JP6818094B2 - Catalyst and method for producing it, method for producing N-alkylimidazole compound - Google Patents
Catalyst and method for producing it, method for producing N-alkylimidazole compound Download PDFInfo
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- JP6818094B2 JP6818094B2 JP2019127903A JP2019127903A JP6818094B2 JP 6818094 B2 JP6818094 B2 JP 6818094B2 JP 2019127903 A JP2019127903 A JP 2019127903A JP 2019127903 A JP2019127903 A JP 2019127903A JP 6818094 B2 JP6818094 B2 JP 6818094B2
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- acid
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- 239000003054 catalyst Substances 0.000 title claims description 147
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- 150000001875 compounds Chemical class 0.000 title claims description 23
- 239000004480 active ingredient Substances 0.000 claims description 78
- 239000012266 salt solution Substances 0.000 claims description 63
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 55
- 125000000217 alkyl group Chemical group 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 37
- -1 imidazole compound Chemical class 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 239000002168 alkylating agent Substances 0.000 claims description 27
- 229940100198 alkylating agent Drugs 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 238000005804 alkylation reaction Methods 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 150000001299 aldehydes Chemical class 0.000 claims description 10
- 150000002576 ketones Chemical class 0.000 claims description 10
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- NNQIBXKOCAMOOS-UHFFFAOYSA-N phenyl hypofluorite Chemical compound FOC1=CC=CC=C1 NNQIBXKOCAMOOS-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 5
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000002152 alkylating effect Effects 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 59
- 238000012360 testing method Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 26
- 238000004458 analytical method Methods 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003929 acidic solution Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 239000012159 carrier gas Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- KPQZUUQMTUIKBP-UHFFFAOYSA-N 1-(2-methyl-5-nitro-1-imidazolyl)-2-propanol Chemical compound CC(O)CN1C(C)=NC=C1[N+]([O-])=O KPQZUUQMTUIKBP-UHFFFAOYSA-N 0.000 description 1
- WYOIGGSUICKDNZ-UHFFFAOYSA-N 2,3,5,6,7,8-hexahydropyrrolizin-1-one Chemical compound C1CCC2C(=O)CCN21 WYOIGGSUICKDNZ-UHFFFAOYSA-N 0.000 description 1
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 description 1
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000002532 enzyme inhibitor Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 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
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229950010610 lutetium chloride Drugs 0.000 description 1
- AEDROEGYZIARPU-UHFFFAOYSA-K lutetium(iii) chloride Chemical compound Cl[Lu](Cl)Cl AEDROEGYZIARPU-UHFFFAOYSA-K 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 1
- 229960000282 metronidazole Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- LDPWMGUFXYRDRG-UHFFFAOYSA-I niobium(5+) pentaacetate Chemical compound [Nb+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O LDPWMGUFXYRDRG-UHFFFAOYSA-I 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 1
- 229960004076 secnidazole Drugs 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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Description
本発明は有機合成の分野に関し、特に触媒及びその製造方法、及びＮ−アルキルイミダゾール系化合物の製造方法に関する。 The present invention relates to the field of organic synthesis, particularly to a catalyst and a method for producing the same, and a method for producing an N-alkylimidazole compound.
Ｎ−アルキルイミダゾール系化合物は、非常に重要なファインケミカルであり、イオン液体、医薬品、抗菌剤、酵素阻害剤、及び他のファインケミカルに広く使用されている。例えば、それはイミダゾリウムイオン液体の最も重要な出発物質であり、それを通して多種多様なイオン液体を合成することができ、それはまた医薬原料であるメトロニダゾール、セクニダゾール及び獣医薬ジメガゾールの合成のためのベース構造でもある。Ｎ-アルキルイミダゾールは、５員複素環の１つの窒素原子上に孤立電子対を有し、また、一定の塩基性及び求核性を有するので、有機合成における有機配位子及び触媒としても使用できる。中、長炭素鎖のＮ−アルキルイミダゾールは、優れた表面特性を有し、両性界面活性剤として最も一般的に使用されているカチオン性官能基の１つであり、エポキシ樹脂の硬化剤としても広く使用できる。 N-alkylimidazole compounds are very important fine chemicals and are widely used in ionic liquids, pharmaceuticals, antibacterial agents, enzyme inhibitors, and other fine chemicals. For example, it is the most important starting material for imidazolium ionic liquids, through which a wide variety of ionic liquids can be synthesized, it is also the base structure for the synthesis of the medicinal raw materials metronidazole, secnidazole and veterinary dimegazol. But also. Since N-alkylimidazole has a lone electron pair on one nitrogen atom of a 5-membered heterocycle and has a certain basicity and nucleophilicity, it is also used as an organic ligand and catalyst in organic synthesis. it can. Medium and long carbon chain N-alkylimidazoles have excellent surface properties, are one of the most commonly used cationic surfactants as amphoteric surfactants, and are also used as curing agents for epoxy resins. Can be widely used.
Ｎ-アルキルイミダゾールは、このような独特の物理的化学的性質、及び、広い用途の可能性を有する。しかしながら、先行文献に報告されているＮ-アルキルイミダゾール製造方法は、苛酷な反応条件、不純な生成物、及び触媒の再利用の不可能性などの欠点を有する。特許文献１には、酸結合剤としての水素化ナトリウムを、相間移動触媒としてのテトラブチルアンモニウムヨージドを使用するセチルイミダゾール製造方法が開示されているが、この方法に使用される水素化ムナトリウは高価であって、安全生産に不利である。また、Ｓｏｏ Ｙ． Ｋｏは、非特許文献１において、均一条件下で、触媒としてのアゾジカルボン酸ジエチルまたはジイソプロピルエステルを使用する一連のＮ−アルキルイミダゾール系化合物合成方法という報告を行っている。しかしながら、この合成方法では、触媒価格が高い上、触媒が分離しにくく、繰り返し使用することが困難なので、規模化生産には不利である。 N-alkylimidazoles have such unique physical and chemical properties and potential for a wide range of applications. However, the N-alkylimidazole production methods reported in the prior art have drawbacks such as harsh reaction conditions, impure products, and the inability to reuse the catalyst. Patent Document 1 discloses a method for producing cetylimidazole using sodium hydride as an acid binder and tetrabutylammonium iodide as a phase transfer catalyst, but the hydrogenated munatoriu used in this method is It is expensive and disadvantageous for safe production. In addition, Soo Y. Ko reports in Non-Patent Document 1 a series of methods for synthesizing N-alkylimidazole compounds using diethyl azodicarboxylate or diisopropyl ester as a catalyst under uniform conditions. However, this synthesis method is disadvantageous for large-scale production because the catalyst price is high, the catalyst is difficult to separate, and it is difficult to use it repeatedly.
このようなＮ-アルキルイミダゾールの製造方法では、反応条件が過酷であり、生成物が不純であり、触媒をリサイクルすることができない等の欠点を有する。 Such a method for producing N-alkylimidazole has drawbacks such as severe reaction conditions, impure product, and inability to recycle the catalyst.
本発明は、触媒及びその製造方法、ならびにＮ−アルキルイミダゾール系化合物の製造方法を提供する。本発明により提供される触媒がＮ-アルキルイミダゾール系化合物の製造に使用される場合、反応条件が温和であるだけでなく、生成物選択性が高く、かつ触媒は容易にリサイクルされて再使用することができる。 The present invention provides a catalyst and a method for producing the same, and a method for producing an N-alkylimidazole compound. When the catalyst provided by the present invention is used in the production of N-alkylimidazole compounds, not only the reaction conditions are mild, but also the product selectivity is high, and the catalyst is easily recycled and reused. be able to.
本発明は、活性成分及び酸処理した担体を含む触媒を提供し、担体はシリコン・アルミナ酸化物及び／またはシリカであり、活性成分は金属酸化物を含み、金属酸化物中の金属元素は、ジルコニウム、ニオブ、ハフニウム、タンタル、カルシウム、マグネシウム、銅、ニッケル、鉄、コバルト、亜鉛、及び希土類元素のうちの１つ以上を含み、この触媒は、Ｎ-アルキルイミダゾール系化合物を得るための、イミダゾール系化合物とアルキル化剤とのアルキル化反応に作用する。 The present invention provides a catalyst containing an active ingredient and an acid-treated carrier, the carrier being silicon-alumina oxide and / or silica, the active ingredient comprising a metal oxide, and the metal elements in the metal oxide being zirconium, niobium, hafnium, tantalum, calcium, magnesium, copper, seen containing nickel, iron, cobalt, zinc, and one or more of the rare earth elements, the catalyst, to obtain N- alkyl imidazole compound, It acts on the alkylation reaction between imidazole compounds and alkylating agents .
好ましくは、触媒中の活性成分の質量分率は、０．１〜２５％である。 Preferably, the mass fraction of the active ingredient in the catalyst is 0.1 to 25%.
好ましくは、担体の比表面積が５０ｍ2／ｇを超え、シリコン・アルミナ酸化物のアルミニウム含有量が０を除いて、０〜２０％である。 Preferably, the specific surface area of the carrier exceeds 50 m 2 / g and the aluminum content of the silicon-alumina oxide is 0 to 20%, excluding zero.
本発明は、（１）担体を酸溶液に浸漬した後、順に乾燥、焼成処理して、酸処理した担体を得る工程と、（２）工程（１）で得られた酸処理した担体を活性成分塩溶液に浸漬した後、順に乾燥、焼成処理して、触媒を得る工程とを含む、上記の技術構成での触媒を製造する方法をさらに提供する。 In the present invention, (1) the carrier is immersed in an acid solution and then dried and calcined in order to obtain an acid-treated carrier, and (2) the acid-treated carrier obtained in step (1) is activated. Further provided is a method for producing a catalyst having the above-mentioned technical configuration, which comprises a step of immersing in a component salt solution and then sequentially drying and calcining to obtain a catalyst.
好ましくは、工程（１）における酸溶液が、塩酸、硫酸、硝酸、リン酸、酢酸及びモリブデン酸の１つ以上を含み、酸溶液の濃度が、１〜５ｍｏｌ／Ｌである。 Preferably, the acid solution in step (1) contains one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and molybdic acid, and the concentration of the acid solution is 1 to 5 mol / L.
好ましくは、工程（２）における活性成分塩溶液が、活性成分塩酸塩溶液、活性成分硝酸塩溶液、活性成分硫酸塩溶液、活性成分リン酸塩溶液及び酢酸塩溶液のうちの１つ以上を含み、活性成分塩溶液の濃度が、０．１〜３ｍｏｌ／Ｌである。 Preferably, the active ingredient salt solution in step (2) comprises one or more of the active ingredient hydrochloride solution, the active ingredient nitrate solution, the active ingredient sulfate solution, the active ingredient phosphate solution and the acetate solution. The concentration of the active ingredient salt solution is 0.1 to 3 mol / L.
好ましくは、工程（１）及び工程（２）における乾燥処理の温度は独立して、８０〜１２０℃であり、乾燥処理時間は独立して３〜６時間であり、焼成処理の温度は独立して３００〜８００℃であり、焼成処理時間は独立して３〜６時間である。 Preferably, the drying treatment temperature in the steps (1) and (2) is independently 80 to 120 ° C., the drying treatment time is independently 3 to 6 hours, and the firing treatment temperature is independent. The temperature is 300 to 800 ° C., and the firing treatment time is independently 3 to 6 hours.
本発明は、触媒の作用下でのイミダゾール系化合物とアルキル化剤とがアルキル化反応して、Ｎ-アルキルイミダゾール系化合物を得る工程を含むこと、を特徴とするＮ-アルキルイミダゾール系化合物の製造方法を提供する。アルキル化反応の温度は１００〜４００℃であり、触媒は、上記の技術構成に記載された触媒、または上記の技術構成に記載された方法により製造された触媒である。 The present invention comprises a step of obtaining an N-alkylimidazole-based compound by an alkylation reaction between an imidazole-based compound and an alkylating agent under the action of a catalyst, wherein the N-alkylimidazole-based compound is produced. Provide a method. The temperature of the alkylation reaction is 100 to 400 ° C., and the catalyst is the catalyst described in the above technical configuration or the catalyst produced by the method described in the above technical configuration.
好ましくは、イミダゾール系化合物とアルキル化剤とのモル比が１：１〜１０である。 Preferably, the molar ratio of the imidazole compound to the alkylating agent is 1: 1-10.
好ましくは、イミダゾール系化合物が、式Ｉ-１〜式Ｉ-３のいずれかで表される構造を有する。 Preferably, the imidazole-based compound has a structure represented by any of formulas I-1 to I-3.
式ＩＶ-１において、Ｒ1、Ｒ2はそれぞれ独立して、炭素原子１〜１８のアルキル基または水素から選択され、式ＩＶ−６〜式ＩＶ−１２において、Ｒ1は炭素原子１〜１８のアルカン、水素、メトキシ基、フェニル基、フェノキシ基、フッ素基、塩素基、臭素基またはヨウ素からなる群から選択され、式ＩＶ−７〜式ＩＶ−９において、Ｒ2は、炭素原子１〜１８のアルキル基、水素、メトキシ、フェニル、フェノキシ、フッ素、塩素、臭素またはヨウ素からなる群から選択され、ｍは１〜６の整数であり、式ＩＶ−３において、ｎは２〜８の整数であり、式ＩＶ−６、式ＩＶ−７及び式ＩＶ−９において、ｎは独立して０〜４の整数である。
In formula IV-1, R 1 and R 2 are independently selected from alkyl groups or hydrogens of carbon atoms 1-18, and in formulas IV-6 to IV-12, R 1 is carbon atoms 1-18. Selected from the group consisting of an alkyl, hydrogen, methoxy group, phenyl group, phenoxy group, fluorine group, chlorine group, bromine group or iodine, in formulas IV-7 to IV-9, R 2 is a carbon atom 1 to 1. Selected from the group consisting of 18 alkyl groups, hydrogen, methoxy, phenyl, phenoxy, fluorine, chlorine, bromine or iodine, m is an integer of 1-6 and in formula IV-3 n is an integer of 2-8. In formulas IV-6, IV-7 and IV-9, n is an independent integer of 0-4.
本発明は、活性成分と酸処理した担体とを含む触媒を提供する。担体はシリコン・アルミナ酸化物及び／またはシリカであり、活性成分は金属酸化物を含み、金属酸化物中の金属元素は、ジルコニウム、ニオブ、ハフニウム、タンタル、カルシウム、マグネシウム、銅、ニッケル、鉄、コバルト、亜鉛、及び希土類元素のうちの１つ以上を含み、この触媒は、Ｎ-アルキルイミダゾール系化合物を得るための、イミダゾール系化合物とアルキル化剤とのアルキル化反応に作用する。本発明では、活性成分は酸処理した担体の細孔内部及び表面に担持されている。本発明の酸処理した担体は、表面及び細孔に多数の酸性部位を形成し、金属活性成分との相乗作用により、活性化アルキル化剤との反応性能を大幅に向上させて、高選択性にイミダゾール系化合物をアルキル化反応させる。本発明により提供される触媒は、Ｎ-アルキルイミダゾール系化合物の触媒の製造に使用されると、製造方法は簡単になり、反応条件は温和であり、かつ反応生成物の収率及び選択率が高く、実施例の結果は反応生成物の収率が５５％〜９３％で、選択率は９０％以上であることを示す。 The present invention provides a catalyst containing an active ingredient and an acid-treated carrier. The carrier is silicon-alumina oxide and / or silica, the active ingredient contains a metal oxide, and the metal elements in the metal oxide are zirconium, niobium, hafnium, tantalum, calcium, magnesium, copper, nickel, iron, cobalt, zinc, and viewed including one or more of the rare earth elements, the catalyst, to obtain N- alkyl imidazole compounds, acting on an alkylation reaction with imidazole compound with an alkylating agent. In the present invention, the active ingredient is supported inside and on the surface of the pores of the acid-treated carrier. The acid-treated carrier of the present invention forms a large number of acidic sites on the surface and pores, and synergistically acts with the metal active ingredient to significantly improve the reaction performance with the activating alkylating agent, resulting in high selectivity. Is alkylated with an imidazole compound. The catalyst provided by the present invention, when used in the preparation of the catalyst of the N- alkyl imidazole compound, the manufacturing method is simplified, the reaction conditions are mild, and yield and selectivity of the reaction product High, the results of the examples show that the yield of the reaction product is 55% to 93% and the selectivity is 90% or more.
本発明はＮ-アルキルイミダゾール系化合物の製造方法を提供する。本発明では、上記の技術構成を有する触媒は、Ｎ-アルキルイミダゾール系化合物の製造方法における触媒であるので、製造方法が簡単であり、反応条件が温和であり、さらに、反応生成物の収率及び選択率が高い。実施例の結果は、反応生成物の収率が５５％〜９３％であり、選択率が９０％以上であることを示している。 The present invention provides a method for producing an N-alkylimidazole compound. In the present invention, the catalyst having the above technical constitution is a catalyst in the method for producing an N-alkylimidazole compound, so that the production method is simple, the reaction conditions are mild, and the yield of the reaction product is mild. And the selectivity is high. The results of the examples show that the yield of the reaction product is 55% to 93% and the selectivity is 90% or more.
本発明は、活性成分と酸処理した担体とを含む触媒を提供する。担体はシリコン・アルミナ酸化物及び／またはシリカであり、活性成分は金属酸化物を含み、金属酸化物中の金属元素は、ジルコニウム、ニオブ、ハフニウム、タンタル、カルシウム、マグネシウム、銅、ニッケル、鉄、コバルト、亜鉛、及び希土類元素のうちの１つ以上を含む。 The present invention provides a catalyst containing an active ingredient and an acid-treated carrier. The carrier is silicon-alumina oxide and / or silica, the active ingredient contains a metal oxide, and the metal elements in the metal oxide are zirconium, niobium, hafnium, tantalum, calcium, magnesium, copper, nickel, iron, Contains one or more of cobalt, zinc, and rare earth elements.
本発明によって提供される触媒は、アルキル化反応触媒であり、本発明において、触媒は、ジルコニウム、ニオブ、ハフニウム、タンタル、カルシウム、マグネシウム、銅、ニッケル、鉄、コバルト、亜鉛、希土類元素を１つ以上含む活性成分を含む。本発明において、希土類元素は、ランタン、セリウム、プラセオジム、ネオジム、サマリウム、テルビウム、ジスプロシウム、ルテチウム、スカンジウム及びイットリウムのうちの１つ以上を含むことが好ましく、活性成分は、ジルコニウム、ニオブ、ハフニウム、タンタル、カルシウム、マグネシウム、銅、ニッケル、鉄、コバルト、亜鉛、ランタン、セリウム、プラセオジム、ネオジム、サマリウム、テルビウム、ジスプロシウム、ルテチウム、スカンジウム及びイットリウムを１つ以上含むことが好ましい。また、ストロンチウム、カルシウム、マグネシウム、銅、ニッケル、鉄、コバルト、亜鉛、バリウム、のうちの１つまたは複数を含むことが好ましい。 The catalyst provided by the present invention is an alkylation reaction catalyst, and in the present invention, the catalyst contains one zirconium, niobium, hafnium, tantalum, calcium, magnesium, copper, nickel, iron, cobalt, zinc and rare earth elements. Contains the active ingredients including the above. In the present invention, the rare earth element preferably contains one or more of lanthanum, cerium, praseodymium, neodymium, samarium, terbium, dysprosium, lutetium, scandium and ittrium, and the active ingredient is zirconium, niobium, hafnium, tantalum , Calcium, magnesium, copper, nickel, iron, cobalt, zinc, lantern, cerium, praseodymium, neodymium, samarium, terbium, dysprosium, lutetium, scandium and yttrium. Further, it is preferable to contain one or more of strontium, calcium, magnesium, copper, nickel, iron, cobalt, zinc and barium.
本発明において、触媒中の活性成分の質量分率は、０．１〜２５％が好ましく、１〜１８％がより好ましく、２〜１５％がさらに好ましく、５〜１０％が最も好ましい。 In the present invention, the mass fraction of the active ingredient in the catalyst is preferably 0.1 to 25%, more preferably 1 to 18%, further preferably 2 to 15%, and most preferably 5 to 10%.
本発明において、触媒は、酸処理した担体をさらに含み、担体はシリコン・アルミナ酸化物及び／またはシリカである。担体の比表面積は、５０ｍ2／ｇを超えることが好ましく、２００〜１０００ｍ2／ｇがより好ましく、４００〜６００ｍ2／ｇがさらに好ましい。担体の粒径は、１〜５ｍｍが好ましく、２〜４ｍｍがより好ましい。担体の孔径は、３Å〜５００ｎｍが好ましく、１〜２００ｎｍがさらに好ましい。本発明において、シリコン・アルミナ酸化物のアルミニウム含有量は、０を除いて、０〜２０％が好ましく、１〜１８％がより好ましく、５〜１５％がさらに好ましい。本発明において、シリコン・アルミナ酸化物及びシリカは市販品を使用してもよい。 In the present invention, the catalyst further comprises an acid-treated carrier, the carrier being silicon-alumina oxide and / or silica. The specific surface area of the support is preferably greater than 50 m 2 / g, more preferably 200~1000m 2 / g, more preferably 400-600m 2 / g. The particle size of the carrier is preferably 1 to 5 mm, more preferably 2 to 4 mm. The pore size of the carrier is preferably 3 Å to 500 nm, more preferably 1 to 200 nm. In the present invention, the aluminum content of the silicon-alumina oxide is preferably 0 to 20%, more preferably 1 to 18%, still more preferably 5 to 15%, excluding 0. In the present invention, commercially available products may be used as the silicon-alumina oxide and silica.
本発明は、（１）担体を酸溶液に浸漬した後、順に乾燥、焼成処理して、酸処理した担体を得る工程と、（２）工程（１）で得られた酸処理した担体を活性成分塩溶液に浸漬した後、順に乾燥、焼成処理して触媒を得る工程を含む、上記の技術構成の触媒を製造する製造方法をさらに提供する。 In the present invention, (1) the carrier is immersed in an acid solution and then dried and calcined in order to obtain an acid-treated carrier, and (2) the acid-treated carrier obtained in step (1) is activated. Further provided is a production method for producing a catalyst having the above-mentioned technical composition, which comprises a step of immersing the catalyst in a component salt solution and then sequentially drying and calcining the catalyst to obtain a catalyst.
本発明においては、担体を酸溶液に浸漬した後、順に乾燥、焼成処理して、酸処理した担体を得る。 In the present invention, the carrier is immersed in an acid solution and then dried and fired in order to obtain an acid-treated carrier.
本発明において、酸性溶液は、塩酸、硫酸、硝酸、リン酸、酢酸、及びモリブデン酸のうちの１つ以上を含み、その酸性溶液の濃度は１〜５ｍｏｌ／Ｌが好ましく、２〜４ｍｏｌ／Ｌがより好ましい。本発明において、担体の質量と酸溶液との体積比は、１ｇ：０．６〜１．３ｍＬが好ましく、１ｇ：１ｍＬがさらに好ましい。本発明において、担体を酸性溶液に浸漬する時間は、３〜８時間が好ましく、４〜６時間がさらに好ましい。本発明において、担体は酸性溶液を完全に吸収することができ、浸漬が完了した後、残った酸性溶液は存在しない。 In the present invention, the acidic solution contains one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, and molybdic acid, and the concentration of the acidic solution is preferably 1 to 5 mol / L, preferably 2 to 4 mol / L. Is more preferable. In the present invention, the volume ratio of the mass of the carrier to the acid solution is preferably 1 g: 0.6 to 1.3 mL, and more preferably 1 g: 1 mL. In the present invention, the time for immersing the carrier in the acidic solution is preferably 3 to 8 hours, more preferably 4 to 6 hours. In the present invention, the carrier can completely absorb the acidic solution and there is no residual acidic solution after the immersion is completed.
本発明は、担体を酸溶液に浸漬した後、順に酸を浸漬した担体を乾燥、焼成処理する。本発明において、乾燥温度は、８０〜１２０℃が好ましく、１００℃がより好ましい。乾燥時間は、３〜６時間が好ましく、４〜５時間がさらに好ましい。本発明において、焼成処理の温度は、３００〜８００℃が好ましく、４００〜７００℃がより好ましく、３〜６時間が好ましく、４〜５時間がより好ましい。本発明において、焼成雰囲気は、空気であることが好ましい。 In the present invention, the carrier is immersed in an acid solution, and then the carrier in which the acid is immersed is dried and fired in order. In the present invention, the drying temperature is preferably 80 to 120 ° C, more preferably 100 ° C. The drying time is preferably 3 to 6 hours, more preferably 4 to 5 hours. In the present invention, the temperature of the firing treatment is preferably 300 to 800 ° C., more preferably 400 to 700 ° C., preferably 3 to 6 hours, and more preferably 4 to 5 hours. In the present invention, the firing atmosphere is preferably air.
本発明においては、担体を酸性溶液に浸漬した後、焼成処理を行うことにより、担体表面及び細孔に多数の酸性部位を形成することができる。触媒作用がある適当強度の酸性部位を形成することに有利であるから、焼成温度を上記の範囲とすること好ましい。 In the present invention, a large number of acidic sites can be formed on the surface of the carrier and the pores by immersing the carrier in an acidic solution and then performing a firing treatment. It is preferable to set the firing temperature in the above range because it is advantageous to form an acidic portion having a catalytic action and an appropriate strength.
本発明において、酸処理した担体を得た後、酸処理した担体を活性成分塩溶液に浸漬する。本発明において、活性成分塩溶液は、活性成分塩酸塩溶液、活性成分硝酸塩溶液、活性成分硫酸塩溶液、活性成分リン酸塩溶液、及び活性成分酢酸塩溶液のうちの１つ以上を含むことが好ましい。活性成分塩溶液の濃度は、０．１〜３ｍｏｌ／Ｌが好ましく、０．５〜２．５ｍｏｌ／Ｌがより好ましく、１〜２ｍｏｌ／Ｌがさらに好ましい。本発明において、活性成分塩溶液の溶媒は水であることが好ましい。本発明において、酸処理した担体と活性成分塩溶液との比は、１ｇ：０．６〜１．３ｍＬが好ましく、１ｇ：１ｍＬがさらに好ましい。本発明においては、酸処理した担体を活性成分塩溶液に３〜８時間浸漬するのが好ましく、４〜６時間浸漬するのがより好ましい。 In the present invention, after obtaining the acid-treated carrier, the acid-treated carrier is immersed in the active ingredient salt solution. In the present invention, the active ingredient salt solution may contain one or more of the active ingredient hydrochloride solution, the active ingredient nitrate solution, the active ingredient sulfate solution, the active ingredient phosphate solution, and the active ingredient acetate solution. preferable. The concentration of the active ingredient salt solution is preferably 0.1 to 3 mol / L, more preferably 0.5 to 2.5 mol / L, and even more preferably 1 to 2 mol / L. In the present invention, the solvent of the active ingredient salt solution is preferably water. In the present invention, the ratio of the acid-treated carrier to the active ingredient salt solution is preferably 1 g: 0.6 to 1.3 mL, more preferably 1 g: 1 mL. In the present invention, the acid-treated carrier is preferably immersed in the active ingredient salt solution for 3 to 8 hours, more preferably 4 to 6 hours.
本発明において、酸処理した担体を活性成分塩溶液に浸漬した後、順に活性成分塩溶液を浸漬した担体を乾燥、焼成処理して、触媒を得る。本発明において、乾燥温度は、８０〜１２０℃が好ましく、１００℃がより好ましい。乾燥時間は、３〜６時間が好ましく、４〜５時間がさらに好ましい。 In the present invention, the acid-treated carrier is immersed in the active ingredient salt solution, and then the carrier in which the active ingredient salt solution is immersed is dried and fired in order to obtain a catalyst. In the present invention, the drying temperature is preferably 80 to 120 ° C, more preferably 100 ° C. The drying time is preferably 3 to 6 hours, more preferably 4 to 5 hours.
本発明において、焼成処理の温度は、３００〜８００℃が好ましく、４００〜７００℃がより好ましく、３〜６時間がさらに好ましく、４〜５時間がさらに好ましい。本発明において、焼成雰囲気は空気であることが好ましい。 In the present invention, the firing treatment temperature is preferably 300 to 800 ° C., more preferably 400 to 700 ° C., even more preferably 3 to 6 hours, still more preferably 4 to 5 hours. In the present invention, the firing atmosphere is preferably air.
本発明は、酸処理した担体を活性成分塩溶液に浸漬し、活性成分の金属イオンを担体の表面及び細孔に吸着させ、次いで乾燥及び焼成処理し、活性成分金属イオンが酸化状態を形成し安定化し、担体に強固に接着されて、使用中に交換しにくくなり、性能安定化に保持される。 In the present invention, the acid-treated carrier is immersed in an active ingredient salt solution, the active ingredient metal ions are adsorbed on the surface and pores of the carrier, and then dried and calcined, so that the active ingredient metal ions form an oxidized state. It stabilizes and is firmly adhered to the carrier, making it difficult to replace during use and maintaining performance stabilization.
本発明は、また、触媒の作用下で、イミダゾール系化合物とアルキル化剤とをアルキル化反応させることにより、製造されるＮ-アルキルイミダゾール系化合物の製造方法を提供する。アルキル化反応の温度は、１００〜４００℃である。触媒は、上記の技術構成に記載された触媒、または上記の技術構成に記載された方法により製造された触媒である。 The present invention also provides a method for producing an N-alkylimidazole compound produced by subjecting an imidazole compound and an alkylating agent to an alkylation reaction under the action of a catalyst. The temperature of the alkylation reaction is 100-400 ° C. The catalyst is the catalyst described in the above technical configuration or the catalyst produced by the method described in the above technical configuration.
本発明において、イミダゾール系化合物とアルキル化剤とのモル比は、１：１〜１０が好ましく、１：２〜８がより好ましく、１：３〜７がさらに好ましい。 In the present invention, the molar ratio of the imidazole compound to the alkylating agent is preferably 1: 1 to 10, more preferably 1: 2 to 8, and even more preferably 1: 3 to 7.
本発明の実施形態において、Ｎ-アルキルイミダゾール系化合物の製造方法は、固定床連続反応方式と回分式反応器反応方式とを含むことが好ましい。 In the embodiment of the present invention, the method for producing the N-alkylimidazole compound preferably includes a fixed bed continuous reaction method and a batch reactor reaction method.
Ｎ-アルキルイミダゾール系化合物の製造方法は、固定床連続反応方式が好ましい場合、反応方式は、具体的には、供給ポンプにより、イミダゾール系化合物及びアルキル化剤を固定床反応器に送り込み、気化器により加熱し、気化された原料混合物をキャリアガスであるＮ2と均一に混合し、触媒床に送り込み、触媒の触媒作用によりアルキル化反応を行い、反応後の混合物を凝縮器で室温まで冷却して、液体を貯蔵槽に収集する。本発明において、イミダゾール系化合物とアルキル化薬剤との混合物の液体対気速度は、０．５〜２０ｈ-1が好ましく、５〜１０ｈ-1がより好ましい。キャリアガスであるＮ2対気速度は、５００〜７００ｈ-1が好ましく、６００ｈ-1がさらに好ましい。 When the fixed bed continuous reaction method is preferable as the method for producing the N-alkyl imidazole compound, the reaction method is specifically that the imidazole compound and the alkylating agent are sent to the fixed bed reactor by a supply pump and vaporized. The vaporized raw material mixture is uniformly mixed with N 2 which is a carrier gas, sent to a catalyst bed, an alkylation reaction is carried out by the catalytic action of the catalyst, and the reaction mixture is cooled to room temperature in a condenser. And collect the liquid in the storage tank. In the present invention, the liquid airspeed imidazole compound and a mixture of an alkylating agent, preferably 0.5~20h- 1, 5~10h- 1 is more preferred. N 2 airspeed which is a carrier gas is preferably 500~700h- 1, 600h- 1 is more preferred.
Ｎ-アルキルイミダゾール系化合物の製造方法は、バッチ式反応器反応方式が好ましい場合、具体的には、反応器に触媒、イミダゾール系化合物及びアルキル化剤を添加し、密閉させた後、保護ガスによりシステム内の空気を置換して、アルキル化反応を行う。反応が終了した後、室温まで冷却し、ろ過により、反応混合液から触媒を濾取する。本発明において、触媒とイミダゾール系化合物との質量比は、０．０１〜０．５：１が好ましく、０．０５〜０．４５：１がより好ましく、０．１〜０．４：１がさらに好ましい。本発明において、反応時間は、６〜２４時間が好ましく、１０〜２０時間がより好ましい。本発明において、アルキル化剤がアルコールである場合、保護ガスは窒素または水素であることが好ましい。アルキル化剤がケトンまたはアルデヒドである場合、保護ガスは水素であることが好ましい。 When the batch reactor reaction method is preferable as the method for producing the N-alkylimidazole compound, specifically, a catalyst, an imidazole compound and an alkylating agent are added to the reactor, sealed, and then sealed with a protective gas. The air in the system is replaced to carry out the alkylation reaction. After completion of the reaction, the catalyst is cooled to room temperature and the catalyst is filtered off from the reaction mixture by filtration. In the present invention, the mass ratio of the catalyst to the imidazole compound is preferably 0.01 to 0.5: 1, more preferably 0.05 to 0.45: 1, and 0.1 to 0.4: 1. More preferred. In the present invention, the reaction time is preferably 6 to 24 hours, more preferably 10 to 20 hours. In the present invention, when the alkylating agent is an alcohol, the protective gas is preferably nitrogen or hydrogen. When the alkylating agent is a ketone or aldehyde, the protective gas is preferably hydrogen.
本発明において、イミダゾール系化合物は、式Ｉ-１〜式Ｉ-３のいずれかで表される構造を有することが好ましい。
式Ｉ-１中のＲ1、Ｒ2及びＲ3は、それぞれ独立して、炭素原子１〜１８のアルキル基、水素、メトキシ、フェニル、フェノキシ、ベンジル、ビニル、トリフルオロメチル、２−イミダゾリル、フッ素、塩素、臭素またはヨウ素からなる群から選択されることが好ましく、炭素数１〜１６のアルキル基であることがより好ましく、炭素数２〜１５のアルキル基であることがさらに好ましく、炭素数３〜１０のアルキル基であることが最も好ましい。本発明において、アルキル基として、直鎖状アルキル基及び異性体状アルキル基を含むことが好ましい。 R 1 , R 2 and R 3 in Formula I-1 are independently alkyl groups of carbon atoms 1-18, hydrogen, methoxy, phenyl, phenoxy, benzyl, vinyl, trifluoromethyl, 2-imidazolyl, respectively. It is preferably selected from the group consisting of fluorine, chlorine, bromine or iodine, more preferably an alkyl group having 1 to 16 carbon atoms, even more preferably an alkyl group having 2 to 15 carbon atoms. Most preferably, it is an alkyl group of 3 to 10. In the present invention, the alkyl group preferably contains a linear alkyl group and an isomeric alkyl group.
本発明において、イミダゾール系化合物は、表１中のいずれかに示す構造を有することが好ましい。 In the present invention, the imidazole compound preferably has the structure shown in any of Table 1.
本発明において、アルキル化剤は、アルデヒド、ケトン、アルコールのいずれかを含むことが好ましい。 In the present invention, the alkylating agent preferably contains any one of aldehyde, ketone and alcohol.
本発明において、アルキル化剤はアルデヒドであることが好ましい場合、アルデヒドは、式ＩＩ-１から式ＩＩ-３のいずれかで表される構造を有することが好ましい。 In the present invention, when the alkylating agent is preferably an aldehyde, the aldehyde preferably has a structure represented by any of formulas II-1 to II-3.
式ＩＩ−１において、Ｒ1は炭素数１〜１８のアルキル基または水素から選択され、炭素数１〜１６のアルキル基であることが好ましく、炭素数２〜１５のアルキル基であることがより好ましく、炭素数３〜１０のアルキル基であることが最も好ましい。式ＩＩ−２〜式ＩＩ−３において、Ｒ1、Ｒ2は、炭素数１〜１８のアルキル基、水素、メトキシ、フェニル、フェノキシ、フッ素、塩素、臭素またはヨウ素からなる群から選択され、炭素数１〜１６のアルキル基であることが好ましく、炭素数２〜１５のアルキル基であることがより好ましく、炭素数３〜１０のアルキル基であることが最も好ましい。本発明において、アルキル基は直鎖アルキルとイソアルキル基であることが好ましい。式ＩＩ-３において、ｎは１〜４の整数である。 In formula II-1, R 1 is selected from an alkyl group having 1 to 18 carbon atoms or hydrogen, preferably an alkyl group having 1 to 16 carbon atoms, and more preferably an alkyl group having 2 to 15 carbon atoms. Most preferably, it is an alkyl group having 3 to 10 carbon atoms. In formulas II-2 to II-3, R 1 and R 2 are selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, hydrogen, methoxy, phenyl, phenoxy, fluorine, chlorine, bromine or iodine, and are carbons. It is preferably an alkyl group having a number of 1 to 16, more preferably an alkyl group having 2 to 15 carbon atoms, and most preferably an alkyl group having 3 to 10 carbon atoms. In the present invention, the alkyl group is preferably a linear alkyl group and an isoalkyl group. In Formula II-3, n is an integer of 1-4.
本発明において、アルキル化剤はアルデヒドであることが好ましい場合、アルデヒドは、表２中のいずれかに示す構造を有することが好ましい。 In the present invention, when the alkylating agent is preferably an aldehyde, the aldehyde preferably has the structure shown in any of Table 2.
本発明において、アルキル化剤がケトンであることが好ましい場合、ケトンは、式ＩＩＩ−１〜式ＩＩＩ−３のいずれかで表される構造を有することが好ましい。 In the present invention, when the alkylating agent is preferably a ketone, the ketone preferably has a structure represented by any of formulas III-1 to III-3.
式ＩＩＩ-１中のＲ1、Ｒ2はそれぞれ独立して、炭素原子１〜１８のアルキル基または置換アルキル基から選択される。炭素原子１〜１８のアルキル基は、炭素原子１〜１６のアルキル基であることが好ましく、炭素原子２〜１５のアルキル基であることがより好ましく、炭素原子３〜１０のアルキル基であることが最も好ましい。置換アルキル基はフェニル、フェノキシ、及びフッ素、塩素、臭素またはヨウ素の置換アルキル基であることが好ましい。式ＩＩＩ-２〜式ＩＩＩ-３中、Ｒ1、Ｒ2及びＲ3はそれぞれ独立して、炭素数１〜１８のアルキル基、水素、メトキシ、フェニル、フェノキシ、フッ素、塩素、臭素またはヨウ素からなる群から選択され、炭素数１〜１６のアルキル基であることがより好ましく、炭素数２〜１５のアルキル基であることがさらに好ましく、炭素数３〜１０のアルキル基であることが最も好ましい。本発明において、アルキルは、直鎖アルキルとイソアルキル基であることが好ましい。 R 1 and R 2 in Formula III-1 are independently selected from alkyl groups or substituted alkyl groups of carbon atoms 1-18. The alkyl group of carbon atoms 1 to 18 is preferably an alkyl group of carbon atoms 1 to 16, more preferably an alkyl group of carbon atoms 2 to 15, and an alkyl group of carbon atoms 3 to 10. Is the most preferable. The substituted alkyl group is preferably a substituted alkyl group of phenyl, phenoxy, and fluorine, chlorine, bromine or iodine. In the formula III-. 2 to Formula III-3, R 1, R 2 and R 3 are each independently an alkyl group having 1 to 18 carbon atoms, hydrogen, methoxy, phenyl, phenoxy, fluorine, chlorine, bromine or iodine It is more preferably an alkyl group having 1 to 16 carbon atoms, further preferably an alkyl group having 2 to 15 carbon atoms, and most preferably an alkyl group having 3 to 10 carbon atoms. .. In the present invention, the alkyl is preferably a linear alkyl and an isoalkyl group.
本発明において、アルキル化剤がケトンであることが好ましい場合、ケトンは、表３中のいずれかに示す構造を有することが好ましい。 In the present invention, when the alkylating agent is preferably a ketone, the ketone preferably has the structure shown in any of Table 3.
本発明において、アルキル化剤がアルコールであることが好ましい場合、アルコールは式ＩＶ−１〜式ＩＶ−１２のいずれかで表される構造を有する。 In the present invention, when the alkylating agent is preferably an alcohol, the alcohol has a structure represented by any of the formulas IV-1 to IV-12.
式ＩＶ-１において、Ｒ1、Ｒ2はそれぞれ独立して、炭素原子１〜１８のアルキル基または水素から選択さることが好ましい。式ＩＶ-６〜式ＩＶ-１２において、Ｒ1は炭素原子１〜１８のアルカン、水素、メトキシ基、フェニル基、フェノキシ基、フッ素基、塩素基、臭素基またはヨウ素からなる群から選択されることが好ましい。式ＩＶ-７〜式ＩＶ-９において、Ｒ2は、炭素原子１〜１８個のアルキル基、水素、メトキシ、フェニル、フェノキシ、フッ素、塩素、臭素またはヨウ素からなる群から選択されることが好ましい。本発明において、炭素原子１〜１８のアルキル基は炭素原子１〜１６のアルキル基であることが好ましく、式炭素原子２〜１５のアルキル基であることがより好ましく、式炭素原子３〜１０のアルキル基であることが最も好ましい。アルキル基は、直鎖アルキルとイソアルキル基であることが好ましい。本発明において、式ＩＶ-２におけるｍは１〜６の整数であることが好ましく、２〜５の整数であることがより好ましい。式ＩＶ-３におけるｎは２〜８の整数であることが好ましく、３〜７の整数であることがより好ましく、４〜６の整数であることが最も好ましい。式ＩＶ-６、式ＩＶ-７及び式ＩＶ-９におけるｎは独立して０〜４の整数であることが好ましく、１〜４の整数であることがより好ましく、２〜３の整数であることがさらに好ましい。 In formula IV-1, R 1 and R 2 are preferably independently selected from alkyl groups of carbon atoms 1 to 18 or hydrogen. In formulas IV-6 to IV-12, R 1 is selected from the group consisting of alkanes, hydrogen, methoxy groups, phenyl groups, phenoxy groups, fluorine groups, chlorine groups, bromine groups or iodine of carbon atoms 1-18. Is preferable. In formulas IV-7 to IV-9, R 2 is preferably selected from the group consisting of alkyl groups with 1 to 18 carbon atoms, hydrogen, methoxy, phenyl, phenoxy, fluorine, chlorine, bromine or iodine. .. In the present invention, the alkyl group of carbon atoms 1 to 18 is preferably an alkyl group of carbon atoms 1 to 16, more preferably an alkyl group of formula carbon atoms 2 to 15, and of the formula carbon atoms 3 to 10. Most preferably it is an alkyl group. The alkyl group is preferably a linear alkyl group and an isoalkyl group. In the present invention, m in the formula IV-2 is preferably an integer of 1 to 6, and more preferably an integer of 2 to 5. In Formula IV-3, n is preferably an integer of 2 to 8, more preferably an integer of 3 to 7, and most preferably an integer of 4 to 6. In formulas IV-6, IV-7 and IV-9, n is preferably an integer of 0 to 4, more preferably an integer of 1 to 4, and an integer of 2 to 3. Is even more preferable.
本発明において、アルキル化剤はアルコールであることが好ましい場合、アルコールは表４中のいずれかに示す構造を有することが好ましい。 In the present invention, when the alkylating agent is preferably an alcohol, the alcohol preferably has the structure shown in any of Table 4.
本発明によって提供されるＮ-アルキルイミダゾール系化合物の製造方法は、上記の技術構成に記載される触媒を採用するので、本発明によって提供される方法は簡単になり、反応条件を温和させ、生成物選択性を上昇させ、かつ触媒が容易に回収されて再使用されることができる。 Since the method for producing the N-alkylimidazole compound provided by the present invention employs the catalyst described in the above technical constitution, the method provided by the present invention is simplified, the reaction conditions are moderated, and the product is produced. The selectivity can be increased and the catalyst can be easily recovered and reused.
本発明において、触媒回収方法として、反応方式が回分式反応方式であることが好ましい場合、反応終了した後に、反応液を濾過し、固体を収集するする方法が好ましく、反応方式は固定床連続反応方式であることが好ましい場合、反応終了した後に、触媒を焼成処理して、触媒を再生活性化することが好ましい。焼成処理温度は、４５０〜５５０℃が好ましく、焼成処理時間は３〜５時間であることが好ましい。 In the present invention, when it is preferable that the reaction method is a batch reaction method as the catalyst recovery method, a method of filtering the reaction solution and collecting solids after the reaction is completed is preferable, and the reaction method is a fixed bed continuous reaction. When the method is preferable, it is preferable to regenerate and activate the catalyst by calcining the catalyst after the reaction is completed. The firing treatment temperature is preferably 450 to 550 ° C., and the firing treatment time is preferably 3 to 5 hours.
以下、本発明の技術構成は、本発明の実施例と共に、明確かつ完全に説明される。 Hereinafter, the technical configuration of the present invention will be clearly and completely described together with examples of the present invention.
［実施例１］
２．０ｇのシリコン・アルミナ酸化物（アルミニウム含有量５％）を秤量し、２ｍＬの５ｍｏｌ／Ｌ硝酸溶液に浸漬し、室温で３時間浸漬し、１００℃で３時間乾燥させ、８００℃で３時間焼成した。２ｍＬの１．５ｍｏｌ／Ｌの硝酸ジルコニウム水溶液を調製して、処理されたシリコン・アルミナ酸化物を硝酸ジルコニウム水溶液に８時間浸漬し、次いで１００℃で６時間乾燥させ、３００℃で６時間焼成し、触媒を得た。
[Example 1]
Weigh 2.0 g of silicon-alumina oxide (aluminum content 5%), soak in 2 mL of 5 mol / L nitric acid solution, soak at room temperature for 3 hours, dry at 100 ° C. for 3 hours, and soak at 800 ° C. for 3 Baked for hours. A 2 mL 1.5 mol / L zirconium nitrate aqueous solution was prepared, the treated silicon-alumina oxide was immersed in the zirconium nitrate aqueous solution for 8 hours, then dried at 100 ° C. for 6 hours and fired at 300 ° C. for 6 hours. , Obtained a catalyst.
［実施例２］
２．０ｇのシリコン・アルミナ酸化物（アルミニウム含有量１０％）を秤量し、２ｍＬの２ｍｏｌ／Ｌ硫酸溶液に浸漬し、室温で８時間浸漬し、１００℃で６時間乾燥させ、６００℃で５時間焼成した。２ｍＬの１．０ｍｏｌ／Ｌの硝酸ランタン溶液を調製し、この溶液に処理されたシリコン・アルミナ酸化物を５時間浸漬し、次いで１００℃で６時間乾燥させ、８００℃で５時間焼成し、触媒を得た。
[Example 2]
Weigh 2.0 g of silicon-alumina oxide (aluminum content 10%), soak in 2 mL of 2 mol / L sulfuric acid solution, soak at room temperature for 8 hours, dry at 100 ° C. for 6 hours, 5 at 600 ° C. Baked for hours. A 2 mL 1.0 mol / L lanthanum nitrate solution was prepared, the treated silicon-alumina oxide was immersed in this solution for 5 hours, then dried at 100 ° C. for 6 hours, calcined at 800 ° C. for 5 hours, and catalyst. Got
［実施例３］
２．０ｇのシリコン・アルミナ酸化物（アルミニウム含有量２０％）を秤量し、２ｍＬの３ｍｏｌ／Ｌリン酸溶液に浸漬し、室温で５時間浸漬し、１００℃で４時間乾燥させ、７００℃で３時間焼成した。２ｍＬの活性成分塩溶液を採取した。活性成分塩溶液中の酢酸ニオブの濃度は、０．２５ｍｏｌ／Ｌであり、活性塩溶液中の硝酸セリウムの濃度は１ｍｏｌ／Ｌであった。処理されたシリコン・アルミナ酸化物をこの活性成分の塩溶液中に８時間浸漬した後、１００℃で４時間乾燥させ、５００℃で５時間焼成し、触媒を得た。
[Example 3]
Weigh 2.0 g of silicon-alumina oxide (aluminum content 20%), soak in 2 mL of 3 mol / L phosphoric acid solution, soak at room temperature for 5 hours, dry at 100 ° C. for 4 hours, at 700 ° C. It was baked for 3 hours. A 2 mL active ingredient salt solution was collected. The concentration of niobium acetate in the active salt solution was 0.25 mol / L, and the concentration of cerium nitrate in the active salt solution was 1 mol / L. The treated silicon-alumina oxide was immersed in a salt solution of this active ingredient for 8 hours, dried at 100 ° C. for 4 hours, and calcined at 500 ° C. for 5 hours to obtain a catalyst.
［実施例４］
２．０ｇのシリカを秤量し、２ｍＬの５ｍｏｌ／Ｌモリブデン酸溶液に浸漬し、室温で５時間浸漬し、１００℃で３時間乾燥させ、５００℃で６時間焼成した。２ｍＬの活性成分塩溶液を採取した。活性成分塩溶液中の硝酸スカンジウム濃度は１ｍｏｌ／Ｌであり、活性成分塩溶液中の硫酸コバルト濃度は０．４ｍｏｌ／Ｌであった。処理されたシリカを活性成分塩溶液中に８時間浸漬した後、１００℃で４時間乾燥させ、４００℃で５時間焼成して、触媒を得た。
[Example 4]
2.0 g of silica was weighed, dipped in 2 mL of 5 mol / L molybdic acid solution, dipped at room temperature for 5 hours, dried at 100 ° C. for 3 hours and calcined at 500 ° C. for 6 hours. A 2 mL active ingredient salt solution was collected. The scandium nitrate concentration in the active ingredient salt solution was 1 mol / L, and the cobalt sulfate concentration in the active ingredient salt solution was 0.4 mol / L. The treated silica was immersed in the active ingredient salt solution for 8 hours, dried at 100 ° C. for 4 hours, and calcined at 400 ° C. for 5 hours to obtain a catalyst.
［実施例５］
２．０ｇのシリカを秤量し、２ｍＬの５ｍｏｌ／Ｌリン酸溶液に浸漬して、室温で８時間浸漬して、１００℃で３時間乾燥させ、５００℃で３時間焼成した。２ｍＬの活性成分塩溶液を採取した。活性成分塩溶液中の硝酸セリウム濃度は１ｍｏｌ／Ｌであった。処理されたシリカをこの活性成分塩溶液に８時間浸漬した後、１００℃で３時間乾燥させ、４００℃で５時間焼成して、触媒を得た。
[Example 5]
2.0 g of silica was weighed, immersed in 2 mL of 5 mol / L phosphoric acid solution, immersed at room temperature for 8 hours, dried at 100 ° C. for 3 hours and calcined at 500 ° C. for 3 hours. A 2 mL active ingredient salt solution was collected. The concentration of cerium nitrate in the active ingredient salt solution was 1 mol / L. The treated silica was immersed in this active ingredient salt solution for 8 hours, dried at 100 ° C. for 3 hours, and calcined at 400 ° C. for 5 hours to obtain a catalyst.
［実施例６］
２．０ｇのシリカを秤量し、２ｍＬの２ｍｏｌ／Ｌ塩酸溶液に浸漬して、室温で８時間浸漬して、１００℃で３時間乾燥させ、５００℃で３時間焼成した。２ｍＬの活性成分塩溶液を採取した。活性成分塩溶液中の硫酸銅濃度は２ｍｏｌ／Ｌ、活性塩溶液中の硝酸ジスプロシウム濃度は０．１ｍｏｌ／Ｌであった。この活性成分塩溶液に処理されたシリカを８時間浸漬した後、１００℃で乾燥させ、６００℃で５時間焼成して、触媒を得た。
[Example 6]
2.0 g of silica was weighed, immersed in 2 mL of 2 mol / L hydrochloric acid solution, immersed at room temperature for 8 hours, dried at 100 ° C. for 3 hours and calcined at 500 ° C. for 3 hours. A 2 mL active ingredient salt solution was collected. The copper sulfate concentration in the active salt solution was 2 mol / L, and the dysprosium nitrate concentration in the active salt solution was 0.1 mol / L. After immersing the treated silica in this active ingredient salt solution for 8 hours, it was dried at 100 ° C. and calcined at 600 ° C. for 5 hours to obtain a catalyst.
［実施例７］
２．０ｇのシリコン・アルミナ酸化物（アルミニウム含有量５％）を秤量して、２ｍＬの３ｍｏｌ／Ｌ酢酸溶液に浸漬し、室温で５時間浸漬し、１００℃で５時間乾燥させ、６００℃で６時間焼成した。２ｍＬの活性塩溶液を採取した。活性成分塩溶液中の酢酸銅の濃度は０．５ｍｏｌ／Ｌであり、活性成分塩溶液中の塩化ハフニウムの濃度は０．２ｍｏｌ／Ｌであり、活性成分塩溶液中の塩化タンタルの濃度は０．１ｍｏｌ／Ｌであった。この活性成分塩溶液に、処理されたシリコン・アルミナ酸化物を８時間浸漬して、１００℃で４時間乾燥させ、４００℃で５時間焼成して、触媒を得た。
[Example 7]
Weigh 2.0 g of silicon-alumina oxide (aluminum content 5%), soak in 2 mL of 3 mol / L acetic acid solution, soak at room temperature for 5 hours, dry at 100 ° C for 5 hours, at 600 ° C. It was baked for 6 hours. A 2 mL active salt solution was collected. The concentration of copper acetate in the active ingredient salt solution is 0.5 mol / L, the concentration of hafnium chloride in the active ingredient salt solution is 0.2 mol / L, and the concentration of tantalum chloride in the active ingredient salt solution is 0. It was .1 mol / L. The treated silicon-alumina oxide was immersed in this active ingredient salt solution for 8 hours, dried at 100 ° C. for 4 hours, and calcined at 400 ° C. for 5 hours to obtain a catalyst.
［実施例８］
２．０ｇのシリコン・アルミナ酸化物（アルミニウム含有量５％）を秤量し、２ｍＬの２ｍｏｌ／Ｌリン酸溶液に浸漬し、室温で５時間浸漬し、１００℃で５時間乾燥し、６００℃で６時間焼成した。２ｍＬの活性塩溶液を採取した。活性成分塩溶液中のリン酸カルシウム濃度は０．５ｍｏｌ／Ｌであり、活性成分塩溶液中の塩化ルテチウム濃度は０．３ｍｏｌ／Ｌであった。この活性成分塩溶液に、処理されたシリコン・アルミナ酸化物を８時間浸漬した後、１００℃で４時間乾燥させ、４００℃で５時間焼成して、触媒を得た。
[Example 8]
Weigh 2.0 g of silicon-alumina oxide (aluminum content 5%), soak in 2 mL of 2 mol / L phosphoric acid solution, soak at room temperature for 5 hours, dry at 100 ° C. for 5 hours, at 600 ° C. It was baked for 6 hours. A 2 mL active salt solution was collected. The calcium phosphate concentration in the active ingredient salt solution was 0.5 mol / L, and the lutetium chloride concentration in the active ingredient salt solution was 0.3 mol / L. The treated silicon-alumina oxide was immersed in this active ingredient salt solution for 8 hours, dried at 100 ° C. for 4 hours, and calcined at 400 ° C. for 5 hours to obtain a catalyst.
［実施例９］
２．０ｇのシリコン・アルミナ酸化物（アルミニウム含有量５％）を秤量し、２ｍＬの５ｍｏｌ／Ｌ硫酸溶液に浸漬し、室温で５時間浸漬し、１００℃で５時間乾燥させ、６００℃で６時間焼成した。２ｍＬの活性塩溶液を採取した。活性成分塩溶液中の硝酸サマリウム濃度は０．１ｍｏｌ／Ｌであり、活性成分塩溶液中の硝酸第二鉄濃度は０．５ｍｏｌ／Ｌであった。処理されたシリコン・アルミナ酸化物をこの活性成分塩溶液に８時間浸漬した後、１００℃で４時間乾燥させ、４００℃で５時間焼成し、触媒を得た。
[Example 9]
Weigh 2.0 g of silicon-alumina oxide (aluminum content 5%), soak in 2 mL of 5 mol / L sulfuric acid solution, soak at room temperature for 5 hours, dry at 100 ° C. for 5 hours, 6 at 600 ° C. Baked for hours. A 2 mL active salt solution was collected. The concentration of samarium nitrate in the active ingredient salt solution was 0.1 mol / L, and the concentration of ferric nitrate in the active ingredient salt solution was 0.5 mol / L. The treated silicon-alumina oxide was immersed in this active ingredient salt solution for 8 hours, dried at 100 ° C. for 4 hours, and calcined at 400 ° C. for 5 hours to obtain a catalyst.
［実施例１０］
２．０ｇのシリコン・アルミナ酸化物（アルミニウム含有量５％）を秤量し、２ｍＬの２ｍｏｌ／Ｌ塩酸溶液に浸漬し、室温で５時間浸漬し、１００℃で５時間乾燥させ、６００℃で６時間焼成した。２ｍＬの活性塩溶液を採取した。活性成分塩溶液中の塩化テルビウム濃度は０．１ｍｏｌ／Ｌであった。活性成分塩溶液に、処理されたシリコン・アルミナ酸化物を８時間浸漬して、１００℃で４時間乾燥させ、４００℃で５時間焼成して、触媒を得た。
[Example 10]
Weigh 2.0 g of silicon-alumina oxide (aluminum content 5%), soak in 2 mL of 2 mol / L hydrochloric acid solution, soak at room temperature for 5 hours, dry at 100 ° C. for 5 hours, 6 at 600 ° C. Baked for hours. A 2 mL active salt solution was collected. The terbium chloride concentration in the active ingredient salt solution was 0.1 mol / L. The treated silicon-alumina oxide was immersed in the active ingredient salt solution for 8 hours, dried at 100 ° C. for 4 hours, and calcined at 400 ° C. for 5 hours to obtain a catalyst.
［実施例１１］
２．０ｇのシリコン・アルミナ酸化物（アルミニウム含有量１０％）を秤量し、２ｍＬの１ｍｏｌ／Ｌ酢酸溶液に浸漬し、室温で５時間浸漬し、１００℃で５時間乾燥させ、６００℃で６時間焼成した。２ｍＬの活性塩溶液を採取した。活性成分塩溶液中の硝酸ネオジム濃度は０．１ｍｏｌ／Ｌであり、活性成分塩溶液中の酢酸亜鉛濃度は０．３ｍｏｌ／Ｌであった。この活性成分塩溶液に、処理されたシリコン・アルミナ酸化物を８時間浸漬した後、１００℃で４時間乾燥させ、４００℃で５時間焼成して、触媒を得た。
[Example 11]
Weigh 2.0 g of silicon-alumina oxide (aluminum content 10%), soak in 2 mL of 1 mol / L acetic acid solution, soak at room temperature for 5 hours, dry at 100 ° C. for 5 hours, 6 at 600 ° C. Baked for hours. A 2 mL active salt solution was collected. The concentration of neodymium nitrate in the active ingredient salt solution was 0.1 mol / L, and the concentration of zinc acetate in the active ingredient salt solution was 0.3 mol / L. The treated silicon-alumina oxide was immersed in this active ingredient salt solution for 8 hours, dried at 100 ° C. for 4 hours, and calcined at 400 ° C. for 5 hours to obtain a catalyst.
［実施例１２］
２．０ｇのシリカを秤量し、２ｍＬの５ｍｏｌ／Ｌモリブデン酸溶液に浸漬し、室温で５時間浸漬し、１００℃で３時間乾燥させ、５００℃で６時間焼成した。２ｍＬの活性成分塩溶液を採取した。活性成分塩溶液中の硝酸マグネシウム濃度は１ｍｏｌ／Ｌであり、活性塩溶液中の硝酸第二鉄濃度は０．２ｍｏｌ／Ｌであった。この活性成分塩溶液に、処理されたシリカを８時間浸漬した後に、１００℃で４時間乾燥させた。４００℃で５時間焼成して、触媒を得た。
[Example 12]
2.0 g of silica was weighed, dipped in 2 mL of 5 mol / L molybdic acid solution, dipped at room temperature for 5 hours, dried at 100 ° C. for 3 hours and calcined at 500 ° C. for 6 hours. A 2 mL active ingredient salt solution was collected. The magnesium nitrate concentration in the active salt solution was 1 mol / L, and the ferric nitrate concentration in the active salt solution was 0.2 mol / L. The treated silica was immersed in this active ingredient salt solution for 8 hours and then dried at 100 ° C. for 4 hours. Baking at 400 ° C. for 5 hours gave a catalyst.
［実施例１３］
２．０ｇのシリカを秤量し、２ｍＬの５ｍｏｌ／Ｌリン酸溶液に浸漬し、室温で８時間浸漬し、１００℃で３時間乾燥し、５００℃で３時間焼成した。２ｍＬの活性成分塩溶液を採取した。活性成分塩溶液中の硝酸イットリウム濃度は０．１ｍｏｌ／Ｌであり、活性塩溶液中の硝酸ニッケル濃度は１ｍｏｌ／Ｌであった。この活性成分塩溶液に、処理されたシリカを８時間浸漬した後に、１００℃で３時間乾燥させ、４００℃で５時間焼成して、触媒を得た。
[Example 13]
2.0 g of silica was weighed, immersed in 2 mL of 5 mol / L phosphoric acid solution, immersed at room temperature for 8 hours, dried at 100 ° C. for 3 hours and calcined at 500 ° C. for 3 hours. A 2 mL active ingredient salt solution was collected. The concentration of ittrium nitrate in the active salt solution was 0.1 mol / L, and the concentration of nickel nitrate in the active salt solution was 1 mol / L. The treated silica was immersed in this active ingredient salt solution for 8 hours, dried at 100 ° C. for 3 hours, and calcined at 400 ° C. for 5 hours to obtain a catalyst.
［実施例１４］
２．０ｇのシリコン・アルミナ酸化物（アルミニウム含有量５％）を秤量し、２ｍＬの１ｍｏｌ／Ｌリン酸溶液に浸漬し、室温で８時間浸漬し、１００℃で３時間乾燥させ、５００℃で３時間焼成した。２ｍＬの活性成分塩溶液を採取した。活性成分塩溶液中の酢酸プラセオジム濃度は０．１ｍｏｌ／Ｌであり、活性成分塩溶液中の硝酸第二鉄濃度は１ｍｏｌ／Ｌであった。この活性成分塩溶液に処理されたシリコン・アルミナ酸化物を８時間浸漬した後、１００℃で３時間乾燥させ、６００℃で５時間焼成して、触媒を得た。
[Example 14]
Weigh 2.0 g of silicon-alumina oxide (aluminum content 5%), soak in 2 mL of 1 mol / L phosphoric acid solution, soak at room temperature for 8 hours, dry at 100 ° C. for 3 hours, at 500 ° C. It was baked for 3 hours. A 2 mL active ingredient salt solution was collected. The praseodymium acetate concentration in the active ingredient salt solution was 0.1 mol / L, and the ferric nitrate concentration in the active ingredient salt solution was 1 mol / L. The treated silicon-alumina oxide was immersed in this active ingredient salt solution for 8 hours, dried at 100 ° C. for 3 hours, and calcined at 600 ° C. for 5 hours to obtain a catalyst.
実施例１、３、５、７、９、１１、及び１３で調製した触媒構造体をキャラクタリゼーションして、Ｋａｎｇｔａ ｉＱ２自動物理化学吸着装置を用いて、７７ＫでＮ2物理吸着及び脱着実験を行った。結果を、表５に示す。 The catalyst structures prepared in Examples 1, 3, 5, 7, 9, 11, and 13 are characterized, and N 2 physical adsorption and desorption experiments are performed at 77K using the Kangta iQ2 automatic physicochemical adsorption device. It was. The results are shown in Table 5.
キャラクタリゼーションの結果によれば、本発明により製造された触媒材料は、大きな比表面積を有し、メソポーラス及びマクロポーラス構造を有するので、活性部位の均一の分布に有利であり、これにより、反応体の拡散及び吸着能力を増大させて、反応性を向上させることができる。 According to the results of characterization, the catalytic materials produced according to the present invention have a large specific surface area and mesoporous and macroporous structures, which is advantageous for the uniform distribution of active sites, thereby the reactants. The diffusion and adsorption capacity of the material can be increased to improve the reactivity.
実施例１の触媒が、Ｔｅｃｎａｉ Ｇ２ Ｆ３０ Ｓ - Ｔｗｉｎ型高分解能透過型電子顕微鏡によって、透過型電子顕微鏡分析された結果が、図１〜４に示されている。図１〜４の左下隅のスケールは、それぞれ２０ｎｍ、５０ｎｍ、１００ｎｍ及び２００ｎｍである。図１から図４から分かるように、金属酸化物粒子は、シリコン・アルミナ酸化物担体に付着している。 The results of the catalyst of Example 1 being analyzed by a transmission electron microscope with a Tecnai G2 F30 S-Twin type high resolution transmission electron microscope are shown in FIGS. 1 to 4. The scales in the lower left corner of FIGS. 1 to 4 are 20 nm, 50 nm, 100 nm, and 200 nm, respectively. As can be seen from FIGS. 1 to 4, the metal oxide particles are attached to the silicon-alumina oxide carrier.
［適用例１］
触媒反応を固定床反応器で行い、イミダゾール系化合物とアルコールをモル比１：１０で混合し、イミダゾール系化合物とアルキル化剤とをフィードポンプで固定床反応器に送り込み、気化器により加熱し、気化された原料混合物をキャリアガスＮ2と共に触媒床中に均一に混合し、触媒の触媒作用下で、アルキル化反応により、得られた混合物を凝縮器で室温まで冷却し、貯蔵タンクに収集した。ここで、触媒は、実施例１で調製した触媒である。イミダゾール系化合物とアルキル化剤との混合物の液体対気速度は、５ｈ-1であった。キャリアガスＮ2対気速度は６００ｈ-1であった。反応温度は２００℃であり、反応時間は２０℃であり、反応時間は５０時間であった。Ａｇｉｌｅｎｔ ５９７７Ａ／７８９０Ｂ ＧＣ - ＭＳガスクロマトグラフ及びＡｇｉｌｅｎｔ ７８９０Ａ（３０ｍ×０．２５ｍｍ×０．３３μｍキャピラリーカラム、水素炎イオン化検出器）を用いて、反応生成物を定性的及び定量的に分析した。反応性能を表６に示す。
[Application example 1]
The catalytic reaction is carried out in a fixed bed reactor, the imidazole compound and alcohol are mixed at a molar ratio of 1:10, and the imidazole compound and the alkylating agent are sent to the fixed bed reactor by a feed pump and heated by a vaporizer. The vaporized raw material mixture was uniformly mixed in the catalyst bed together with the carrier gas N 2 , and the obtained mixture was cooled to room temperature by an alkylation reaction under the catalytic action of the catalyst and collected in a storage tank. .. Here, the catalyst is the catalyst prepared in Example 1. The liquid airspeed of the mixture of the imidazole compound and the alkylating agent was 5h- 1 . The carrier gas N 2 airspeed was 600 h- 1 . The reaction temperature was 200 ° C., the reaction time was 20 ° C., and the reaction time was 50 hours. Reaction products were analyzed qualitatively and quantitatively using an Agilent 5977A / 7890B GC-MS gas chromatograph and an Agilent 7890A (30 m x 0.25 mm x 0.33 μm capillary column, flame ionization detector). The reaction performance is shown in Table 6.
［適用例２］
適用例２の試験は、触媒が実施例２で調製した触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application example 2]
The test of Application Example 2 was carried out according to the method of Application Example 1 under the same reaction conditions and product analysis as in Application Example 1 except that the catalyst was the catalyst prepared in Example 2. The reaction performance is shown in Table 6.
［適用例３］
適用例３の試験は、触媒が実施例３で調製した触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application example 3]
The test of Application Example 3 was carried out according to the method of Application Example 1 under the same reaction conditions and product analysis as in Application Example 1 except that the catalyst was the catalyst prepared in Example 3. The reaction performance is shown in Table 6.
［適用例４］
適用例４の試験は、触媒が実施例４で調製した触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application example 4]
The test of Application Example 4 was carried out according to the method of Application Example 1 under the same reaction conditions and product analysis as in Application Example 1 except that the catalyst was the catalyst prepared in Example 4. The reaction performance is shown in Table 6.
［適用例５］
適用例５の試験は、触媒が実施例５で調製した触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application example 5]
The test of Application Example 5 was carried out according to the method of Application Example 1 under the same reaction conditions and product analysis as in Application Example 1 except that the catalyst was the catalyst prepared in Example 5. The reaction performance is shown in Table 6.
［適用例６］
適用例６の試験は、触媒が実施例６で調製した触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application example 6]
The test of Application Example 6 was carried out according to the method of Application Example 1 under the same reaction conditions and product analysis as in Application Example 1 except that the catalyst was the catalyst prepared in Example 6. The reaction performance is shown in Table 6.
［適用例７］
適用例７の試験は、触媒が実施例７で調製した触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application 7]
The test of Application Example 7 was carried out according to the method of Application Example 1 under the same reaction conditions and product analysis as in Application Example 1 except that the catalyst was the catalyst prepared in Example 7. The reaction performance is shown in Table 6.
［適用例８］
適用例８の試験は、触媒が実施例８で調製した触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application Example 8]
The test of Application Example 8 was carried out according to the method of Application Example 1 under the same reaction conditions and product analysis as in Application Example 1 except that the catalyst was the catalyst prepared in Example 8. The reaction performance is shown in Table 6.
［適用例９］
適用例９の試験は、触媒が実施例９で調製した触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application 9]
The test of Application Example 9 was carried out according to the method of Application Example 1 under the same reaction conditions and product analysis as in Application Example 1 except that the catalyst was the catalyst prepared in Example 9. The reaction performance is shown in Table 6.
［適用例１０］
適用例１０の試験は、触媒が実施例１０で調製した触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application Example 10]
The test of Application Example 10 was carried out according to the method of Application Example 1 under the same reaction conditions and product analysis as in Application Example 1, except that the catalyst was the catalyst prepared in Example 10. The reaction performance is shown in Table 6.
［適用例１１］
適用例１１の試験は、触媒が実施例１１で調製した触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application Example 11]
The test of Application Example 11 was carried out according to the method of Application Example 1 under the same reaction conditions and product analysis as in Application Example 1 except that the catalyst was the catalyst prepared in Example 11. The reaction performance is shown in Table 6.
［適用例１２］
適用例１２の試験は、触媒が実施例１２で調製した触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application 12]
The test of Application Example 12 was carried out according to the method of Application Example 1 under the same reaction conditions and product analysis as in Application Example 1, except that the catalyst was the catalyst prepared in Example 12. The reaction performance is shown in Table 6.
［適用例１３］
適用例１３の試験は、触媒が実施例１３で調製した触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application 13]
The test of Application Example 13 was carried out according to the method of Application Example 1 under the same reaction conditions and product analysis as in Application Example 1, except that the catalyst was the catalyst prepared in Example 13. The reaction performance is shown in Table 6.
［適用例１４］
適用例１４の試験は、触媒が実施例１４で調製した触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application 14]
The test of Application Example 14 was carried out according to the method of Application Example 1 under the same reaction conditions and product analysis as in Application Example 1, except that the catalyst was the catalyst prepared in Example 14. The reaction performance is shown in Table 6.
［適用例１５〜２８］
適用例１５〜２８の試験は、実施例３の触媒２ｇを秤量し、メタノールを用いて、異なるイミダゾール系化合物（具体的な構造については表５を参照。）のメチル化反応を固定床反応器中で実施した。イミダゾール系化合物とアルコールとの混合物の液体対気速度は５ｈ-1であり、キャリアガスＮ2液体対気速度は６００ｈ-1であった。反応温度は４００℃であり、反応時間は５０ｈであった。反応性能を表６に示す。
[Application Examples 15 to 28]
In the tests of Application Examples 15 to 28, 2 g of the catalyst of Example 3 was weighed, and the methylation reaction of different imidazole compounds (see Table 5 for the specific structure) was carried out using methanol in a fixed bed reactor. Conducted inside. The liquid airspeed of the mixture of the imidazole compound and the alcohol was 5h -1 , and the carrier gas N 2 liquid airspeed was 600h -1 . The reaction temperature was 400 ° C. and the reaction time was 50 hours. The reaction performance is shown in Table 6.
［適用例２９］
適用例２９の試験は、適用例１の反応完了後の触媒を用いて、空気中、５００℃で４時間焼成し、活性化して再生して触媒を回収する方法により、回収された触媒であることを除いて、適用例１と同じ反応条件及び生成物分析で、適用例１の方法に従って行った。反応性能を表６に示す。
[Application 29]
The test of Application Example 29 is a catalyst recovered by a method of calcining in air at 500 ° C. for 4 hours, activating and regenerating the catalyst after completion of the reaction of Application Example 1 to recover the catalyst. Except for this, the same reaction conditions and product analysis as in Application Example 1 were performed according to the method of Application Example 1. The reaction performance is shown in Table 6.
表６において、収率計算方法は、収率＝実際の目標生成物生成量／理論目標生成物生成量×１００％であり、表６における収率と選択率との関係は、収率＝転化率×選択率である。 In Table 6, the yield calculation method is yield = actual target product production amount / theoretical target product production amount × 100%, and the relationship between the yield and the selectivity in Table 6 is yield = conversion. Rate x selection rate.
表６の試験結果によれば、本発明によって提供される触媒は様々なイミダゾール系化合物とアルキル化剤との反応を触媒することができる。本発明によって提供される触媒を用いて、Ｎ-アルキルイミダゾール系化合物を調製する方法は簡単であり、条件が温和であり、生成物の選択率及び収率は比較的高く、収率が５６％〜９２％である。かつ、その触媒は活性化して再生し、再使用することができる。 According to the test results in Table 6, the catalyst provided by the present invention can catalyze the reaction of various imidazole compounds with alkylating agents. The method of preparing an N-alkylimidazole compound using the catalyst provided by the present invention is simple, the conditions are mild, the product selectivity and yield are relatively high, and the yield is 56%. ~ 92%. Moreover, the catalyst can be activated, regenerated and reused.
［適用例３０］
適用例３０の試験は、５０ｍｇの実施例１で調製した触媒、５ｍｍｏｌ（３４０ｍｇ）のイミダゾール、及び２０ｍｍｏｌ（６４０ｍｇ）メタノールをそれぞれ秤量し、それらが投入された４０ｍＬのマグネチックスターラー付き反応器を密封した後、システム中の空気をＨ2で３回置換し、加熱して撹拌した。１００℃に加熱した後、６時間保持した。反応を停止し、室温までに冷却し、触媒を濾過により反応混合液から回収した。
[Application Example 30]
The test of Application Example 30 weighed 50 mg of the catalyst prepared in Example 1 and 5 mmol (340 mg) of imidazole and 20 mmol (640 mg) of methanol, respectively, and sealed the reactor with a 40 mL magnetic stirrer into which they were charged. After that, the air in the system was replaced with H 2 three times, and the mixture was heated and stirred. After heating to 100 ° C., it was held for 6 hours. The reaction was stopped, cooled to room temperature, and the catalyst was recovered from the reaction mixture by filtration.
Ａｇｉｌｅｎｔ ５９７７Ａ ／ ７８９０Ｂ ＧＣ - ＭＳガスクロマトグラフ及びＡｇｉｌｅｎｔ ７８９０Ａ（３０ｍ×０．２５ｍｍ×０．３３μｍキャピラリーカラム、水素炎イオン検出器）を用いて、反応生成物を定性的及び定量的に分析した。その結果を表７に示す。 Reaction products were analyzed qualitatively and quantitatively using an Agilent 5977A / 7890B GC-MS gas chromatograph and an Agilent 7890A (30 m x 0.25 mm x 0.33 μm capillary column, flame ion detector). The results are shown in Table 7.
［適用例３１］
適用例３１の試験は、使用した触媒が実施例２で調製した触媒であることを除いて、適用例３０と同じ方法で行った。結果を表７に示す。
[Application Example 31]
The test of Application Example 31 was carried out in the same manner as in Application Example 30, except that the catalyst used was the catalyst prepared in Example 2. The results are shown in Table 7.
［適用例３２］
適用例３２の試験は、使用した触媒が実施例３で調製した触媒であることを除いて、適用例３０と同じ方法で行った。結果を表７に示す。
[Application 32]
The test of Application Example 32 was carried out in the same manner as in Application Example 30, except that the catalyst used was the catalyst prepared in Example 3. The results are shown in Table 7.
［適用例３３］
適用例３２の試験は、使用した触媒が実施例４で調製した触媒であることを除いて、適用例３０と同じ方法で行った。結果を表７に示す。
[Application 33]
The test of Application Example 32 was carried out in the same manner as in Application Example 30, except that the catalyst used was the catalyst prepared in Example 4. The results are shown in Table 7.
［適用例３４］
適用例３４の試験は、使用した触媒が実施例５で調製した触媒であることを除いて、適用例３０と同じ方法で行った。結果を表７に示す。
[Application 34]
The test of Application Example 34 was carried out in the same manner as in Application Example 30, except that the catalyst used was the catalyst prepared in Example 5. The results are shown in Table 7.
［適用例３５］
適用例３５の試験は、使用した触媒が実施例６で調製した触媒であることを除いて、適用例３０と同じ方法で行った。結果を表７に示す。
[Application 35]
The test of Application Example 35 was carried out in the same manner as in Application Example 30, except that the catalyst used was the catalyst prepared in Example 6. The results are shown in Table 7.
［適用例３６］
適用例３６の試験は、使用した触媒が実施例７で調製した触媒であることを除いて、適用例３０と同じ方法で行った。結果を表７に示す。
[Application 36]
The test of Application Example 36 was carried out in the same manner as in Application Example 30, except that the catalyst used was the catalyst prepared in Example 7. The results are shown in Table 7.
［適用例３７］
適用例３７の試験は、使用した触媒が実施例８で調製した触媒であることを除いて、適用例３０と同じ方法で行った。結果を表７に示す。
[Application 37]
The test of Application Example 37 was carried out in the same manner as in Application Example 30, except that the catalyst used was the catalyst prepared in Example 8. The results are shown in Table 7.
［適用例３８］
適用例３８の試験は、使用した触媒が実施例９で調製した触媒であることを除いて、適用例３０と同じ方法で行った。結果を表７に示す。
[Application 38]
The test of Application Example 38 was carried out in the same manner as in Application Example 30, except that the catalyst used was the catalyst prepared in Example 9. The results are shown in Table 7.
［適用例３９］
適用例３９の試験は、使用した触媒が実施例１０で調製した触媒であることを除いて、適用例３０と同じ方法で行った。結果を表７に示す。
[Application 39]
The test of Application Example 39 was carried out in the same manner as in Application Example 30, except that the catalyst used was the catalyst prepared in Example 10. The results are shown in Table 7.
［適用例４０］
適用例４０の試験は、使用した触媒が適用例３２で調製した触媒であることを除いて、適用例３０と同じ方法で行った。結果を表７に示す。
[Application Example 40]
The test of Application Example 40 was carried out in the same manner as in Application Example 30 except that the catalyst used was the catalyst prepared in Application Example 32. The results are shown in Table 7.
表７において、収率の計算方法は収率＝実際の目標生成物生成量／理論目標生成物生成量×１００％であり、表７における収率と選択率との関係は、収率＝転化率×選択率である。 In Table 7, the method of calculating the yield is yield = actual target product production amount / theoretical target product production amount × 100%, and the relationship between the yield and the selectivity in Table 7 is yield = conversion. Rate x selection rate.
表７の試験結果によれば、本発明により提供される触媒を用いて、Ｎ-アルキルイミダゾール系化合物を調製する方法は方法が簡単であり、条件が穏やかであり、かつ生成物の選択率及び収率は高く、収率は５５〜９３％であった。また、反応終了後、本発明により提供される触媒は、反応液を濾過して、固体を収集して触媒を回収するので、触媒を再利用することができ、良好な性能を有する。 According to the test results in Table 7, the method for preparing an N-alkylimidazole compound using the catalyst provided by the present invention is simple, the conditions are mild, and the product selectivity and product selectivity and The yield was high, with a yield of 55-93%. Further, after the reaction is completed, the catalyst provided by the present invention filters the reaction solution to collect the solid and recovers the catalyst, so that the catalyst can be reused and has good performance.
上述の説明は本発明の好ましい実施形態にすぎず、当業者は本発明の原理から逸脱することなく、いくつかの改良及び修正を行うこともでき、改良及び修正された発明は、本発明の保護範囲とみなされるべきである。 The above description is merely a preferred embodiment of the invention, and one of ordinary skill in the art can make some improvements and modifications without departing from the principles of the invention, the improved and modified inventions of the invention. It should be considered a scope of protection.
Claims (10)
前記触媒は、Ｎ-アルキルイミダゾール系化合物を得るための、イミダゾール系化合物とアルキル化剤とのアルキル化反応に作用する
こと、を特徴とする触媒。 A catalyst containing an active ingredient and an acid-treated carrier, wherein the carrier is silicon-alumina oxide and / or silica, the active ingredient comprises a metal oxide, and the metal element in the metal oxide is zirconium. , niobium, seen containing hafnium, tantalum, calcium, magnesium, copper, nickel, iron, cobalt, zinc, and one or more of the rare earth elements,
The catalyst acts on an alkylation reaction between an imidazole compound and an alkylating agent to obtain an N-alkylimidazole compound.
Catalyst and the child, the features.
（２）工程（１）で得られた、酸処理した担体を活性成分塩溶液に浸漬した後、順に乾燥、焼成処理して触媒を得る工程と、
を含むこと、を特徴とする請求項１から３のいずれか一項に記載の触媒を製造する製造方法。 (1) A step of immersing the carrier in an acid solution and then drying and firing the carrier in order to obtain an acid-treated carrier.
(2) A step of immersing the acid-treated carrier obtained in step (1) in an active ingredient salt solution, and then drying and firing in order to obtain a catalyst.
The method for producing a catalyst according to any one of claims 1 to 3, wherein the catalyst is produced.
前記活性成分塩溶液の濃度が、０．１〜３ｍｏｌ／Ｌであること、を特徴とする請求項４に記載の製造方法。 The active ingredient salt solution in the step (2) contains one or more of the active ingredient hydrochloride solution, the active ingredient nitrate solution, the active ingredient sulfate solution, the active ingredient phosphate solution and the acetate solution.
The production method according to claim 4, wherein the concentration of the active ingredient salt solution is 0.1 to 3 mol / L.
前記アルキル化反応の温度は１００〜４００℃であり、前記触媒が、請求項１から３のいずれか一項に記載の触媒、又は請求項４から７のいずれか一項に記載の方法によって製造された触媒である
ことを特徴とする製造方法。 A method for producing an N-alkylimidazole compound, which comprises a step of alkylating an imidazole compound and an alkylating agent under the action of a catalyst to obtain an N-alkylimidazole compound.
The temperature of the alkylation reaction is 100 to 400 ° C., and the catalyst is produced by the catalyst according to any one of claims 1 to 3 or the method according to any one of claims 4 to 7. A manufacturing method characterized by being a catalyst.
前記アルキル化剤は、アルデヒド、ケトンまたはアルコールを含み、
前記アルデヒドは、式ＩＩ−１〜式ＩＩ−３のいずれかに示される構造を有し、
前記ケトンは、式ＩＩＩ−１〜式ＩＩＩ−３のいずれかに示される構造を有し、
前記アルコールは、式ＩＶ-１から式ＩＶ-１２のいずれか１つに示される構造を有し、
前記式ＩＶ-１において、Ｒ1、Ｒ2はそれぞれ独立して、炭素原子１〜１８のアルキル基または水素から選択され、前記式ＩＶ-６〜式ＩＶ-１２において、Ｒ1は炭素原子１〜１８のアルカン、水素、メトキシ基、フェニル基、フェノキシ基、フッ素基、塩素基、臭素基またはヨウ素からなる群から選択され、前記式ＩＶ-７〜式ＩＶ-９において、Ｒ2は、炭素原子１〜１８個のアルキル基、水素、メトキシ、フェニル、フェノキシ、フッ素、塩素、臭素またはヨウ素からなる群から選択され、前記式ＩＶ−２において、ｍは１〜６の整数であり、前記式ＩＶ-３において、ｎは２〜８の整数であり、前記式ＩＶ-６、式ＩＶ-７及び式ＩＶ-９において、ｎは独立して０〜４の整数であることを特徴とする製造方法。 The production method according to claim 9, wherein the imidazole-based compound has a structure represented by any of formulas I-1 to I-3.
The alkylating agent comprises an aldehyde, a ketone or an alcohol and contains
The aldehyde has a structure represented by any of formulas II-1 to II-3.
The ketone has a structure represented by any of formulas III-1 to III-3.
The alcohol has a structure represented by any one of formulas IV-1 to IV-12.
In the formula IV-1, R 1 and R 2 are independently selected from the alkyl group of carbon atoms 1 to 18 or hydrogen, and in the formulas IV-6 to IV-12, R 1 is carbon atom 1. to 18 alkane, hydrogen, methoxy, phenyl group, a phenoxy group, a fluorine group, chlorine group, selected from the group consisting of bromine group or iodine, in the formula IV-. 7 to formula IV-9, R 2 is carbon It is selected from the group consisting of an alkyl group having 1 to 18 atoms, hydrogen, methoxy, phenyl, phenoxy, fluorine, chlorine, bromine or iodine. In the above formula IV-2, m is an integer of 1 to 6 and the above formula. In IV-3, n is an integer of 2 to 8, and in the formulas IV-6, IV-7 and IV-9, n is independently an integer of 0 to 4. Method.
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