JP6150285B2 - Carbon-based solid acid containing fibrous activated carbon with sulfonic acid groups - Google Patents
Carbon-based solid acid containing fibrous activated carbon with sulfonic acid groups Download PDFInfo
- Publication number
- JP6150285B2 JP6150285B2 JP2013145946A JP2013145946A JP6150285B2 JP 6150285 B2 JP6150285 B2 JP 6150285B2 JP 2013145946 A JP2013145946 A JP 2013145946A JP 2013145946 A JP2013145946 A JP 2013145946A JP 6150285 B2 JP6150285 B2 JP 6150285B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- acid
- activated carbon
- fibrous activated
- based solid
- 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.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 354
- 239000011973 solid acid Substances 0.000 title claims description 144
- 229910052799 carbon Inorganic materials 0.000 title claims description 121
- 125000000542 sulfonic acid group Chemical group 0.000 title claims description 55
- 239000002253 acid Substances 0.000 claims description 59
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 44
- 229910052796 boron Inorganic materials 0.000 claims description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000003575 carbonaceous material Substances 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 25
- 238000004448 titration Methods 0.000 claims description 23
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- -1 nitrogen-containing compound Chemical class 0.000 claims description 17
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 17
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 15
- 229910001882 dioxygen Inorganic materials 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 17
- 238000006277 sulfonation reaction Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 238000003795 desorption Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000003377 acid catalyst Substances 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- 150000001555 benzenes Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 230000009229 glucose formation Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- QPKFVRWIISEVCW-UHFFFAOYSA-N 1-butane boronic acid Chemical compound CCCCB(O)O QPKFVRWIISEVCW-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- VOXXGUAZBWSUSS-UHFFFAOYSA-N 2,4,6-triphenyl-1,3,5,2,4,6-trioxatriborinane Chemical compound O1B(C=2C=CC=CC=2)OB(C=2C=CC=CC=2)OB1C1=CC=CC=C1 VOXXGUAZBWSUSS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- HCAUQPZEWLULFJ-UHFFFAOYSA-N benzo[f]quinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=N1 HCAUQPZEWLULFJ-UHFFFAOYSA-N 0.000 description 1
- BMWYMEQOMFGKSN-UHFFFAOYSA-N benzo[g]cinnoline Chemical compound N1=NC=CC2=CC3=CC=CC=C3C=C21 BMWYMEQOMFGKSN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 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
- FTSSQIKWUOOEGC-RULYVFMPSA-N fructooligosaccharide Chemical compound OC[C@H]1O[C@@](CO)(OC[C@@]2(OC[C@@]3(OC[C@@]4(OC[C@@]5(OC[C@@]6(OC[C@@]7(OC[C@@]8(OC[C@@]9(OC[C@@]%10(OC[C@@]%11(O[C@H]%12O[C@H](CO)[C@@H](O)[C@H](O)[C@H]%12O)O[C@H](CO)[C@@H](O)[C@@H]%11O)O[C@H](CO)[C@@H](O)[C@@H]%10O)O[C@H](CO)[C@@H](O)[C@@H]9O)O[C@H](CO)[C@@H](O)[C@@H]8O)O[C@H](CO)[C@@H](O)[C@@H]7O)O[C@H](CO)[C@@H](O)[C@@H]6O)O[C@H](CO)[C@@H](O)[C@@H]5O)O[C@H](CO)[C@@H](O)[C@@H]4O)O[C@H](CO)[C@@H](O)[C@@H]3O)O[C@H](CO)[C@@H](O)[C@@H]2O)[C@@H](O)[C@@H]1O FTSSQIKWUOOEGC-RULYVFMPSA-N 0.000 description 1
- 229940107187 fructooligosaccharide Drugs 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 235000021255 galacto-oligosaccharides Nutrition 0.000 description 1
- 150000003271 galactooligosaccharides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 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
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000003272 mannan oligosaccharides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- AXFBAIOSECPASO-UHFFFAOYSA-N pentacyclo[6.6.2.02,7.04,16.011,15]hexadeca-1(14),2(7),3,5,8(16),9,11(15),12-octaene Chemical compound C1=C(C=C23)C4=C5C3=CC=CC5=CC=C4C2=C1 AXFBAIOSECPASO-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 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
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Description
本発明は、スルホン酸基を有する繊維状活性炭を含む炭素系固体酸、これを用いた固体酸触媒、及びこれらの製造方法に関する。 The present invention relates to a carbon-based solid acid containing fibrous activated carbon having a sulfonic acid group, a solid acid catalyst using the same, and a production method thereof.
従来、エステル化、加水分解、アルキル化、アルコールの脱水縮合、オレフィンの水和などの各種の化学反応には、種々の酸触媒が用いられており、化学工業などにおいては、酸触媒として硫酸が広く用いられている。硫酸は安価であるため、多量に使用される。しかしながら、硫酸は液体であるため、反応後の生成物からの硫酸の分離、回収、精製、再利用の工程、生成物中に残留する硫酸の中和工程、中和で生成した塩の除去工程、廃水処理工程などに、多大なエネルギーが必要という問題がある。 Conventionally, various acid catalysts have been used in various chemical reactions such as esterification, hydrolysis, alkylation, dehydration condensation of alcohol, and olefin hydration. In the chemical industry, sulfuric acid is used as an acid catalyst. Widely used. Since sulfuric acid is inexpensive, it is used in large quantities. However, since sulfuric acid is a liquid, the process for separating, recovering, purifying and reusing sulfuric acid from the product after the reaction, the process for neutralizing the sulfuric acid remaining in the product, and the process for removing the salt produced by the neutralization There is a problem that a large amount of energy is required in the wastewater treatment process.
一方、固体酸触媒は、硫酸などの液体酸に比して、分離、回収が容易であり、繰り返し使用しやすいため、硫酸などの液体酸触媒の代替として、固体酸触媒も用いられるようになっている。 On the other hand, solid acid catalysts are easier to separate and recover than liquid acids such as sulfuric acid, and are easy to use repeatedly. Therefore, solid acid catalysts are also used as an alternative to liquid acid catalysts such as sulfuric acid. ing.
固体酸触媒しては、例えば、シリカ−アルミナ、ゼオライトなどが使用されている。しかしながら、これらの固体酸触媒は、例えば水中で使用すると触媒活性が低下するため、硫酸の代替として工業的に用いることは困難である。 As the solid acid catalyst, for example, silica-alumina, zeolite or the like is used. However, these solid acid catalysts are difficult to use industrially as an alternative to sulfuric acid, for example, because their catalytic activity decreases when used in water.
近年、水中でも使用し得る固体酸触媒として、炭素質材料にスルホン酸基を導入した炭素系固体酸が開発されている。 In recent years, carbon-based solid acids in which sulfonic acid groups are introduced into carbonaceous materials have been developed as solid acid catalysts that can be used in water.
炭素質材料にスルホン酸基を導入した炭素系固体酸として、例えば、特許文献１には、多環式芳香族炭化水素類を濃硫酸または発煙硫酸で加熱処理し、多環式芳香族炭化水素の縮合及びスルホン化を行うことによって得られる固体酸が開示されている。また、例えば、特許文献２には、フェノール樹脂を炭化処理及びスルホン化処理して得られるスルホン酸基含有炭素質材料を含む固体酸触媒が開示されている。さらに、例えば、特許文献３には、グルコース、セルロースなどを部分炭化して得られる無定形炭素にスルホン酸基を導入した固体酸が開示されている。
As a carbon-based solid acid in which a sulfonic acid group is introduced into a carbonaceous material, for example, in
しかしながら、これらの炭素系固体酸では、触媒活性が十分でなかったり、繰り返し使用した場合に、触媒活性が低下しやすいという問題がある。このような状況下、優れた触媒活性を有し、かつ、繰り返し使用しても触媒活性が低下し難い新規な炭素系固体酸の開発が求められている。 However, these carbon-based solid acids have a problem that the catalytic activity is not sufficient or the catalytic activity tends to decrease when used repeatedly. Under such circumstances, development of a novel carbon-based solid acid that has excellent catalytic activity and is difficult to decrease even when used repeatedly is demanded.
本発明は、滴定法で測定される酸量が大きく、優れた触媒活性を有し、繰り返し使用しても触媒活性が劣化し難い新規な炭素系固体酸を提供することを主な目的とする。さらに、本発明は、当該炭素系固体酸からなる炭素系固体酸触媒、及びこれらの製造方法を提供することも目的とする。 The main object of the present invention is to provide a novel carbon-based solid acid that has a large amount of acid measured by a titration method, has excellent catalytic activity, and does not easily deteriorate catalytic activity even when used repeatedly. . Furthermore, another object of the present invention is to provide a carbon-based solid acid catalyst comprising the carbon-based solid acid and a method for producing them.
本発明者は、上記のような課題を解決すべく鋭意検討を行った。その結果、スルホン酸基を有する繊維状活性炭を含む炭素系固体酸であって、炭素系固体酸を１００℃の熱水中で１時間処理した後、滴定法で測定した酸量が、１．０ｍｍｏｌ／ｇ以上を示す炭素系固体酸は、優れた触媒活性を有し、かつ、繰り返し使用しても触媒活性が劣化し難くなることが明らかとなった。本発明は、このような知見に基づいて、さらに検討を重ねることにより完成された発明である。 The present inventor has intensively studied to solve the above problems. As a result, it was a carbon-based solid acid containing fibrous activated carbon having a sulfonic acid group, and after the carbon-based solid acid was treated in hot water at 100 ° C. for 1 hour, the acid amount measured by a titration method was 1. It has been clarified that a carbon-based solid acid exhibiting 0 mmol / g or more has excellent catalytic activity, and the catalytic activity is hardly deteriorated even when used repeatedly. The present invention has been completed by further studies based on such findings.
すなわち、本発明は、下記に掲げる態様の発明を提供する。
項１． スルホン酸基を有する繊維状活性炭を含む炭素系固体酸であって、
前記炭素系固体酸を１００℃の熱水中で１時間処理した後、滴定法で測定した酸量が、１．０ｍｍｏｌ／ｇ以上を示す、炭素系固体酸。
項２． 前記スルホン酸基を有する繊維状活性炭は、繊維状活性炭を酸素ガスの存在下に加熱した後、スルホン酸基を導入することにより得られたものである、項１に記載の炭素系固体酸。
項３． 前記酸素ガスの存在下における加熱温度が、３００℃以上である、項１または２に記載の炭素系固体酸。
項４． 前記繊維状活性炭が、窒素及びホウ素の少なくとも一方を含む、項１〜３のいずれかに記載の炭素系固体酸。
項５． 項１〜４のいずれかに記載の炭素系固体酸からなる、固体酸触媒。
項６． 繊維状活性炭を酸素ガスの存在下に加熱する酸化工程と、
前記酸化工程の後、酸化された繊維状活性炭と、濃硫酸、発煙硫酸、及び三酸化硫黄からなる群から選択された少なくとも１種とを混合して、前記酸化された繊維状活性炭にスルホン酸基を導入するスルホン酸基導入工程と、
を備える、項１〜４のいずれかに記載の炭素系固体酸の製造方法。
項７． 炭素質材料前駆体とホウ素含有化合物とを混合するホウ素ドープ工程と、
前記ホウ素ドープ工程を経て得られたホウ素含有炭素質材料前駆体を前記酸化された繊維状活性炭に担持させる工程と、
をさらに備える、項６に記載の炭素系固体酸の製造方法。
項８． 前記繊維状活性炭と窒素含有化合物とを混合する窒素ドープ工程をさらに備える、項６に記載の炭素系固体酸の製造方法。
That is, this invention provides the invention of the aspect hung up below.
A carbon-based solid acid in which the amount of acid measured by a titration method is 1.0 mmol / g or more after treating the carbon-based solid acid in hot water at 100 ° C. for 1 hour.
Item 3. Item 3. The carbon-based solid acid according to
Item 4. Item 4. The carbon-based solid acid according to any one of
Item 6. An oxidation step of heating fibrous activated carbon in the presence of oxygen gas;
After the oxidation step, the oxidized fibrous activated carbon is mixed with at least one selected from the group consisting of concentrated sulfuric acid, fuming sulfuric acid, and sulfur trioxide, and the oxidized fibrous activated carbon is mixed with sulfonic acid. A sulfonic acid group introduction step for introducing a group;
The manufacturing method of the carbon-type solid acid in any one of claim | item 1-4 provided with these.
Item 7. A boron doping step of mixing a carbonaceous material precursor and a boron-containing compound;
Supporting the boron-containing carbonaceous material precursor obtained through the boron doping step on the oxidized fibrous activated carbon;
Item 7. The method for producing a carbon-based solid acid according to Item 6, further comprising:
Item 8. Item 7. The method for producing a carbon-based solid acid according to Item 6, further comprising a nitrogen doping step of mixing the fibrous activated carbon and a nitrogen-containing compound.
本発明によれば、滴定法で測定される酸量が大きく、優れた触媒活性を有し、繰り返し使用しても触媒活性が劣化し難い新規な炭素系固体酸を提供することができる。さらに、本発明によれば、当該炭素系固体酸からなる炭素系固体酸触媒、及びこれらの製造方法を提供することができる。当該炭素系固体酸触媒は、水中でも使用することができるため、例えば硫酸を酸触媒として用いる化学反応用の酸触媒として好適に使用することができる。 According to the present invention, it is possible to provide a novel carbon-based solid acid that has a large amount of acid measured by a titration method, has excellent catalytic activity, and does not easily deteriorate catalytic activity even when used repeatedly. Furthermore, according to this invention, the carbon-type solid acid catalyst which consists of the said carbon-type solid acid, and these manufacturing methods can be provided. Since the carbon-based solid acid catalyst can be used in water, for example, it can be suitably used as an acid catalyst for chemical reaction using sulfuric acid as an acid catalyst.
本発明の炭素系固体酸は、スルホン酸基を有する繊維状活性炭を含む炭素系固体酸であって、炭素系固体酸を１００℃の熱水中で１時間処理した後、滴定法で測定した酸量が、１．０ｍｍｏｌ／ｇ以上を示すことを特徴とする。以下、本発明の炭素系固体酸、当該炭素系固体酸を用いた炭素系固体酸触媒、及びこれらの製造方法について詳述する。 The carbon-based solid acid of the present invention is a carbon-based solid acid containing fibrous activated carbon having a sulfonic acid group, and the carbon-based solid acid was measured by a titration method after being treated in hot water at 100 ° C. for 1 hour. The acid amount is 1.0 mmol / g or more. Hereinafter, the carbon-based solid acid of the present invention, the carbon-based solid acid catalyst using the carbon-based solid acid, and the production methods thereof will be described in detail.
本発明の炭素系固体酸に含まれる繊維状活性炭は、スルホン酸基を有する。後述の通り、本発明の炭素系固体酸に含まれる繊維状活性炭においては、例えば、原料となる繊維状活性炭を酸素ガスの存在下に加熱した後、酸化された繊維状活性炭にスルホン酸基を導入することにより、炭素系固体酸を１００℃の熱水中で１時間処理した後、滴定法により測定される酸量が、１．０ｍｍｏｌ／ｇ以上を示す炭素系固体酸とすることができる。 The fibrous activated carbon contained in the carbon-based solid acid of the present invention has a sulfonic acid group. As described later, in the fibrous activated carbon contained in the carbon-based solid acid of the present invention, for example, after heating the fibrous activated carbon used as a raw material in the presence of oxygen gas, a sulfonic acid group is added to the oxidized fibrous activated carbon. By introducing the carbon-based solid acid, after treating the carbon-based solid acid in hot water at 100 ° C. for 1 hour, the amount of acid measured by a titration method can be a carbon-based solid acid showing 1.0 mmol / g or more. .
炭素系固体酸の原料となる繊維状活性炭としては、酸素ガスの存在下に加熱することにより酸化され、かつ、スルホン酸基を導入できるものであれば特に制限されず、例えば、ＪＩＳ Ｋ１４７７に記載されたような多孔質繊維状の活性炭が挙げられる。本発明において、繊維状活性炭の繊維径は特に制限されないが、好ましくは１〜３０μｍ程度が挙げられる。また、繊維状活性炭の平均繊維長さは、特に制限されないが、好ましくは０．１ｍｍ以上が挙げられる。なお、繊維状活性炭の平均繊維長さは、ＪＩＳ Ｋ１４７７に記載された方法により求めた値である。また、繊維状活性炭の比表面積は、特に制限されないが、好ましくは５００〜２０００ｍ2／ｇ程度が挙げられる。繊維状活性炭の比表面積は、ＪＩＳ Ｋ１４７７に記載されたＢＥＴ法により求めた値である。 The fibrous activated carbon used as a raw material for the carbon-based solid acid is not particularly limited as long as it is oxidized by heating in the presence of oxygen gas and can introduce a sulfonic acid group. For example, it is described in JIS K1477. And porous fibrous activated carbon as described above. In the present invention, the fiber diameter of the fibrous activated carbon is not particularly limited, but preferably about 1 to 30 μm. The average fiber length of the fibrous activated carbon is not particularly limited, but preferably 0.1 mm or more. In addition, the average fiber length of fibrous activated carbon is the value calculated | required by the method described in JISK1477. Further, the specific surface area of the fibrous activated carbon is not particularly limited, but preferably about 500 to 2000 m 2 / g. The specific surface area of the fibrous activated carbon is a value determined by the BET method described in JIS K1477.
本発明の炭素系固体酸は、例えば、原料となる上記の繊維状活性炭を酸素ガスの存在下に加熱した後、スルホン酸基を導入することにより得られる。具体的には、まず、スルホン酸基を導入する前に、原料となる繊維状活性炭を酸素ガスの存在下に加熱することにより、繊維状活性炭を酸化する。この酸化により、繊維状活性炭中にカルボキシル基、水酸基などの酸基が導入される。繊維状活性炭にカルボキシル基などが導入されることにより、その後、繊維状活性炭にスルホン酸基が導入された際に、カルボキシル基などがスルホン酸基を安定化すると考えられる。このため、滴定法で測定される酸量が大きくなると共に、炭素系固体酸の触媒活性を高め、繰り返し使用しても触媒活性が劣化し難い炭素系固体酸とし得る。カルボキシル基などによるスルホン酸基の安定化効果は、例えば、次のように考えることができる。カルボキシル基などが繊維状活性炭中に導入されることより、例えば水中などにおいてイオン化したカルボキシル基などの電子がスルホン酸基に供給され、スルホン酸基の硫黄原子とこれが結合した炭素原子との結合が強められ、スルホン酸基が安定化すると考えられる。この結果、スルホン酸基が触媒として効果的に機能し、かつ、繰り返し使用してもスルホン酸基が繊維状活性炭から脱離し難く、触媒活性が劣化し難い炭素系固体酸とすることが可能になると考えられる。 The carbon-based solid acid of the present invention can be obtained, for example, by heating the fibrous activated carbon as a raw material in the presence of oxygen gas and then introducing a sulfonic acid group. Specifically, first, before introducing the sulfonic acid group, the fibrous activated carbon is heated in the presence of oxygen gas to oxidize the fibrous activated carbon. By this oxidation, acid groups such as carboxyl groups and hydroxyl groups are introduced into the fibrous activated carbon. By introducing a carboxyl group or the like into the fibrous activated carbon, it is considered that the carboxyl group or the like stabilizes the sulfonic acid group when the sulfonic acid group is subsequently introduced into the fibrous activated carbon. For this reason, the amount of acid measured by the titration method is increased, the catalytic activity of the carbon-based solid acid is increased, and the carbon-based solid acid is hardly deteriorated even when used repeatedly. The stabilizing effect of the sulfonic acid group due to the carboxyl group or the like can be considered as follows, for example. By introducing a carboxyl group or the like into the fibrous activated carbon, for example, an electron such as a carboxyl group ionized in water or the like is supplied to the sulfonic acid group, and the bond between the sulfur atom of the sulfonic acid group and the carbon atom to which the sulfonic acid group is bonded. It is believed that the sulfonic acid group is stabilized. As a result, it is possible to obtain a carbon-based solid acid in which the sulfonic acid group functions effectively as a catalyst, and the sulfonic acid group is not easily detached from the fibrous activated carbon even when used repeatedly, and the catalytic activity is not easily deteriorated. It is considered to be.
さらに、本発明において、炭素系固体酸に繊維状活性炭を用いることにより、粉末状活性炭、粒状活性炭などを用いる場合に比して、滴定法で測定される酸量が大きく、触媒活性を高めつつ、繰り返し使用しても触媒活性が劣化し難い炭素系固体酸とすることが可能となる。これは、粉末状活性炭、粒状活性炭などに比して、繊維状活性炭の比表面積が大きいため、触媒として機能するスルホン酸基、及びスルホン酸基を安定化させるカルボキシル基などの他の酸基をより多く導入できることなどに起因すると考えられる。さらに、繊維状活性炭を用いることにより、後述の固体酸触媒として用いる際の取り扱い性（反応後の生成物からの固体酸触媒の分離、回収、精製、再利用のしやすさなど）がより一層高められる。さらに、繊維状活性炭を用いることにより、例えばフィルター状の固体酸触媒などとして好適に使用することができる。 Furthermore, in the present invention, by using fibrous activated carbon as the carbon-based solid acid, the amount of acid measured by the titration method is larger than when using powdered activated carbon, granular activated carbon, etc., and the catalytic activity is enhanced. Thus, it becomes possible to obtain a carbon-based solid acid whose catalytic activity does not easily deteriorate even when used repeatedly. This is because the specific surface area of fibrous activated carbon is larger than that of powdered activated carbon, granular activated carbon, etc., so other sulfonic acid groups that function as catalysts and other acid groups such as carboxyl groups that stabilize sulfonic acid groups This may be due to the fact that more can be introduced. Furthermore, by using fibrous activated carbon, handling properties (e.g. ease of separation, recovery, purification, and reuse of the solid acid catalyst from the product after the reaction) when used as a solid acid catalyst described later are further increased. Enhanced. Furthermore, by using fibrous activated carbon, it can be suitably used as, for example, a filter-like solid acid catalyst.
酸素ガスの存在下における繊維状活性炭の加熱は、例えば、空気中で行うことができる。また、加熱温度としては、繊維状活性炭を酸化できる温度であれば特に制限されないが、例えば３００℃以上、好ましくは３５０℃以上、より好ましくは４００℃以上が挙げられる。なお、加熱温度が高すぎると、燃え尽きてしまう場合があるため、加熱温度の上限値としては、通常、５５０℃程度、好ましくは５００℃程度が挙げられる。加熱時間としては、加熱温度等に応じて適宜設定すればよく、例えば、１〜２０時間程度、好ましくは１〜５時間程度が挙げられる。 The heating of the fibrous activated carbon in the presence of oxygen gas can be performed in air, for example. The heating temperature is not particularly limited as long as it is a temperature at which fibrous activated carbon can be oxidized, and for example, 300 ° C or higher, preferably 350 ° C or higher, more preferably 400 ° C or higher. In addition, since it may burn out when heating temperature is too high, as an upper limit of heating temperature, about 550 degreeC is mentioned normally, Preferably about 500 degreeC is mentioned. What is necessary is just to set suitably as heating time according to heating temperature etc., for example, about 1 to 20 hours, Preferably about 1 to 5 hours is mentioned.
次に、酸化した繊維状活性炭にスルホン酸基を導入するスルホン化処理を行う。スルホン化処理の方法としては、特に制限されず、例えば、酸化した繊維状活性炭と、濃硫酸、発煙硫酸、及び三酸化硫黄の少なくとも一種とを混合する方法が挙げられる。より詳細には、濃硫酸または発煙硫酸と酸化した繊維状活性炭とをアルゴン、窒素などの不活性ガスの存在下に混合する方法や、三酸化硫黄ガスと酸化した繊維状活性炭とをアルゴン、窒素などの不活性ガスの存在下に接触させる方法などが挙げられる。 Next, a sulfonation treatment for introducing sulfonic acid groups into the oxidized fibrous activated carbon is performed. The method for the sulfonation treatment is not particularly limited, and examples thereof include a method in which oxidized fibrous activated carbon is mixed with at least one of concentrated sulfuric acid, fuming sulfuric acid, and sulfur trioxide. More specifically, a method of mixing concentrated sulfuric acid or fuming sulfuric acid with oxidized fibrous activated carbon in the presence of an inert gas such as argon or nitrogen, or sulfur trioxide gas and oxidized fibrous activated carbon with argon or nitrogen. And a method of contacting in the presence of an inert gas.
濃硫酸または発煙硫酸を用いてスルホン酸基を導入する場合、酸化した繊維状活性炭に対する濃硫酸または発煙硫酸の量としては、特に制限されず、酸化した繊維状活性炭１質量部に対して、濃硫酸または発煙硫酸が、例えば５〜１０００質量部程度、好ましくは１００〜５００質量部程度が挙げられる。濃硫酸または発煙硫酸を用いる場合、スルホン化処理の温度としては、例えば２０〜２５０℃程度、好ましくは５０〜２００℃程度が挙げられる。濃硫酸または発煙硫酸を用いる場合、スルホン化処理の時間としては、例えば５〜１５０分間程度、好ましくは３０〜１２０分間程度が挙げられる。 When the sulfonic acid group is introduced using concentrated sulfuric acid or fuming sulfuric acid, the amount of concentrated sulfuric acid or fuming sulfuric acid with respect to the oxidized fibrous activated carbon is not particularly limited, and it is concentrated with respect to 1 mass part of oxidized fibrous activated carbon. Sulfuric acid or fuming sulfuric acid is, for example, about 5 to 1000 parts by mass, preferably about 100 to 500 parts by mass. When concentrated sulfuric acid or fuming sulfuric acid is used, the temperature of the sulfonation treatment is, for example, about 20 to 250 ° C, preferably about 50 to 200 ° C. In the case of using concentrated sulfuric acid or fuming sulfuric acid, the time for the sulfonation treatment is, for example, about 5 to 150 minutes, preferably about 30 to 120 minutes.
三酸化硫黄ガスを用いてスルホン酸基を導入する場合、スルホン化処理における三酸化硫黄ガスの濃度としては、特に制限されず、例えば５〜１００体積％程度、好ましくは２０〜５０体積％程度が挙げられる。三酸化硫黄ガスを用いる場合、スルホン化処理の温度としては、特に制限されず、例えば２０〜２５０℃程度、好ましくは５０〜２００℃程度が挙げられる。三酸化硫黄ガスを用いる場合、スルホン化処理の時間としては、例えば５〜１５０分間程度、好ましくは３０〜１５０分間程度が挙げられる。 When introducing a sulfonic acid group using sulfur trioxide gas, the concentration of sulfur trioxide gas in the sulfonation treatment is not particularly limited, and is, for example, about 5 to 100% by volume, preferably about 20 to 50% by volume. Can be mentioned. When using sulfur trioxide gas, it does not restrict | limit especially as temperature of a sulfonation process, For example, about 20-250 degreeC, Preferably about 50-200 degreeC is mentioned. In the case of using sulfur trioxide gas, the time for the sulfonation treatment is, for example, about 5 to 150 minutes, preferably about 30 to 150 minutes.
本発明の炭素系固体酸は、スルホン化処理の後、１００℃の熱水などによりスルホン酸基を導入した繊維状活性炭を洗浄、乾燥して、余剰の硫酸、発煙硫酸、三酸化硫黄などを除去することができる。熱水による洗浄は、例えばソックスレー抽出法などにより、１００℃での環流下で行うことができる。さらに、加圧下で洗浄を行うことにより、洗浄時間を短縮することも可能である。 The carbon-based solid acid of the present invention is obtained by washing and drying the fibrous activated carbon into which the sulfonic acid group has been introduced with hot water at 100 ° C. after the sulfonation treatment, and removing excess sulfuric acid, fuming sulfuric acid, sulfur trioxide, etc. Can be removed. Washing with hot water can be performed under reflux at 100 ° C., for example, by a Soxhlet extraction method. Further, the cleaning time can be shortened by performing the cleaning under pressure.
本発明の炭素系固体酸は、１００℃の熱水中で１時間処理した後、滴定法で測定した酸量が１．０ｍｍｏｌ／ｇ以上を示す。本発明において、滴定法によって測定される酸量とは、具体的には、炭素系固体酸を適量の水に浸漬し、濃度０．１Ｎまたは０．０１ＮのＮａＯＨ水溶液を用いた単純滴定法、または濃度０．１Ｎまたは０．０１ＮのＮａＯＨ水溶液と濃度０．１Ｎまたは０．０１ＮのＨＣｌ水溶液を用いた逆滴定法により測定して求められる値である。単純滴定法は、簡便に行えるため、炭素系固体酸の酸量を予備的に測定する方法として適している。また、逆滴定法は、炭素系固体酸の酸量をより正確に測定する方法として適している。本発明の炭素系固体酸は、１００℃の熱水中で１時間処理した後、上記の逆滴定法で測定した酸量が１．０ｍｍｏｌ以上を示す。また、本発明の炭素系固体酸中において、スルホン酸基以外に例えばカルボキシル基や水酸基などの他の酸基が含まれる場合には、本発明における酸量とは、スルホン酸基と他の酸基とを併せた酸量である。炭素系固体酸が示す酸量としては、好ましくは１．５ｍｍｏｌ／ｇ以上が挙げられる。当該酸量が１．０ｍｍｏｌ／ｇ未満の場合には、炭素系固体酸を化学反応に対する酸触媒として使用する場合に、酸触媒としての活性が不十分となる場合がある。本発明の炭素系固体酸は、１００℃の熱水中で１時間処理した後、滴定法で測定した酸量が１．０ｍｍｏｌ／ｇ以上を示すことにより、後述の固体酸触媒として好適に使用することができる。 The carbon-based solid acid of the present invention exhibits an acid amount of 1.0 mmol / g or more measured by a titration method after being treated in hot water at 100 ° C. for 1 hour. In the present invention, the acid amount measured by the titration method is specifically a simple titration method using a 0.1N or 0.01N NaOH aqueous solution in which a carbon-based solid acid is immersed in an appropriate amount of water. Alternatively, it is a value obtained by measurement by a back titration method using a 0.1 N or 0.01 N NaOH aqueous solution and a 0.1 N or 0.01 N HCl aqueous solution. Since the simple titration method can be easily performed, it is suitable as a method for preliminary measurement of the acid amount of the carbon-based solid acid. Moreover, the back titration method is suitable as a method for measuring the acid amount of the carbon-based solid acid more accurately. The carbon-based solid acid of the present invention is treated in hot water at 100 ° C. for 1 hour, and then the acid amount measured by the back titration method is 1.0 mmol or more. In addition, in the carbon-based solid acid of the present invention, when other acid groups such as a carboxyl group and a hydroxyl group are included in addition to the sulfonic acid group, the acid amount in the present invention is the sulfonic acid group and the other acid. The acid amount combined with the group. The acid amount indicated by the carbon-based solid acid is preferably 1.5 mmol / g or more. When the acid amount is less than 1.0 mmol / g, the activity as an acid catalyst may be insufficient when a carbon-based solid acid is used as an acid catalyst for a chemical reaction. The carbon-based solid acid of the present invention is suitably used as a solid acid catalyst to be described later by treating it in hot water at 100 ° C. for 1 hour and then showing an acid amount measured by a titration method of 1.0 mmol / g or more. can do.
本発明の炭素系固体酸においては、繊維状活性炭が窒素及びホウ素の少なくとも一方を含んでいてもよい。繊維状活性炭に窒素を含有させる（ドープする）方法としては、特に制限されず、例えば、上記の酸素ガスの存在下における繊維状活性炭の加熱を行う前に、原料となる繊維状活性炭と窒素含有化合物とを混合する方法が挙げられる。窒素含有化合物としては、繊維状活性炭に窒素をドープできるものであれば、特に制限されず、好ましくはフェナントロリン（ジアザフェナントロレン）、アザフェナントレン、アザアントラセン、ジアザアントラセンなどが挙げられる。窒素含有化合物は、１種類単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。原料となる繊維状活性炭と窒素含有化合物との混合は、例えば、窒素含有化合物の溶液に繊維状活性炭を浸漬する方法などが挙げられる。本発明の炭素系固体酸が窒素を含む場合、窒素の含有量としては、好ましくは１質量％以上、より好ましくは１．５質量％以上が挙げられる。本発明において、炭素系固体酸中の窒素の含有量は、元素分析法により測定することができる。 In the carbon-based solid acid of the present invention, the fibrous activated carbon may contain at least one of nitrogen and boron. The method for incorporating (doping) nitrogen into the fibrous activated carbon is not particularly limited. For example, before heating the fibrous activated carbon in the presence of the above-described oxygen gas, the fibrous activated carbon used as a raw material and the nitrogen are contained. The method of mixing with a compound is mentioned. The nitrogen-containing compound is not particularly limited as long as fibrous activated carbon can be doped with nitrogen, and preferably includes phenanthroline (diazaphenanthrolene), azaphenanthrene, azaanthracene, diazaanthracene and the like. A nitrogen-containing compound may be used individually by 1 type, and may be used in combination of 2 or more types. Examples of the mixing of the fibrous activated carbon used as the raw material with the nitrogen-containing compound include a method of immersing the fibrous activated carbon in a solution of the nitrogen-containing compound. When the carbon-based solid acid of the present invention contains nitrogen, the nitrogen content is preferably 1% by mass or more, more preferably 1.5% by mass or more. In the present invention, the nitrogen content in the carbon-based solid acid can be measured by elemental analysis.
繊維状活性炭にホウ素を含有させる方法としては、特に制限されず、例えば、炭素質材料前駆体にホウ素がドープされたホウ素含有炭素質材料前駆体を、上記の酸化された繊維状活性炭に担持させる方法が挙げられる。炭素質材料前駆体にホウ素をドープして、ホウ素含有炭素質材料前駆体を得る方法としては、特に制限されず、例えば、炭素質材料前駆体とホウ素含有化合物とを混合する方法が挙げられる。 The method for incorporating the boron into the fibrous activated carbon is not particularly limited. For example, the boron-containing carbonaceous material precursor obtained by doping the carbonaceous material precursor with boron is supported on the oxidized fibrous activated carbon. A method is mentioned. The method for obtaining a boron-containing carbonaceous material precursor by doping boron into the carbonaceous material precursor is not particularly limited, and examples thereof include a method of mixing a carbonaceous material precursor and a boron-containing compound.
炭素質材料前駆体としては、ホウ素を担持できるものであれば特に制限されず、好ましくは糖質、芳香族化合物、樹脂などが挙げられる。炭素質材料前駆体は、１種類単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。 The carbonaceous material precursor is not particularly limited as long as it can support boron, and preferably includes a saccharide, an aromatic compound, a resin, and the like. A carbonaceous material precursor may be used individually by 1 type, and may be used in combination of 2 or more types.
糖質としては、特に制限されないが、好ましくはグルコース、スクロース（砂糖）、マルトース、フルクトース、ラクトース、フラクトオリゴ糖、ガラクトオリゴ糖、マンナンオリゴ糖、セルロース、デンプン、アミロースなどが挙げられる。 Although it does not restrict | limit especially as carbohydrate, Preferably glucose, sucrose (sugar), maltose, fructose, lactose, fructooligosaccharide, galactooligosaccharide, mannan oligosaccharide, cellulose, starch, amylose etc. are mentioned.
芳香族化合物としては、特に制限されないが、例えば、単環芳香族化合物、多環芳香族化合物が挙げられる。単環芳香族化合物としては、好ましくはベンゼンまたは置換ベンゼンが挙げられる。置換ベンゼンの置換基としては、例えば、メチル基、エチル基、プロピル基、ブチル基などの炭素数１〜４のアルキル基；メトキシ基、エトキシ基、プロポキシ基、ブトシキ基などの炭素数１〜４のアルコキシ基、フッ素、塩素、臭素、ヨウ素などのハロゲン原子；水酸基、アミノ基、ビニル基などが挙げられる。また、多環芳香族化合物としては、好ましくはナフタレン、ピレン、ベンゾ（α）ピレン、ベンゾアントラセン、アントラセン、フェナントレン、コロネン、ケクレン、ビフェニル、ターフェニルなどが挙げられる。多環芳香族化合物は、置換基を有していてもよい。多環芳香族化合物が有し得る置換基としては、例えば、置換ベンゼンと同様のものが例示できる。なお、これらの芳香族化合物は、タール、ピッチなどに含まれており、タール、ピッチなど芳香族化合物として用いてもよい。 Although it does not restrict | limit especially as an aromatic compound, For example, a monocyclic aromatic compound and a polycyclic aromatic compound are mentioned. The monocyclic aromatic compound is preferably benzene or substituted benzene. Examples of the substituent of the substituted benzene include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group; and 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Alkoxy groups, halogen atoms such as fluorine, chlorine, bromine and iodine; hydroxyl groups, amino groups and vinyl groups. The polycyclic aromatic compound is preferably naphthalene, pyrene, benzo (α) pyrene, benzoanthracene, anthracene, phenanthrene, coronene, keklen, biphenyl, terphenyl and the like. The polycyclic aromatic compound may have a substituent. As a substituent which a polycyclic aromatic compound may have, the thing similar to substituted benzene can be illustrated, for example. In addition, these aromatic compounds are contained in tar, pitch, etc., and may be used as aromatic compounds such as tar, pitch.
樹脂としては、特に制限されないが、例えば、フェノール樹脂、フラン樹脂、尿素樹脂、メラミン樹脂、不飽和ポリエステル樹脂、エポキシ樹脂等の熱硬化性樹脂などが挙げられる。 The resin is not particularly limited, and examples thereof include thermosetting resins such as phenol resins, furan resins, urea resins, melamine resins, unsaturated polyester resins, and epoxy resins.
ホウ素含有化合物としては、炭素質材料前駆体にホウ素をドープできるものであれば、特に制限されず、好ましくはホウ酸、フェニルボロン酸、ｎ−ブチルボロン酸、トリフェニルボロキシン、ホウ酸トリメチルなどが挙げられる。ホウ素含有化合物は、１種類単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。例えば、ホウ素含有化合物としてホウ酸などを用いる場合、上記の炭素質材料前駆体は、水酸基を有することが好ましい。炭素質材料前駆体が水酸基を有する場合、当該水酸基とホウ酸などの水酸基との間の加熱・脱水でエステル結合を形成することにより、好適にホウ素をドープさせ得るからである。炭素質材料前駆体とホウ素含有化合物との混合は、加熱下に行うことが好ましい。加熱温度としては、特に制限されないが、好ましくは５０℃〜１８０℃程度が挙げられる。また、ホウ素のドープは、加圧下に行ってよい。さらに、炭素質材料前駆体にホウ素をドープする際には、溶媒を用いてもよい。溶媒としては、炭素質材料前駆体及びホウ含有化合物の溶解性などに応じて、適宜選択することができ、例えば水、エタノールなどが挙げられる。 The boron-containing compound is not particularly limited as long as the carbonaceous material precursor can be doped with boron, and preferably boric acid, phenylboronic acid, n-butylboronic acid, triphenylboroxine, trimethylborate and the like. Can be mentioned. One type of boron-containing compound may be used alone, or two or more types may be used in combination. For example, when boric acid or the like is used as the boron-containing compound, the carbonaceous material precursor preferably has a hydroxyl group. This is because when the carbonaceous material precursor has a hydroxyl group, boron can be preferably doped by forming an ester bond by heating and dehydration between the hydroxyl group and a hydroxyl group such as boric acid. The mixing of the carbonaceous material precursor and the boron-containing compound is preferably performed under heating. Although it does not restrict | limit especially as heating temperature, Preferably about 50 to 180 degreeC is mentioned. Boron doping may be performed under pressure. Furthermore, a solvent may be used when doping the carbonaceous material precursor with boron. The solvent can be appropriately selected according to the solubility of the carbonaceous material precursor and the boron-containing compound, and examples thereof include water and ethanol.
ホウ素含有炭素質材料前駆体を、上記の酸化された繊維状活性炭に担持させる方法としては、特に制限されず、例えば、ホウ素含有炭素質材料前駆体が溶解した溶液に上記の酸化された繊維状活性炭を浸漬し、乾燥させる方法などが挙げられる。ホウ素含有炭素質材料前駆体を溶解する溶媒としては、例えば、水、エタノールなどが挙げられる。なお、上記のスルホン化処理は、酸化された繊維状活性炭にホウ素含有炭素質材料前駆体を担持させた後に行うことができる。 The method for supporting the boron-containing carbonaceous material precursor on the oxidized fibrous activated carbon is not particularly limited. For example, the oxidized fibrous material is dissolved in a solution in which the boron-containing carbonaceous material precursor is dissolved. Examples include a method of immersing activated carbon and drying. Examples of the solvent for dissolving the boron-containing carbonaceous material precursor include water and ethanol. In addition, said sulfonation process can be performed after carrying | supporting a boron containing carbonaceous material precursor to the oxidized fibrous activated carbon.
本発明の炭素系固体酸において、ホウ素を担持する場合、ホウ素の含有量としては、好ましくは０．０００１質量％〜２０質量％の範囲、より好ましくは０．００５質量％〜２０質量％の範囲が挙げられる。本発明において、炭素系固体酸中のホウ素の含有量は、元素分析法により測定することができる。 In the carbon-based solid acid of the present invention, when boron is supported, the boron content is preferably in the range of 0.0001% by mass to 20% by mass, more preferably in the range of 0.005% by mass to 20% by mass. Is mentioned. In the present invention, the boron content in the carbon-based solid acid can be measured by elemental analysis.
本発明の炭素系固体酸は、滴定法で測定される酸量が大きく、酸触媒を用いる化学反応に対して、優れた触媒活性を有し、繰り返し使用しても触媒活性が劣化し難い。このため、本発明の炭素系固体酸は、固体酸触媒として好適に使用することができる。特に、本発明の炭素系固体酸は、水中においても触媒として機能し得るため、例えば硫酸触媒の代替となる固体酸触媒として好適に使用することができる。 The carbon-based solid acid of the present invention has a large amount of acid measured by a titration method, has excellent catalytic activity for chemical reactions using an acid catalyst, and the catalytic activity does not easily deteriorate even when used repeatedly. For this reason, the carbonaceous solid acid of this invention can be used conveniently as a solid acid catalyst. In particular, since the carbon-based solid acid of the present invention can function as a catalyst even in water, it can be suitably used as, for example, a solid acid catalyst that can replace a sulfuric acid catalyst.
本発明の炭素系固体酸が固体酸触媒として触媒し得る化学反応としては、例えば公知の酸触媒を用いた化学反応が挙げられる。このような化学反応としては、例えば、エステル化、加水分解、アルキル化、アルコールの脱水縮合、オレフィンの水和などが挙げられる。 Examples of the chemical reaction that the carbon-based solid acid of the present invention can catalyze as a solid acid catalyst include a chemical reaction using a known acid catalyst. Examples of such chemical reactions include esterification, hydrolysis, alkylation, alcohol dehydration condensation, olefin hydration, and the like.
本発明の炭素系固体酸は、例えば、以下のようにして製造することができる。まず、原料となる上記の繊維状活性炭を酸素ガスの存在下に加熱する酸化工程を行う。繊維状活性炭を酸素ガスの存在下に加熱する方法は、上記の通りである。次に、酸化工程の後、酸化された繊維状活性炭と、濃硫酸、発煙硫酸、及び三酸化硫黄からなる群から選択された少なくとも１種とを混合して、酸化された繊維状活性炭にスルホン酸基を導入するスルホン酸基導入工程を行う。当該スルホン酸基導入工程についても、上記のスルホン化処理の通りである。 The carbon-based solid acid of the present invention can be produced, for example, as follows. First, the oxidation process which heats said fibrous activated carbon used as a raw material in presence of oxygen gas is performed. The method for heating the fibrous activated carbon in the presence of oxygen gas is as described above. Next, after the oxidation step, the oxidized fibrous activated carbon is mixed with at least one selected from the group consisting of concentrated sulfuric acid, fuming sulfuric acid, and sulfur trioxide, and the oxidized fibrous activated carbon is mixed with sulfone. A sulfonic acid group introduction step for introducing an acid group is performed. The sulfonic acid group introduction step is also as described above for the sulfonation treatment.
また、本発明の炭素系固体酸の製造方法においては、繊維状活性炭と窒素含有化合物とを混合する窒素ドープ工程を備えていてもよい。本発明の製造方法において、窒素ドープ工程をさらに備えることにより、繊維状活性炭に窒素がドープされた炭素系固体酸が得られる。繊維状活性炭と窒素含有化合物とを混合して、窒素がドープされた繊維状活性炭を得る方法は、上記の通りである。なお、窒素ドープ工程は、繊維状活性炭の酸化工程の前に行うことができる。 Moreover, in the manufacturing method of the carbon-type solid acid of this invention, you may provide the nitrogen dope process which mixes a fibrous activated carbon and a nitrogen-containing compound. In the production method of the present invention, a carbon-based solid acid in which fibrous activated carbon is doped with nitrogen is obtained by further providing a nitrogen doping step. The method for obtaining fibrous activated carbon doped with nitrogen by mixing fibrous activated carbon and a nitrogen-containing compound is as described above. In addition, a nitrogen dope process can be performed before the oxidation process of fibrous activated carbon.
また、本発明の炭素系固体酸の製造方法においては、炭素質材料前駆体とホウ素含有化合物とを混合するホウ素ドープ工程と、ホウ素ドープ工程を経て得られたホウ素含有炭素質材料前駆体を上記の酸化された繊維状活性炭に担持させる工程とをさらに備えていてもよい。本発明の製造方法において、これらの工程をさらに備えることにより、繊維状活性炭にホウ素がドープされた炭素系固体酸が得られる。炭素質材料前駆体とホウ素含有化合物とを混合する方法、及びホウ素ドープ工程を経て得られたホウ素含有炭素質材料前駆体を上記の酸化された繊維状活性炭に担持させる方法は、上記の通りである。なお、ホウ素含有炭素質材料前駆体を上記の酸化された繊維状活性炭に担持させる工程は、前記スルホン酸基導入工程の前に行うことができる。 Further, in the method for producing a carbon-based solid acid of the present invention, a boron doping step of mixing a carbonaceous material precursor and a boron-containing compound, and a boron-containing carbonaceous material precursor obtained through the boron doping step are described above. And a step of supporting the oxidized fibrous activated carbon. In the production method of the present invention, by further including these steps, a carbon-based solid acid in which fibrous activated carbon is doped with boron is obtained. The method of mixing the carbonaceous material precursor and the boron-containing compound and the method of supporting the boron-containing carbonaceous material precursor obtained through the boron doping step on the oxidized fibrous activated carbon are as described above. is there. The step of supporting the boron-containing carbonaceous material precursor on the oxidized fibrous activated carbon can be performed before the sulfonic acid group introduction step.
以下に、実施例及び比較例を示して本発明を詳細に説明する。ただし、本発明は、実施例に限定されない。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.
＜参考例１＞
１×３ｃｍに切り出したフェルト状の繊維状活性炭（東洋紡株式会社製の商品名「Ｋフィルター ＫＦ−１０００Ｆ」）を、管状炉を用いて空気中４５０℃で１時間加熱（１時間かけて昇温した後、４５０℃で１時間保持）して酸化した（酸化処理）。次に、酸化した繊維状活性炭を丸底フラスコ内の濃硫酸（２５ｍｌ）中に沈め、このフラスコを表１に記載の温度に設定したマントルヒーターにセットし、表１に記載の時間環流し、繊維状活性炭にスルホン酸基を導入して炭素系固体酸を得た（スルホン化処理）。次に、得られた炭素系固体酸を純水で何度もすすいだ後、５０℃で１時間乾燥させた。乾燥後の炭素系固体酸を３０ｍｌの水に沈め、濃度０．１ＮのＮａＯＨ水溶液を用いた滴定法により測定し、炭素系固体酸の酸量を簡便な方法で予備的に測定した。結果を表１に示す。
<Reference Example 1>
A felt-like fibrous activated carbon (trade name “K filter KF-1000F” manufactured by Toyobo Co., Ltd.) cut into 1 × 3 cm is heated in air at 450 ° C. for 1 hour using a tubular furnace (heated up over 1 hour). After that, it was oxidized at 450 ° C. for 1 hour) (oxidation treatment). Next, the oxidized fibrous activated carbon was submerged in concentrated sulfuric acid (25 ml) in a round bottom flask, this flask was set in a mantle heater set to the temperature described in Table 1, and refluxed for the time described in Table 1. A sulfonic acid group was introduced into the fibrous activated carbon to obtain a carbon-based solid acid (sulfonation treatment). Next, after rinsing the obtained carbon-based solid acid many times with pure water, it was dried at 50 ° C. for 1 hour. The carbon solid acid after drying was submerged in 30 ml of water and measured by a titration method using a 0.1N NaOH aqueous solution, and the acid amount of the carbon solid acid was preliminarily measured by a simple method. The results are shown in Table 1.
＜参考例２＞
繊維状活性炭を加熱しなかったこと以外は、参考例１と同様にして硫酸処理を行い、炭素系固体酸を得た。得られた炭素系固体酸の酸量を、参考例１と同様の簡便な方法で予備的に測定した。結果を表１に示す。
<Reference Example 2>
Sulfuric acid treatment was performed in the same manner as in Reference Example 1 except that the fibrous activated carbon was not heated to obtain a carbon-based solid acid. The acid amount of the resulting carbon-based solid acid, was preliminarily measured in the same simple manner as in Reference Example 1. The results are shown in Table 1.
＜参考例３＞
表１の硫酸処理を発煙硫酸処理としたこと以外は、参考例１と同様にして得られた炭素系固体酸の酸量を、参考例１と同様の簡便な方法で予備的に測定した。結果を表１に示す。
<Reference Example 3>
Sulfuric acid process in Table 1 except that the fuming sulfuric acid treatment, the acid amount of the carbon-based solid acid obtained in the same manner as in Reference Example 1 was preliminarily measured in the same simple manner as in Reference Example 1. The results are shown in Table 1.
＜参考例４＞
繊維状活性炭を加熱しなかったこと以外は、参考例３と同様にして発煙硫酸処理を行い、炭素系固体酸を得た。得られた炭素系固体酸の酸量を、参考例１と同様の簡便な方法で予備的に測定した。結果を表１に示す。
<Reference Example 4>
A fuming sulfuric acid treatment was performed in the same manner as in Reference Example 3 except that the fibrous activated carbon was not heated to obtain a carbon-based solid acid. The acid amount of the resulting carbon-based solid acid, was preliminarily measured in the same simple manner as in Reference Example 1. The results are shown in Table 1.
参考例１〜４の予備的な実験結果から、繊維状活性炭を加熱処理した場合、加熱処理しなかった場合に比して酸量が大きくなり、さらに、スルホン化処理による酸量の増加も非常に大きくなることが明らかとなった。 From the preliminary experimental results of Reference Examples 1 to 4, when the fibrous activated carbon was heat-treated, the amount of acid increased compared to the case where heat treatment was not performed, and the increase in the amount of acid due to the sulfonation treatment was also extremely high. It became clear that it became bigger.
＜参考例５＞
繊維状活性炭の加熱条件を、それぞれ表２のようにしたこと以外は、参考例３と同様にして、炭素系固体酸を得た。得られた炭素系固体酸の酸量を、参考例１と同様の簡便な方法で予備的に測定した。結果を表２に示す。なお、スルホン化処理条件は、発煙硫酸（３０％）を用い、１５０℃で１時間とした。
<Reference Example 5>
A carbon-based solid acid was obtained in the same manner as in Reference Example 3 except that the heating conditions for the fibrous activated carbon were as shown in Table 2. The acid amount of the resulting carbon-based solid acid, was preliminarily measured in the same simple manner as in Reference Example 1. The results are shown in Table 2. The sulfonation treatment conditions were fuming sulfuric acid (30%) and 150 ° C. for 1 hour.
参考例５の結果から、空気中での加熱温度が３５０℃〜４５０℃と高くなるにつれて、炭素系固体酸の酸量が大きくなることが明らかとなった。 From the result of Reference Example 5, it became clear that the acid amount of the carbon-based solid acid increases as the heating temperature in air increases to 350 ° C. to 450 ° C.
＜実施例１＞
１×３ｃｍに切り出したフェルト状の繊維状活性炭（東洋紡株式会社製の商品名「Ｋフィルター ＫＦ−１０００Ｆ」）を、管状炉を用いて空気中４００℃で２時間加熱（１時間かけて昇温した後、４００℃で２時間保持）して酸化した（酸化処理）。次に、酸化した繊維状活性炭を丸底フラスコ内の３０％発煙硫酸（２５ｍｌ）中に沈め、このフラスコを１５０℃の温度に設定したマントルヒーターにセットし、１時間環流し、繊維状活性炭にスルホン酸基を導入して炭素系固体酸を得た（スルホン化処理）。次に、得られた炭素系固体酸を純水で何度もすすいだ後、１００℃の熱水で１時間処理した。その後、５０℃で１時間乾燥させた。乾燥後の炭素系固体酸を３０ｍｌの水に沈め、濃度０．１ＮのＮａＯＨ水溶液と濃度０．０１ＮのＨＣｌ水溶液を用いた逆滴定法により、炭素系固体酸の酸量を測定したところ、酸量は１．２ｍｍｏｌ／ｇであった。結果を表３に示す。
<Example 1>
A felt-like fibrous activated carbon (trade name “K Filter KF-1000F” manufactured by Toyobo Co., Ltd.) cut into 1 × 3 cm is heated in air at 400 ° C. for 2 hours using a tubular furnace (heated up over 1 hour). Then, it was kept at 400 ° C. for 2 hours) and oxidized (oxidation treatment). Next, the oxidized fibrous activated carbon is submerged in 30% fuming sulfuric acid (25 ml) in a round bottom flask, and the flask is set in a mantle heater set at a temperature of 150 ° C. and refluxed for 1 hour to form fibrous activated carbon. A sulfonic acid group was introduced to obtain a carbon-based solid acid (sulfonation treatment). Next, the obtained carbon-based solid acid was rinsed many times with pure water and then treated with hot water at 100 ° C. for 1 hour. Then, it was dried at 50 ° C. for 1 hour. The carbon solid acid after drying was submerged in 30 ml of water, and the acid amount of the carbon solid acid was measured by a back titration method using a 0.1N NaOH aqueous solution and a 0.01N HCl aqueous solution. The amount was 1.2 mmol / g. The results are shown in Table 3.
＜比較例１＞
繊維状活性炭を空気中で加熱する代わりに、窒素中で加熱したこと以外は、実施例１と同様にして炭素系固体酸を得た。実施例１と同様にして炭素系固体酸の酸量を測定したところ、酸量は０．８５ｍｍｏｌ／ｇであった。結果を表３に示す。
<Comparative Example 1>
A carbon-based solid acid was obtained in the same manner as in Example 1 except that the fibrous activated carbon was heated in nitrogen instead of in air. When the acid amount of the carbon-based solid acid was measured in the same manner as in Example 1, the acid amount was 0.85 mmol / g. The results are shown in Table 3.
＜比較例２＞
繊維状活性炭を空気中で加熱せずにそのまま用いたこと以外は、実施例１と同様にして炭素系固体酸を得た。実施例１と同様にして炭素系固体酸の酸量を測定したところ、酸量は０．６０ｍｍｏｌ／ｇであった。結果を表３に示す。
<Comparative example 2>
A carbon-based solid acid was obtained in the same manner as in Example 1 except that the fibrous activated carbon was used as it was without heating in air. When the acid amount of the carbon-based solid acid was measured in the same manner as in Example 1, the acid amount was 0.60 mmol / g. The results are shown in Table 3.
表３に示されるように、繊維状活性炭を空気中で加熱し、スルホン酸基を導入した実施例１の炭素系固体酸は、滴定で測定した酸量が大きかった。一方、繊維状活性炭を窒素中で加熱し、スルホン酸基を導入した比較例１の炭素系固体酸では、酸量は小さかった。また、繊維状活性炭を加熱せずにスルホン酸基を導入した比較例２についても、酸量は小さかった。 As shown in Table 3, the carbon-based solid acid of Example 1 in which fibrous activated carbon was heated in air and sulfonic acid groups were introduced had a large acid amount measured by titration. On the other hand, in the carbon-based solid acid of Comparative Example 1 in which fibrous activated carbon was heated in nitrogen and sulfonic acid groups were introduced, the acid amount was small. Moreover, the acid amount was small also about the comparative example 2 which introduce | transduced the sulfonic acid group, without heating fibrous activated carbon.
＜実施例２＞
フェナントロリン１ｇを、エタノール９ｇに溶かした水溶液を得た。得られた水溶液に、１×３ｃｍに切り出したフェルト状の繊維状活性炭（東洋紡株式会社製の商品名「Ｋフィルター ＫＦ−１０００Ｆ」）を浸漬し、取り出して乾燥させ、繊維状活性炭に窒素をドープした。次に、この繊維状活性炭を乾燥した後、管状炉を用いて空気中４５０℃で１時間加熱（１時間かけて昇温した後、４５０℃で１時間保持）して酸化した。次に、実施例１と同様にして、酸化された繊維状活性炭にスルホン酸基を導入して炭素系固体酸を得た。次に、得られた炭素系固体酸を純水で何度もすすいだ後、１００℃の熱水で１時間処理した。その後、５０℃で１時間乾燥させた。乾燥後の炭素系固体酸の酸量を、実施例１と同様にして測定した。その結果、炭素系固体酸の酸量は１．７ｍｍｏｌ／ｇであった。結果を表４に示す。また、後述の実施例４と同様にして、実施例２で得られた炭素系固体酸を用いてセロビオース加水分解反応速度を測定した。結果を表６に示す。
<Example 2>
An aqueous solution in which 1 g of phenanthroline was dissolved in 9 g of ethanol was obtained. A felt-like fibrous activated carbon (trade name “K Filter KF-1000F” manufactured by Toyobo Co., Ltd.) cut into 1 × 3 cm is immersed in the obtained aqueous solution, taken out and dried, and the fibrous activated carbon is doped with nitrogen. did. Next, after drying this fibrous activated carbon, it oxidized by heating at 450 degreeC in the air for 1 hour (it heated up over 1 hour and hold | maintained at 450 degreeC for 1 hour) using the tubular furnace. Next, in the same manner as in Example 1, sulfonic acid groups were introduced into the oxidized fibrous activated carbon to obtain a carbon-based solid acid. Next, the obtained carbon-based solid acid was rinsed many times with pure water and then treated with hot water at 100 ° C. for 1 hour. Then, it was dried at 50 ° C. for 1 hour. The acid amount of the carbon-based solid acid after drying was measured in the same manner as in Example 1. As a result, the acid amount of the carbon-based solid acid was 1.7 mmol / g. The results are shown in Table 4. Further, in the same manner as in Example 4 described later, the cellobiose hydrolysis reaction rate was measured using the carbon-based solid acid obtained in Example 2. The results are shown in Table 6.
表４に示される様に、繊維状活性炭に窒素を含ませた実施例２の炭素系固体酸についても、繊維状活性炭を空気中で加熱し、スルホン酸基を導入することにより、滴定で測定した酸量が大きくなることが明らかとなった。 As shown in Table 4, the carbon-based solid acid of Example 2 in which fibrous activated carbon was nitrogen-containing was also measured by titration by heating the fibrous activated carbon in air and introducing sulfonic acid groups. It was found that the acid amount increased.
＜実施例３＞
１×３ｃｍに切り出したフェルト状の繊維状活性炭（東洋紡株式会社製の商品名「Ｋフィルター ＫＦ−１０００Ｆ」）を、管状炉を用いて空気中４００℃で２時間加熱処理（１時間かけて昇温した後、４００℃で２時間保持）して酸化した。一方、グルコース(１．４０ｇ)とホウ酸(１．００ｇ)とを、水に溶かして約３５ｍｌの水溶液を得た。得られた水溶液をオートクレーブ容器（５０ｍｌに入れ、１２０℃設定の乾燥機で１２時間加熱に供した。次に、得られた水溶液に、上記で酸化した繊維状活性炭を浸漬し、取り出して乾燥させた。次に、実施例１と同様にして、スルホン酸基を導入し、炭素系固体酸を得た。次に、得られた炭素系固体酸を純水で何度もすすいだ後、１００℃の熱水で１時間処理した。その後、５０℃で１時間乾燥させた。乾燥後の炭素系固体酸の酸量を、実施例１と同様にして測定した。その結果、炭素系固体酸の酸量は２．１ｍｍｏｌ／ｇであった。結果を表５に示す。
<Example 3>
A felt-like fibrous activated carbon (trade name “K Filter KF-1000F” manufactured by Toyobo Co., Ltd.) cut into 1 × 3 cm is heated in air at 400 ° C. for 2 hours (ascending over 1 hour). After warming, it was oxidized at 400 ° C. for 2 hours). Meanwhile, glucose (1.40 g) and boric acid (1.00 g) were dissolved in water to obtain about 35 ml of an aqueous solution. The obtained aqueous solution was put into an autoclave container (50 ml, and subjected to heating for 12 hours in a dryer set at 120 ° C. Next, the fibrous activated carbon oxidized above was immersed in the obtained aqueous solution, taken out and dried. Next, a sulfonic acid group was introduced to obtain a carbon-based solid acid in the same manner as in Example 1. Next, the obtained carbon-based solid acid was rinsed with pure water many times, and then 100 It was treated with hot water at 1 ° C. for 1 hour, and then dried for 1 hour at 50 ° C. The acid amount of the carbon-based solid acid after drying was measured in the same manner as in Example 1. As a result, the carbon-based solid acid was measured. The acid amount of was 2.1 mmol / g, and the results are shown in Table 5.
表５に示される様に、繊維状活性炭にホウ素を含ませた実施例３の炭素系固体酸についても、繊維状活性炭を空気中で加熱し、スルホン酸基を導入することにより、滴定で測定した酸量が大きくなることが明らかとなった。 As shown in Table 5, the carbon-based solid acid of Example 3 in which boron was included in the fibrous activated carbon was also measured by titration by heating the fibrous activated carbon in air and introducing sulfonic acid groups. It was found that the acid amount increased.
＜実施例４＞
繊維状活性炭の加熱温度を４５０℃とし、加熱時間を１時間（１時間かけて昇温した後、４５０℃で１時間保持）としたこと以外は、実施例１と同様にして炭素系固体酸を得た。実施例１と同様にして炭素系固体酸の酸量を測定したところ、酸量は１．１ｍｍｏｌ／ｇであった。また、得られた炭素系固体酸を触媒として用いて、セロビオース加水分解反応速度を以下のようにして測定した。結果を表６に示す。
<Example 4>
The carbon-based solid acid was the same as in Example 1 except that the heating temperature of the fibrous activated carbon was 450 ° C. and the heating time was 1 hour (the temperature was raised over 1 hour and then held at 450 ° C. for 1 hour). Got. When the acid amount of the carbon-based solid acid was measured in the same manner as in Example 1, the acid amount was 1.1 mmol / g. Moreover, using the obtained carbon-based solid acid as a catalyst, the cellobiose hydrolysis reaction rate was measured as follows. The results are shown in Table 6.
［セロビオース加水分解反応速度の測定］
ねじ口試験管（マルエムＮＲ−１０）に水（３ｍｌ）と、実施例４で得られた炭素系固体酸（それぞれ、表６の［ ］内に示した重量）と、セロビオース（１５ｍｇ）と、撹拌子を加え、キャップを閉めて密閉した。１００℃に保った恒温槽の中に設置した耐熱マグネチックスターラーにより、試験管の加熱撹拌を行い反応させた。４５分経過後に恒温槽から出して反応液の一部（０．３ｍＬ）をサンプリングした後、恒温槽に戻して更に４５分反応させ、１回目の反応終了とした。４５分、９０分にサンプリングした反応液中のグルコース量をＭｅｒｃｋ社製ＲＱフレックス装置と同装置用のグルコース試験紙（１６７２０−１Ｍ）を用いて定量した。グラフの横軸に反応時間（４５分（すなわち０．７５時間）及び９０分（すなわち１．５時間））、縦軸に各々のグルコース生成量（μｍｏｌ）をプロットし、原点を通る最小二乗法により傾きを求めた。この値を触媒量で除することによりグルコース生成速度（μｍｏｌ／ｈ／ｇ）を求めた。反応後の炭素系固体酸はろ過して回収し、イオン交換蒸留水中で３回すすいで洗浄した後、室温で乾燥して２回目の反応に用いた。以下、同様に反応を繰り返し、実施例４で得られた炭素系固体酸を用いたセロビオース加水分解反応速度の測定をそれぞれ３回ずつ行った。セロビオース加水分解反応速度、及びセロビオース加水分解反応速度の保持率（［３回目の収率］／［１回目の収率］×１００（％）で定義）の測定結果を表６に示す。
[Measurement of cellobiose hydrolysis rate]
In a screw test tube (Marem NR-10), water (3 ml), the carbon-based solid acid obtained in Example 4 (each weight shown in [] in Table 6), cellobiose (15 mg), A stir bar was added and the cap was closed and sealed. The test tube was heated and stirred for reaction with a heat-resistant magnetic stirrer installed in a thermostat kept at 100 ° C. After 45 minutes, the sample was taken out of the thermostat and a part of the reaction solution (0.3 mL) was sampled, then returned to the thermostat and reacted for 45 minutes to complete the first reaction. The amount of glucose in the reaction solution sampled at 45 minutes and 90 minutes was quantified using a Merck RQ flex apparatus and a glucose test paper (16720-1M) for the apparatus. The reaction time (45 minutes (ie, 0.75 hours) and 90 minutes (ie, 1.5 hours)) is plotted on the horizontal axis of the graph, and the amount of each glucose production (μmol) is plotted on the vertical axis. The inclination was obtained by The glucose production rate (μmol / h / g) was determined by dividing this value by the catalytic amount. The carbon-based solid acid after the reaction was collected by filtration, rinsed three times in ion exchange distilled water, washed, dried at room temperature, and used for the second reaction. Thereafter, the reaction was repeated in the same manner, and the cellobiose hydrolysis reaction rate using the carbon-based solid acid obtained in Example 4 was measured three times. Table 6 shows the measurement results of the cellobiose hydrolysis reaction rate and the retention rate of the cellobiose hydrolysis reaction rate (defined by [3rd yield] / [1st yield] × 100 (%)).
＜比較例３＞
１×３ｃｍに切り出したフェルト状の繊維状活性炭（東洋紡株式会社製の商品名「Ｋフィルター ＫＦ−１０００Ｆ」）をそのまま炭素系固体酸として用いた。実施例４と同様にして、炭素系固体酸の酸量を測定したところ、酸量は０．０４ｍｍｏｌ／ｇであった。また、実施例４と同様にして、セロビオース加水分解反応速度の測定を行った。結果を表６に示す。
<Comparative Example 3>
Felt-like fibrous activated carbon (trade name “K filter KF-1000F” manufactured by Toyobo Co., Ltd.) cut into 1 × 3 cm was used as a carbon-based solid acid as it was. When the acid amount of the carbon-based solid acid was measured in the same manner as in Example 4, the acid amount was 0.04 mmol / g. Further, in the same manner as in Example 4, the cellobiose hydrolysis reaction rate was measured. The results are shown in Table 6.
＜比較例４＞
スルホン酸基を導入しなかったこと以外は、実施例４と同様にして得た炭素系固体酸の酸量を測定したところ、酸量は０．３ｍｍｏｌ／ｇであった。また、実施例４と同様にして、セロビオース加水分解反応速度の測定を行った。結果を表６に示す。
<Comparative example 4>
When the acid amount of the carbon-based solid acid obtained in the same manner as in Example 4 was measured except that the sulfonic acid group was not introduced, the acid amount was 0.3 mmol / g. Further, in the same manner as in Example 4, the cellobiose hydrolysis reaction rate was measured. The results are shown in Table 6.
表６に示されるように、繊維状活性炭を空気中で酸化し、スルホン酸基を導入した実施例２及び４の炭素系固体酸では、酸化しなかった比較例３及び４の炭素系固体酸に比して、酸量が著しく大きくなり、セロビオース加水分解反応速度が大きく、さらに繰り返し使用しても、セロビオース加水分解反応速度が高いままに維持されることが明らかとなった。 As shown in Table 6, in the carbon-based solid acids of Examples 2 and 4 in which fibrous activated carbon was oxidized in air and sulfonic acid groups were introduced, the carbon-based solid acids of Comparative Examples 3 and 4 that were not oxidized As compared with the above, the acid amount was remarkably increased, the cellobiose hydrolysis reaction rate was large, and it was revealed that the cellobiose hydrolysis reaction rate was maintained high even after repeated use.
［アンモニア昇温脱離実験］
実施例４、比較例３及び４で得た炭素系固体酸について、アンモニア昇温脱離（Ｔｅｍｐｅｒａｔｕｒｅ−Ｐｒｏｇｒａｍｍｅｄ Ｄｅｓｏｒｐｔｉｏｎ）実験を行い、炭素系固体酸の酸強度及び酸量を評価した。アンモニアの吸着は、アンモニア水の蒸気を用い湿式で行った。それぞれ、所定量の炭素系固体酸を２０ｍＬのスクリュー管瓶に入れ、２００ｍＬの広口瓶の中に置いた。炭素系固体酸に触れないように広口瓶の底に約１０ｍＬの３０％アンモニア水を注ぎ、広口瓶の蓋をして室温で３０〜６０分間静置して試料にアンモニアを飽和吸着させた。アンモニア吸着後の炭素系固体酸を内径６ｍｍの石英反応管に入れ、上下に石英ウールを詰めて保持し、ＴＰ５０００型昇温脱離測定装置（ヘンミ計算尺株式会社製）にセットした。反応管を１００℃に加熱し、水蒸気を含んだＨｅガスを１００ｍＬ／ｍｉｎで流通して、弱い酸点に吸着したアンモニアを除去した。続けてドライなＨｅを流通してパージした後、１０℃／ｍｉｎで昇温し、脱離ガスを装置付属の質量分析計にて測定し、アンモニア由来のシグナルとしてｍ／ｅ＝１６の信号強度を温度に対してプロットして得られたグラフを図１に示す。図１に示されるように、比較例３の未処理の繊維状活性炭を用いた場合には、大きな脱離は観測されなかった。一方、空気中４５０℃で加熱した比較例４の繊維状活性炭では、約１８０℃に脱離ピークが観測された。このピークは、繊維状活性炭表面のカルボキシル基に吸着したアンモニアの脱離ピークであると考えられる。また、空気中４５０℃で加熱した後、スルホン酸基を導入した実施例２では、同じく１８０℃に脱離ピークが見られる他、更に高温側の２６０℃にも脱離ピークが観測された。２６０℃の脱離ピークは、スルホン酸基の導入により生成した強酸点に吸着したアンモニアの脱離ピークであると考えられる。
[Ammonia temperature programmed desorption experiment]
The carbon-based solid acid obtained in Example 4 and Comparative Examples 3 and 4 was subjected to an ammonia temperature-desorption (Temperature-Programmed Desorption) experiment to evaluate the acid strength and acid amount of the carbon-based solid acid. Adsorption of ammonia was performed wet using steam of ammonia water. A predetermined amount of carbon-based solid acid was placed in a 20 mL screw tube bottle and placed in a 200 mL wide-mouth bottle. About 10 mL of 30% ammonia water was poured into the bottom of the jar so as not to touch the carbon-based solid acid, and the jar was covered and allowed to stand at room temperature for 30 to 60 minutes to saturate the sample with ammonia. The carbon-based solid acid after ammonia adsorption was placed in a quartz reaction tube having an inner diameter of 6 mm, and was filled with quartz wool on top and bottom, and set in a TP5000 type temperature programmed desorption measuring device (manufactured by Henmi Kakusha Co., Ltd.). The reaction tube was heated to 100 ° C., and He gas containing water vapor was circulated at 100 mL / min to remove ammonia adsorbed on weak acid sites. Subsequently, dry He was circulated and purged, the temperature was raised at 10 ° C./min, the desorbed gas was measured with a mass spectrometer attached to the apparatus, and the signal intensity of m / e = 16 as a signal derived from ammonia. FIG. 1 shows a graph obtained by plotting the temperature with respect to the temperature. As shown in FIG. 1, when the untreated fibrous activated carbon of Comparative Example 3 was used, no large desorption was observed. On the other hand, in the fibrous activated carbon of Comparative Example 4 heated at 450 ° C. in air, a desorption peak was observed at about 180 ° C. This peak is considered to be a desorption peak of ammonia adsorbed on the carboxyl group on the surface of the fibrous activated carbon. In Example 2 in which sulfonic acid groups were introduced after heating at 450 ° C. in air, a desorption peak was also observed at 180 ° C., and a desorption peak was also observed at 260 ° C. on the higher temperature side. The elimination peak at 260 ° C. is considered to be the elimination peak of ammonia adsorbed on the strong acid point generated by the introduction of the sulfonic acid group.
Claims (6)
前記炭素系固体酸を１００℃の熱水中で１時間処理した後、滴定法で測定した酸量が、１．０ｍｍｏｌ／ｇ以上を示し、
前記繊維状活性炭が、窒素及びホウ素の少なくとも一方を含む、炭素系固体酸。 A carbon-based solid acid containing fibrous activated carbon having a sulfonic acid group,
After the carbon-based solid acid for 1 hour in hot water at 100 ° C., the amount of acid was measured by titration method, shows the above 1.0 mmol / g,
A carbon-based solid acid in which the fibrous activated carbon contains at least one of nitrogen and boron .
前記酸化工程の後、酸化された繊維状活性炭と、濃硫酸、発煙硫酸、及び三酸化硫黄からなる群から選択された少なくとも１種とを混合して、前記酸化された繊維状活性炭にスルホン酸基を導入するスルホン酸基導入工程と、
を備え、
炭素質材料前駆体とホウ素含有化合物とを混合するホウ素ドープ工程と、
前記ホウ素ドープ工程を経て得られたホウ素含有炭素質材料前駆体を前記酸化された繊維状活性炭に担持させる工程と、
をさらに備える、請求項１〜３のいずれかに記載の炭素系固体酸の製造方法。 An oxidation step of heating fibrous activated carbon in the presence of oxygen gas;
After the oxidation step, the oxidized fibrous activated carbon is mixed with at least one selected from the group consisting of concentrated sulfuric acid, fuming sulfuric acid, and sulfur trioxide, and the oxidized fibrous activated carbon is mixed with sulfonic acid. A sulfonic acid group introduction step for introducing a group;
Equipped with a,
A boron doping step of mixing a carbonaceous material precursor and a boron-containing compound;
Supporting the boron-containing carbonaceous material precursor obtained through the boron doping step on the oxidized fibrous activated carbon;
Further Ru comprising a method of producing a carbon-based solid acid according to any one of claims 1-3.
前記酸化工程の後、酸化された繊維状活性炭と、濃硫酸、発煙硫酸、及び三酸化硫黄からなる群から選択された少なくとも１種とを混合して、前記酸化された繊維状活性炭にスルホン酸基を導入するスルホン酸基導入工程と、
を備え、
前記繊維状活性炭と窒素含有化合物とを混合する窒素ドープ工程をさらに備える、請求項１〜３のいずれかに記載の炭素系固体酸の製造方法。 An oxidation step of heating fibrous activated carbon in the presence of oxygen gas;
After the oxidation step, the oxidized fibrous activated carbon is mixed with at least one selected from the group consisting of concentrated sulfuric acid, fuming sulfuric acid, and sulfur trioxide, and the oxidized fibrous activated carbon is mixed with sulfonic acid. A sulfonic acid group introduction step for introducing a group;
With
The manufacturing method of the carbon-type solid acid in any one of Claims 1-3 further equipped with the nitrogen dope process which mixes the said fibrous activated carbon and a nitrogen-containing compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013145946A JP6150285B2 (en) | 2013-07-12 | 2013-07-12 | Carbon-based solid acid containing fibrous activated carbon with sulfonic acid groups |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013145946A JP6150285B2 (en) | 2013-07-12 | 2013-07-12 | Carbon-based solid acid containing fibrous activated carbon with sulfonic acid groups |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015017018A JP2015017018A (en) | 2015-01-29 |
| JP6150285B2 true JP6150285B2 (en) | 2017-06-21 |
Family
ID=52438395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013145946A Active JP6150285B2 (en) | 2013-07-12 | 2013-07-12 | Carbon-based solid acid containing fibrous activated carbon with sulfonic acid groups |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6150285B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106938196A (en) | 2015-12-10 | 2017-07-11 | 财团法人工业技术研究院 | Solid catalyst and preparation method of saccharide using the same |
| CN105728001B (en) * | 2016-02-26 | 2019-02-22 | 江西理工大学 | A kind of catalyst and its preparation method and application |
| CN108163854A (en) * | 2017-12-25 | 2018-06-15 | 河南师范大学 | For the universality preparation method of the porous C catalyst of organic pollutants in water body degradation |
| CN109046381B (en) * | 2018-06-02 | 2021-06-01 | 太原理工大学 | Sulfur-carbon based solid acid catalyst |
| CN109734722B (en) * | 2019-01-21 | 2021-08-24 | 中国科学院成都有机化学有限公司 | Method for preparing isosorbide by dehydrating sorbitol |
| CN110862084B (en) * | 2019-12-04 | 2021-06-08 | 安徽裕民生态农业有限公司 | Camellia seed shell activated carbon and preparation process thereof |
| CN114602505B (en) * | 2022-03-16 | 2023-04-25 | 重庆工商大学 | Magnetic carbon-based solid acid catalyst, preparation method thereof, application thereof in sludge treatment and method for recycling nitrogen and phosphorus by hydrothermal carbonization |
| CN114797712B (en) * | 2022-04-23 | 2024-01-26 | 石河子大学 | Method for preparing mixed solid acid from fish bones by aid of microwaves |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54478A (en) * | 1978-06-07 | 1979-01-05 | Hitachi Ltd | Method of activating electrode constituting substance |
| JPH04146220A (en) * | 1990-09-29 | 1992-05-20 | Kawasaki Steel Corp | Production of high-performance activated carbon fiber |
| JP5655337B2 (en) * | 2010-03-26 | 2015-01-21 | 株式会社エクォス・リサーチ | Method for controlling Hammett acidity function of sulfonated carbon |
| US10493439B2 (en) * | 2013-07-12 | 2019-12-03 | National Institute Of Advanced Industrial Science And Technology | Carbon-containing solid acid having sulfonate group |
-
2013
- 2013-07-12 JP JP2013145946A patent/JP6150285B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015017018A (en) | 2015-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6150285B2 (en) | Carbon-based solid acid containing fibrous activated carbon with sulfonic acid groups | |
| Pang et al. | Cellulose-derived carbon bearing–Cl and–SO 3 H groups as a highly selective catalyst for the hydrolysis of cellulose to glucose | |
| CN104583120B (en) | Activated carbon with high active surface area | |
| JP5528036B2 (en) | Carbon-based solid acid and method for producing the same | |
| WO2016013619A1 (en) | Activated carbon with excellent adsorption performance and process for producing same | |
| JP6351181B2 (en) | Carbon-based solid acid having sulfonic acid group | |
| CN103395768B (en) | A kind of preparation method of porous nano carbon ball of high-specific surface area uniform pore diameter rule | |
| JP2017222547A (en) | Method for producing activated carbon, and activated carbon production system | |
| JP7397093B2 (en) | Molecular polar substance adsorption carbon | |
| Khan et al. | Developments in activated functionalized carbons and their applications in water decontamination: a review | |
| Liao et al. | A process for desulfurization of coking benzene by a two-step method with reuse of sorbent/thiophene and its key procedures | |
| Boehm | Catalytic properties of nitrogen‐containing carbons | |
| KR20150064978A (en) | Manufacturing method of carbon-based carbon dioxide adsorbents | |
| JPH0881210A (en) | Carbon material having high specific surface area and its production | |
| JP6042922B2 (en) | Porous carbon, production method thereof, and ammonia adsorbent | |
| CN103495395A (en) | Preparation method of g-C3N4-suppurted active carbon with photocatalytic function | |
| CN112794325A (en) | Method for preparing porous carbon-silicon composite material by using papermaking sludge in one step | |
| JP2009067730A (en) | Method for producing anhydrosugar, organic acid and furfural | |
| JP2007197314A (en) | Method for refining composition containing carbon nanotube | |
| JP6607673B2 (en) | Method for producing resin solid acid | |
| CN108516532A (en) | Porous carbon materials and its preparation based on two-dimensional polymer and application | |
| JP6624993B2 (en) | Activated carbon production method | |
| Tao et al. | Microporous nitrogen-doped carbon from polyaniline as a highly efficient and stable catalyst for acetylene hydrochlorination | |
| JP7006239B2 (en) | Porous carbon material | |
| JP2003138433A (en) | Method for producing active carbon fiber for flue gas desulfurization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160309 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160307 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20161115 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20161117 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170113 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170425 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170517 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6150285 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |