WO2013129424A1 - アクリロニトリルの製造方法 - Google Patents
アクリロニトリルの製造方法 Download PDFInfo
- Publication number
- WO2013129424A1 WO2013129424A1 PCT/JP2013/055014 JP2013055014W WO2013129424A1 WO 2013129424 A1 WO2013129424 A1 WO 2013129424A1 JP 2013055014 W JP2013055014 W JP 2013055014W WO 2013129424 A1 WO2013129424 A1 WO 2013129424A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- fluidized bed
- ammonia
- reaction
- bed catalyst
- Prior art date
Links
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 275
- 239000003054 catalyst Substances 0.000 claims abstract description 229
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 134
- 238000001179 sorption measurement Methods 0.000 claims abstract description 87
- 239000007789 gas Substances 0.000 claims abstract description 64
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 45
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 22
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 17
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052701 rubidium Inorganic materials 0.000 claims description 7
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052716 thallium Inorganic materials 0.000 claims description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 110
- 239000012071 phase Substances 0.000 description 42
- 239000012495 reaction gas Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 28
- 230000000694 effects Effects 0.000 description 26
- 239000000203 mixture Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 239000002002 slurry Substances 0.000 description 20
- 238000002485 combustion reaction Methods 0.000 description 16
- 239000007788 liquid Substances 0.000 description 14
- 238000004868 gas analysis Methods 0.000 description 12
- 239000001307 helium Substances 0.000 description 12
- 229910052734 helium Inorganic materials 0.000 description 12
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000007423 decrease Effects 0.000 description 11
- 238000001354 calcination Methods 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 125000004430 oxygen atom Chemical group O* 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 230000001737 promoting effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000003795 desorption Methods 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- -1 or the like Chemical compound 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 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 2
- 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 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 150000003498 tellurium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
Definitions
- the present invention relates to a process for producing acrylonitrile by vapor phase catalytic ammoxidation of propylene with molecular oxygen and ammonia.
- the present invention claims priority based on Japanese Patent Application No. 2012-042832 filed in Japan on February 29, 2012, the contents of which are incorporated herein by reference.
- a method for producing acrylonitrile by gas phase catalytic ammoxidation reaction using propylene, ammonia and molecular oxygen (oxygen-containing gas) as raw materials in a fluidized bed reactor is widely known.
- composite oxide catalysts containing iron and antimony are useful for ammoxidation reactions and are widely used industrially.
- Patent Document 1 discloses a composite oxide catalyst with at least one element selected from the group consisting of iron, antimony, cobalt, and nickel.
- Patent Documents 2 to 8 disclose composite oxide catalysts containing iron, antimony, tellurium, vanadium, molybdenum, tungsten and the like.
- Patent Documents 9 to 11 disclose methods for producing these iron and antimony containing catalysts.
- Patent Document 12 specifies that the selectivity of the target product and the catalytic activity are improved by enriching the catalyst whose performance is reduced by the use of the reaction with enrichment of tellurium and heating at a high temperature of 900 ° C. or less. ing. And it is disclosed that a high acrylonitrile yield is maintained by replacing the tellurium-enriched catalyst with a catalyst in the reactor.
- Patent Document 13 during the ammoxidation reaction using the tellurium-containing oxide catalyst, the selectivity of the target product and the catalytic activity are obtained by adding a tellurium carrier, a tellurium compound, and a molybdenum compound to the reactor. It has been disclosed that the decrease in the aging is improved.
- the catalyst disclosed in these conventional techniques, the method for producing the catalyst, and the method for producing acrylonitrile are effective to some extent in maintaining a high acrylonitrile yield, they are not always sufficient. Therefore, a method for producing acrylonitrile in a higher yield is desired.
- This invention is made
- One embodiment of the method for producing acrylonitrile according to the present invention is to use a fluidized bed catalyst containing iron, antimony and tellurium in a fluidized bed reactor, and subject propylonitrile to vapor phase catalytic ammoxidation with molecular oxygen and ammonia.
- the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst during the gas phase catalytic ammoxidation reaction is maintained in the range of 0.01 to 0.22 ⁇ mol / m 2. And performing a gas phase catalytic ammoxidation reaction.
- the fluidized bed catalyst is preferably represented by the following general formula (1).
- Fe, Sb, Te, O and SiO 2 represent iron, antimony, tellurium, oxygen and silica, respectively
- A is at least one element selected from the group consisting of vanadium, molybdenum and tungsten
- D is magnesium, Group consisting of calcium, strontium, barium, titanium, zirconium, niobium, chromium, manganese, cobalt, nickel, copper, silver, zinc, boron, aluminum, gallium, indium, thallium, germanium, tin, lead, phosphorus, arsenic and bismuth
- at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium, and a, b, c, d, e, x, and y are atomic ratios.
- the manufacturing method of the acrylonitrile of this invention has the following side surfaces.
- a method for producing acrylonitrile Including a gas phase catalytic ammoxidation step in which a raw material gas containing propylene, molecular oxygen, and ammonia is brought into contact with a fluidized bed catalyst to perform gas phase ammoxidation to obtain acrylonitrile.
- the fluidized bed catalyst is a catalyst containing iron, antimony and tellurium;
- the gas phase catalytic ammoxidation step is performed while maintaining the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst in a range of 0.01 to 0.22 ⁇ mol / m 2.
- a process for producing acrylonitrile; ⁇ 2> The method for producing acrylonitrile according to ⁇ 1>, wherein the fluidized bed catalyst is represented by the following general formula (1): Fe 10 Sb a A b Te c D d E e O x ⁇ (SiO 2) y ⁇ (1) Wherein Fe, Sb, Te, O, and SiO 2 represent iron, antimony, tellurium, oxygen, and silica, respectively, A represents at least one element selected from the group consisting of vanadium, molybdenum, and tungsten; D is magnesium, calcium, strontium, barium, titanium, zirconium, niobium, chromium, manganese, cobalt, nickel, copper, silver, zinc, boron, aluminum, gallium, indium, thallium, germanium, tin, lead, phosphorus, arsenic, And at least one element selected from the group consisting of bismuth, E represents at least one element selected from the group consisting of lithium,
- a high acrylonitrile yield can be stably maintained over a long period of time.
- One aspect of the present invention is a method for producing acrylonitrile by using a fluidized bed catalyst containing iron, antimony and tellurium in a fluidized bed reactor, and subjecting propylene to gas phase catalytic ammoxidation with molecular oxygen and ammonia.
- the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst during the gas phase catalytic ammoxidation reaction is maintained in the range of 0.01 to 0.22 ⁇ mol / m 2 , It is a method for producing acrylonitrile characterized by carrying out an oxidation reaction.
- a gas phase catalytic ammoxidation in which a raw material gas containing propylene, molecular oxygen, and ammonia is brought into contact with a fluidized bed catalyst to perform gas phase ammoxidation to obtain acrylonitrile.
- the fluidized bed catalyst is a catalyst containing iron, antimony and tellurium, and the gas phase catalytic ammoxidation step determines the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst. It is a method for producing acrylonitrile, which is carried out while maintaining a range of 0.01 to 0.22 ⁇ mol / m 2 .
- the acrylonitrile yield may decrease over time.
- the decrease in the acrylonitrile yield with time is due to the change in the ability of the fluidized bed catalyst to adsorb ammonia over time.
- the acrylonitrile yield was maintained by maintaining the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst in the gas phase catalytic ammoxidation reaction in the range of 0.01 to 0.22 ⁇ mol / m 2.
- the present inventors have found that a decrease in rate over time can be suppressed, and have completed the present invention.
- the amount of ammonia adsorbed per specific surface area (m 2 / g) of the fluidized bed catalyst in the gas phase catalytic ammoxidation reaction step is maintained in the range of 0.01 to 0.22 ⁇ mol / m 2.
- the lower limit of the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst in the gas phase catalytic ammoxidation reaction step is preferably 0.03 ⁇ mol / m 2
- the upper limit is preferably 0.18 ⁇ mol / m 2. a m 2.
- the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst that has not been reacted that is, before the fluidized bed catalyst is subjected to the gas phase catalytic ammoxidation reaction
- the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst during the oxidation reaction step can be maintained in the range of 0.01 to 0.22 ⁇ mol / m 2 .
- the ammonia adsorption amount per specific surface area (m 2 / g) of the unreacted fluidized bed catalyst is preferably 0.01 to 0.22 ⁇ mol / m 2 .
- ammonia adsorption amount of the fluidized bed catalyst satisfies the above conditions, good catalyst performance, that is, high acrylonitrile yield can be maintained.
- the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst in the gas phase catalytic ammoxidation reaction step was determined by extracting a part of the fluidized bed catalyst from the fluidized bed reactor during the step, It is the value quantified by the method.
- the ammonia adsorption amount of the fluidized bed catalyst is described in zeolite (Vol. 21, No. 2, p. 45-52, 2004) and surface science (Vol. 24, No. 10, p. 635-641, 2003). It is a value measured as follows with reference to the ammonia temperature-programmed desorption method. Note that an inert gas such as helium, nitrogen, or argon can be used as the carrier gas. The case where helium is used as the carrier gas will be described below.
- the ammonia adsorption amount of the present invention refers to a value obtained by measuring the ammonia amount desorbed from the fluidized bed catalyst with an ammonia adsorption amount measuring device. A specific measurement method is described below.
- a fluidized bed catalyst was charged into the apparatus, and helium was flowed at a flow rate of 50 mL / min.
- the catalyst is pretreated by maintaining at 400 ° C. for 1 hour while circulating the catalyst. After completion of the pretreatment, the temperature of the catalyst is lowered to 100 ° C. and kept in that state for 10 minutes.
- 0.1 vol% ammonia-99.9 vol% helium mixed gas is passed for 5 minutes to adsorb ammonia on the catalyst. Thereafter, helium was flowed at a flow rate of 50 mL / min. And keep in that state for 60 minutes. Subsequently, helium was supplied to the catalyst at a flow rate of 50 mL / min.
- the ammonia gas desorbed from the catalyst is analyzed by a quadrupole mass spectrometer during that time, and the amount of ammonia desorbed from the catalyst is quantified.
- a calibration curve prepared by introducing a known amount of ammonia gas into a quadrupole mass spectrometer is used.
- BET method specific surface area measuring apparatus
- the method it can measure with reference to the conditions described in the use conditions of the powder for specific surface area test Annex A (reference) powder for specific surface area test.
- the amount of ammonia quantified by the measurement method is defined as the amount of ammonia adsorbed on the fluidized bed catalyst (ammonia adsorbed amount), which is converted into the amount per specific surface area (m 2 / g) of the fluidized bed catalyst in the gas phase contact.
- ammonia adsorption amount of the fluidized bed catalyst during the ammoxidation reaction is defined as the amount of ammonia adsorbed on the fluidized bed catalyst (ammonia adsorbed amount), which is converted into the amount per specific surface area (m 2 / g) of the fluidized bed catalyst in the gas phase contact.
- the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst in the gas phase catalytic ammoxidation step is smaller than the above lower limit value, that is, 0.01 ⁇ mol / m 2 , acrolein, acrylic acid, etc.
- the amount of by-products increases and the acrylonitrile yield decreases.
- Acrolein, acrylic acid, and the like are easily polymerized in a purification step subsequent to the reactor, and as a result, blockage of lines, towers, and the like may be caused, so that stable operation over a long period of time may be difficult.
- ammonia basic unit means the amount of ammonia necessary to obtain a certain amount of acrylonitrile.
- ammonia adsorption amount is within the above range, that is, 0.01 to 0.22 ⁇ mol / m 2 , the reaction can be continued as it is.
- the amount may be increased or decreased.
- the gas phase catalytic ammoxidation step is carried out so that the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst is 0.01 to 0.22 ⁇ mol / m 2. It is characterized by being carried out while maintaining the range. That is, in the method for producing acrylonitrile of the present invention, the gas phase catalytic ammoxidation reaction step further includes a step of maintaining the ammonia adsorption amount per specific surface area in the range of 0.01 to 0.22 ⁇ mol / m 2. preferable.
- a method for increasing the ammonia adsorption amount or a method for reducing the ammonia adsorption amount examples include a method of adding a compound having an effect of promoting the adsorption of ammonia.
- Specific examples of compounds having an effect of promoting ammonia adsorption include compounds containing acidic elements such as tellurium and molybdenum, and the method of adding them to the reactor increases the amount of ammonia adsorbed. This is an effective method.
- a catalyst having a large ammonia adsorption amount can be produced by adjusting the catalyst composition, for example, by increasing the content of an element having an effect of promoting the adsorption of ammonia, such as tellurium or molybdenum.
- a catalyst having a large ammonia adsorption amount can also be produced by impregnating the fluidized bed catalyst of the present invention with an element having an effect of promoting adsorption of ammonia. Examples of the element having an effect of promoting the adsorption of ammonia include tellurium and molybdenum.
- a method for reducing the ammonia adsorption amount of the fluidized bed catalyst during the gas phase catalytic ammoxidation step a method of adding a compound having an effect of inhibiting the adsorption of ammonia can be mentioned.
- Specific examples of the compound having an effect of inhibiting the adsorption of ammonia include compounds containing basic elements such as potassium, rubidium, and cesium. It is also effective to add a catalyst having a small ammonia adsorption amount, or to replace a part of the catalyst in the reactor with a catalyst whose ammonia adsorption amount has been reduced by reaction.
- a catalyst with a small ammonia adsorption amount can be produced by adjusting the catalyst composition, such as increasing the content of elements having an effect of inhibiting the adsorption of ammonia, such as potassium, rubidium, and cesium.
- a catalyst with a small ammonia adsorption amount can be produced by impregnating an element having an effect of inhibiting the adsorption of ammonia to produce the fluidized bed catalyst of the present invention.
- the element having an effect of inhibiting the adsorption of ammonia include potassium, rubidium, cesium and the like.
- tellurium, molybdenum, and the like which are elements that promote ammonia adsorption, have a property of being easily volatilized during the gas phase ammoxidation process as compared with other components constituting the catalyst. Utilizing this property, the ammonia adsorption amount of the fluidized bed catalyst during the reaction is controlled by promoting (or reducing) the volatilization of tellurium, molybdenum, etc. by temporarily raising (or lowering) the reaction temperature. May be.
- the timing for adding the compound having the effect of promoting the adsorption of ammonia and the compound having the effect of inhibiting the adsorption of ammonia, or the amount of addition is not particularly limited as long as it has the effect of the present invention.
- the ammonia adsorption amount of the fluidized bed catalyst during the reaction tends to decrease. Therefore, the timing and amount of addition are preferred so that the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst during the gas phase catalytic ammoxidation reaction falls within the above range.
- the method of controlling the ammonia adsorption amount of the fluidized bed catalyst in the reactor is not limited to the method described above, and can be carried out by any known method.
- the gas phase catalytic ammoxidation step includes a fluidized bed reactor filled with a fluidized bed catalyst to form a catalyst layer, and the catalyst layer contains a raw material gas containing propylene, molecular oxygen, and ammonia.
- the raw material gas is not particularly limited as long as it has the effect of the present invention, but propylene / ammonia / oxygen is 1 / 1.0 to 2.0 / 1.0 to 5.0 (molar ratio).
- a source gas in the range is preferred.
- the amount of supply of molecular oxygen as an oxygen source is not particularly limited as long as it has the effect of the present invention, but air is preferably used.
- the source gas may be diluted with an inert gas such as nitrogen or carbon dioxide, saturated hydrocarbon, or the like, or pure oxygen may be mixed to increase the oxygen concentration.
- the reaction temperature of the gas phase catalytic ammoxidation reaction is preferably 350 to 500 ° C., and the reaction pressure is preferably within the range of normal pressure (100 kPa) to 500 kPa.
- the contact time between the fluidized bed catalyst and the reaction gas is preferably 0.1 to 20 seconds.
- the fluidized bed catalyst used in the present invention is not particularly limited as long as it satisfies the above requirements and contains iron, antimony and tellurium, so long as it has the effect of the present invention, a high acrylonitrile yield can be obtained.
- the composition represented by the following general formula (1) is preferable. Fe 10 Sb a A b Te c D d E e O x ⁇ (SiO 2) y ⁇ (1)
- Fe, Sb, Te, O, and SiO 2 represent iron, antimony, tellurium, oxygen, and silica, respectively
- A represents at least one element selected from the group consisting of vanadium, molybdenum, and tungsten
- D is magnesium, calcium, strontium, barium, titanium, zirconium, niobium, chromium, manganese, cobalt, nickel, copper, silver, zinc, boron, aluminum, gallium, indium, thallium, germanium, tin, lead, phosphorus, arsenic
- E represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium
- the method for producing a fluidized bed catalyst used in the present invention is not particularly limited as long as it has the effects of the present invention.
- the method for producing a catalyst described in Patent Documents 1 to 13 described above may be followed. Specifically, a method of preparing a solution or an aqueous slurry containing raw materials for each element constituting the fluidized bed catalyst, drying the obtained solution or aqueous slurry, and calcining the obtained dried product, etc. It is done. That is, in the method for producing a fluidized bed catalyst of the present invention, the respective elements constituting the fluidized bed catalyst are mixed to prepare a solution or an aqueous slurry, and the solution or aqueous solution obtained in the step (I).
- the solution or aqueous slurry may contain all of the desired elements constituting the fluidized bed catalyst of the present invention in a desired atomic ratio. Further, a solution or an aqueous slurry containing a part of the elements constituting the fluidized bed catalyst may be prepared, and the remaining elements may be added to the catalyst composition after drying or calcination by a method such as impregnation.
- the raw material of each element constituting the fluidized bed catalyst is determined according to its purpose, application, etc., and is an oxide, or nitrate, carbonate, organic acid salt, water that can be easily converted into an oxide when heated. It is preferable to use an oxide, an ammonium salt or the like, or a mixture thereof. These raw materials are solid or dissolved in water or dilute nitric acid to form a solution, and then mixed to obtain a solution or an aqueous slurry.
- the fluidized bed catalyst of this invention contains a silica, it is preferable to use a silica sol as said silica.
- the pH may be adjusted by adding nitric acid, aqueous ammonia, or the like, if necessary, or by concentration treatment or heat treatment.
- Step (II) is a step of baking the obtained dried product after drying the solution or aqueous slurry obtained in the step (I).
- step (II) it is preferable to obtain a spherical dried product (dry particles) as much as possible by drying the solution or slurry containing the elements constituting the fluidized bed catalyst. Drying is usually performed by spray drying.
- the dryer a general one such as a rotary disk type or a nozzle type can be used.
- the drying conditions can be appropriately adjusted.
- the obtained dry particles exhibit activity as a catalyst by firing.
- the firing temperature is preferably 300 to 1000 ° C.
- the calcination temperature is lower than the above lower limit value, that is, 300 ° C.
- the activity as a catalyst is hardly exhibited.
- the firing temperature is higher than the above upper limit, that is, 1000 ° C.
- the activity tends to be excessive or the acrylonitrile yield tends to decrease. That is, a calcination temperature of 300 to 1000 ° C. is preferable because the activity as a catalyst is easily developed and the acrylonitrile yield is hardly lowered. If the calcination time is too short, the activity as a catalyst is not sufficiently exhibited, so 0.5 hour or more is preferable.
- the upper limit is not particularly limited, but even if the calcination time is extended more than necessary, the performance of the catalyst does not become a certain level, so it is usually within 20 hours. That is, the firing time is preferably 0.5 to 20 hours.
- the furnace used for baking A box furnace, a rotary kiln, a fluidized-fired furnace, etc. can be used.
- a rotary kiln or a fluidized firing furnace that fires particles while flowing is preferred, and a fluidized firing furnace is particularly preferred because uniform firing is possible. Firing is preferably performed twice or more because physical properties such as acrylonitrile yield and particle strength are improved.
- the amount of each catalyst raw material added in the above-described solution or aqueous slurry preparation step (I), or after the preparation step of the solution or aqueous slurry is dried is just to select suitably the addition amount of the catalyst raw material added at each process to a process.
- the addition amount of the catalyst raw material added by impregnation or the like may be appropriately selected.
- the composition of the catalyst can be confirmed by performing elemental analysis by ICP (inductively coupled radio frequency plasma) emission analysis, XRF (fluorescence X-ray) analysis, atomic absorption analysis or the like. In the case where an element having extremely high volatility is not used, it may be calculated from the amount of each raw material used at the time of catalyst production.
- ICP inductively coupled radio frequency plasma
- XRF fluorescence X-ray
- the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst during the gas phase catalytic ammoxidation reaction is 0.01-0.
- the manufacturing method of the fluidized bed catalyst used in each Example is shown below.
- the composition of the fluidized bed catalyst was determined from the amount of each raw material used for the production of the catalyst.
- the activity test of a fluidized bed catalyst and the measuring method of the ammonia adsorption amount of a fluidized bed catalyst are shown below.
- solution B in which 37.7 g of ammonium paratungstate was dissolved in 700 g of pure water
- solution C a solution in which 31.9 g of ammonium paramolybdate were dissolved in 100 g of pure water
- 6508.0 g of 20 mass% colloidal silica, 1052.6 g of antimony trioxide powder, B liquid, and C liquid were sequentially added to the A liquid with stirring to obtain an aqueous slurry.
- 15% by mass aqueous ammonia was added dropwise to adjust the pH to 2.0, and the resulting aqueous slurry was heat-treated at the boiling point for 3 hours under reflux.
- the aqueous slurry after the heat treatment was cooled to 80 ° C., and 20.8 g of 85% by mass phosphoric acid and 40.2 g of boric acid were sequentially added.
- the obtained aqueous slurry was spray-dried with a spray dryer at a drying air temperature of 330 ° C. at the dryer inlet and 160 ° C. at the dryer outlet to obtain spherical dry particles.
- the obtained dried particles were calcined at 250 ° C. for 2 hours and at 400 ° C. for 2 hours, and finally fluidized and calcined at 800 ° C. for 3 hours using a fluidized calciner to obtain a fluidized bed catalyst 1.
- the composition of the obtained fluidized bed catalyst 1 was as follows.
- x is the number of oxygen atoms necessary to satisfy the valence of each component excluding silica.
- composition of the fluidized bed catalyst 1 is also shown in Table 1, the description of oxygen and the number of atoms (x) is omitted in Table 1.
- ⁇ Fluidized bed catalyst 2 To 150 g of pure water heated to 50 ° C., 51.0 g of ammonium paramolybdate, 253.4 g of tellurium powder, and 200 g of 35% hydrogen peroxide solution were sequentially added and dissolved, followed by stirring and holding for 3 hours. By adding pure water thereto, the liquid volume was adjusted to 720 mL to prepare a D liquid. The liquid D was added little by little to 3000 g of the fluidized bed catalyst 1 to obtain a mixture impregnated with the liquid D. This mixture was calcined at 500 ° C. for 3 hours in a rotary calcining furnace to obtain a fluidized bed catalyst 2. The composition of the obtained fluidized bed catalyst 2 was as follows.
- x is the number of oxygen atoms necessary to satisfy the valence of each component excluding silica.
- composition of the fluidized bed catalyst 2 is also shown in Table 1, the description of oxygen and the number of atoms (x) is omitted in Table 1.
- ⁇ Fluidized bed catalyst 3> After adding and dissolving 3.65 g of potassium nitrate in 150 g of pure water heated to 50 ° C., the mixture was stirred for 30 minutes. By adding pure water thereto, the liquid volume was adjusted to 720 mL to prepare E liquid. The liquid E was added little by little to 3000 g of the fluidized bed catalyst 1 to obtain a mixture impregnated with the liquid E. This mixture was calcined at 500 ° C. for 3 hours in a rotary calcining furnace to obtain a fluidized bed catalyst 3. The composition of the obtained fluidized bed catalyst 3 was as follows.
- x is the number of oxygen atoms necessary to satisfy the valence of each component excluding silica.
- composition of the fluidized bed catalyst 3 is also shown in Table 1, the description of oxygen and the number of atoms (x) is omitted in Table 1.
- solution G in which 10.0 g of ammonium paratungstate was dissolved in 270 g of pure water
- solution H a solution in which 40.6 g of ammonium paramolybdate were dissolved in 30 g of pure water were prepared.
- 5178.4 g of 20 mass% silica sol in liquid F and 1395.9 g of antimony trioxide powder were added dropwise with 15 mass% aqueous ammonia to adjust the pH to 1.8, and the resulting aqueous slurry was refluxed Then, heat treatment was performed for 3 hours.
- the slurry after the heat treatment was cooled to 80 ° C., and 4.4 g of 85 mass% phosphoric acid, G solution, and H solution were sequentially added.
- the obtained aqueous slurry was spray-dried with a spray dryer at a drying air temperature of 330 ° C. at the dryer inlet and 160 ° C. at the dryer outlet to obtain spherical dry particles.
- the obtained dried particles were calcined at 250 ° C. for 2 hours and 400 ° C. for 2 hours, and finally fluidized and calcined at 810 ° C. for 3 hours using a fluidized calcining furnace to obtain a fluidized bed catalyst 4.
- the composition of the obtained fluidized bed catalyst 4 was as follows.
- x is the number of oxygen atoms necessary to satisfy the valence of each component excluding silica.
- composition of the fluidized bed catalyst 4 is also shown in Table 1, the description of oxygen and the number of atoms (x) is omitted in Table 1.
- ⁇ Fluidized bed catalyst 5 In the production of the fluidized bed catalyst 4, the production is performed in the same manner as the fluidized bed catalyst 4 except that the amount of tellurium powder used at the preparation of the F liquid is changed from 88.0 g to 219.9 g. It was.
- the composition of the obtained fluidized bed catalyst 5 was as follows. Fe 10 Sb 25 Mo 0.6 W 0.1 Te 2.5 Cu 2 Ni 0.5 Mg 0.3 P 0.1 Li 0.05 O x (SiO 2 ) 45
- x is the number of oxygen atoms necessary to satisfy the valence of each component excluding silica.
- the composition of the fluidized bed catalyst 5 is also shown in Table 1, the description of oxygen and the number of atoms (x) is omitted in Table 1.
- the reaction pressure was 200 kPa, and the reaction temperature was 460 ° C.
- the reaction product was quantified using gas chromatography and analyzed at a frequency of at least once every 100 hours. At that time, the amount of the catalyst was appropriately adjusted so that the conversion rate of propylene was 97.8 to 98.2%. Specifically, when the propylene conversion rate was smaller than this range, a new catalyst was added to adjust the catalyst amount.
- Propylene conversion rate (%) ⁇ (carbon mass of supplied propylene ⁇ carbon mass of unreacted propylene) / carbon mass of supplied propylene ⁇ ⁇ 100
- Acrylonitrile yield (%) ⁇ (carbon mass of produced acrylonitrile) / carbon mass of supplied propylene ⁇ ⁇ 100
- Ammonia combustion rate (%) ⁇ (nitrogen mass of supplied ammonia ⁇ nitrogen mass of unreacted ammonia ⁇ nitrogen mass of collected nitrogen-containing organic compound) / (nitrogen mass of supplied ammonia) ⁇ ⁇ 100
- Ammonia adsorption amount of fluidized bed catalyst is described in zeolite (Vol. 21, No. 2, p. 45-52, 2004) and surface science (Vol. 24, No. 10, p. 635-641, 2003).
- the measurement was performed as follows.
- a fully automatic temperature-programmed desorption gas analyzer manufactured by Nippon Bell Co., Ltd., “Multitask TPD” was used.
- Helium was used as the carrier gas.
- helium was flowed at a flow rate of 50 mL / min.
- the catalyst was pretreated by maintaining the temperature of the catalyst at 400 ° C. for 1 hour. After completion of the pretreatment, the temperature of the catalyst was lowered to 100 ° C. and kept in that state for 10 minutes.
- 0.1 vol% ammonia-99.9 vol% helium mixed gas was passed for 5 minutes to adsorb ammonia on the catalyst. Thereafter, helium was flowed at a flow rate of 50 mL / min. And kept in that state for 60 minutes.
- helium was supplied to the catalyst at a flow rate of 50 mL / min. At a heating rate of 10 ° C./min.
- the temperature was raised to 500 ° C., during which time ammonia gas desorbed from the catalyst was analyzed using a quadrupole mass spectrometer, and the amount of ammonia desorbed from the catalyst was quantified.
- a calibration curve prepared separately by introducing a known amount of ammonia gas into a quadrupole mass spectrometer was used for quantification of the ammonia amount.
- the setting conditions of the quadrupole mass spectrometer are as follows.
- the specific surface area (m 2 / g) of the fluidized bed catalyst was calculated using the BET method.
- the method refer to the conditions described in the specifications for the specific surface area test powder in Annex A (reference) for the specific surface area test powder of the Japan Powder Industrial Technology Association. It was measured.
- a specific surface area measuring apparatus a BET specific surface area measuring apparatus (manufactured by Mountec Co., Ltd., “Macsorb HM Model-1208”) was used. First, about 0.5 g of the target fluidized bed catalyst was collected and set in a measuring cell of a BET specific surface area measuring device. While passing nitrogen gas through this catalyst, the temperature of the catalyst was kept at 200 ° C. for 40 minutes, and the catalyst was pretreated.
- the mixture was allowed to cool at room temperature for 4 minutes, and then cooled to liquid nitrogen while adsorbing nitrogen by adsorbing 30 volume% nitrogen-70 volume% helium mixed gas at a flow rate of 25 ml / min.
- the amount of nitrogen in the outlet gas was detected by a TCD detector, and the catalyst was sufficiently adsorbed with nitrogen until stabilized at a constant amount. Thereafter, nitrogen adsorbed sufficiently at room temperature was desorbed, and the desorbed amount was detected by the TCD detector.
- the nitrogen gas filled in the column in the apparatus was pushed out to the mixed gas line for calibration. After the measurement was completed, the weight of the sample cell that had reached room temperature was measured, and the weight of the catalyst was calculated.
- the specific surface area (m 2 / g) per gram of catalyst was calculated from the nitrogen desorption amount, the calibration value, the sample weight, and the like. Using the values of the ammonia adsorption amount ( ⁇ mol / g) and specific surface area (m 2 / g) of the catalyst determined by the above measurement method, the ammonia adsorption amount per specific surface area of the catalyst ( ⁇ mol / m) by the following equation: 2 ) was calculated.
- Ammonia adsorption amount ( ⁇ mol / m 2 ) per specific surface area (m 2 / g) of fluidized bed catalyst ammonia adsorption amount ( ⁇ mol / g) / specific surface area of fluidized bed catalyst (m 2 / g)
- Example 1 The activity test and the ammonia adsorption amount and specific surface area of the catalyst extracted from the reactor were measured as follows. Using the fluidized bed catalyst 1, an acrylonitrile synthesis reaction by a gas phase catalytic ammoxidation reaction was performed. The ammonia adsorption amount per specific surface area of the unreacted catalyst was 0.13 ⁇ mol / m 2 . The reaction gas was analyzed 100 hours after the start of the reaction, and the propylene conversion rate, acrylonitrile yield, and ammonia combustion rate were determined. Immediately after the reaction gas analysis, about 5 g of catalyst was extracted from the reactor, and the ammonia adsorption amount and specific surface area 100 hours after the start of the reaction were measured.
- reaction was continued, and the reaction gas was analyzed 300 hours after the start of the reaction to determine the propylene conversion rate, the acrylonitrile yield, and the ammonia combustion rate.
- reaction gas analysis about 5 g of catalyst was extracted from the reactor, and the ammonia adsorption amount and specific surface area 300 hours after the start of the reaction were measured.
- an amount of metal tellurium corresponding to 0.2% of the catalyst mass in the reactor was added, and the reaction was continued.
- the reaction gas was analyzed 500 hours after the start of the reaction, and the propylene conversion rate, the acrylonitrile yield, and the ammonia combustion rate were determined.
- Example 2 Using the same fluidized bed catalyst 1 as in Example 1, an acrylonitrile synthesis reaction by a gas phase catalytic ammoxidation reaction was performed as follows. The same operation as in Example 1 was performed from the start of the reaction to 525 hours. After 525 hours from the start of the reaction, an amount of the fluidized bed catalyst 2 corresponding to 4% of the catalyst mass in the reactor was added, and the reaction was continued. In addition, the same operation as in Example 1 was performed thereafter. The reaction gas was analyzed 100, 300, 500, 700, and 1000 hours after the start of the reaction to determine propylene conversion rate, acrylonitrile yield, and ammonia combustion rate.
- Example 3 An acrylonitrile synthesis reaction by a gas phase catalytic ammoxidation reaction was performed using the fluidized bed catalyst 4.
- the ammonia adsorption amount per specific surface area of the unreacted catalyst was 0.05 ⁇ mol / m 2 .
- the reaction gas was analyzed 100 hours after the start of the reaction, and the propylene conversion rate, acrylonitrile yield, and ammonia combustion rate were determined.
- about 5 g of catalyst was extracted from the reactor, and the ammonia adsorption amount and specific surface area 100 hours after the start of the reaction were measured.
- reaction gas was analyzed 300 hours after the start of the reaction to determine the propylene conversion rate, the acrylonitrile yield, and the ammonia combustion rate.
- reaction gas analysis about 5 g of catalyst was extracted from the reactor, and the ammonia adsorption amount and specific surface area 300 hours after the start of the reaction were measured.
- an amount of catalyst corresponding to 10% of the catalyst mass in the reactor was withdrawn from the reactor, and an amount of fluidized bed catalyst 5 equivalent to the withdrawn catalyst was added to continue the reaction.
- the reaction gas was analyzed 500 hours after the start of the reaction, and the propylene conversion rate, the acrylonitrile yield, and the ammonia combustion rate were determined.
- Example 1 The same operation as in Example 3 was carried out except that the same fluidized bed catalyst 4 as in Example 3 was used and that the fluidized bed catalyst 5 and ammonium molybdate were not added during the reaction.
- the reaction gas was analyzed 100, 300, 500, 700, and 1000 hours after the start of the reaction to determine propylene conversion rate, acrylonitrile yield, and ammonia combustion rate.
- about 5 g of catalyst was extracted from the reactor immediately after analysis of the reaction gas, and the ammonia adsorption amount and specific surface area after 100, 300, 500, 700, and 1000 hours from the start of the reaction were measured. These results are shown in Table 2.
- the reaction gas was analyzed 300 hours after the start of the reaction. Immediately after the reaction gas analysis, about 5 g of catalyst was extracted from the reactor, and the ammonia adsorption amount and specific surface area 300 hours after the start of the reaction were measured. These results are shown in Table 2.
- the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst during the gas phase catalytic ammoxidation process is maintained in the range of 0.01 to 0.22 ⁇ mol / m 2.
- the gas phase catalytic ammoxidation reaction was carried out while maintaining the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst during the reaction in the range of 0.03 to 0.18 ⁇ mol / m 2.
- acrylonitrile could be produced while maintaining a higher acrylonitrile yield of 80.5% or higher.
- the acrylonitrile yield when the ammonia adsorption amount in the gas phase catalytic ammoxidation process is within the range of 0.01 to 0.22 ⁇ mol / m 2 is the yield when the ammonia adsorption amount is outside the above range. Higher than. It was confirmed that the decrease in the yield of acrylonitrile could be effectively suppressed if the relationship between the ammonia adsorption amount and the acrylonitrile yield, that is, the ammonia adsorption amount was within the above range.
- the ammonia adsorption amount per specific surface area (m 2 / g) of the fluidized bed catalyst during the gas phase catalytic ammoxidation process is maintained in the range of 0.01 to 0.22 ⁇ mol / m 2.
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Abstract
Description
本発明は、2012年2月29日に日本国に出願された特願2012-042832号に基づき優先権を主張し、その内容をここに援用する。
例えば、特許文献1には鉄、アンチモン、およびコバルト、ニッケルよりなる群から選ばれた少なくとも一種の元素との複合酸化物触媒が開示されている。
また、特許文献2~8には、鉄、アンチモン、テルル、さらにバナジウム、モリブデン、タングステン等を含有する複合酸化物触媒が開示されている。さらに、特許文献9~11にはこれら鉄、アンチモンを含有する触媒の製造方法が開示されている。
例えば、特許文献12には、反応使用によって性能が低下した触媒にテルルを富化し、900℃以下の高温で加熱することにより、目的生成物の選択率および触媒活性が改善されることが明記されている。そして、このテルル富化触媒を反応器内の触媒と入れ替えることにより、高いアクリロニトリル収率を維持することが開示されている。
また、特許文献13では、テルル含有酸化物触媒を用いたアンモ酸化反応中に、テルル担体、テルル化合物、及びモリブデン化合物を反応器中に添加することにより、目的生成物の選択率、および触媒活性の経時的な低下が改善されることが開示されている。
Fe10SbaAbTecDdEeOx・(SiO2)y ・・・(1)
<1>アクリロニトリルの製造方法であって、
プロピレンと、分子状酸素と、アンモニアとを含む原料ガスを、流動層触媒に接触させて気相接触アンモ酸化を行い、アクリロニトリルを得る、気相接触アンモ酸化工程を含み、
前記流動層触媒が、鉄、アンチモンおよびテルルを含有する触媒であり、
前記気相接触アンモ酸化工程が、前記流動層触媒の比表面積(m2/g)あたりのアンモニア吸着量を0.01~0.22μmol/m2の範囲に維持しながら行われることを特徴とする、アクリロニトリルの製造方法;
<2>前記流動層触媒が、下記一般式(1)で表されることを特徴とする、<1>に記載のアクリロニトリルの製造方法;
Fe10SbaAbTecDdEeOx・(SiO2)y ・・・(1)
式中、Fe、Sb、Te、O、およびSiO2はそれぞれ鉄、アンチモン、テルル、酸素およびシリカを表し、Aはバナジウム、モリブデン、およびタングステンからなる群より選ばれた少なくとも一種の元素を表し、Dはマグネシウム、カルシウム、ストロンチウム、バリウム、チタン、ジルコニウム、ニオブ、クロム、マンガン、コバルト、ニッケル、銅、銀、亜鉛、ホウ素、アルミニウム、ガリウム、インジウム、タリウム、ゲルマニウム、スズ、鉛、リン、ヒ素、およびビスマスからなる群より選ばれた少なくとも一種の元素を表し、Eはリチウム、ナトリウム、カリウム、ルビジウム、およびセシウムからなる群から選ばれた少なくとも一種の元素を表し、a、b、c、d、e、xおよびyは原子比を表し、a=3~100、b=0.1~5、c=0.1~10、d=0~50、e=0~5、y=10~200であり、xはシリカを除く前記各成分の原子価を満足するのに必要な酸素の原子数である。ただし、A、D、およびEが、2種以上の元素を含む場合、b、d、およびeは、各元素の原子比の合計を表す。
本発明の1つの態様は、流動層反応器にて、鉄、アンチモンおよびテルルを含有する流動層触媒を用い、プロピレンを分子状酸素およびアンモニアにより気相接触アンモ酸化してアクリロニトリルを製造する方法において、前記気相接触アンモ酸化反応中における前記流動層触媒の比表面積(m2/g)あたりのアンモニア吸着量を0.01~0.22μmol/m2の範囲に維持しながら、気相接触アンモ酸化反応を行うことを特徴とするアクリロニトリルの製造方法である。
また、本発明のその他の態様は、プロピレンと、分子状酸素と、アンモニアとを含む原料ガスを、流動層触媒に接触させて気相接触アンモ酸化を行い、アクリロニトリルを得る、気相接触アンモ酸化工程を含み、前記流動層触媒が、鉄、アンチモンおよびテルルを含有する触媒であり、前記気相接触アンモ酸化工程が、前記流動層触媒の比表面積(m2/g)あたりのアンモニア吸着量を0.01~0.22μmol/m2の範囲に維持しながら行われることを特徴とする、アクリロニトリルの製造方法である。
気相接触アンモ酸化反応工程中の流動層触媒の比表面積(m2/g)あたりのアンモニア吸着量の下限値は好ましくは0.03μmol/m2であり、上限値は好ましくは0.18μmol/m2である。
なお、気相接触アンモ酸化反応工程中の流動層触媒の比表面積(m2/g)あたりのアンモニア吸着量は、前記工程中に流動層反応器から前記流動層触媒の一部を抜き出し、下記の方法で定量した値である。
本発明のアンモニア吸着量は、流動層触媒から脱離したアンモニア量をアンモニア吸着量測定装置で測定した値のことを指す。以下に、具体的な測定方法について記載する。まず、流動層触媒約0.3gを装置に仕込み、ヘリウムを流速50mL/min.で流通させながら400℃で1時間保持し、触媒の前処理を行う。
前処理終了後、100℃まで触媒を降温し、その状態で10分間保持する。
ついで、0.1容量%アンモニア-99.9容量%ヘリウム混合ガスを5分間流通し、触媒上にアンモニアを吸着させる。
その後、ヘリウムを流速50mL/min.で流通させ、その状態で60分間保持する。
ついで、触媒にヘリウムを流速50mL/min.で流通させながら、昇温速度10℃/min.で500℃まで昇温し、その間、四重極質量分析計によって、触媒から脱離したアンモニアガスを分析し、触媒から脱離したアンモニア量を定量する。アンモニア量の定量には、別途、既知量のアンモニアガスを四重極質量分析計に導入して作成した検量線を用いる。
流動層触媒の比表面積(m2/g)については、比表面積測定装置(BET法)を用いて算出した。なお、その方法については、日本粉体工業技術協会規格 比表面積検定用粉体 附属書A(参考)比表面積検定用粉体の使用条件に記載されている条件を参考に測定することができる。
前記測定方法により定量したアンモニア量を、流動層触媒に吸着したアンモニア量(アンモニア吸着量)とし、これを流動層触媒の比表面積(m2/g)あたりの量に換算したものを気相接触アンモ酸化反応中における流動層触媒のアンモニア吸着量とする。
気相接触アンモ酸化工程中の流動層触媒のアンモニア吸着量を増大させる方法としては、アンモニアの吸着を促進する効果を有する化合物を添加する方法が挙げられる。アンモニアの吸着を促進する効果を有する化合物としては、具体的にはテルルやモリブデン等の酸性を有する元素を含む化合物等が挙げられ、これらを反応器中に添加する方法が、アンモニア吸着量を増大させる方法として有効である。
また、アンモニア吸着量の多い触媒を添加したり、反応器中の触媒の一部を新品の触媒で置換する方法なども有効である。
アンモニア吸着量の多い触媒は、テルルやモリブデン等、アンモニアの吸着を促進する効果を有する元素の含有量を高めるなど、触媒組成を調節することにより製造することができる。また、本発明の流動層触媒にアンモニアの吸着を促進する効果を有する元素を含浸することによりアンモニア吸着量の多い触媒を製造することもできる。アンモニアの吸着を促進する効果を有する元素としては、テルルやモリブデン等が挙げられる。
アンモニア吸着量の少ない触媒は、カリウム、ルビジウム、セシウム等、アンモニアの吸着を阻害する効果を有する元素の含有量を高めるなど、触媒組成を調節することにより製造することができる。また、アンモニアの吸着を阻害する効果を有する元素を含浸して、本発明の流動層触媒を製造することによりアンモニア吸着量の少ない触媒を製造することもできる。アンモニアの吸着を阻害する効果を有する元素としては、例えば、カリウム、ルビジウム、セシウム等が挙げられる。
なお、反応器中の流動層触媒のアンモニア吸着量を制御する方法は、上述した方法に限定されず、公知の任意の方法で実施することができる。
原料ガスとしては本発明の効果を有する限り特に限定されないが、プロピレン/アンモニア/酸素が1/1.0~2.0/1.0~5.0(モル比)の範囲の原料ガスが好ましい。
酸素源である分子状酸素の供給減としては本発明の効果を有する限り特に限定されないが、空気を用いることが好ましい。
原料ガスは窒素、二酸化炭素等の不活性ガスや飽和炭化水素等で希釈してもよく、また、純酸素を混合して酸素濃度を高めて用いてもよい。
気相接触アンモ酸化反応の反応温度は350~500℃が好ましく、反応圧力は常圧(100kPa)から500kPaの範囲内が好ましい。流動層触媒と反応ガスの接触時間は、0.1~20秒間であることが好ましい。
Fe10SbaAbTecDdEeOx・(SiO2)y ・・・(1)
工程(I)において、溶液または水性スラリーには、本発明の流動層触媒を構成する所望の元素の全てが、所望の原子比で含有されていてもよい。また、流動層触媒を構成する、一部の元素を含む溶液または水性スラリーを調製し、残りの元素を、乾燥後あるいは焼成後の触媒組成物に含浸等の方法により添加してもよい。
これらの原料を固体のまま、あるいは水や希硝酸等に溶解して溶液とした後に混合し、溶液または水性スラリーを得る。また、本発明の流動層触媒はシリカを含むが、前記シリカとしては、シリカゾルを用いることが好ましい。
溶液または水性スラリーのpH調製に際しては、必要に応じて硝酸やアンモニア水等を添加してpH調整を行ってもよく、また、濃縮処理や加熱処理により行ってもよい。
焼成時間は、短すぎると触媒としての活性が十分に発現しにくいことから、0.5時間以上が好ましい。上限は特に限定されないが、必要以上に焼成時間を延長しても、触媒の性能は一定以上とはならないため、通常は20時間以内である。すなわち、焼成時間は、0.5~20時間であることが好ましい。
焼成に用いられる炉については特に制限はなく、箱型炉、ロータリーキルン、流動焼成炉等を用いることができる。流動層触媒の製造には、粒子を流動させながら焼成するロータリーキルンや流動焼成炉が好ましく、特に均一な焼成が可能であるという点で流動焼成炉が好ましい。焼成は二回、あるいはそれ以上に分けて行うことでアクリロニトリル収率や粒子強度等の物性が向上するため好ましい。
各実施例で用いた流動層触媒の製造方法を以下に示す。なお、流動層触媒の組成は、触媒の製造に用いた各原料の仕込み量から求めた。
また、流動層触媒の活性試験、および流動層触媒のアンモニア吸着量の測定方法を以下に示す。
<流動層触媒1>
まず、63質量%の硝酸2400gに銅粉末68.8gを溶解した。この溶液に純水2300gを添加してから60℃に加熱し、電解鉄粉201.7g、テルル粉末64.5gを少量ずつ添加し、溶解した。溶解を確認した後、この溶液に硝酸ニッケル105.0g、硝酸クロム43.3g、硝酸マンガン10.4gを順次添加し、溶解した(A液)。
別途、純水700gにパラタングステン酸アンモニウム37.7gを溶解した溶液(B液)、純水100gにパラモリブデン酸アンモニウム31.9gを溶解した溶液(C液)を各々調製した。
次いで、攪拌しながらA液に20質量%コロイダルシリカ6508.0g、三酸化アンチモン粉末1052.6g、B液、C液を順次添加して水性スラリーを得た。
この水性スラリーに15質量%アンモニア水を滴下してpHを2.0に調整し、得られた水性スラリーを還流下、沸点で3時間加熱処理した。
加熱処理後の水性スラリーを80℃まで冷却し、85質量%リン酸20.8g、ホウ酸40.2gを順次添加した。
得られた水性スラリーを、噴霧乾燥機により、乾燥空気の温度を乾燥機入口で330℃、乾燥機出口で160℃として噴霧乾燥し、球状の乾燥粒子を得た。次いで、得られた乾燥粒子を250℃で2時間、400℃で2時間焼成し、最終的に流動焼成炉を用いて800℃で3時間流動焼成し、流動層触媒1を得た。
得られた流動層触媒1の組成は、以下の通りであった。
Fe10Sb20Mo0.5W0.4Te1.4Cu3Ni1P0.5B1.8Cr0.3Mn0.1Ox(SiO2)60
ここで、xは、シリカを除く前記各成分の原子価を満足するのに必要な酸素の原子数である。なお、流動層触媒1の組成を表1にも示すが、表1においては酸素とその原子数(x)の記載を省略する。
50℃に加熱した純水150gに、パラモリブデン酸アンモニウム51.0g、テルル粉末253.4g、35%過酸化水素水200gを順次添加して溶解した後、3時間攪拌保持した。そこに純水を添加することにより、液量を720mLに調節し、D液を調製した。
3000gの流動層触媒1に、D液を少しずつ添加し、D液を含浸した混合物を得た。
この混合物を回転焼成炉内で、500℃で、3時間焼成を行うことにより、流動層触媒2を得た。
得られた流動層触媒2の組成は、以下の通りであった。
Fe10Sb20Mo1.3W0.4Te6.9Cu3Ni1P0.5B1.8Cr0.3Mn0.1Ox(SiO2)60
ここで、xは、シリカを除く前記各成分の原子価を満足するのに必要な酸素の原子数である。なお、流動層触媒2の組成を表1にも示すが、表1においては酸素とその原子数(x)の記載を省略する。
50℃に加熱した純水150gに、硝酸カリウム3.65gを添加して溶解した後、30分間攪拌した。そこに純水を添加することにより、液量を720mLに調節し、E液を調製した。
3000gの流動層触媒1に、E液を少しずつ添加し、E液を含浸した混合物を得た。
この混合物を回転焼成炉内で、500℃で、3時間焼成を行うことにより、流動層触媒3を得た。
得られた流動層触媒3の組成は、以下の通りであった。
Fe10Sb20Mo0.5W0.4Te1.4Cu3Ni1P0.5B1.8Cr0.3Mn0.1K0.1Ox(SiO2)60
ここで、xは、シリカを除く前記各成分の原子価を満足するのに必要な酸素の原子数である。なお、流動層触媒3の組成を表1にも示すが、表1においては酸素とその原子数(x)の記載を省略する。
63質量%硝酸2110gに銅粉末48.7gを溶解した。この溶液に純水2710gを添加してから60℃に加熱し、電解鉄粉213.9g、テルル粉末88.0gを少量ずつ添加し、溶解した。溶解を確認した後、硝酸マグネシウム29.5g、硝酸ニッケル55.7g、硝酸リチウム1.3gを順次添加し、溶解した(F液)。
別途、純水270gにパラタングステン酸アンモニウム10.0gを溶解した液(G液)、純水30gにパラモリブデン酸アンモニウム40.6gを溶解した液(H液)を各々調製した。
次いで、攪拌しながら、F液に20質量%シリカゾル5178.4g、三酸化アンチモン粉末1395.9gに15質量%アンモニア水を滴下してpHを1.8に調整し、得られた水性スラリーを還流下、3時間加熱処理した。
加熱処理後のスラリーを80℃まで冷却し、85質量%リン酸4.4g、G液、H液を順次添加した。
得られた水性スラリーを、噴霧乾燥機により、乾燥空気の温度を乾燥機入口で330℃、乾燥機出口で160℃として噴霧乾燥し、球状の乾燥粒子を得た。次いで、得られた乾燥粒子を250℃で2時間、400℃で2時間焼成し、最終的に流動焼成炉を用いて810℃で3時間流動焼成し、流動層触媒4を得た。
得られた流動層触媒4の組成は、以下の通りであった。
Fe10Sb25Mo0.6W0.1Te1.0Cu2Ni0.5Mg0.3P0.1Li0.05Ox(SiO2)45
ここで、xは、シリカを除く前記各成分の原子価を満足するのに必要な酸素の原子数である。なお、流動層触媒4の組成を表1にも示すが、表1においては酸素とその原子数(x)の記載を省略する。
流動層触媒4の製造において、F液調製時に使用するテルル粉末の量を88.0gから219.9gに変更した点以外は、流動層触媒4と同様に製造を行い、流動層触媒5を得た。
得られた流動層触媒5の組成は、以下の通りであった。
Fe10Sb25Mo0.6W0.1Te2.5Cu2Ni0.5Mg0.3P0.1Li0.05Ox(SiO2)45
ここで、xは、シリカを除く前記各成分の原子価を満足するのに必要な酸素の原子数である。なお、流動層触媒5の組成を表1にも示すが、表1においては酸素とその原子数(x)の記載を省略する。
得られた流動層触媒を用い、以下の要領でプロピレンの気相接触アンモ酸化反応によるアクリロニトリル合成反応を実施した。
触媒流動部の内径が55mm、高さが2000mmの流動層反応器に、接触時間が3.2秒間となるように流動層触媒を充填した。流動層触媒と反応ガスの接触時間は下記式により求めた。
接触時間(秒)=見掛け嵩密度基準の触媒容積(mL)/反応条件に換算した供給原料ガス量(mL/秒)
反応生成物の定量にはガスクロマトグラフィーを用い、100時間に1回以上の頻度で分析を行った。その際、プロピレンの転化率が97.8~98.2%となるように、触媒量を適宜調整した。具体的には、プロピレン転化率がこの範囲よりも小さい場合、新品触媒を添加し、触媒量を調整した。また、プロピレン転化率がこの範囲よりも大きい場合、反応器から触媒を抜き出し、プロピレンの転化率を調整した。
プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率は下記式により求めた。
プロピレン転化率(%)={(供給したプロピレンの炭素質量-未反応プロピレンの炭素質量)/供給したプロピレンの炭素質量}×100
アクリロニトリル収率(%)={(生成したアクリロニトリルの炭素質量)/供給したプロピレンの炭素質量)}×100
アンモニア燃焼率(%)={(供給したアンモニアの窒素質量-未反応アンモニアの窒素質量-捕集された窒素含有有機化合物の窒素質量)/(供給したアンモニアの窒素質量)}×100
流動層触媒のアンモニア吸着量について、ゼオライト(Vol.21,No.2,p.45-52,2004)や、表面科学(Vol.24,No.10,p.635-641,2003)に記載されているアンモニア昇温脱離法を参考にし、以下のようにして測定した。なお、アンモニア吸着量測定装置としては、全自動昇温脱離ガス分析装置(日本ベル株式会社製、「マルチタスクTPD」)を用いた。また、キャリアーガスとしては、ヘリウムを用いた。
まず、対象とする流動層触媒約0.3gを分取し、全自動昇温脱離ガス分析装置の測定用セルにセットした。この触媒に、ヘリウムを流速50mL/min.で流通させながら、触媒の温度を400℃として1時間保持し、触媒の前処理を行った。
前処理終了後、100℃まで触媒を降温し、その状態で10分間保持した。
ついで、0.1容量%アンモニア-99.9容量%ヘリウム混合ガスを5分間流通し、触媒上にアンモニアを吸着させた。
その後、ヘリウムを流速50mL/min.で流通させ、その状態で60分間保持した。
ついで、触媒にヘリウムを流速50mL/min.で流通させながら、昇温速度10℃/min.で500℃まで昇温し、その間、四重極質量分析計を用いて触媒から脱離したアンモニアガスを分析し、触媒から脱離したアンモニア量を定量した。アンモニア量の定量には、別途、既知量のアンモニアガスを四重極質量分析計に導入して作成した検量線を用いた。
なお、四重極質量分析計の設定条件は下記の通りである。
<設定条件>
・積算回数:5回
・MCP(Micro Channel Plate 光電子倍増素子電圧):720eV・Emission(放出電流):2mA
・IE(Ion Energy イオン化エネルギー):8V
・EE(Electron Energy 電子エネルギー):70eV
・ScanTime(走査時間):300ms
前記測定方法により定量したアンモニア量、測定に用いた触媒重量などから、触媒1gあたりのアンモニア吸着量(μmol/g)を求めた。
流動層触媒の比表面積(m2/g)は、BET法を用いて算出した。なお、その方法については、日本粉体工業技術協会規格 比表面積検定用粉体 附属書A(参考)比表面積検定用粉体の使用条件に記載されている条件を参考にし、以下のようにして測定した。なお、比表面積測定装置としては、BET比表面積測定装置((株)マウンテック社製、「Macsorb HM Model-1208」)を用いた。
まず、対象とする流動層触媒約0.5gを分取し、BET比表面積測定装置の測定用セルにセットした。この触媒に、窒素ガスを流通させながら、触媒の温度を200℃として40分保持し、触媒の前処理を行った。
前処理終了後、4分間室温で放冷し、ついで、30容量%窒素-70容量%ヘリウム混合ガスを流速25ml/minで流通させながら、液体窒素まで冷却して窒素を吸着させた。出口ガス中の窒素量をTCD検出器にて検出し、一定量で安定するまで、触媒に充分窒素を吸着させた。
その後、室温にて充分吸着させた窒素を脱離させ、脱離した量を同じくTCD検出器により検出した。
脱離完了後、装置内のカラムに充満された窒素ガスを混合ガスラインに押し出し、キャリブレーションを行った。
測定が終了し、室温になったサンプルセルの重量を測定し、触媒の重量を算出した。窒素脱離量、キャリブレーションの値、サンプル重量などから、触媒1gあたりの比表面積(m2/g)を算出した。
上記測定法により求めた、触媒のアンモニア吸着量(μmol/g)および比表面積(m2/g)の値を用いて、以下の式により、触媒の比表面積あたりのアンモニア吸着量(μmol/m2)を算出した。
流動層触媒の比表面積(m2/g)あたりのアンモニア吸着量(μmol/m2)=アンモニア吸着量(μmol/g)/流動層触媒の比表面積(m2/g)
以下のようにして活性試験および反応器より抜き出した触媒のアンモニア吸着量および比表面積の測定を行った。
流動層触媒1を用いて気相接触アンモ酸化反応によるアクリロニトリル合成反応を行った。なお、未反応の触媒の比表面積あたりのアンモニア吸着量は0.13μmol/m2であった。
反応開始から100時間後に反応ガスを分析し、プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率を求めた。また、反応ガス分析直後に反応器から触媒約5gを抜き出し、反応開始から100時間後のアンモニア吸着量および比表面積を測定した。
引き続き、反応を継続し、反応開始から300時間後に反応ガスを分析し、プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率を求めた。また、反応ガス分析直後に反応器から触媒約5gを抜き出し、反応開始から300時間後のアンモニア吸着量および比表面積を測定した。反応開始から325時間後に反応器中の触媒質量の0.2%に相当する量の金属テルルを添加して、反応を継続した。
反応開始から500時間後に反応ガスを分析し、プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率を求めた。また、反応ガス分析直後に反応器から触媒約5gを抜き出し、反応開始から500時間後のアンモニア吸着量および比表面積を測定した。反応開始から525時間後に反応器中の触媒質量の2%に相当する量の流動層触媒2を添加して、反応を継続した。
反応開始から700時間後に反応ガスを分析し、プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率を求めた。また、反応ガス分析直後に反応器から触媒約5gを抜き出し、反応開始から700時間後のアンモニア吸着量および比表面積を測定した。反応開始から725時間後に反応器中の触媒質量の5%に相当する量の流動層触媒3を添加して、反応を継続した。
反応開始から1000時間後に反応ガスを分析し、プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率を求めた。また、反応ガス分析直後に反応器から触媒約5gを抜き出し、反応開始から1000時間後のアンモニア吸着量および比表面積を測定した。
これらの結果を表2に示す。
実施例1と同じ流動層触媒1を用い、以下のように気相接触アンモ酸化反応によるアクリロニトリル合成反応を行った。
反応開始から525時間まで実施例1と同様の運転を行い、反応開始から525時間後に反応器中の触媒質量の4%に相当する量の流動層触媒2を添加して、反応を継続した。また、これ以降も実施例1と同様の運転を行った。
反応開始から100、300、500、700、1000時間後に反応ガスを分析し、プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率を求めた。また、それぞれ反応ガスの分析直後に反応器から触媒約5gを抜き出し、反応開始から100、300、500、700、1000時間後のアンモニア吸着量および比表面積を測定した。
これらの結果を表2に示す。
流動層触媒4を用いて気相接触アンモ酸化反応によるアクリロニトリル合成反応を行った。なお、未反応の触媒の比表面積あたりのアンモニア吸着量は0.05μmol/m2であった。
反応開始から100時間後に反応ガスを分析し、プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率を求めた。また、反応ガス分析直後に反応器から触媒約5gを抜き出し、反応開始から100時間後のアンモニア吸着量および比表面積を測定した。
引き続き、反応を継続し、反応開始から300時間後に反応ガスを分析し、プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率を求めた。また、反応ガス分析直後に反応器から触媒約5gを抜き出し、反応開始から300時間後のアンモニア吸着量および比表面積を測定した。反応開始から325時間後に反応器中の触媒質量の10%に相当する量の触媒を反応器から抜き出し、抜き出した触媒と等量の流動層触媒5を添加して、反応を継続した。
反応開始から500時間後に反応ガスを分析し、プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率を求めた。また、反応ガス分析直後に反応器から触媒約5gを抜き出し、反応開始から500時間後のアンモニア吸着量および比表面積を測定した。反応開始から525時間後に反応器中の触媒質量の8%に相当する量のモリブデン酸アンモニウムを添加して、反応を継続した。
反応開始から700時間後に反応ガスを分析し、プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率を求めた。また、反応ガス分析直後に反応器から触媒約5gを抜き出し、反応開始から700時間後のアンモニア吸着量および比表面積を測定した。反応開始から725時間後に反応器中の触媒質量の2%に相当する量の流動層触媒4を添加して、反応を継続した。
反応開始から1000時間後に反応ガスを分析し、プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率を求めた。また、反応ガス分析直後に反応器から触媒約5gを抜き出し、反応開始から1000時間後のアンモニア吸着量および比表面積を測定した。
これらの結果を表2に示す。
実施例3と同じ流動層触媒4を用い、かつ、反応途中で流動層触媒5およびモリブデン酸アンモニウムの添加を行わない以外は、実施例3と同様の運転を行った。
反応開始から100、300、500、700、1000時間後に反応ガスを分析し、プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率を求めた。また、それぞれ反応ガスの分析直後に反応器から触媒約5gを抜き出し、反応開始から100、300、500、700、1000時間後のアンモニア吸着量および比表面積を測定した。
これらの結果を表2に示す。
実施例1と同じ流動層触媒1を用い、以下のように気相接触アンモ酸化反応によるアクリロニトリル合成反応を行った。
反応開始から100時間後に反応ガスを分析し、プロピレン転化率、アクリロニトリル収率、アンモニア燃焼率を求めた。また、反応ガス分析直後に反応器から触媒約5gを抜き出し、反応開始から100時間後のアンモニア吸着量および比表面積を測定した。反応開始から125時間後に反応器中の触媒質量の10%に相当する量の触媒を反応器から抜き出し、抜き出した触媒と等量の流動層触媒2を添加して、反応を継続した。
反応開始から300時間後に反応ガスを分析した。また、反応ガス分析直後に反応器から触媒約5gを抜き出し、反応開始から300時間後のアンモニア吸着量および比表面積を測定した。
これらの結果を表2に示す。
また、比較例2の場合、気相接触アンモ酸化反応の途中で、反応中の流動層触媒の比表面積(m2/g)あたりのアンモニア吸着量が0.22μmol/m2を超えると、アクリロニトリルの収率が低下した。
Claims (2)
- アクリロニトリルの製造方法であって、
プロピレンと、分子状酸素と、アンモニアとを含む原料ガスを、流動層触媒に接触させて気相接触アンモ酸化を行い、アクリロニトリルを得る、気相接触アンモ酸化工程を含み、
前記流動層触媒が、鉄、アンチモンおよびテルルを含有する触媒であり、
前記気相接触アンモ酸化工程が、前記流動層触媒の比表面積(m2/g)あたりのアンモニア吸着量を0.01~0.22μmol/m2の範囲に維持しながら行われることを特徴とする、アクリロニトリルの製造方法。 - 前記流動層触媒が、下記一般式(1)で表されることを特徴とする請求項1に記載のアクリロニトリルの製造方法。
Fe10SbaAbTecDdEeOx・(SiO2)y ・・・(1)
(式中、Fe、Sb、Te、O、およびSiO2はそれぞれ鉄、アンチモン、テルル、酸素およびシリカを表し、Aはバナジウム、モリブデン、およびタングステンからなる群より選ばれた少なくとも一種の元素を表し、Dはマグネシウム、カルシウム、ストロンチウム、バリウム、チタン、ジルコニウム、ニオブ、クロム、マンガン、コバルト、ニッケル、銅、銀、亜鉛、ホウ素、アルミニウム、ガリウム、インジウム、タリウム、ゲルマニウム、スズ、鉛、リン、ヒ素、およびビスマスからなる群より選ばれた少なくとも一種の元素を表し、Eはリチウム、ナトリウム、カリウム、ルビジウム、およびセシウムからなる群から選ばれた少なくとも一種の元素を表し、a、b、c、d、e、xおよびyは原子比を表し、a=3~100、b=0.1~5、c=0.1~10、d=0~50、e=0~5、y=10~200であり、xはシリカを除く前記各成分の原子価を満足するのに必要な酸素の原子数である。ただし、A、D、およびEが、2種以上の元素を含む場合、b、d、およびeは、各元素の原子比の合計を表す。)
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KR101648284B1 (ko) | 2016-08-12 |
KR20140117599A (ko) | 2014-10-07 |
JP6264283B2 (ja) | 2018-01-24 |
JP2017149737A (ja) | 2017-08-31 |
JPWO2013129424A1 (ja) | 2015-07-30 |
EP2821391B1 (en) | 2019-05-08 |
EP2821391A1 (en) | 2015-01-07 |
EP2821391A4 (en) | 2015-04-08 |
CN104136412B (zh) | 2016-12-28 |
US9181178B2 (en) | 2015-11-10 |
CN104136412A (zh) | 2014-11-05 |
US20150057463A1 (en) | 2015-02-26 |
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