JPS63250357A - Production of chlorobenzonitriles - Google Patents
Production of chlorobenzonitrilesInfo
- Publication number
- JPS63250357A JPS63250357A JP62084596A JP8459687A JPS63250357A JP S63250357 A JPS63250357 A JP S63250357A JP 62084596 A JP62084596 A JP 62084596A JP 8459687 A JP8459687 A JP 8459687A JP S63250357 A JPS63250357 A JP S63250357A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- component
- element selected
- vanadium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 72
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical class ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052770 Uranium Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 2
- 229910052790 beryllium Inorganic materials 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 abstract description 16
- 229910052787 antimony Inorganic materials 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 50
- 239000002994 raw material Substances 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000011651 chromium Substances 0.000 description 12
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- DMEDNTFWIHCBRK-UHFFFAOYSA-N 1,3-dichloro-2-methylbenzene Chemical compound CC1=C(Cl)C=CC=C1Cl DMEDNTFWIHCBRK-UHFFFAOYSA-N 0.000 description 9
- RYMMNSVHOKXTNN-UHFFFAOYSA-N 1,3-dichloro-5-methyl-benzene Natural products CC1=CC(Cl)=CC(Cl)=C1 RYMMNSVHOKXTNN-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- OHDYZVVLNPXKDX-UHFFFAOYSA-N 2,3-dichlorobenzonitrile Chemical compound ClC1=CC=CC(C#N)=C1Cl OHDYZVVLNPXKDX-UHFFFAOYSA-N 0.000 description 5
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 5
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- 150000002823 nitrates Chemical class 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 4
- -1 vanadium halides Chemical class 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 2
- FUNUTBJJKQIVSY-UHFFFAOYSA-N 2,4-Dichlorotoluene Chemical compound CC1=CC=C(Cl)C=C1Cl FUNUTBJJKQIVSY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 159000000014 iron salts Chemical class 0.000 description 2
- 239000007788 liquid Substances 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
- 150000002739 metals Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 2
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadis***e 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- GRUHREVRSOOQJG-UHFFFAOYSA-N 2,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C(Cl)=C1 GRUHREVRSOOQJG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- OPCVYFAEEVMIFL-UHFFFAOYSA-N [V].[Fe].[Sb] Chemical compound [V].[Fe].[Sb] OPCVYFAEEVMIFL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Substances N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- NCCSSGKUIKYAJD-UHFFFAOYSA-N rubidium(1+) Chemical compound [Rb+] NCCSSGKUIKYAJD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- SITVSCPRJNYAGV-UHFFFAOYSA-L tellurite Chemical compound [O-][Te]([O-])=O SITVSCPRJNYAGV-UHFFFAOYSA-L 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はクロルトルエン類の気相接触アンモ酸化反応に
よるクロルベンゾニトリル類の製造方法に関する。更に
詳しくは鉄・バナジウムおよびアンチモンを含む金属酸
化物触媒を使用するクロルトルエン類の気相接触アンモ
酸化反応によるクロルベンゾニトリル類の製造方法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing chlorobenzonitrile by gas phase catalytic ammoxidation reaction of chlorotoluene. More specifically, the present invention relates to a method for producing chlorobenzonitrile by gas-phase catalytic ammoxidation reaction of chlorotoluene using a metal oxide catalyst containing iron, vanadium, and antimony.
クロルベンゾニトリル類は農薬、医薬、染料などの重要
な中間体として利用されている。特に２．６．ジクロル
ベンゾニトリルは除草剤として重要であるばかりでなく
、近年殺虫剤の原料としても極めて重要になってきてい
る。Chlorobenzonitrile is used as an important intermediate for agricultural chemicals, medicines, dyes, etc. Especially 2.6. Dichlorobenzonitrile is not only important as a herbicide, but has also become extremely important as a raw material for insecticides in recent years.
クロルトルエン類の気相接触アンモ酸化反応により対応
するクロルベンゾニトリルを得る方法には、従来触媒と
して酸化バナジウム系触媒を用いることが知られている
。モノクロルトルエンを原料としてモノクロルベンゾニ
トリルを製造する方法では、たとえばｖ−ｐ系触媒（特
公昭５５−４９０７０号、特開昭５３−９０２３８号、
特開昭５６−７７２５０号各公報１、Ｖ−Ｃｒ系触媒（
特公昭６１−４３８８号、特公昭５７−２７１０４
号、特公昭５７−２６５９４号、特公昭４３−１０６２
３号、特公昭３８−１５３７１号各公報１、ｖ −ｓｂ
系触媒（特公昭４２−７６１１号公報）などが、またジ
クロルトルエンを原料としてジクロルベンゾニトリルを
製造する方法では、たとえばＶ系触媒（特公昭３８−１
５３７１、特公昭４３−１０６２３号各公報号各Ｖ −
Ｆｅ系触媒（特公昭４２−７９０２号、特公昭４３−５
３８６号各公１）、Ｖ−Ｐ系触媒（特公昭５３−１２１
７３８号公報）などがある０通常、これらの触媒は、担
体としてアルミナ、−シリカ、チタニアなどが用いられ
、固定床触媒として使用されることが多い、しかし、こ
れらの触媒は取得目的物の収率の点で充分であるとは云
えない。たとえば、２．６−ベンゾニトリルを製造する
場合、収率はＶ−Ｃｒ−ＡＩＩＯｓ触媒で５６％、Ｖ−
Ｆｅ−ＡｌｚＯｚ触媒テロ８〜７９％、Ｖ−Ｐ−Ｃｏ−
Ｓｉｎｇ触媒テア４〜７５％である。Conventionally, it is known that a vanadium oxide catalyst is used as a catalyst in a method for obtaining the corresponding chlorobenzonitrile by gas-phase catalytic ammoxidation reaction of chlorotoluenes. In the method of producing monochlorobenzonitrile using monochlorotoluene as a raw material, for example, v-p type catalysts (Japanese Patent Publication No. 55-49070, JP-A No. 53-90238,
JP-A-56-77250, each publication 1, V-Cr catalyst (
Special Publication No. 61-4388, Special Publication No. 57-27104
No., Special Publication No. 57-26594, Special Publication No. 43-1062
No. 3, Special Publication No. 38-15371, each publication 1, v-sb
In the method for producing dichlorobenzonitrile using dichlorotoluene as a raw material, for example, a V-based catalyst (Japanese Patent Publication No. 1983-1983) is used.
5371, Special Publication No. 43-10623, each publication number V -
Fe-based catalyst (Special Publication No. 42-7902, Special Publication No. 43-5
No. 386 (1), V-P system catalyst (Special Publication No. 121/1986)
738 Publication) etc. 0 These catalysts usually use alumina, silica, titania, etc. as a carrier and are often used as fixed bed catalysts. It cannot be said that the rate is sufficient. For example, when producing 2,6-benzonitrile, the yield was 56% with V-Cr-AIIOs catalyst;
Fe-AlzOz catalyst terror 8-79%, V-P-Co-
Sing catalyst tear is 4-75%.
ジクロルトルエンの気相接触アンモ酸化反応によるジク
ロルベンゾニトリルの製造は、モノクロルトルエンの気
相接触アンモ酸化反応によるモノクロルベンゾニトリル
の製造の場合に比べて、その収率は低い。また、モノク
ロルトルエンのアンモ酸化に用いた触媒をジクロルトル
エンのアンモ酸化に用いた場合には、得られるジクロル
ベンゾニトリルの収率はモノクロルベンゾニトリルの製
造の場合より一般に低下する（特公昭３ト１５３７１号
、特開昭５３−１２１７３８号各公報）１これは、芳香
核中にあるクロル基は非常に活性で、シアン基の存在に
よって核より脱離する傾向があり、クロル基の数が殖え
る程、その傾向が強（なるためと思われる。The yield of dichlorobenzonitrile produced by gas-phase catalytic ammoxidation of dichlorotoluene is lower than that of monochlorobenzonitrile produced by vapor-phase catalytic ammoxidation of monochlorotoluene. Furthermore, when the same catalyst used for ammoxidation of monochlorotoluene is used for ammoxidation of dichlorotoluene, the yield of dichlorobenzonitrile obtained is generally lower than that for the production of monochlorobenzonitrile (Japanese Patent Publication No. 3 15371 and JP-A No. 53-121738) 1 This is because the chlorine groups in the aromatic nucleus are very active and tend to detach from the nucleus due to the presence of cyanide groups, and the number of chlorine groups increases. The more they multiply, the stronger this tendency becomes.
通常、気相接触アンモ酸化反応は、固定床反応器又は流
動床反応器にて行われる。一般的に大きな発熱を伴う反
応を固定床反応器で行うと、局部加熱が生じ昌く触媒層
の全域にわたって、その温度を均一に保つことが難しく
、特に工業的規模の装置においては、非常に困難である
。クロルトルエン類の気相接触アンモ酸化反応によるク
ロルベンゾニトリル類を製造する場合もこれに該当する
。Gas phase catalytic ammoxidation reactions are usually carried out in fixed bed reactors or fluidized bed reactors. Generally, when a reaction that generates a large amount of heat is carried out in a fixed bed reactor, it is difficult to maintain the temperature uniformly over the entire area of the catalyst bed, which causes local heating, which is especially difficult in industrial scale equipment. Have difficulty. This also applies to the production of chlorobenzonitrile by gas phase catalytic ammoxidation reaction of chlorotoluene.
固定床反応に対して流動床反応の方が温度制御が容易で
かつ局部加熱が非常に少ないことは知られている。しか
し、局部加熱の問題は、クロルトルエン類のアンモ酸化
反応においては他の場合とは、比較にならない程有害で
ある０反応温度が高温になる程、クロル基の脱離が増加
する。すなわち、目的とする特定のクロルベンゾニトリ
ルが生成しても局部加熱帯域で多量のクロル基の離脱が
促進され、そのため目的とする生成物の収率が著しく低
下する。しかも離脱したクロル基は、反応帯域に存在す
るアンモニアと結合して塩化アンモニウムを生成する。It is known that temperature control is easier in fluidized bed reactions than in fixed bed reactions and local heating is much less. However, the problem of local heating is incomparably more harmful in the ammoxidation reaction of chlorotoluenes than in other cases.The higher the reaction temperature, the more the elimination of chloro groups increases. That is, even if the desired specific chlorobenzonitrile is produced, the removal of a large amount of chloro groups is promoted in the local heating zone, resulting in a significant decrease in the yield of the desired product. Moreover, the separated chloro group combines with ammonia present in the reaction zone to produce ammonium chloride.
これは高い昇華点（３３５℃）を有するため、反応器出
口付近ですぐに凝結し易く、パイプを閉塞する傾向があ
る。固定床で反応を行う場合、局部加熱をさけるため、
原料ガスを不活性な気体で希釈するなどの適当な手段を
講じなければならず、設備の大型化をまねき、経済的に
は問題がある。流動床ではこの点の問題は、軽減される
ものの、なお十分に良好な性能の触媒を開発することが
望まれている。Since it has a high sublimation point (335° C.), it tends to condense quickly near the reactor outlet and tends to clog the pipes. When conducting a reaction in a fixed bed, to avoid local heating,
Appropriate measures such as diluting the raw material gas with an inert gas must be taken, which leads to an increase in the size of the equipment and is economically problematic. Although this problem is alleviated in a fluidized bed, it is still desired to develop a catalyst with sufficiently good performance.
本発明の目的は、工業的に有利に実施することのできる
クロルベンゾニトリル類の製造方法を提供することにあ
り、より具体的には活性、物性共に良好な鉄、バナジウ
ム、アンチモン系酸化物触媒を用いるアンモ酸化によっ
てクロルトルエン類より対応するクロルベンゾニトリル
類を高収率で取得する方法を提供することにある。The purpose of the present invention is to provide a method for producing chlorobenzonitrile that can be carried out industrially advantageously, and more specifically, to provide an iron, vanadium, and antimony-based oxide catalyst with good activity and physical properties. The object of the present invention is to provide a method for obtaining the corresponding chlorobenzonitrile from chlorotoluene in high yield by ammoxidation using chlorotoluene.
〔問題点を解決するための手段］
本発明によるクロルベンゾニトリル類の製造方法は、分
子中に少なくとも１個のクロル基を有するクロルトルエ
ン、アンモニアおよび酸素を、下記実験式で表わされる
金属酸化物触媒の存在下に反応せしめることを特徴とす
るものである。[Means for Solving the Problems] The method for producing chlorobenzonitrile according to the present invention involves converting chlorotoluene, ammonia, and oxygen having at least one chloro group in the molecule into a metal oxide represented by the following empirical formula. It is characterized in that the reaction is carried out in the presence of a catalyst.
実験式 ＦｅｍＶ）ＣｒｃＳｂＪａＹｒＺｇＱｈＯｔ
（ＳｉＯｚ）ｊ（ただし、ＸはＣｏ、 Ｎｉ＋ Ｓｎ、
Ｕ＋ Ｃｕ、 Ｍｎ、 Ｔｉｔ Ｃｅ。Empirical formula FemV)CrcSbJaYrZgQhOt
(SiOz)j (X is Co, Ni+Sn,
U+ Cu, Mn, Tit Ce.
Ｂｅ、Ｌｇ、Ｃａｔ Ｓｒ、Ｂａｔ Ｙ＋ Ｌａ
、ｚｒ、Ｈｆ＋ Ｎｂ、Ｔａ。Be, Lg, Cat Sr, Bat Y+ La
, zr, Hf+ Nb, Ta.
Ｒｅ、Ｒｕ、Ｏｓ、Ｒｈ＋ Ｉｒ、Ｐｄ、Ｐｔ、Ａｇ
＋ Ｚｎ＋ ｃｄ、Ａｌ、Ｇａ、 Ｉｎ、 Ｇｏお
よびＰｂからなる群から選ばれた少なくとも１種の元素
であり、ＹはＭｏおよび／またはＷであり、ＺはＰ＋
Ｂ＋ ＢｉおよびＴｅからなる群から選ばれた少なくと
も１種の元素であり、ＱはＬｉ。Re, Ru, Os, Rh+ Ir, Pd, Pt, Ag
+ Zn+ is at least one element selected from the group consisting of cd, Al, Ga, In, Go and Pb, Y is Mo and/or W, and Z is P+
B+ At least one element selected from the group consisting of Bi and Te, and Q is Li.
Ｎａ、Ｌ Ｒｂ＋ ＣｓおよびＴｉからなる群から選ば
れた少なくとも１種の元素であり、添字ａｔ Ｊ （−
＋ ｄ＋” ’＋ ｇ＋ ！Ｉｔ １ は原子比を示し
、ａ＝１０のとき、ｂ＝０．０５〜１０． ｃ＝ Ｏ〜
２５、ｄ−５〜６０、ｅ−０〜１０、ｆ・０〜５、ｇ・
０〜５、ｈ＝ｏ〜２、ｌ・上記各成分が結合して生成す
る酸化物に対応する数およびｊ−２０〜２００を示す、
）
以下、本発明を具体的に説明する。At least one element selected from the group consisting of Na, L Rb+ Cs and Ti, with the subscript at J (-
+ d+” '+ g+ !It 1 indicates the atomic ratio, and when a=10, b=0.05~10. c= O~
25, d-5~60, e-0~10, f・0~5, g・
0 to 5, h = o to 2, l - Indicates the number corresponding to the oxide formed by combining each of the above components and j-20 to 200,
) The present invention will be specifically explained below.
分子中に少なくとも１個のクロル基を有するクロルトル
エン類のアンモ酸化は公知の技術であって、本発明と矛
盾しない限り公知の技術を利用することができる。Ammoxidation of chlorotoluenes having at least one chloro group in the molecule is a known technique, and any known technique can be used as long as it does not contradict the present invention.
本発明は、この反応をシリカに鉄、バナジウムおよびア
ンチモンの各成分を担持させてなる酸化物組成物あるい
はこれら成分の外に、更に他の成分たとえばクロム、銅
、亜鉛、モリブデン、タングステン、テルル、リン等を
含有せしめた酸化物組成物の存在下に実施するものであ
る。The present invention carries out this reaction using an oxide composition in which silica supports each component of iron, vanadium, and antimony, or in addition to these components, other components such as chromium, copper, zinc, molybdenum, tungsten, tellurium, This is carried out in the presence of an oxide composition containing phosphorus or the like.
本発明の重要な点は使用する触媒にあり、この触媒は前
記実験式で示した触媒成分を含有するいかなる触媒でも
よい、好ましい触媒は、前記式においてＸがＣａｔ Ｎ
Ｉ＋ Ｓｎ１１１１ Ｃ１１ｌ ＭＦＩＩ Ｔｌｌ Ｃ
ａｔ Ｆ’ｇ＋Ｃａ、 Ｓｒ＋ ｌ、ａｔ Ｚｒ、 Ｎ
ｂ＋ Ｔａ、 Ｐｄ、 ＺｎおよびＡｔ、、 ＱがＬｉ
＋ Ｎａ＋ Ｋ＋ １７１）およびＣｓ、ｂ＝０．１〜
Ｂ、ｃ−Ｑ〜２０、ｄ −８〜４５、ｅ＝−θ〜７、ｆ
−０〜３、ｇ−Ｏ〜３、ｈ−０〜１、ｊ−２５〜１００
なる範囲内にある酸化物触媒組成物である。An important aspect of the present invention lies in the catalyst used, and this catalyst may be any catalyst containing the catalyst components shown in the above empirical formula. A preferred catalyst is a catalyst in which X is Cat N
I+ Sn1111 C11l MFII Tll C
at F'g+Ca, Sr+ l, at Zr, N
b+ Ta, Pd, Zn and At, Q is Li
+ Na+ K+ 171) and Cs, b=0.1~
B, c-Q~20, d -8~45, e=-θ~7, f
-0~3, g-O~3, h-0~1, j-25~100
The oxide catalyst composition falls within the range.
触媒中で触媒成分がどのような形態をしているかは必ず
しも明らがではないが、触媒調製過程に高温焼成工程が
含まれていることがら、それぞれの金属元素はアンチモ
ンと特定の複合酸化物を形成したり、安定な固溶体を形
成したりしていることが考えられる。Although it is not necessarily clear what form the catalyst components take in the catalyst, since the catalyst preparation process includes a high-temperature firing process, each metal element is composed of antimony and a specific composite oxide. It is conceivable that they form a stable solid solution.
本発明の触媒は公知の任意の方法で製造することができ
る。たとば、固定床用触媒を製造する場合には各成分よ
り調製したスラリーを乾固し、１’！和し、円柱状また
は球状に成型し、これを約２００℃から約８００ ”Ｃ
の温度で約０．５時間ないし約５０時間焼成することに
よって製造することができるし、また流動床用触媒を製
造する場合には各成分より調製したスラリーを適当な手
段で噴霧乾燥して微粒状に成型し、それを前記のような
高温で焼成することによって製造することができる。好
ましくは、本発明者らの提案による特願昭６２−２１７
９１号明ｔａ書に記載の方法に従って、アンチモン、鉄
およびシリカを必須成分として含む金属酸化物組成物を
約５００°Ｃないし約９５０ ’Ｃの温度で焼成するこ
とにより調製した基体触媒にバナジウム化合物含有溶液
を含浸し、乾燥後、約３００℃ないし約８００℃の温度
で焼成することによって製造する。これにより活性、物
性共に良好な触媒が再現性よく得られる。The catalyst of the present invention can be produced by any known method. For example, when manufacturing a fixed-bed catalyst, a slurry prepared from each component is dried and 1'! 200℃ to 800''C.
When producing a fluidized bed catalyst, a slurry prepared from each component is spray-dried using an appropriate means to form fine particles. It can be manufactured by molding it into a shape and firing it at a high temperature as described above. Preferably, the patent application 1986-217 proposed by the present inventors
A vanadium compound is added to a base catalyst prepared by calcining a metal oxide composition containing antimony, iron and silica as essential components at a temperature of about 500° C. to about 950° C. according to the method described in Patent No. 91. It is manufactured by impregnating a solution containing the material, drying, and then firing at a temperature of about 300°C to about 800°C. As a result, a catalyst having good activity and physical properties can be obtained with good reproducibility.
本発明の触媒を構成している各成分の出発原料としては
、それぞれの成分の酸化物、水酸化物、塩化物、硝酸塩
など多くの種類のものの中から選ぶことができる。The starting materials for each component constituting the catalyst of the present invention can be selected from among many types of oxides, hydroxides, chlorides, nitrates, etc. of each component.
鉄成分の原料としては、たとえば酸化第一鉄、酸化第二
鉄、四二酸化鉄や硝酸鉄、塩化鉄のような無機質の鉄塩
および酢酸鉄、蓚酸鉄のような有機質の鉄塩類が用いら
れる。As raw materials for the iron component, for example, inorganic iron salts such as ferrous oxide, ferric oxide, iron tetroxide, iron nitrate, and iron chloride, and organic iron salts such as iron acetate and iron oxalate are used. .
バナジウム成分の原料としては、たとえば五酸化バナジ
ウム、メタバナジン酸アンモニウム、蓚酸バナジル、ハ
ロゲン化バナジウム類などが用いられる。As raw materials for the vanadium component, for example, vanadium pentoxide, ammonium metavanadate, vanadyl oxalate, vanadium halides, etc. are used.
アンチモン成分の原料としては、たとえば二酸化アンチ
モン、四酸化アンチモン、金属アンチモンの硝酸酸化物
、アンチモンの鉱酸、有機酸塩などが用いられる。As the raw material for the antimony component, for example, antimony dioxide, antimony tetroxide, nitrate oxide of antimony metal, mineral acid of antimony, organic acid salt, etc. are used.
クロム成分の原料としては、たとえば硝酸クロム、１Ｍ
クロム、重クロム酸アンモニウム、クロム酸化物、無水
クロム酸などが用いられる。As a raw material for the chromium component, for example, chromium nitrate, 1M
Chromium, ammonium dichromate, chromium oxide, chromic anhydride, etc. are used.
ｘ成分中、コバルト、ニッケル、ウラン、マンガンおよ
びセリウム成分の原料としてはそれら金属の可溶性塩類
、特に硝酸塩を用いるのが便利であるが、それら金属の
塩化物を使用することもできる。スズおよびチタン成分
の原料としては、酸化物、塩化物、硝酸塩などを用いる
のがよい、スズ成分については、金属スズを硝酸に溶解
したもの、酸化第一スズ、酸化第二スズも用いられる。As raw materials for the cobalt, nickel, uranium, manganese and cerium components in component x, it is convenient to use soluble salts of these metals, especially nitrates, but chlorides of these metals can also be used. As raw materials for the tin and titanium components, it is preferable to use oxides, chlorides, nitrates, etc. As for the tin component, metal tin dissolved in nitric acid, stannous oxide, and stannic oxide can also be used.
銅成分の原料としては、金属銅または酸化銅を硝酸に溶
解したもの、硝酸塩、塩化銅を用いることができる。マ
グネシウムの原料としては硝酸マグネシウム、酸化マグ
ネシウムなど、ジルコニウム成分の原料としては、オキ
シ硝酸ジルコニウム、水酸化ジルコニウムなどを用いる
ことができる。As raw materials for the copper component, metallic copper or copper oxide dissolved in nitric acid, nitrates, and copper chloride can be used. As raw materials for magnesium, magnesium nitrate, magnesium oxide, etc. can be used, and as raw materials for the zirconium component, zirconium oxynitrate, zirconium hydroxide, etc. can be used.
バリウム、カルシウム、ストロンチウム、バリウム、ラ
ンタン、銀、亜鉛、カドミウム、アルミニウム、ガリウ
ム、ゲルマニウムおよび鉛成分の原料としては、硝酸塩
を用いるのがよい、イツトリウム、ハフニウム、ニオブ
、タンタル、レニウム、ルテニウム、オスミウム、ロジ
ウム、イリジウム、パラジウム、白金およびインジウム
成分の原料としては水可溶性化合物を用いるのがよいが
、酸化物、水和物、有機酸塩などを用いることｔ’でき
る。Nitrate is preferably used as a raw material for barium, calcium, strontium, barium, lanthanum, silver, zinc, cadmium, aluminum, gallium, germanium, and lead components, such as yttrium, hafnium, niobium, tantalum, rhenium, ruthenium, osmium, As raw materials for rhodium, iridium, palladium, platinum and indium components, water-soluble compounds are preferably used, but oxides, hydrates, organic acid salts, etc. can also be used.
Ｙ成分中、モリブデン成分の原料としては、三酸化モリ
ブデン、モリブデン酸、パラモリブデン酸アンモニウム
、メタモリブデン酸アンモニウム、ハロゲン化モリブデ
ン類などが、タングステン成分の原料としては、二酸化
タングステン、パラタングステン酸アンモニウム、メタ
タングステン酸アンモニウム、タングステン酸などが用
いられる。In the Y component, raw materials for the molybdenum component include molybdenum trioxide, molybdic acid, ammonium paramolybdate, ammonium metamolybdate, molybdenum halides, etc., and raw materials for the tungsten component include tungsten dioxide, ammonium paratungstate, Ammonium metatungstate, tungstic acid, etc. are used.
Ｚ成分中、リン成分の原料としてはリン酸を、ホウ素成
分の原料としてはホウ酸が用いられる。Among the Z components, phosphoric acid is used as a raw material for the phosphorus component, and boric acid is used as a raw material for the boron component.
ビスマス成分の原料としては、ビスマスの硝酸塩、塩化
物、水酸化物を用いるのがよい。テルル成分の原料とし
ては金属テルル、二酸化テルル、亜テルル酸などを硝酸
に溶解したものおよびテルル酸などが用いられる。As raw materials for the bismuth component, bismuth nitrates, chlorides, and hydroxides are preferably used. As raw materials for the tellurium component, metal tellurium, tellurium dioxide, tellurite acid, etc. dissolved in nitric acid, telluric acid, etc. are used.
Ｑ成分、すなわちアルカリ金属であるリチウム、ナトリ
ウム、カリウム、ルビジウム、セシウムおよびタリウム
成分の原料としては、各成分の硝酸塩、水酸化物、塩化
物などを用いるのがよい。As raw materials for the Q component, that is, the alkali metals lithium, sodium, potassium, rubidium, cesium, and thallium components, it is preferable to use nitrates, hydroxides, chlorides, etc. of each component.
本発明の触媒の担体成分であるシリカの原料としては市
販のシリカゾルを用いることができる。Commercially available silica sol can be used as a raw material for silica, which is a carrier component of the catalyst of the present invention.
好ましいシリカゾルとしては、シリカ濃度が約５ないし
約９４１％の範囲内のものである。Preferred silica sols have silica concentrations ranging from about 5 to about 941%.
本発明は、このようにして調製した触媒が充填されてい
る反応器へ、分子中に少なくとも１個のクロル基を有す
るクロルトルエン類、アンモニアおよび酸素を供給する
ことによって行う０反応は固定床反応あるいは流動床反
応何れでもよい、好ましくは流動床反応である。In the present invention, the zero reaction is a fixed bed reaction, which is carried out by supplying chlorotoluenes having at least one chloro group in the molecule, ammonia, and oxygen to a reactor filled with the catalyst prepared in this way. Alternatively, it may be a fluidized bed reaction, preferably a fluidized bed reaction.
原料クロルトルエン類としてはモノクロルトルエンまた
はジクロルトルエンが用いられる。モノクロルトルエン
としては、オルト−、メタ−およびパラ−クロルトルエ
ンが、ジクロルトルエンとしては２．３−、２．４−、
２．５−および２．６−ジクロルトナが使用できる。酸
素源としては空気を用いるのカイよい。Monochlorotoluene or dichlorotoluene is used as the raw material chlorotoluene. Monochlorotoluenes include ortho-, meta- and para-chlorotoluenes; dichlorotoluenes include 2.3-, 2.4-,
2.5- and 2.6-dichlortona can be used. It is best to use air as the oxygen source.
反応器へ供給するガスは、アンモニア／クロルトルエン
頻のモル比を約１ないし約１０の範囲内で増減すること
ができるが、約１．５ないし約７の範囲とするのが好ま
しい、また、酸素／クロルトルエン類のモル比は約２．
０ないし約１０の範囲がよく、好ましくは約２．５ない
し約７の範囲である。The gas fed to the reactor can have an ammonia/chlorotoluene molar ratio ranging from about 1 to about 10, preferably from about 1.5 to about 7; The molar ratio of oxygen/chlorotoluenes is approximately 2.
A range of 0 to about 10 is good, preferably a range of about 2.5 to about 7.
反応温度は、約３００”Ｃないし約５００″Ｃの範囲、
特に約３４０°Ｃないし約４５０℃の範囲が好ましい。The reaction temperature ranges from about 300"C to about 500"C,
Particularly preferred is a temperature range of about 340°C to about 450°C.
反応圧力は、常圧、加圧、減圧いずれでもよいが、常圧
附近から約２ ｋｇ ／ ｃｄ Ｇの範囲が適当である
。The reaction pressure may be normal pressure, increased pressure, or reduced pressure, but is suitably in the range from around normal pressure to about 2 kg/cd G.
接触時間は、反応温度および圧力におけるガス容積を基
準として約２秒ないし約２０秒の範囲、特に約３秒ない
し約１０秒の範囲が好ましい。Contact times are preferably in the range of about 2 seconds to about 20 seconds, particularly in the range of about 3 seconds to about 10 seconds, based on the gas volume at the reaction temperature and pressure.
本発明の鉄・バナジウム・アンチモン系酸化物触媒は、
クロルトルエン類より対応するクロルベンゾニトリル類
を製造する反応に対して、すぐれた活性を示し、かつ機
械的強度の大きい性能を有する。従って、本発明の方法
によれば、クロルトルエン類の気相接触アンモ酸化反応
により対応するクロルベンゾニトリル類を高収率で得る
ことができ、従来の方法に比ベニ業的に有利に実施する
ことができる。The iron-vanadium-antimony-based oxide catalyst of the present invention is
It shows excellent activity in the reaction to produce the corresponding chlorobenzonitrile from chlorotoluene and has high mechanical strength. Therefore, according to the method of the present invention, the corresponding chlorobenzonitrile can be obtained in high yield through the gas-phase catalytic ammoxidation reaction of chlorotoluene, and it can be carried out industrially more advantageously than the conventional method. be able to.
以下、実施例によって本発明を具体的に説明するが、本
発明はこの実施例にのみ限定されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited only to these Examples.
なお、本明細書中の原料クロルトルエン類の転化率、目
的生成物の収率および選択率は次の定義による。In addition, the conversion rate of the raw material chlorotoluenes, the yield of the target product, and the selectivity in this specification are based on the following definitions.
のモル数 触媒の活性試験は次のようにしておこなった。number of moles of The catalyst activity test was conducted as follows.
触媒活性試験方法
触媒流動部の内径が、１＋Ａインチで高さ１．５ ｍの
流動床反応器を用い、−稟かけのガス線速度が８ｃｍ／
ｓｅｃとなるように反応原料ガス（クロルトルエン類、
アンモニアおよび空気）を供給する。Catalyst activity test method A fluidized bed reactor with an inner diameter of the catalyst flow section of 1+A inches and a height of 1.5 m was used, and the linear gas velocity at - end was 8 cm/
The reaction raw material gas (chlorotoluenes,
ammonia and air).
反応条件は目的に応じ適宜変化させる。The reaction conditions are changed as appropriate depending on the purpose.
反応圧力は常圧である。The reaction pressure is normal pressure.
実施例１
実験式がＦｅ＋＊ Ｖｔ Ｓｂｚ。５ｉｓｓ ＯＩ？Ｏ
Ｔ！ある触媒を次のようにして調製した。Example 1 The experimental formula is Fe+*Vt Sbz. 5iss OI? O
T! A catalyst was prepared as follows.
硝酸（比重１．３８） ６００ｍｊ！を純水３００＋ｗ
ｌと混合し加温する。これに電解鉄粉７５．９ ｇを
加え溶解させる。（溶液Ｉ）
純水６００ｍ ｌ−を加温し、メタバナジン酸アンモニ
ウム３１．８ ｇを溶解する。（溶液■）２０％シリカ
ゾル２２４５ ｇに、溶液■および溶液■を加え、更に
三酸化アンチモン３９６ｇを加え混合する。Nitric acid (specific gravity 1.38) 600mj! Pure water 300+w
Mix with l and warm. Add 75.9 g of electrolytic iron powder to this and dissolve. (Solution I) 600 ml of pure water is heated and 31.8 g of ammonium metavanadate is dissolved therein. (Solution ■) Add solution ■ and solution ■ to 2245 g of 20% silica sol, and then add 396 g of antimony trioxide and mix.
このスラリー液に１５％アンモニア水を少しづつ加え、
ｐＨを２．５に調整する。これを１ｏｏ″０５時間加熱
した後、常法により噴霧乾燥し３００″０３時間、８０
０°Ｃ５時間焼成した。Add 15% ammonia water little by little to this slurry liquid,
Adjust pH to 2.5. After heating this for 10"05 hours, it was spray-dried by a conventional method to 300"03 hours and 80%
It was baked at 0°C for 5 hours.
この触媒を、前記反応器に充てんし、２，６−ジクロル
トルエン、アンモニアおよび酸素をモル比１ ： ５
： ３．５で供給し３５０℃で反応させた。（酸素は空
気として送入した。以下同じ）
その結果、２．６−ジクロルトルエンの転化率は９３％
、２．６−ジクロルベンゾニトリルの収率は７７％、選
択率は８３％であった。This catalyst was charged into the reactor, and 2,6-dichlorotoluene, ammonia and oxygen were mixed in a molar ratio of 1:5.
: 3.5 and reacted at 350°C. (Oxygen was introduced as air. The same applies hereinafter.) As a result, the conversion rate of 2,6-dichlorotoluene was 93%.
The yield of 2,6-dichlorobenzonitrile was 77%, and the selectivity was 83%.
実施例２
実験式がＦｅｌ０ｖ１． ｓｃｒｉｓｂｔｏｃｕ３ＭＯ
ｏ、 ｓＬ、 ｌＴｅ１＋ ａＳｉｓｓＯ＋、ｓである
触媒を次のようにして調製した。Example 2 The experimental formula is Fel0v1. scrisbtocu3MO
A catalyst of o, sL, lTe1+ aSissO+, s was prepared as follows.
硝酸（比重１．３８ ） ６７０ｓ １ ニｖＲ２３，
５ｇを溶解し純水４００ｍ ！！を加え加熱する。鉄粉
６８．９ ｇおよびテルル粉２２．Ｏｇを加え溶解させ
る。（溶液Ｉ）純水２５０ｎ ｌにタングステン酸アン
モニウム３．２ｇおよびモリブデン酸アンモニウム１０
．９を溶解させる。（溶液■）
２０％シリカゾル２０４０ ｇに溶液■および溶液■を
加え、更に二酸化アンチモン３６０ｇを加え混合する。Nitric acid (specific gravity 1.38) 670s 1 NivR23,
Dissolve 5g in 400m of pure water! ! Add and heat. 68.9 g of iron powder and 22.9 g of tellurium powder. Add Og and dissolve. (Solution I) 3.2 g of ammonium tungstate and 10 ammonium molybdate in 250 nl of pure water
．． 9 is dissolved. (Solution ■) Add solution ■ and solution ■ to 2040 g of 20% silica sol, and then add 360 g of antimony dioxide and mix.
このスラリー液に１５％アンモニア水を少しづつ加えＰ
ｌｌを２．５に調整する。これを１００°Ｃ５時間加熱
した後、常法により噴霧乾燥し、３００″０３時間、８
００°Ｃ５時間焼成することにより基体触媒を得る。Add 15% ammonia water little by little to this slurry.
Adjust ll to 2.5. After heating this at 100°C for 5 hours, it was spray-dried using a conventional method and heated to 300°C for 3 hours.
A base catalyst is obtained by calcining at 00°C for 5 hours.
一方、純水２００ｍ ｌに五酸化バナジウム１６．８
ｇを加え加熱し、蓚酸５２．４ ｇを少しづつ加え溶解
させる０次いで硝酸クロム（９水和物） １４８．２ｇ
を加え溶解させる。（溶液■）
この溶液■を上に調製した基体触媒に含浸し、２００
’Ｃ４時間、４５０℃４時間焼成し、目的の組成をもつ
触媒を得た。On the other hand, add 16.8 vanadium pentoxide to 200 ml of pure water.
Add 52.4 g of oxalic acid and dissolve it little by little. Next, add 148.2 g of chromium nitrate (9 hydrate).
Add and dissolve. (Solution ■) This solution ■ was impregnated into the base catalyst prepared above,
The mixture was calcined at 450° C. for 4 hours to obtain a catalyst having the desired composition.
この触媒を前記反応器に充てんし、２．６−ジクロルト
ルエン、アンモニアおよび酸素をモル比１：５：Ｓで供
給し３６０℃で反応させた。This catalyst was filled in the reactor, and 2,6-dichlorotoluene, ammonia, and oxygen were supplied at a molar ratio of 1:5:S, and the reaction was carried out at 360°C.
その結果、２．゛６−ジクロルトルエンの転化率は９６
％、２．６−ジクロルベンゾニトリルの収率は８３％、
選択率は８７％であった。As a result, 2. The conversion rate of ゛6-dichlorotoluene is 96
%, the yield of 2.6-dichlorobenzonitrile is 83%,
The selectivity was 87%.
実施例３
実験式がＦｅ＋ ｅＶ＋、 ５ｃｒ３ｓｂｔｓｃｕａＺ
ｎｏ、 ５Ｍ０ｅ、 ｓＷｏ、 ｔＴｅｌ、 ３ＰＯ，
＋Ｂｏ、 ５ｓｉＳｓｏｒｑａである触媒を実施例２と
同様の方法で調製した。含浸液成分はバナジウム、クロ
ムである。Example 3 Empirical formula is Fe+ eV+, 5cr3sbtscuaZ
no, 5M0e, sWo, tTel, 3PO,
+Bo, 5siS sorqa catalyst was prepared in the same manner as in Example 2. The impregnating liquid components are vanadium and chromium.
この触媒を用い、実施例２と同様の方法で反応した。そ
の結果、２．６−ジクロルトルエンの転化率は９５％、
２．６−ジクロルベンゾニトリルの収率は８４％、選択
率は８８％であった。A reaction was carried out in the same manner as in Example 2 using this catalyst. As a result, the conversion rate of 2,6-dichlorotoluene was 95%,
The yield of 2,6-dichlorobenzonitrile was 84%, and the selectivity was 88%.
実施例４
実験式がＦｅｌ ６Ｖ５ＳｂａｏＣｏ＋、 ｏＭｇｏ、
ｓＢｉ＋、 ｓＣ！９ｏ、 ｏｓｓｉｓ。Example 4 The experimental formula is Fel 6V5SbaoCo+, oMgo,
sBi+, sC! 9o, ossis.
０１？Ｉである触媒を実施例２と同様の方法で調製した
。含浸成分はバナジウム、ビスマスである。01? Catalyst I was prepared in a similar manner to Example 2. Impregnation components are vanadium and bismuth.
この触媒を用い、実施例２と同様の方法で反応した。そ
の結果、２．６−ジクロルトルエンの転化率は９４％、
２．６−ジクロルベンゾニトリルの収率は８１％、選択
率は８６％であった。A reaction was carried out in the same manner as in Example 2 using this catalyst. As a result, the conversion rate of 2,6-dichlorotoluene was 94%,
The yield of 2,6-dichlorobenzonitrile was 81%, and the selectivity was 86%.
実施例５
実験式がＦｅ＋ ｏＶｏ、 ５ｃｒｓｓｔｌ＋ ｏＶｏ
６．５Ｓｎｏ、 ｌ？ｂｏ、 ｏｓｓｔｇａａｘｅｓで
ある触媒を実施例２と同様の方法で調製した。含浸成分
は、バナジウム、クロム、マンガンである。Example 5 Empirical formula is Fe+ oVo, 5crsstl+ oVo
6.5Sno, l? A catalyst, bo, osstgaaxes, was prepared in a manner similar to Example 2. The impregnating components are vanadium, chromium, and manganese.
この触媒を用い、実施例２と同様の方法で反応した。そ
の結果、２．６−ジクロルトルエンの転化率ハ９５％、
２．６−ジクロルベンゾニトリルの収率は７９％、選択
率は８３％であった。A reaction was carried out in the same manner as in Example 2 using this catalyst. As a result, the conversion rate of 2,6-dichlorotoluene was 95%,
The yield of 2,6-dichlorobenzonitrile was 79%, and the selectivity was 83%.
実施例６
実験式がＦ８＋ ｅＶ＠ＣｒｚｏＳｂｓｓＺｒｏ、 ５
Ａｌｅ、 ＋Ｎａ、 ｚｓＩｈ。Example 6 The experimental formula is F8+ eV@CrzoSbssZro, 5
Ale, +Na, zsIh.
Ｏ１４，である触媒を実施例２と同様の方法で調製した
。含浸成分は、バナジウム、クロムである。A catalyst, O14, was prepared in a similar manner to Example 2. Impregnation components are vanadium and chromium.
この触媒を用い、実施例２と同様の方法で反応した。そ
の結果２，６−ジクロルトルエンの転化率は８８％、２
．６−ジクロルベンゾニトリルの収率は７５％、選択率
は８５％であった。A reaction was carried out in the same manner as in Example 2 using this catalyst. As a result, the conversion rate of 2,6-dichlorotoluene was 88%, 2
．． The yield of 6-dichlorobenzonitrile was 75%, and the selectivity was 85%.
実施例７
実験式がＦｅｌ ｏＶｚｃｒ＋１ｓｔｌｚｏｃｕｚ、
ｓＮｉ ｏ、 ｚＭｏａ、 ４ｗ０．３Ｔｅ＋、 ＋Ｐ
ｏ、 ＋５ｉａｓＯＩｂｑである触媒を実施例２と同様
の方法で調製した。含浸成分は、バナジウム、クロムで
ある。Example 7 The empirical formula is Fel oVzcr+1stlzocuz,
sNio, zMoa, 4w0.3Te+, +P
o, +5iasOIbq was prepared in a similar manner to Example 2. Impregnation components are vanadium and chromium.
この触媒を用い、実施例２と同様の方法で反応した。そ
の結果、２．６−ジクロルトルエンの転化率は９６％、
２．６−ジクロルベンゾニトリルの収率は８３％、選択
率８７％であった。A reaction was carried out in the same manner as in Example 2 using this catalyst. As a result, the conversion rate of 2,6-dichlorotoluene was 96%,
The yield of 2,6-dichlorobenzonitrile was 83%, and the selectivity was 87%.
実施例８
実験式がＦ１１１＋＊Ｖ３Ｃｒ＋ＳｂｇｏＣｔｌ！ＭＯ
ｏ、 ５ｓｌｓｓｏ＋ｔｑである触媒と実施例２と同様
の方法で調製した。Example 8 The experimental formula is F111+*V3Cr+SbgoCtl! M.O.
o, 5slsso+tq catalyst was prepared in the same manner as in Example 2.
含浸成分は、バナジウム、クロムである。Impregnation components are vanadium and chromium.
この触媒を前記反応器に充てんし、２．４−ジクロルト
ルエン、アンモニアおよび酸素をモル比１：１：１で供
給し３８０°Ｃで反応した。その結果、２．４−ジクロ
ルトルエンの転化率は９９％、２．４−ジクロルベンゾ
ニトリルの収率は８７％、選択率８８％であった。This catalyst was filled in the reactor, and 2,4-dichlorotoluene, ammonia and oxygen were supplied in a molar ratio of 1:1:1 and reacted at 380°C. As a result, the conversion rate of 2,4-dichlorotoluene was 99%, the yield of 2,4-dichlorobenzonitrile was 87%, and the selectivity was 88%.
実施例９
実験式がＰｅ１ｏＶ３ＣｒｎＳｂｉｏＣｅ６． ＋Ｌｉ
ａ、 ＋５ｉｓｓＯ＋ｙ雫である触媒を実施例２と同様
の方法で調製した。含浸成分は、バナジウム、クロムで
ある。Example 9 The experimental formula is Pe1oV3CrnSbioCe6. +Li
A catalyst with +5issO+y drops was prepared in the same manner as in Example 2. Impregnation components are vanadium and chromium.
この触媒を前記反応器に充てんし、オルトクロルトルエ
ン、アンモニアおよび酸素をモル比１ ： ５ ： ３
．５で供給し３７０°Ｃで反応した。その結果、オルト
クロルトルエンの転化率は９６％、オルトクロルベンゾ
ニトリルの収率は８４％、選択率８８％であった。This catalyst was filled in the reactor, and orthochlorotoluene, ammonia and oxygen were mixed in a molar ratio of 1:5:3.
．． 5 and reacted at 370°C. As a result, the conversion rate of orthochlorotoluene was 96%, the yield of orthochlorobenzonitrile was 84%, and the selectivity was 88%.
実施例１０
実験式がＦｅ１ｏＶ１ＣｒｘＳｂｔｏＴｉｅ、 ＋Ｎａ
ｏ、 ＋５ｉｓｓＯ１＋ である触媒を実施例２と同様
の方法で調製した。含浸成分は、バナジウム、クロムで
ある。Example 10 The experimental formula is Fe1oV1CrxSbtoTie, +Na
o, +5issO1+ catalyst was prepared in a similar manner to Example 2. Impregnation components are vanadium and chromium.
この触媒と前記反応器に充てんし、メタクロルトルエン
、アンモニアおよび酸素をモル比１：３．５：５で供給
し３６０°Ｃで反応した。その結果、メタクロルトルエ
ンの転化率は９２％、メタクロルベンゾニトリルの収率
は８１％、選択率８８％であった。This catalyst and the reactor were filled, and methachlorotoluene, ammonia and oxygen were supplied in a molar ratio of 1:3.5:5, and the reaction was carried out at 360°C. As a result, the conversion rate of methachlorotoluene was 92%, the yield of methachlorobenzonitrile was 81%, and the selectivity was 88%.
比較例１
実験式がＦｅ＋ｅＶ１Ｓｉ、。Ｏ１２゜である触媒を実
施例２と同様の方法で調製した。含浸成分はバナジウム
である。この触媒を用い、実施例２と同様の反応を行っ
た。その結果、２．６−ジクロルトルエンの転化率は７
８％、２．６−ジクロルベンゾニトリルの収率は５４％
、選択率６９％であった。Comparative Example 1 The experimental formula is Fe+eV1Si. A catalyst with 012° was prepared in a manner similar to Example 2. The impregnating component is vanadium. Using this catalyst, the same reaction as in Example 2 was carried out. As a result, the conversion rate of 2,6-dichlorotoluene was 7
8%, yield of 2,6-dichlorobenzonitrile is 54%
, the selectivity was 69%.
比較例２
実験式がＶｚＣｒｌＳｂｚｏＳｉｉｏＯ＋ ６！１であ
る触媒を実施例２と同様の方法で調製した。含浸成分は
、バナジウム、クロムである。Comparative Example 2 A catalyst having the empirical formula VzCrlSbzoSiioO+ 6!1 was prepared in the same manner as in Example 2. Impregnation components are vanadium and chromium.
この触媒を用い、実施例２と同様の反応を行った。その
結果２．６−ジクロルトルエンの転化率は８５％、・２
．６−ジクロルベンゾニトリルの収率は６２％、選択率
７３％であった。Using this catalyst, the same reaction as in Example 2 was carried out. As a result, the conversion rate of 2.6-dichlorotoluene was 85%, ・2
．． The yield of 6-dichlorobenzonitrile was 62%, and the selectivity was 73%.
比較例３
実験式がＦｅ＋ｏＳｂｚｏＣｕｓＳｉｓｓＯ＋４＊であ
る触媒を実施例１と同様の方法で調製した。Comparative Example 3 A catalyst having the empirical formula Fe+oSbzoCusSissO+4* was prepared in the same manner as in Example 1.
この触媒を用い、実施例１と同様の反応を行った。Using this catalyst, the same reaction as in Example 1 was carried out.
２．６−ジクロルトルエンの転化率は５３％、２．６〜
ジクロルベンゾニトリルの収率は２８％、選択率５３％
であった。The conversion rate of 2.6-dichlorotoluene was 53%, 2.6~
Yield of dichlorobenzonitrile is 28%, selectivity 53%
Met.
Claims (1)
エン、アンモニアおよび酸素を、下記実験式で表わされ
る金属酸化物触媒の存在下に反応せしめることを特徴と
する対応するクロルベンゾニトリル類の製造方法。 実験式 Ｆｅ＿ａＶ＿ｂＣｒ＿ｃＳｂ＿ｄＸ＿ｅＹ＿ｆ
Ｚ＿ｇＱ＿ｈＯ＿ｉ（ＳｉＯ＿２）＿ｊ（ただし、Ｘは
Ｃｏ、Ｎｉ、Ｓｎ、Ｕ、Ｃｕ、Ｍｎ、Ｔｉ、Ｃｅ、Ｂｅ
、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｙ、Ｌａ、Ｚｒ、Ｈｆ、Ｎ
ｂ、Ｔａ、Ｒｅ、Ｒｕ、Ｏｓ、Ｒｈ、Ｉｒ、Ｐｄ、Ｐｔ
、Ａｇ、Ｚｎ、Ｃｄ、Ａｌ、Ｇａ、Ｉｎ、Ｇｅ、および
Ｐｂからなる群から選ばれた少なくとも１種の元素であ
り、ＹはＭｏおよび／またはＷであり、ＺはＰ、Ｂ、Ｂ
ｉおよびＴｅからなる群から選ばれた少なくとも１種の
元素であり、ＱはＬｉ、Ｎａ、Ｋ、Ｒｂ、ＣｓおよびＴ
ｉからなる群から選ばれた少なくとも１種の元素であり
、添字ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈ、ｉは原子比を
示し、ａ＝１０のとき、ｂ＝０．０５〜１０、ｃ＝０〜
２５、ｄ＝５〜６０、ｅ＝０〜１０、ｆ＝０〜５、ｇ＝
０〜５、ｈ＝０〜２、ｉ＝上記各成分が結合して生成す
る酸化物に対応する数およびｊ＝２０〜２００を示す。 ）[Scope of Claims] A corresponding chlorobenzene, which is characterized in that chlorotoluene having at least one chloro group in the molecule, ammonia and oxygen are reacted in the presence of a metal oxide catalyst represented by the following empirical formula. Method for producing nitriles. Empirical formula Fe_aV_bCr_cSb_dX_eY_f
Z_gQ_hO_i(SiO_2)_j (X is Co, Ni, Sn, U, Cu, Mn, Ti, Ce, Be
, Mg, Ca, Sr, Ba, Y, La, Zr, Hf, N
b, Ta, Re, Ru, Os, Rh, Ir, Pd, Pt
, Ag, Zn, Cd, Al, Ga, In, Ge, and Pb, Y is Mo and/or W, and Z is P, B, B.
is at least one element selected from the group consisting of i and Te, and Q is Li, Na, K, Rb, Cs and T
At least one element selected from the group consisting of i, where the subscripts a, b, c, d, e, f, g, h, and i indicate the atomic ratio, and when a=10, b=0. 05~10, c=0~
25, d=5-60, e=0-10, f=0-5, g=
0 to 5, h=0 to 2, i=the number corresponding to the oxide formed by combining each of the above components, and j=20 to 200. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62084596A JPH0629231B2 (en) | 1987-04-08 | 1987-04-08 | Method for producing chlorobenzonitriles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62084596A JPH0629231B2 (en) | 1987-04-08 | 1987-04-08 | Method for producing chlorobenzonitriles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63250357A true JPS63250357A (en) | 1988-10-18 |
| JPH0629231B2 JPH0629231B2 (en) | 1994-04-20 |
Family
ID=13835063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62084596A Expired - Lifetime JPH0629231B2 (en) | 1987-04-08 | 1987-04-08 | Method for producing chlorobenzonitriles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0629231B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002083302A1 (en) * | 2001-04-13 | 2002-10-24 | Dia-Nitrix Co., Ltd. | Method for producing molybdenum-bismuth-iron containing composite oxide fluid bed catalyst |
| CN103102287A (en) * | 2013-01-31 | 2013-05-15 | 湖北郡泰医药化工有限公司 | Production process for preparing chlorobenzonitrile through ammoxidation |
| CN112143932A (en) * | 2020-09-10 | 2020-12-29 | 深圳金斯达应用材料有限公司 | Copper-based palladium coating bonding lead and manufacturing method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5145587A (en) * | 1974-10-16 | 1976-04-19 | Hitachi Ltd | |
| JPS56500775A (en) * | 1979-03-06 | 1981-06-11 | ||
| JPS56139444A (en) * | 1980-04-01 | 1981-10-30 | Takeda Chem Ind Ltd | Production of aromatic nitrile |
| JPS58121262A (en) * | 1982-01-12 | 1983-07-19 | Nitto Chem Ind Co Ltd | Ammoxidation of organic compound |
| JPS58140056A (en) * | 1982-02-16 | 1983-08-19 | Nitto Chem Ind Co Ltd | Ammoxidation process |
| JPS59139938A (en) * | 1983-01-31 | 1984-08-11 | Nitto Chem Ind Co Ltd | Preparation of fluidized bed catalyst for phosphorus- containing metal oxide |
-
1987
- 1987-04-08 JP JP62084596A patent/JPH0629231B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5145587A (en) * | 1974-10-16 | 1976-04-19 | Hitachi Ltd | |
| JPS56500775A (en) * | 1979-03-06 | 1981-06-11 | ||
| JPS56139444A (en) * | 1980-04-01 | 1981-10-30 | Takeda Chem Ind Ltd | Production of aromatic nitrile |
| JPS58121262A (en) * | 1982-01-12 | 1983-07-19 | Nitto Chem Ind Co Ltd | Ammoxidation of organic compound |
| JPS58140056A (en) * | 1982-02-16 | 1983-08-19 | Nitto Chem Ind Co Ltd | Ammoxidation process |
| JPS59139938A (en) * | 1983-01-31 | 1984-08-11 | Nitto Chem Ind Co Ltd | Preparation of fluidized bed catalyst for phosphorus- containing metal oxide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002083302A1 (en) * | 2001-04-13 | 2002-10-24 | Dia-Nitrix Co., Ltd. | Method for producing molybdenum-bismuth-iron containing composite oxide fluid bed catalyst |
| KR100870790B1 (en) | 2001-04-13 | 2008-11-27 | 다이야니트릭스 가부시키가이샤 | Method for producing molybdenum-bismuth-iron containing composite oxide fluid bed catalyst |
| CN103102287A (en) * | 2013-01-31 | 2013-05-15 | 湖北郡泰医药化工有限公司 | Production process for preparing chlorobenzonitrile through ammoxidation |
| CN112143932A (en) * | 2020-09-10 | 2020-12-29 | 深圳金斯达应用材料有限公司 | Copper-based palladium coating bonding lead and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0629231B2 (en) | 1994-04-20 |
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