisms, particularly freshwater and seawater aquatic organisms, and the cause of hemolytic anemia. There is a demand for development. In addition, when tap water sterilized with chloramine is used in an artificial dialyzer, chloramine comes into contact with blood through a semipermeable membrane, so a high chloramine removal ability is required in a kidney dialysis unit or the like.
- JP-A-60-246328 (Claims, page 2, lower left column to lower right column) Japanese Patent No. 2685356 (claims, column 4, line 37 to column 5, line 27) Japanese Patent No. 3719756 (Claims [0017] [0020]) JP-A-5-811 (Claims, Examples and Comparative Examples)
- an object of the present invention is to provide activated carbon useful as an oxidation catalyst (or decomposition catalyst) and its use.
- Another object of the present invention is to provide an activated carbon catalyst that retains high catalytic activity even after repeated use and its application.
- Still another object of the present invention is to provide an activated carbon catalyst capable of effectively decomposing or removing peroxide (such as hydrogen peroxide) and / or chloramine (such as monochloramine) in an aqueous solution and its use.
- peroxide such as hydrogen peroxide
- chloramine such as monochloramine
- Another object of the present invention is to provide a method capable of efficiently producing N-phosphonomethylglycine using the catalytic activity of the activated carbon, a peroxide (such as hydrogen peroxide) and / or a chloramine (such as monochloramine).
- the object is to provide a method capable of efficiently decomposing or removing.
- the present inventors have found that the use of activated carbon containing oxygen, nitrogen, sulfur and hydrogen atoms at a predetermined concentration greatly improves the resolution of hydrogen peroxide, Found that it efficiently catalyzes the oxidation of N-phosphonomethyliminodiacetic acid, efficiently produces N-phosphonomethylglycine, and effectively oxidatively decomposes chloramine, thereby completing the present invention.
- the activated carbon of the present invention has an oxygen content of 1.40 to 4.30% by mass, a nitrogen content of 0.90 to 2.30% by mass, a sulfur content of 0.50 to 1.20% by mass,
- the hydrogen content is in the range of 0.40 to 0.65 mass%.
- the activated carbon of the present invention is useful as an oxidation catalyst (or decomposition catalyst), for example, as a catalyst for decomposing peroxide or chloramine.
- This activated carbon catalyst (oxidation catalyst or decomposition catalyst) has an oxygen content of 1.40 to 4.30% by mass (for example, 1.40 to 3.5% by mass), and a nitrogen content of 0.90 to 2.30. Mass% (for example, 0.90 to 2.0 mass%), sulfur content is 0.50 to 1.20 mass% (for example, 0.50 to 1.00 mass%), and hydrogen content is 0.40. It is composed of activated carbon that is ⁇ 0.65 mass% (for example, 0.40 to 0.62 mass%). In the activated carbon catalyst, the oxygen content is 1.40 to 3.0% by mass, the nitrogen content is 0.90 to 1.75% by mass, the sulfur content is 0.50 to 0.90% by mass, and hydrogen is contained. The amount may be 0.40 to 0.65% by weight.
- the peroxide may be hydrogen peroxide
- the chloramine may be monochloroamine
- the activated carbon (activated carbon catalyst such as an oxidation catalyst or a decomposition catalyst) further has at least one of the following (e) acidic surface functional group amount, (f) basic surface functional group amount, and (g) benzene adsorption performance. You may have.
- the amount of acidic surface functional groups is 0.10 to 0.36 meq / g (for example, 0.10 to 0.30 meq / g)
- Basic surface functional group amount 0.50 to 1.30 meq / g (for example, 0.50 to 1.00 meq / g)
- the activated carbon of the present invention catalyzes the oxidation of N-phosphonomethyliminodiacetic acid in the presence of peroxide.
- the present invention is a method for producing N-phosphonomethylglycine by oxidizing N-phosphonomethyliminodiacetic acid with an oxidizing agent in the presence of activated carbon, and having an oxygen content of 1.40-4.
- Activated carbon having 30% by mass, nitrogen content of 0.90 to 2.30% by mass, sulfur content of 0.50 to 1.20% by mass, and hydrogen content of 0.40 to 0.65% by mass.
- a method for producing N-phosphonomethylglycine which uses a peroxide as an oxidizing agent.
- the proportion of activated carbon used may be 0.5 to 300 parts by weight or 10 to 100 parts by weight with respect to 100 parts by weight of N-phosphonomethyliminodiacetic acid.
- the peroxide may be hydrogen peroxide.
- the decomposition rate of hydrogen peroxide per 1 g of activated carbon is 1000 mg or more (that is, the decomposition rate of hydrogen peroxide is 1,000 mg-H 2 O 2 / g-activated carbon / hr or more). It may be.
- the present invention is a method for removing chloramine by contacting with activated carbon, having an oxygen content of 1.40 to 4.30% by mass, a nitrogen content of 0.90 to 2.30% by mass, and a sulfur content
- a method of removing chloramine using activated carbon having an amount of 0.50 to 1.20% by mass and a hydrogen content of 0.40 to 0.65% by mass is also included. In this method, chloramine is effectively decomposed to release chlorine, and chloramine can be efficiently removed.
- the oxygen content, nitrogen content, sulfur content, hydrogen content, acidic surface functional group content, basic surface functional group content, and benzene adsorption performance of the activated carbon can be measured by the methods described in the examples.
- the decomposition rate of hydrogen peroxide can also be measured by the method described in the examples.
- the activated carbon of the present invention exhibits high catalytic activity as an oxidation catalyst or a decomposition catalyst. Moreover, the activated carbon catalyst retains high catalytic activity even after repeated use. Therefore, the activated carbon catalyst can effectively decompose peroxides (such as hydrogen peroxide) in an aqueous solution. Furthermore, the activated carbon of the present invention catalyzes an oxidation reaction and utilizes the catalytic activity of the activated carbon to convert N-phosphonomethyliminodiacetic acid to N-phosphonomethylglycine in the presence of peroxide (such as hydrogen peroxide). Can be manufactured efficiently.
- the activated carbon of the present invention is suitable for, for example, decomposing chloramine (monochloramine, etc.) to liberate and remove chlorine. Furthermore, compared with activated carbon produced by conventional means, the activated carbon of the present invention is not limited to the decomposition and removal of peroxides and chloramines, but also sulfides (such as hydrogen sulfide), sulfur dioxide SO 2 and oxidation. It is very useful as a catalyst for many oxidation reactions such as oxidation of nitrogen.
- the activated carbon of the present invention has the following characteristics.
- the activated carbon has an oxygen content of 1.40 to 4.30% by mass, preferably 1.40 to 3.5% by mass (eg, 1.40 to 3.0% by mass), more preferably 1. It is about 40 to 2.8% by mass (for example, 1.40 to 2.75% by mass). If the oxygen content is too low, the catalytic activity is reduced, and if the oxygen content is too high, the activity is reduced by repeated use.
- the nitrogen content of the activated carbon is 0.90 to 2.30% by mass, preferably 0.90 to 2.0% by mass (for example, 0.90 to 1.75% by mass), and more preferably 0.7%. It is about 90 to 1.50 mass% (for example, 0.90 to 1.25 mass%). If the nitrogen content is too low, the activity decreases due to repeated use, and if the nitrogen content is too high, the catalytic activity decreases.
- the sulfur content of the activated carbon is 0.50 to 1.20% by mass, preferably 0.50 to 1.00% by mass, more preferably 0.50 to 0.90% by mass (for example, 0.50 About 0.85 mass%). If the sulfur content is too low, the activity decreases due to repeated use, and if the sulfur content is too high, the catalytic activity decreases.
- the hydrogen content of the activated carbon is 0.40 to 0.65 mass% (for example, 0.45 to 0.65 mass%), preferably 0.40 to 0.62 mass% (for example, 0 .50 to 0.62 mass%), and may be about 0.55 to 0.65 mass%. If the hydrogen content is too low, the catalytic activity is reduced, and if the hydrogen content is too high, the activity is reduced due to repeated use.
- the activated carbon of the present invention preferably has at least one of the following (e) acidic surface functional group amount, (f) basic surface functional group amount, and (g) benzene adsorption performance.
- the amount of the acidic surface functional group of the activated carbon is 0.10 to 0.36 meq / g, preferably 0.10 to 0.30 meq / g (for example, 0.11 to 0.27 meq / g), more preferably It is in the range of 0.12 to 0.25 meq / g. Whether the amount of the acidic surface functional group is too small or too large, the activity is lowered by repeated use.
- the amount of the basic surface functional group of the activated carbon is 0.50 to 1.30 meq / g, preferably 0.50 to 1.00 meq / g (for example, 0.52 to 0.80 meq / g), and more preferably Is in the range of 0.55 to 0.75 meq / g. Whether the amount of the basic surface functional group is too small or too large, the activity is lowered by repeated use.
- the benzene adsorption performance of the activated carbon is 25 to 50%, preferably 25 to 47%, more preferably 27 to 45%, and may be 30 to 50%. Whether the benzene adsorption performance is too low or too high, the activity decreases due to repeated use.
- the activated carbon having such characteristics is useful as a catalyst such as an oxidation catalyst or a decomposition catalyst.
- the activated carbon catalyst of the present invention is useful for peroxide, chloramine decomposition (or oxidation), and the like.
- peroxides include hydrogen peroxide, peracids (performic acid, peracetic acid, perbenzoic acid, etc.), peroxides (benzoyl peroxide, diacetyl peroxide, lauroyl peroxide, ethyl methyl ketone peroxide, etc.), etc. Can be illustrated.
- a typical peroxide is hydrogen peroxide.
- Chloramine may be monochloroamine NH 2 Cl, dichloroamine NHCl 2 , or trichloroamine NCl 3 .
- a typical chloramine widely used for disinfection of tap water or the like is monochloroamine, which has low volatility and high stability. Therefore, the remaining monochloroamine is treated with sodium thiosulfate or the like.
- the activated carbon catalyst of the present invention efficiently decomposes such chloramine (monochloroamine or the like) to liberate chlorine.
- the activated carbon catalyst of the present invention is useful for catalysts for many reactions other than the peroxides and chloramines, for example, oxidation or conversion of sulfides (hydrogen sulfide, etc.), sulfur dioxide SO 2 and nitrogen oxides NOx. It is.
- Decomposition (or oxidation) of peroxides, chloramines, etc. can be done with organic solvents (hydrocarbons such as toluene, alcohols such as ethanol, esters, ketones, ethers, carboxylic acids, etc.) or aqueous solvents (water, water and water). In a mixed solvent with a water-soluble organic solvent), and usually in water. In addition, the decomposition or oxidation reaction is often performed in the presence of an excess amount of solvent. Further, a gaseous substrate such as sulfide (hydrogen sulfide, etc.), sulfur dioxide SO 2 and nitrogen oxide NOx may be brought into contact with the activated carbon in the form of an air flow together with air or an oxygen-containing gas if necessary.
- organic solvents hydrocarbons such as toluene, alcohols such as ethanol, esters, ketones, ethers, carboxylic acids, etc.
- aqueous solvents water, water and water.
- a gaseous substrate such as
- the concentration of the substrate such as peroxide (hydrogen peroxide, etc.) and chloramine (monochloroamine, etc.) is not particularly limited.
- the concentration of peroxide (hydrogen peroxide, etc.) in the reaction system is 0.1 It may be about 50% by mass, preferably about 0.5-30% by mass, more preferably about 1-20% by mass.
- the activated carbon catalyst of the present invention is useful for removing substrates such as trace amounts of peroxides (such as hydrogen peroxide) and chloramines (such as monochloroamine). is there.
- the concentration of the substrate may be about 0.1 ppb to 1000 ppm.
- the amount of the activated carbon catalyst used is 0.1 to 500 parts by weight, preferably 1 to 250 parts by weight, more preferably 5 to 100 parts by weight (for example, 10 parts by weight) with respect to 100 parts by weight of a substrate such as peroxide or chloramine. About 50 parts by mass).
- the decomposition or oxidation reaction can be carried out, for example, at about 10 to 70 ° C., preferably about 20 to 50 ° C.
- the decomposition or oxidation reaction can be performed, for example, in air, in an oxygen-containing atmosphere, or in an inert gas atmosphere.
- the activated carbon catalyst of the present invention is also useful as a catalyst for producing N-phosphonomethylglycine by oxidizing N-phosphonomethyliminodiacetic acid with an oxidizing agent. That is, the present invention is a method for producing N-phosphonomethylglycine by oxidizing N-phosphonomethyliminodiacetic acid with an oxidizing agent in the presence of activated carbon, wherein the activated carbon has an oxygen content of 1 In the range of .40 to 4.30% by mass, the nitrogen content in the range of 0.90 to 2.30% by mass, the sulfur content in the range of 0.50 to 1.20% by mass, and hydrogen
- a method for producing N-phosphonomethylglycine using activated carbon having a content of 0.40 to 0.65% by mass and using a peroxide as an oxidizing agent is also included.
- peroxide examples include the same peroxides as described above. These peroxides can be used alone or in combination of two or more. Among the peroxides, water-soluble peroxides, usually hydrogen peroxide, are used. As the hydrogen peroxide, a commercially available 30 to 60% by mass aqueous solution can be used, and it may be diluted if necessary.
- the amount of the peroxide (such as hydrogen peroxide) used is 1.5 to 10 mol, preferably 2 to 5 mol, more preferably 2 to 3 mol per mol of N-phosphonomethyliminodiacetic acid ( For example, about 2 to 2.5 mol).
- the use ratio of the activated carbon can be selected from a range in which oxidation by an oxidizing agent can be catalyzed, for example, from 0.1 to 500 parts by mass with respect to 100 parts by mass of N-phosphonomethyliminodiacetic acid.
- the amount is about 300 parts by mass, preferably about 5 to 200 parts by mass, more preferably about 10 to 100 parts by mass (for example, 20 to 80 parts by mass).
- the above reaction may be performed in the presence of an organic solvent, but is usually performed in the presence of an aqueous solvent, particularly in the presence of water.
- the amount of the solvent (especially water) used is only required to form a uniform reaction system, and is usually 1 to 50 parts by weight, preferably 2 to 25 parts by weight with respect to 1 part by weight of N-phosphonomethyliminodiacetic acid. It may be a degree.
- the reaction can be carried out at a temperature of 50 to 100 ° C., preferably 55 to 90 ° C., more preferably about 60 to 80 ° C.
- the reaction can be carried out under pressure or normal pressure, and is usually carried out under atmospheric pressure.
- the reaction can be performed, for example, in air or in an oxygen-containing atmosphere, and can also be performed in an inert gas atmosphere.
- the reaction mixture can be subjected to a conventional separation and purification process such as concentration, precipitation, solvent extraction, recrystallization and the like to obtain high-purity N-phosphonomethylglycine in a high yield.
- a conventional separation and purification process such as concentration, precipitation, solvent extraction, recrystallization and the like to obtain high-purity N-phosphonomethylglycine in a high yield.
- N-phosphonomethylglycine having a purity of 93% or more can be obtained in a yield of 80% or more.
- N-phosphonomethylglycine is usually obtained in a crystalline form by a method such as precipitation from a reaction system or recrystallization.
- the activated carbon catalyst of the present invention maintains a high catalytic ability without reducing the catalytic activity even when used repeatedly.
- the hydrogen peroxide decomposition rate per hour per 1 g of activated carbon is 1,000mg-H 2 O 2 / g- charcoal / hr or more (e.g., 2,000 ⁇ 100,000mg-H 2 O 2 / g- activated carbon / hr, preferably from 2,500 ⁇ 75,000mg-H 2 O 2 / g-activated carbon / hr, more preferably 3,000 to 50,000 mg-H 2 O 2 / g-activated carbon / hr).
- the activated carbon catalyst of the present invention can be repeatedly used 10 times or more while maintaining the hydrogen peroxide decomposition performance in an aqueous solution of 1,000 mg-H 2 O 2 / g-activated carbon / hr or more in the test method.
- activated carbon catalysts are produced by oxidizing activated carbon with nitric acid, sulfuric acid, sodium hypochlorite, etc., and then bringing it into contact with ammonia at a high temperature or by active carbonization from a nitrogen-rich raw material such as polyacrylonitrile. .
- activated carbon having various high catalytic activities can be produced at a low production cost by managing a plurality of parameters.
- the activated carbon catalyst of the present invention can be obtained by carbonizing a carbonaceous material and heat-treating it at a temperature of 850 ° C. to 1000 ° C. for 3 to 48 hours in a mixed gas atmosphere containing water vapor, nitrogen and carbon dioxide. it can. In the heat treatment, the carbonized carbon material may be partially gasified.
- the carbonaceous material can be selected from all known materials suitable for the production of activated carbon, such as plants (coconut husk, coconut husk, coconut pod, wood, etc.), natural polymers (starch, cellulose, lignins, etc.), Examples include semi-synthetic polymers (cellulose esters, cellulose ethers, lignin resins, etc.), synthetic polymers (phenolic resins, furan resins, epoxy resins, etc.), bituminous substances, and the like. These raw materials can be used alone or in combination of two or more.
- Preferable raw materials may be plant raw materials such as wood, but especially coals containing nitrogen and sulfur, such as coal selected from peat, lignite, subbituminous coal, bituminous coal, semi-anthracite, anthracite coal. Preferably used.
- the activated carbon of the present invention is produced using a fluidized bed, a multistage furnace, a rotary furnace, or the like, which is a general activated carbon production facility.
- the dry distillation can be performed by a conventional method, for example, by heating the carbonaceous material at 400 to 800 ° C., preferably 500 to 800 ° C., more preferably 600 to 800 ° C. while blocking oxygen or air. .
- the heat treatment (activation or activation) is performed in a fluidized bed, a multi-stage furnace, a rotary furnace, and the dry distillate is heated to a temperature exceeding 750 ° C., preferably 850 to 1000 ° C. (eg, 850 to 950 ° C.), steam, nitrogen and It can be carried out in an atmosphere of a mixture of carbon dioxide.
- the dry distillation product is partially gasified to obtain activated carbon.
- the gas gas mixture consisting of water vapor, nitrogen, and carbon dioxide
- the gas for gasifying a part of the carbonaceous material is obtained by burning natural gas, petroleum, or other combustible materials including hydrocarbons. Can also be obtained.
- the activation temperature usually varies in a range of about ⁇ 25 ° C. in many cases.
- the activation time may be about 3 to 48 hours, preferably about 4 to 24 hours, more preferably about 5 to 20 hours (for example, 6 to 12 hours). When activation time is too short, the activity of activated carbon will fall, and when too long, productivity will fall.
- the gas partial pressure is a water vapor partial pressure of 7.5 to 40%, preferably 10 to 30% (eg 10 to 20%), a carbon dioxide partial pressure of 10 to 50%, preferably 15 to 45% (eg 20 to 20%). 40%), the partial pressure of nitrogen is 30 to 80%, preferably about 40 to 70% (for example, 45 to 65%), and the partial pressure of gas is 10 to 40% of water vapor and 10 to 40 of carbon dioxide. % And the nitrogen partial pressure may be about 40 to 80%.
- the total pressure of the gas is usually 1 atmosphere (about 0.1 MPa). If the water vapor partial pressure is too low, activation (activation) is not sufficient, and if it is too high, the activity of the activated carbon decreases.
- the total gas supply rate (flow rate) is 10 to 50 L / min, preferably 15 to 45 L / min, more preferably about 20 to 40 L / min, with respect to 100 g of the raw material for dry distillation. If the flow rate is too low, activation is not sufficient, and if it is too high, the activity of the activated carbon decreases.
- an activated carbon catalyst having a target oxygen content, nitrogen content, sulfur content, and hydrogen content can be obtained.
- the Example can be referred for the detail of the manufacturing method of the activated carbon catalyst of this invention.
- the activated carbon may be powdery, granular, or granulated, and may be formed into a honeycomb-like form if necessary.
- the hydrogen peroxide decomposition performance evaluation at the time of repetition was performed by adding a 30% by mass hydrogen peroxide aqueous solution to the solution in which the residual amount became zero to 3000 mg / L and again remaining in the aqueous solution. The hydrogen oxide concentration is measured, and the change over time is evaluated until the residual amount becomes zero. This operation was repeated until a hydrogen peroxide decomposition rate of 1,000 mg-H 2 O 2 / g-activated carbon / hr or higher could not be obtained.
- Nitrogen, sulfur and hydrogen contents of activated carbon were measured using Vario EL III manufactured by ELEMENTAR and using sulfanilic acid as a reference substance. In addition, taking into account variations in the measured values, Kuraray Chemical's activated carbon P-GLCR was simultaneously measured and corrected as a standard sample, and the contents of nitrogen, sulfur and hydrogen in the activated carbon were determined.
- the oxygen content of the activated carbon was measured using Vario EL III manufactured by ELEMENTAR and using benzoic acid as a reference substance.
- Kuraray Chemical's activated carbon P-GLCR was simultaneously measured and corrected as a standard sample to determine the oxygen content in the activated carbon.
- activated carbon was produced from different raw materials. Specifically, carbonaceous raw material is carbonized at 700 ° C., and then 500 g of the obtained carbonized product is put into a furnace, and steam, carbon dioxide gas, and nitrogen gas are changed to arbitrary partial pressures at 850-980 ° C. The activated carbon was produced by supplying the gas into the furnace at a total pressure of 1 atm and an arbitrary flow rate, and changing the activation time arbitrarily.
- Comparative Example 1 Anthracitic Coal Comparative Example 2: Anthracitic Coal Comparative Example 3: Bituminous Coal Comparative Example 4: Petro Coke Comparative Example 5: Infusible Fibrous Polyacrylonitrile (PAN) Comparative Example 6: Coconut shell charcoal Comparative example 7: Charcoal The activated carbon (raw material: anthracite) of Comparative Example 1 has a nitrogen content, a sulfur content, and a hydrogen content outside the predetermined ranges, and the number of repeated uses as a catalyst is also once. And confirmed that it is low.
- the activated carbon (raw material: bituminous coal) of Comparative Example 3 had an oxygen content, a nitrogen content, and a sulfur content outside the predetermined ranges, and the number of repeated uses as a catalyst was as low as 3 times.
- the activated carbon (raw material: Petro coke) of Comparative Example 4 had an oxygen content, a sulfur content, and a hydrogen content outside the predetermined ranges, and the number of repeated uses as a catalyst was as low as 5 times.
- the activated carbon (raw material: coconut shell charcoal) of Comparative Example 6 had a sulfur content and a hydrogen content outside the predetermined ranges, and the number of repeated uses as a catalyst was as low as one.
- the activated carbon (raw material: charcoal) of Comparative Example 7 had an oxygen content, a nitrogen content, and a hydrogen content outside the predetermined ranges, and the number of repeated uses as a catalyst was as low as 3 times.
- the activated carbon of Comparative Example 8 was heat-treated at 930 ° C. for 3 hours under a nitrogen atmosphere to prepare the activated carbon of Comparative Example 9.
- the activated carbon of Comparative Example 9 was confirmed to have a sulfur content outside the predetermined range, and the number of repeated uses as a catalyst was as low as 4 times.
- Comparative Example 11 The activated carbon of Comparative Example 11 was prepared by treating under the same conditions as in Comparative Examples 1-7 except that the carbonaceous raw material was bituminous coal, the amount of mixed gas introduced was 20 L / min, and the activation time was 2 hours. It was confirmed that the obtained activated carbon was free of oxygen content and the number of repeated use as a catalyst was 6 times.
- Comparative Example 12 The carbonaceous raw material was treated with smoky coal and treated under the same conditions as in Comparative Example 11 to produce the activated carbon of Comparative Example 12. It was confirmed that the obtained activated carbon was free from hydrogen content and was repeatedly used three times as a catalyst.
- Example 1 After the dry distillation treatment of bituminous coal as a carbonaceous raw material, a mixed gas having a water vapor partial pressure of 20%, a carbon dioxide partial pressure of 40%, and a nitrogen partial pressure of 40% is supplied into the furnace at a flow rate of 10 L / min with respect to 500 g of the dry distillation product. And activated under the conditions of an activation temperature of 900 ° C. and an activation time of 5 hours to produce activated carbon of Example 1. It was confirmed that the obtained activated carbon was within a predetermined range in all physical property values and the number of repeated uses as a catalyst was 15 times.
- Example 2 The carbonaceous raw material was anthracite and treated under the same conditions as in Example 1 to produce activated carbon of Example 2. It was confirmed that the obtained activated carbon was within a predetermined range in all physical property values, and the number of repeated use as a catalyst was 14 times.
- Example 3 The carbonaceous raw material was charcoal and treated under the same conditions as in Example 1 to produce activated carbon of Example 3. It was confirmed that the obtained activated carbon was within a predetermined range in all physical property values, and the number of repeated uses as a catalyst was 13 times.
- Example 4 After the dry distillation treatment of bituminous coal as a carbonaceous material, a mixed gas having a water vapor partial pressure of 10%, a carbon dioxide partial pressure of 20%, and a nitrogen partial pressure of 70% is supplied into the furnace at a flow rate of 20 L / min with respect to 500 g of the dry distillation product. And activated carbon of Example 4 was produced under the conditions of an activation temperature of 900 ° C. and an activation time of 20 hours. It was confirmed that the obtained activated carbon was within a predetermined range in all physical property values, and the number of repeated uses as a catalyst was 13 times.
- Example 5 After the dry distillation treatment of bituminous coal as a carbonaceous material, a mixed gas having a water vapor partial pressure of 15%, a carbon dioxide partial pressure of 30%, and a nitrogen partial pressure of 55% is supplied into the furnace at a flow rate of 10 L / min with respect to 500 g of the dry distillation product.
- the activated carbon of Example 5 was produced under the conditions of an activation temperature of 900 ° C. and an activation time of 10 hours. It was confirmed that the obtained activated carbon was within a predetermined range in all physical property values, and the number of repeated use as a catalyst was 14 times.
- Example 6 After the dry distillation treatment of bituminous coal as a carbonaceous material, a mixed gas having a steam partial pressure of 15%, a carbon dioxide partial pressure of 20% and a nitrogen partial pressure of 65% is supplied into the furnace at a flow rate of 10 L / min with respect to 500 g of the dry distillation product.
- the activated carbon of Example 6 was produced by treating the sample under the conditions of an activation temperature of 900 ° C. and an activation time of 18 hours. It was confirmed that the obtained activated carbon was within a predetermined range in all physical property values and the number of repeated uses as a catalyst was 15 times.
- Table 1 shows the evaluation results of the activated carbon obtained in Examples 1 to 6 and Comparative Examples 1 to 16.
- the activated carbons obtained in Comparative Examples 1 to 16 had at least one of oxygen content (O), nitrogen content (N), sulfur content (S), and hydrogen content (H).
- O oxygen content
- N nitrogen content
- S sulfur content
- H hydrogen content
- One content is excessive or too small with respect to a predetermined content, and the number of repeated uses as a catalyst is 1 to 9 times. The catalyst activity is greatly reduced by repeated use.
- the oxygen content (O), the nitrogen content (N), the sulfur content (S), and the hydrogen content (H) are in a predetermined concentration range, It is clear that the number of repeated use is greatly improved to 13 to 15 times, and it can be used repeatedly while maintaining high catalytic activity.
- Comparative Example 17 As Comparative Example 17, the NORIT activated carbon SA-1 described in the example of the prior art document 3 was also evaluated. This activated carbon confirmed that the oxygen content and sulfur content were out of the predetermined ranges, and the number of repetitions as a catalyst was 7 times.
- coconut shell which is a carbonaceous raw material
- Activation was performed under the conditions of an activation temperature of 900 ° C. and an activation time of 60 hours to prepare activated carbon of Comparative Example 24. It was confirmed that the obtained activated carbon had a hydrogen content outside the predetermined range and the number of repetitions as a catalyst was two.
- Example 7 After the above carbonization process using carbonaceous raw material as charcoal, a mixed gas of 30% water vapor partial pressure, 30% carbon dioxide partial pressure and 40% nitrogen partial pressure is introduced into the furnace at a flow rate of 40 L / min with respect to 500 g of dry distillation product.
- the activated carbon of Example 7 was produced under the conditions of an activation temperature of 850 ° C. and an activation time of 3 hours. It was confirmed that the obtained activated carbon was within a predetermined range in all physical property values and the number of repeated uses as a catalyst was 12 times.
- Example 8 After the above carbonization treatment using carbonaceous raw material as charcoal, a mixed gas having a water vapor partial pressure of 20%, a carbon dioxide partial pressure of 40% and a nitrogen partial pressure of 40% is introduced into the furnace at a flow rate of 10 L / min with respect to 500 g of the dry distillation product.
- the activated carbon of Example 8 was produced under the conditions of an activation temperature of 900 ° C. and an activation time of 7 hours. It was confirmed that the obtained activated carbon was within a predetermined range in all physical property values, and the number of repeated uses as a catalyst was 13 times.
- Example 9 The carbonaceous raw material is anthracite, and after the above-mentioned carbonization treatment, a mixed gas having a water vapor partial pressure of 30%, a carbon dioxide partial pressure of 30%, and a nitrogen partial pressure of 40% is introduced into the furnace at a flow rate of 10 L / min with respect to 500 g of the dry distillation product.
- the activated carbon of Example 9 was produced under the conditions of an activation temperature of 900 ° C. and an activation time of 9 hours. It was confirmed that the obtained activated carbon was within a predetermined range in all physical property values, and the number of repeated uses as a catalyst was 13 times.
- Example 10 After the above carbonization treatment using carbonaceous raw material as charcoal, a mixed gas having a water vapor partial pressure of 30%, a carbon dioxide partial pressure of 30% and a nitrogen partial pressure of 40% is introduced into the furnace at a flow rate of 10 L / min with respect to 600 g of the dry distillation product.
- An activated carbon having a hardness of 10 was produced under the conditions of an activation temperature of 900 ° C. and an activation time of 3 hours. It was confirmed that the obtained activated carbon was within a predetermined range in all physical property values, and the number of repeated use as a catalyst was 15 times.
- Example 11 After the above carbonization treatment using bituminous carbon as the carbonaceous raw material, a mixed gas having a water vapor partial pressure of 30%, a carbon dioxide partial pressure of 30% and a nitrogen partial pressure of 40% is introduced into the furnace at a flow rate of 10 L / min with respect to 500 g of the dry distillation product.
- Activated carbon of Example 11 was produced under the conditions of an activation temperature of 950 ° C. and an activation time of 3 hours. It was confirmed that the obtained activated carbon was within a predetermined range in all physical property values, and the number of repeated use as a catalyst was 14 times.
- Example 12 After the above carbonization process using carbonaceous raw material as charcoal, a mixed gas of 10% steam partial pressure, 20% carbon dioxide partial pressure, and 70% nitrogen partial pressure is introduced into the furnace at a flow rate of 10 L / min for 500 g of dry distillation product.
- the activated carbon of Example 12 was produced under the conditions of an activation temperature of 900 ° C. and an activation time of 5 hours. It was confirmed that the obtained activated carbon was within a predetermined range in all physical property values and the number of repeated uses as a catalyst was 12 times.
- Example 13 The carbonaceous raw material is anthracite and after the above-mentioned carbonization treatment, a mixed gas having a water vapor partial pressure of 30%, a carbon dioxide partial pressure of 30% and a nitrogen partial pressure of 40% is introduced into the furnace at a flow rate of 40 L / min with respect to 500 g of the dry distillation product.
- Activated carbon of Example 13 was produced under conditions of an activation temperature of 900 ° C. and an activation time of 7 hours. It was confirmed that the obtained activated carbon was within a predetermined range in all physical property values and the number of repeated uses as a catalyst was 11 times.
- Table 2 shows the evaluation results of the activated carbon obtained in Examples 7 to 13 and Comparative Examples 17 to 25.
- the activated carbons obtained in Comparative Examples 17 to 25 had at least one of oxygen content (O), nitrogen content (N), sulfur content (S), and hydrogen content (H).
- O oxygen content
- N nitrogen content
- S sulfur content
- H hydrogen content
- One content is excessive or too small with respect to a predetermined content, and the number of repeated uses as a catalyst is 2 to 7 times. The catalyst activity is greatly reduced by repeated use.
- the oxygen content (O), the nitrogen content (N), the sulfur content (S), and the hydrogen content (H) are in a predetermined concentration range, It is clear that the number of times of repeated use is greatly improved to 11 to 15 times, and it can be used repeatedly while maintaining high catalyst activity.
- N-phosphonomethylglycine can be efficiently converted by using N-phosphonomethyliminodiacetic acid in the presence of water and hydrogen peroxide in the presence of activated carbon of the present invention. Can be manufactured.
- Activated carbon is added to 100 mL of a chloramine (monochloroamine) aqueous solution adjusted to about 100 ppm, shaken at 25 ° C. for 2 hours, filtered through filter paper, and the filtrate is measured for residual chloramine concentration by the following DPD spectrophotometry. From the relationship between the chloramine concentration and free residual chlorine, the amount of chloramine decomposition (mg / g-activated carbon) at a residual concentration of 3 ppm was determined.
- the activated carbon of the example has an extremely high decomposition amount of chloramine compared to the activated carbon of the comparative example.
- the activated carbon of the present invention is useful as an oxidation catalyst or decomposition catalyst for peroxides (such as hydrogen peroxide), sulfides, sulfur dioxide, and nitric oxide, and is also useful as a decomposition catalyst for chloramine.
- the activated carbon catalyst of the present invention catalyzes an oxidation reaction, and can efficiently produce N-phosphonomethylglycine from N-phosphonomethyliminodiacetic acid in the presence of water and hydrogen peroxide.
- high catalytic activity can be maintained, the recyclability is high, the amount of activated carbon waste can be reduced, and the cost can be reduced. Therefore, it is useful as an activated carbon catalyst that catalyzes many oxidation reactions.
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Abstract
Description
(f)塩基性表面官能基量0.50~1.30meq/g(例えば、0.50~1.00meq/g)
(g)ベンゼン吸着性能25~50%(例えば、25~47%)
本発明の活性炭は、過酸化物の存在下、N-ホスホノメチルイミノジ酢酸の酸化を触媒する。そのため、本発明は、活性炭の存在下、N-ホスホノメチルイミノジ酢酸を酸化剤で酸化してN-ホスホノメチルグリシンを製造する方法であって、酸素含有量が1.40~4.30質量%、窒素含有量が0.90~2.30質量%、硫黄含有量が0.50~1.20質量%、及び水素含有量が0.40~0.65質量%である活性炭を用い、酸化剤として過酸化物を用いるN-ホスホノメチルグリシンの製造方法も包含する。この方法において、活性炭の使用割合は、N-ホスホノメチルイミノジ酢酸100重量部に対して0.5~300重量部であってもよく、10~100重量部であってもよい。また、過酸化物は過酸化水素であってもよい。さらに、前記方法において、活性炭1g当たり1時間での過酸化水素の分解速度は、1000mg以上(すなわち、過酸化水素の分解速度は、1,000mg-H2O2/g-活性炭/hr以上)であってもよい。
(a)酸素含有量が1.40~4.30質量%の範囲であり、
(b)窒素含有量が0.90~2.30質量%の範囲であり、
(c)硫黄含有量が0.50~1.20質量%の範囲であり、
(d)水素含有量が0.40~0.65質量%の範囲である。
25℃における3,000mg/L過酸化水素濃度の水溶液400mLに乾燥した活性炭0.1gを添加し、水溶液中に残留している過酸化水素濃度を測定し、経時変化を残留量がゼロになるまで評価した。
Co=過酸化水素初濃度(mg/L),C=任意時間経過後の過酸化水素濃度(mg/L),
A=活性炭量(g),T=任意時間(hr)
繰り返し時における過酸化水素分解性能評価は、残留量がゼロになった溶液に、30質量%濃度の過酸化水素水溶液を3000mg/Lになるように添加し、再び水溶液中に残留している過酸化水素濃度を測定し、経時変化を残留量がゼロになるまで評価する。この操作を1,000mg-H2O2/g-活性炭/hr以上の過酸化水素分解速度が得られなくなるまで繰り返した。
ELEMENTAR社製Vario EL IIIを使用し、基準物質にスルファニル酸を用いて、活性炭の窒素、硫黄及び水素含有量を測定した。また、各測定値のバラツキを考慮し、標準サンプルとしてクラレケミカル製活性炭P-GLCRを同時に測定して補正し、活性炭中の窒素、硫黄及び水素の含有量を決定した。
ELEMENTAR社製Vario EL IIIを使用し、基準物質に安息香酸を用いて、活性炭の酸素含有量を測定した。また、各測定値のバラツキを考慮し、標準サンプルとしてクラレケミカル製活性炭P-GLCRを同時に測定して補正し、活性炭中の酸素の含有量を決定した。
25℃において、0.1mol/L-ナトリウムエトキシド水溶液25mLに活性炭0.5gを添加し24時間振とう後、遠心分離機により活性炭を沈降させ、上澄み液10mLを採取し0.1mol/L-HClで滴定し、酸性表面官能基量を決定した。
25℃において、0.1mol/L-HCl水溶液25mLに活性炭0.5gを添加し24時間振とう後、遠心分離機により活性炭を沈降させ、上澄み液10mLを採取し0.1mol/L-NaOHで滴定し、塩基性表面官能基量を決定した。
日本工業規格における活性炭試験方法JIS K1474に準拠し、活性炭のベンゼン吸着性能を測定した。
種々の原料による影響を確認するために、異なる原料により活性炭を作製した。具体的には、炭素質原料を700℃で乾留し、続いて得られた乾留品500gを炉に投入し、850~980℃において、水蒸気、二酸化炭素ガス、窒素ガスを任意の分圧に変化させ、ガスの全圧1気圧でかつ任意の流量で炉内に供給し、賦活時間を任意に変えて、活性炭を作製した。
水100mL中に、表1に示す活性炭5gとN-ホスホノメチルイミノジ酢酸20.0gとを加え、攪拌下、65℃にて30質量%過酸化水素水20.0gを、65℃を保持しつつ、3時間で滴下した。滴下終了後、1時間保持した後、N-ホスホノメチルグリシンを結晶単離し、高速液体クロマトグラフィーにより定量し、重量収率及び純度を測定した。
表に示す各種原料を上記乾留処理した後、水蒸気分圧30%、二酸化炭素分圧30%、窒素分圧40%の混合ガスを、乾留品500gに対して流量40L/分で炉内に導入し、賦活温度900℃、賦活時間1時間の条件下で処理して活性炭を作製した。
比較例2:有煙炭
比較例3:瀝青炭
比較例4:ペトロコークス
比較例5:不融化した繊維状のポリアクリロニトリル(PAN)
比較例6:ヤシ殻炭
比較例7:木炭
比較例1の活性炭(原料:無煙炭)は、窒素含有量、硫黄含有量、水素含有量が所定範囲から外れ、触媒としての繰り返し使用回数も1回と低いことを確認した。
比較例2の活性炭100gに対して6N硝酸1Lを加え、1時間に亘り煮沸した後、水洗し、比較例8の活性炭を調製した。比較例8の活性炭は、酸素含有量、硫黄含有量、水素含有量が所定範囲から外れ、触媒としての繰り返し使用回数も1回と低いことを確認した。
比較例4の活性炭100gに対して6N硝酸1Lを加え、1時間に亘り煮沸した後、水洗し、比較例10の活性炭を調製した。得られた活性炭は、酸素含有量、窒素含有量、硫黄含有量、水素含有量が外れ、触媒としての繰返し使用回数も1回と低いことを確認した。
炭素質原料を瀝青炭とし、混合ガスの導入量を20L/分とし、賦活時間を2時間とする以外、比較例1~7と同様の条件で処理し、比較例11の活性炭を作製した。得られた活性炭は、酸素含有量が外れ、触媒としての繰返し使用回数も6回であることを確認した。
炭素質原料を有煙炭とし、比較例11と同様の条件で処理し、比較例12の活性炭を作製した。得られた活性炭は、水素含有量が外れ、触媒としての繰り返し使用回数も3回であることを確認した。
活性炭として先行文献3に記載のクラレケミカル社製「クラレコールKW」(瀝青炭を原料とした活性炭)を用いた。この活性炭は、酸素含有量、窒素含有量、硫黄含有量が所定範囲から外れ、触媒としての繰り返し使用回数も3回と低いことを確認した。
活性炭として先行文献3に記載のクラレケミカル社製「クラレコールGC」(ヤシガラを原料とした活性炭)を用いた。この活性炭は、硫黄含有量が所定範囲から外れ、触媒としての繰り返し使用回数も1回と低いことを確認した。
活性炭として先行文献3に記載のクラレケミカル社製「クラレコールGLC」(ヤシガラを原料とした活性炭)を用いた。この活性炭は、酸素含有量、窒素含有量、硫黄含有量、水素含有量のすべてが所定範囲から外れ、触媒としての繰り返し使用回数も1回と低いことを確認した。
比較例5の活性炭に窒素雰囲気下で930℃、3時間で熱処理を行い、比較例16の活性炭を調製した。得られた活性炭は、窒素含有量、硫黄含有量、水素含有量が所定範囲から外れ、触媒としての繰り返し回数も9回であることを確認した。
炭素質原料としての瀝青炭を前記乾留処理した後、水蒸気分圧20%、二酸化炭素分圧40%、窒素分圧40%の混合ガスを、乾留品500gに対して10L/分の流量で炉内に導入し、賦活温度900℃、賦活時間5時間の条件下で処理し、実施例1の活性炭を作製した。得られた活性炭は、物性値のすべてにおいて所定範囲内であり、触媒としての繰り返し使用回数も15回であることを確認した。
炭素質原料を無煙炭とし、実施例1と同様の条件で処理し、実施例2の活性炭を作製した。得られた活性炭は、物性値のすべてにおいて所定範囲内であり、触媒としての繰り返し使用回数も14回であることを確認した。
炭素質原料を木炭とし、実施例1と同様の条件で処理し、実施例3の活性炭を作製した。得られた活性炭は、物性値のすべてにおいて所定範囲内であり、触媒としての繰り返し使用回数も13回であることを確認した。
炭素質材料としての瀝青炭を前記乾留処理した後、水蒸気分圧10%、二酸化炭素分圧20%、窒素分圧70%の混合ガスを、乾留品500gに対して20L/分の流量で炉内に導入し、賦活温度900℃、賦活時間20時間の条件下で処理し、実施例4の活性炭を作製した。得られた活性炭は、物性値のすべてにおいて所定範囲内であり、触媒としての繰り返し使用回数も13回であることを確認した。
炭素質材料としての瀝青炭を前記乾留処理した後、水蒸気分圧15%、二酸化炭素分圧30%、窒素分圧55%の混合ガスを、乾留品500gに対して10L/分の流量で炉内に導入し、賦活温度900℃、賦活時間10時間の条件下で処理し、実施例5の活性炭を作製した。得られた活性炭は、物性値のすべてにおいて所定範囲内であり、触媒としての繰り返し使用回数も14回であることを確認した。
炭素質材料としての瀝青炭を前記乾留処理した後、水蒸気分圧15%、二酸化炭素分圧20%、窒素分圧65%の混合ガスを、乾留品500gに対して10L/分の流量で炉内に導入し、賦活温度900℃、賦活時間18時間の条件下で処理し、実施例6の活性炭を作製した。得られた活性炭は、物性値のすべてにおいて所定範囲内であり、触媒としての繰り返し使用回数も15回であることを確認した。
比較例17として、先行文献3の実施例に記載のNORIT製活性炭SA-1についても評価した。この活性炭は、酸素含有量、硫黄含有量が所定範囲から外れ、触媒としての繰り返し回数も7回であることを確認した。
炭素質原料である瀝青炭を上記乾留処理後に水蒸気分圧3%、二酸化炭素分圧3%、窒素分圧94%の混合ガスを乾留品500gに対して50L/分の流量で炉内に導入し賦活温度900℃、賦活時間60時間の条件下で賦活を行い比較例18の活性炭を調製した。この活性炭は、酸素含有量が所定範囲から外れ、触媒としての繰り返し回数も3回であることを確認した。
炭素質原料である木炭を上記乾留処理後に水蒸気分圧50%、二酸化炭素分圧30%、窒素分圧20%の混合ガスを乾留品500gに対して50L/分の流量で炉内に導入し賦活温度900℃、賦活時間2時間の条件下で賦活を行い比較例19の活性炭を調製した。この活性炭は、酸素含有量が所定範囲から外れ、触媒としての繰り返し回数も5回であることを確認した。
炭素質原料である無煙炭を上記乾留処理後に水蒸気分圧50%、二酸化炭素分圧30%、窒素分圧20%の混合ガスを乾留品500gに対して50L/分の流量で炉内に導入し賦活温度900℃、賦活時間2時間の条件下で賦活を行い比較例20の活性炭を調製した。この活性炭は、窒素含有量が所定範囲から外れ、触媒としての繰り返し回数も2回であることを確認した。
比較例4の活性炭100gに対して1N硝酸をlL加え、1時間の煮沸を実施後水洗を行い、比較例21の活性炭を調製した。この活性炭は、窒素含有量が所定範囲から外れ、触媒としての繰り返し回数も5回であることを碗認した。
炭素質原料である無煙炭を上記乾留処理後に水蒸気分圧30%、二酸化炭素分圧30%、窒素分圧40%の混合ガスを乾留品500gに対して40L/分の流量で炉内に導入し賦活温度900℃、賦活時間2時間の条件下で賦活を行い比較例22の活性炭を調製した。この活性炭は、硫黄含有量が所定範囲から外れ、触媒としての繰り返し回数も4回であることを確認した。
炭素質原料であるペトロコークスを上記乾留処理後に水蒸気分圧5%、二酸化炭素分圧5%、窒素分圧90%の混合ガスを乾留品500gに対して30L/分の流量で炉内に導入し賦活温度900℃、賦活時間3時間の条件下で賦活を行い比較例23の活性炭を調製した。この活性炭は、硫黄含有量が所定範囲から外れ、触媒としての繰り返し回数も3回であることを確認した。
炭素質原料であるヤシ殻を上記乾留処理後に水蒸気分圧5%、二酸化炭素分圧5%、窒素分圧90%の混合ガスを乾留品500gに対して30L/分の流量で炉内に導入し賦活温度900℃、賦活時間60時間の条件下で賦活を行い比較例24の活性炭を調製した。得られた活性炭は、水素含有量が所定範囲から外れ、触媒としての繰り返し回数も2回であることを確認した。
炭素質原料である木炭を上記乾留処理後に水蒸気分圧40%、二酸化炭素分圧5%、窒素分圧55%の混合ガスを乾留品500gに対して20L/分の流量で炉内に導入し賦活温度900℃、賦活時間3時間の条件下で賦活を行い比較例25の活性炭を調製した。得られた活性炭は、水素含有量が所定範囲から外れ、触媒としての繰り返し回数も6回であることを確認した。
炭素質原料を木炭とし上記乾留処理後、水蒸気分圧30%、二酸化炭素分圧30%、窒素分圧40%の混合ガスを乾留品500gに対して40L/分の流量で炉内に導入し賦活温度850℃、賦活時間3時間の条件下で実施例7の活性炭を作製した。得られた活性炭は、物性値のすべてにおいて所定範囲内であり、触媒としての繰り返し使用回数も12回であることを確認した。
炭素質原料を木炭とし上記乾留処理後、水蒸気分圧20%、二酸化炭素分圧40%、窒素分圧40%の混合ガスを乾留品500gに対して10L/分の流量で炉内に導入し賦活温度900℃、賦活時間7時間の条件下で実施例8の活性炭を作製した。得られた活性炭は、物性値のすべてにおいて所定範囲内であり、触媒としての繰り返し使用回数も13回であることを確認した。
炭素質原料を無煙炭とし上記乾留処理後、水蒸気分圧30%、二酸化炭素分圧30%、窒素分圧40%の混合ガスを乾留品500gに対して10L/分の流量で炉内に導入し賦活温度900℃、賦活時間9時間の条件下で実施例9の活性炭を作製した。得られた活性炭は、物性値のすべてにおいて所定範囲内であり、触媒としての繰り返し使用回数も13回であることを確認した。
炭素質原料を木炭とし上記乾留処理後、水蒸気分圧30%、二酸化炭素分圧30%、窒素分圧40%の混合ガスを乾留品600gに対して10L/分の流量で炉内に導入し賦活温度900℃、賦活時間3時間の条件下で実施剛10の活性炭を作製した。得られた活性炭は、物性値のすべてにおいて所定範囲内であり、触媒としての繰り返し使用回数も15回であることを硅認した。
炭素質原料を瀝青炭とし上記乾留処理後、水蒸気分圧30%、二酸化炭素分圧30%、窒素分圧40%の混合ガスを乾留品500gに対して10L/分の流量で炉内に導入し賦活温度950℃、賦活時間3時間の条件下で実施例11の活性炭を作製した。得られた活性炭は、物性値のすべてにおいて所定範囲内であり、触媒としての繰り返し使用回数も14回であることを確認した。
炭素質原料を木炭とし上記乾留処理後、水蒸気分圧10%、二酸化炭素分圧20%、窒素分圧70%の混合ガスを乾留品500gに対して10L/分の流量で炉内に導入し賦活温度900℃、賦活時間5時間の条件下で実施例12の活性炭を作製した。得られた活性炭は、物性値のすべてにおいて所定範囲内であり、触媒としての繰り返し使用回数も12回であることを確認した。
炭素質原料を無煙炭とし上記乾留処理後、水蒸気分圧30%、二酸化炭素分圧30%、窒素分圧40%の混合ガスを乾留品500gに対して40L/分の流量で炉内に導入し賦活温度900℃、賦活時間7時間の条件下で実施例13の活性炭を作製した。得られた活性炭は、物性値のすべてにおいて所定範囲内であり、触媒としての繰り返し使用回数も11回であることを確認した。
比較例及び実施例で得られた活性炭を用いて、以下のようにして、クロラミンの分解量を測定した。
(1)遊離残留塩素の測定
リン酸緩衝液2.5mLを共栓付き比色管50mLに採り、この緩衝液にN,N-ジエチル-p-フェニレンジアミン(DPD)試薬0.5gを加える。次に、前記濾液を加えて全量を50mLとし、混和後、呈色した検液の適量を吸収セルに採り、光電分光光度計を用いて波長510~555nm付近における吸光度を測定し、下記(2)で作成した検量線によって試料1L中の遊離残留塩素(mg/L)を求める。
調整した標準塩素水を用いて希釈水で希釈し、数段階の標準列を調製する。次に、直ちに各標準列について(1)と同様に操作して吸光度を測定し、それぞれの遊離残留塩素の濃度(mg/L)を求め、それらの吸光度を基準として検量線を作成する。
上記(1)で発色させた溶液にヨウ化カリウム約0.5gを加えて溶解し、約2分間静置後、上記(1)と同様に測定して試料の残留塩素(mg/L)を求める。
上記残留塩素と遊離残留塩素の差を結合残留塩素(クロラミン)濃度(mg/L)とする。
Claims (12)
- (a)酸素含有量が1.40~4.30質量%、(b)窒素含有量が0.90~2.30質量%、(c)硫黄含有量が0.50~1.20質量%、(d)水素含有量が0.40~0.65質量%の範囲にある活性炭。
- 過酸化物又はクロラミンを分解するための触媒であって、(a)酸素含有量が1.40~4.30質量%、(b)窒素含有量が0.90~2.30質量%、(c)硫黄含有量が0.50~1.20質量%、(d)水素含有量が0.40~0.65質量%である活性炭で構成されている分解触媒。
- (a)酸素含有量が1.40~3.5質量%、(b)窒素含有量が0.90~2.0質量%、(c)硫黄含有量が0.50~1.00質量%、及び(d)水素含有量が0.40~0.65質量%である活性炭で構成されている請求項2記載の分解触媒。
- 過酸化水素又はモノクロロアミンを分解するための触媒であって、酸素含有量が1.40~3.0質量%、(b)窒素含有量が0.90~1.75質量%、(c)硫黄含有量が0.50~0.90質量%、及び(d)水素含有量が0.40~0.65質量%である活性炭で構成されている請求項2又は3記載の分解触媒。
- さらに、下記(e)酸性表面官能基量、(f)塩基性表面官能基量及び(g)ベンゼン吸着性能のうち少なくとも1つの特性を有する請求項2~4のいずれかに記載の分解触媒。
(e)酸性表面官能基量が0.10~0.36meq/g
(f)塩基性表面官能基量0.50~1.30meq/g
(g)ベンゼン吸着性能25~50% - さらに、下記(e)酸性表面官能基量、(f)塩基性表面官能基量及び(g)ベンゼン吸着性能のうち少なくとも1つの特性を有する請求項2~5のいずれかに記載の分解触媒。
(e)酸性表面官能基量0.10~0.30meq/g
(f)塩基性表面官能基量が0.50~1.00meq/g
(g)ベンゼン吸着性能が25~47% - 活性炭の存在下、N-ホスホノメチルイミノジ酢酸を酸化剤で酸化してN-ホスホノメチルグリシンを製造する方法であって、(a)酸素含有量が1.40~4.30質量%、(b)窒素含有量が0.90~2.30質量%、(c)硫黄含有量が0.50~1.20質量%、及び(d)水素含有量が0.40~0.65質量%である活性炭を用い、酸化剤として過酸化物を用いるN-ホスホノメチルグリシンの製造方法。
- 活性炭の使用割合が、N-ホスホノメチルイミノジ酢酸100重量部に対して0.5~300重量部である請求項7記載のN-ホスホノメチルグリシンの製造方法。
- 過酸化物の使用割合が、N-ホスホノメチルイミノジ酢酸100重量部に対して10~100重量部である請求項7又は8記載のN-ホスホノメチルグリシンの製造方法。
- 過酸化物が過酸化水素である請求項7~9いずれかに記載のN-ホスホノメチルグリシンの製造方法。
- 過酸化水素の分解速度が1,000mg-H2O2/g-活性炭/hr以上である請求項10記載のN-ホスホノメチルグリシンの製造方法。
- 活性炭と接触させて過酸化物又はクロラミンを除去する方法であって、(a)酸素含有量が1.40~4.30質量%、(b)窒素含有量が0.90~2.30質量%、(c)硫黄含有量が0.50~1.20質量%、及び(d)水素含有量が0.40~0.65質量%である活性炭を用いる方法。
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JPWO2011125504A1 (ja) | 2013-07-08 |
JP5815506B2 (ja) | 2015-11-17 |
TW201202136A (en) | 2012-01-16 |
US9359390B2 (en) | 2016-06-07 |
CN102822093B (zh) | 2015-02-25 |
KR101840488B1 (ko) | 2018-03-20 |
CN102822093A (zh) | 2012-12-12 |
TWI505987B (zh) | 2015-11-01 |
KR20130049185A (ko) | 2013-05-13 |
US20130023405A1 (en) | 2013-01-24 |
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