CN116351434B - 用于制备2,4-二氯苯腈的催化剂及制备方法和用途 - Google Patents
用于制备2,4-二氯苯腈的催化剂及制备方法和用途 Download PDFInfo
- Publication number
- CN116351434B CN116351434B CN202310127785.8A CN202310127785A CN116351434B CN 116351434 B CN116351434 B CN 116351434B CN 202310127785 A CN202310127785 A CN 202310127785A CN 116351434 B CN116351434 B CN 116351434B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- silicon
- precursor
- dichlorobenzonitrile
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- GRUHREVRSOOQJG-UHFFFAOYSA-N 2,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C(Cl)=C1 GRUHREVRSOOQJG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 27
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 10
- 239000013122 aluminium-based metal-organic framework Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 4
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 3
- 229910001593 boehmite Inorganic materials 0.000 claims abstract 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 239000004005 microsphere Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 3
- 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 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000013260 porous coordination network Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 claims description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910000904 FeC2O4 Inorganic materials 0.000 claims description 2
- 229910003893 H2WO4 Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910010062 TiCl3 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910003091 WCl6 Inorganic materials 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims description 2
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 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 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 2
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000344 rubidium sulfate Inorganic materials 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 238000009718 spray deposition Methods 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims 1
- 229910003206 NH4VO3 Inorganic materials 0.000 claims 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims 1
- 229910003074 TiCl4 Inorganic materials 0.000 claims 1
- 229910007932 ZrCl4 Inorganic materials 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 229910001626 barium chloride Inorganic materials 0.000 claims 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims 1
- 239000001110 calcium chloride Substances 0.000 claims 1
- 229910001628 calcium chloride Inorganic materials 0.000 claims 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 1
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims 1
- 229910052808 lithium carbonate Inorganic materials 0.000 claims 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 229910001631 strontium chloride Inorganic materials 0.000 claims 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 22
- FUNUTBJJKQIVSY-UHFFFAOYSA-N 2,4-Dichlorotoluene Chemical compound CC1=CC=C(Cl)C=C1Cl FUNUTBJJKQIVSY-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 5
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000013206 MIL-53 Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- ATCRIUVQKHMXSH-UHFFFAOYSA-N 2,4-dichlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1Cl ATCRIUVQKHMXSH-UHFFFAOYSA-N 0.000 description 2
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 2
- KUWBYWUSERRVQP-UHFFFAOYSA-N 3,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1Cl KUWBYWUSERRVQP-UHFFFAOYSA-N 0.000 description 2
- 229930003827 cannabinoid Natural products 0.000 description 2
- 239000003557 cannabinoid Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- XXFUNTSOBHSMBU-UHFFFAOYSA-N 2,4-dichlorobenzamide Chemical compound NC(=O)C1=CC=C(Cl)C=C1Cl XXFUNTSOBHSMBU-UHFFFAOYSA-N 0.000 description 1
- CEPCPXLLFXPZGW-UHFFFAOYSA-N 2,4-difluoroaniline Chemical compound NC1=CC=C(F)C=C1F CEPCPXLLFXPZGW-UHFFFAOYSA-N 0.000 description 1
- NJYBIFYEWYWYAN-UHFFFAOYSA-N 2,4-difluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C=C1F NJYBIFYEWYWYAN-UHFFFAOYSA-N 0.000 description 1
- LJFDXXUKKMEQKE-UHFFFAOYSA-N 2,4-difluorobenzonitrile Chemical compound FC1=CC=C(C#N)C(F)=C1 LJFDXXUKKMEQKE-UHFFFAOYSA-N 0.000 description 1
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 1
- 239000013279 Al(OH)(ndc) Substances 0.000 description 1
- 239000013291 MIL-100 Substances 0.000 description 1
- 239000013216 MIL-68 Substances 0.000 description 1
- 239000013255 MILs Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 208000025966 Neurological disease Diseases 0.000 description 1
- 208000028017 Psychotic disease Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000005557 antagonist Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004031 partial agonist Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000018 receptor agonist Substances 0.000 description 1
- 229940044601 receptor agonist Drugs 0.000 description 1
- -1 so that the physical Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000005062 synaptic transmission Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- C07C253/28—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing six-membered aromatic rings, e.g. styrene
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种用于制备2,4‑二氯苯腈的催化剂,该催化剂是硅铝复合氧化物载体负载的多组分含钒铁钛复合氧化物,其载体为以硅溶胶为硅源、以Al‑MOF材料、拟薄水铝石、薄水铝石和铝溶胶前驱体中的至少一种为铝源,混合后煅烧形成的硅铝复合氧化物。本发明还公开了该催化剂的制备方法及用途。本发明通过加入铝氧化物前驱体,与硅氧化物前驱体混合后煅烧形成硅铝复合氧化物载体,强化了无机氧化物与载体的作用,提高了催化剂的强度和耐磨性;使无机氧化物分散更均匀,减少了催化剂组分流失,延长了催化剂的寿命;利用铝氧化物前驱体特殊的结构和形貌可有效调控催化剂的结构和性能,提高催化剂的活性和选择性。催化剂热稳定性和机械强度好。
Description
技术领域
本发明涉及一种用于制备2,4-二氯苯腈的催化剂及制备方法和用途。它属于有机化学技术领域,也属于有机精细化学品技术领域。
背景技术
2,4-二氯苯腈又名2,4-二氯苯甲腈。氯代苯腈作为高附加值的精细化学品,是制造一些高效低毒农药、新型医药、高性能材料、染料等的关键原料,广泛应用于国民经济的各个领域。从2,4-二氯苯腈出发,可以制得2,4-二氯苯甲酸、2,4-二氯苯甲酰胺、2,4-二氟苯腈、2,4-二氟苯甲酸、2,4-二氟苯胺,这些化学品可广泛应用于医药、农药、染料、工程塑料和感光材料等行业。2,4-二氯苯腈也可以用作制备聚芳醚腈类材料的单体。典型的2,4-二氯苯腈的下游产品1H-咪唑类衍生物是非常有效的大麻素CB1的受体激动剂、部分激动剂或拮抗剂,可用于治疗精神病、神经障碍以及涉及大麻素神经传递的其他疾病。
2,4-二氯苯腈的一般制备方法是经相应的醛肟脱水或羧酸与尿素反应而得,这些方法存在着原料来源困难、反应路线长、污染大等缺点,而氨氧化法制备2,4-二氯苯腈的工艺简捷,可连续进行,生产能力强,经济效益显著,对环境友好等优点;核心是工业催化剂的开发。
一些论文和专利对2,4-二氯甲苯氨氧化反应制备2,4-二氯苯腈进行了报道,Martin等用未负载的VPO复合氧化物作为氨氧化催化剂来制备2,4二氯苯腈,在415℃反应时,原料2,4二氯甲苯转化率只有85%,产品2,4二氯苯腈收率不到50%,难以达到工业化生产的要求;此外,该催化剂机械强度不高,也无法用于流化床反应器(Catalysis Today,2000,57,61-70;Catalysis Today,1996,32,279-283)。我们曾将钒磷复合氧化物负载在硅胶上,催化2,4-二氯甲苯氨氧化反应时2,4二氯苯腈收率可提高到70%(Indian JournalofChemical Technology,2007,14(4),371-375)。郑穹等通过浸渍法制备硅胶负载型催化剂DC-108催化2,4-二氯甲苯氨氧化反应制备2,4-二氯苯腈,收率为84%(SyntheticCommunications,1999,29(13),2349-2353);但是硅胶负载型催化剂在工业上使用一般寿命不长。专利CN102744090A和CN102746192A通过喷雾干燥制备了硅溶胶型多组分复合氧化物催化剂,产品收率可达85%。李雄健通过水热反应制备一些含钒复合氧化物催化剂,用于2,4-二氯甲苯氨氧化反应制备2,4-二氯苯腈时收率一般低于80%(Catalysis Letters,2020,150(5),1489-1495;Journal of the Chinese Chemical Society,2021,68(5),866-870;Inorganic Chemistry,2018,57(23),14758-14763)。这些论文和专利所用催化剂仍然很难满足工业上对催化剂高强度、长寿命、高负荷和高活性高选择性的要求。
发明内容
本发明所要解决的一个技术问题是提供一种用于制备2,4-二氯苯腈的催化剂。
本发明所要解决的另一个技术问题是提供上述催化剂的制备方法。
本发明所要解决的第三个技术问题是提供上述催化剂的用途。
为解决上述第一个技术问题,本发明提供的用于制备2,4-二氯苯腈的催化剂是硅铝氧化物复合载体负载的多组分含钒铁钛复合氧化物催化剂,其载体为以硅溶胶为硅源、以Al-MOF材料、拟薄水铝石、薄水铝石和铝溶胶等前驱体中的至少一种为铝源混合后煅烧形成的硅铝氧化物复合载体,其活性组分的组成表示为:VFebTicDdEeOx;其中D为硼、镧、铈、钐、铕、钪、铬、钼、铋、钨、锆、锰、钴、镍和锌中的一种或多种,E为锂、钠、钾、铷、铯、镁、钙、锶和钡中至少一种;b=0.3~2.2;c=0.1~1.5;d=0~1.0;e=0~0.8;x则根据以上各元素的含量按价态平衡而定。活性组分与硅铝氧化物复合载体均匀混合形成复合微球;所述催化剂中活性组分的重量之和占复合微球总重量的百分比为10~80%,优选为30~70%。所述复合微球直径范围为20~120μm,平均直径为40~60μm。优选地,所述b=0.5~2.0;c=0.1~1.0;d=0~0.8;e=0~0.5。
所述催化剂的硅铝氧化物复合载体中氧化铝占载体的重量百分比为5%~80%,优选为10%~60%。所述硅溶胶可以是酸性、碱性或中性硅溶胶。铝氧化物前驱体中Al-MOF材料包括MIL(MaterialsInstitute Lavoisier),CAU(Christian-Albrechts-University),DUT(Dresden University ofTechnology),PCN(Porous coordinationnetwork)等类型,如MIL-53、MIL-96、MIL-100、MIL-110、MIL-68、MIL-101-NH2、MIL-12、MIL-14、MIL-27、MIL-32、MIL-34、MIL-64、MIL-69、MIL-91、MIL-116、MIL-118、MIL-120、MIL-121、MIL-122、MIL-160、DUT-4、CAU-1、CAU-3、CAU-4、CAU-6、CAU-8、CAU-10、CAU-10-H、CAU-10-NO2、CAU-10-NH2、CAU-10-OH、CAU-10-CH3、CAU-10-OCH3、CAU-11、CAU-12、CAU-13、CAU-15、CAU-23、Al-fumarate等。催化剂制备时,铝氧化物前驱体的加入一方面可以强化活性中心与载体的作用,减少活性组分的流失,并且提高催化剂的强度和耐磨性,大大延长催化剂的使用寿命;另一方面,通过加入铝氧化物前驱体形成复合载体,可调控载体中非质子酸和质子酸(氧化物表面的羟基)的比例和强度,从而调节催化剂酸碱性、氧化还原能力及与反应物的配位能力,提高催化剂的活性和选择性;第三方面,利用铝氧化物前驱体特殊的结构和形貌等可以调控催化剂的结构和形貌,包括粒度、比表面积、孔体积等,从而调控催化剂的物理、化学及催化性能。
为解决上述第二个技术问题,本发明所设计的技术方案思路如下:
本发明采用喷雾干燥法制备催化剂,其具体步骤为:首先将硅氧化物前驱体硅溶胶与铝氧化物前驱体Al-MOF材料、拟薄水铝石、薄水铝石和铝溶胶等中的至少一种混合均匀,将转化形成为催化剂活性组分VFebTicDdEeOx的各前驱体溶解、混合并与上述作载体用的硅、铝氧化物前驱体按一定比例均匀混合成悬浮液或浆料;通过高速离心式喷雾干燥器喷雾成型,干燥后高温活化而成微米级的硅铝复合氧化物载体负载的多组分无机氧化物微球型催化剂。活化温度在623~973K之间,最好温度范围为673~873K。活化时间为2~15小时,最佳活化时间范围为3~8小时。
所述催化剂活性组分各前驱体是指含有V、Fe、Ti、D和E中的至少一种元素的化合物,各前驱体中V的物质的量的和、Fe的物质的量的和、Ti的物质的量的和、D的物质的量的和、E的物质的量的和的比值为1:b:c:d:e;d为零时,则任一前驱体都不含D元素;e为零时,则任一前驱体都不含E元素。
制备催化剂时,任一前驱体都可用至少含有V、Fe、Ti、D和E中的一种元素的氧化物、盐、酸或碱等。例如,钒可以用V2O5或NH4VO3等;铁可以用FeCl3、Fe2O3、Fe3O4、Fe(NO3)3·9H2O、Fe(OAc)2、FeC2O4·2H2O或Fe2(C2O4)3·6H2O等;钛可以用TiCl4、TiCl3或TiO2等;硼可以用H3BO3、B2O3等;稀土镧、铈、钐、铕、钪等可以用稀土的硝酸盐、乙酸盐、硫酸盐、(对甲)苯磺酸盐、氯化物、氧化物等;铬可以用Cr(NO3)3·9H2O、Cr2O3、CrO3或(NH4)2Cr2O7等;钼可以用MoO3、(NH4)6Mo7O24等;铋可以用Bi(NO3)3、BiCl3、Bi2O3等;钨可以用WO3、WCl6、WOCl4、WO2Cl2、H2WO4或(NH4)2WO4等;锆可以用ZrCl4、ZrO2或乙酰丙酮锆等;锰可以用MnO2、MnCl2、Mn(NO3)2等;钴可以用Co(OAc)2、Co(NO3)2·6H2O、Co3O4或CoCl2等;镍可以用NiCl2·6H2O或Ni(NO3)2·6H2O等;锌可用ZnO、ZnCl2、Zn(NO3)2或Zn(OAc)2·2H2O等;锂可以用Li2O、LiCl、LiNO3或Li2CO3等;钠可以用Na2CO3、NaHCO3、NaOH、NaCl、NaNO3、Na2SO4、NaOAc或Na2C2O4等;钾可以用KOH、KCl、KNO3、K2CO3、K2SO4、KOAc或K2C2O4等;铷可以用RbCl、RbNO3、Rb2CO3、Rb2SO4、RbOAc或Rb2C2O4等;铯可以用CsCl、CsNO3、Cs2CO3、Cs2SO4、CsOAc或Cs2C2O4等;镁可以用MgO、MgCl2或Mg(NO3)2·6H2O等;钙可以用CaCl2·6H2O、Ca(OH)2或Ca(NO3)2等;锶可以用SrCl2、Sr(OH)2或Sr(NO3)2等;钡可以用BaCl2、Ba(OH)2或Ba(NO3)2等。制备溶液时采用本领域的公知的常用方法,例如V2O5等用H2C2O4水溶液溶解制备溶液,而KCl、KNO3、K2CO3等则直接用水溶解制备溶液。
为解决上述第三个技术问题,本发明提供的催化剂用于2,4-二氯甲苯氨氧化反应制备2,4-二氯苯甲腈。
以2,4-二氯甲苯为原料,与氨气、氧气在催化剂作用下发生氨氧化反应得到2,4-二氯苯甲腈;反应收率为85~98%。使用上述催化剂催化2,4-二氯甲苯氨氧化反应制备2,4-二氯苯甲腈的最佳工艺条件范围如下:反应温度633~723K,空气与2,4-二氯甲苯摩尔比为10~50,氨气与2,4-二氯甲苯摩尔比为1~10,催化剂负荷30~150g/(kgcat·h)。在内径为30mm的石英管流化床反应器和稳定的反应条件下,2,4-二氯甲苯的转化率可高于98%,2,4-二氯苯甲腈的摩尔收率可达95%以上。
与其它方法相比,本发明具有反应原料价廉易得、工艺路线简捷、对环境友好、成本低、收率高等优点,特别是催化剂强度和耐磨性大大提高,寿命大为延长,催化剂活性和产品的选择性也有所提高。氨氧化反应催化剂具较高选择性和活性;制备方法简单,成本低,有较好的热稳定性和机械强度,在固定床和流化床反应器上均能使用,具有较好的应用价值。
具体实施方式
通过下述实施例将有助于进一步理解本发明,但并不能限制本发明的内容。
实施例1
将18g的Al-MOF材料MIL-53(Al)加入240g含量为30%的硅溶胶中搅拌混合成均匀的悬浮液;将61.80克H2C2O4·2H2O溶于300mL80℃蒸馏水中,缓慢加入29.73克V2O5反应至无气体产生,然后加入198.04克Fe(NO3)3·9H2O、31.05克TiCl4、11.55克(NH4)6Mo7O24·4H2O和0.87克Na2CO3,待形成均一溶液后,缓慢加入上述硅溶胶与Al-MOF的混合悬浮液中。搅拌均匀后,然后通过高速喷雾离心干燥得到催化剂前体,在马福炉中于383K干燥,然后逐步升温到823K,保温6小时。自然冷却后,待用。催化剂的活性组成为:VFe1.5Ti0.5Mo0.2Na0.05O6.375;活性组分含量为50%,硅铝复合氧化物载体中氧化铝重量百分含量为20%。催化剂平均粒径50μm,堆密度为0.95g/ml,比表面积为75m2/g,磨耗率(按照美国ASTM D5757-00“测定空气喷射下粉末催化剂磨损和磨蚀的标准实验方法”测量)为1.9%。
在内径为30mm的石英管流化床反应器中装填100g上述固体催化剂,反应原料的摩尔配比为:2,4-二氯甲苯:NH3:Air=1:3:20,反应温度为663±1K,催化剂的负荷为80g/(kgcat·h)。反应8小时后,2,4-二氯甲苯的转化率99.3%,2,4-二氯苯腈的摩尔收率为95.7%。
实施例2
对照例:催化剂制备方法同实施例1,只是硅溶胶中不加MOF材料MIL-53(Al),30%含量的硅溶胶用量为300克,催化剂活性组分相同。经测试催化剂平均粒度48μm,堆密度为0.91g/ml,比表面积为68m2/g,磨耗率为3.2%,磨耗率比实施例1高68%以上;因此相比较而言实施例1所制的催化剂更耐磨、强度更大。催化2,4-二氯甲苯氨氧化反应实验条件与实施例1相同,反应8小时后,2,4-二氯甲苯的转化率98.8%,2,4-二氯苯腈的摩尔收率为91.2%。
实施例3~8
催化剂配方不同,反应条件同实施例1,结果如下表。其中实施例8是实施例6中不含铁的对照例。实施例3-8中制备得到的催化剂磨耗率都在1.8%到2.2%之间。
从实施例6和8可以看出,铁组分的加入能够显著提高反应的收率和选择性。
本发明的催化剂还可用于制备3,4-二氯苯腈和2,6-二氯苯腈,但收率明显降低,例如,将实施例6的催化剂用于制备3,4-二氯苯腈,转化率和收率分别可达到95.1%和82.3%;用于制备2,6-二氯苯腈,转化率和收率分别可达到93.7%和78.8%。
本领域的人员公知,按上述方法还可以制备包含有其它可选活性组分的本发明所述催化剂。制备时,参照上述实施例将其它可选活性组分的对应前驱体物质按照比例作相应替换即可得到所需催化剂。其中其它可选活性组分的对应前驱体可用其氧化物、盐、酸或碱等。
Claims (10)
1.一种用于制备2,4-二氯苯甲腈的催化剂,其特征在于:
该催化剂是硅铝复合氧化物载体负载的多组分含钒铁钛复合氧化物,其载体为以硅溶胶为硅源,以Al-MOF材料、拟薄水铝石、薄水铝石和铝溶胶前驱体中的至少一种为铝源,混合后煅烧形成的硅铝复合氧化物载体,其活性组分的组成表示为:VFebTicDdEeOx;其中D为硼、镧、铈、钐、铕、钪、铬、钼、铋、钨、锆、锰、钴、镍和锌中的一种或多种,E为锂、钠、钾、铷、铯、镁、钙、锶和钡中至少一种;b=0.3~2.2;c=0.1~1.5;d=0~1.0;e=0~0.8;x则根据以上各元素的含量按价态平衡而定;
所述活性组分与硅铝复合氧化物载体均匀混合形成复合微球型的催化剂;所述催化剂中活性组分的重量百分比含量为10~80%;所述复合微球直径范围为20~120μm,平均直径为40~60μm。
2.根据权利要求1所述的用于制备2,4-二氯苯甲腈的催化剂,其特征在于:所述硅溶胶是酸性、碱性或中性硅溶胶。
3.根据权利要求1或2所述的用于制备2,4-二氯苯甲腈的催化剂,其特征在于:所述Al-MOF材料包括MIL、CAU、DUT和PCN类型。
4.根据权利要求1或2所述的用于制备2,4-二氯苯甲腈的催化剂,其特征在于:所述催化剂的硅铝复合氧化物载体中氧化铝占载体的重量百分比为5%~80%。
5.根据权利要求1或2所述的用于制备2,4-二氯苯甲腈的催化剂,其特征在于:所述催化剂中活性组分的重量百分比含量为30~70%。
6.权利要求1至5任一项所述的催化剂的制备方法,其特征在于:
该制备方法采用高速离心喷雾干燥,具体步骤为:
1)将硅氧化物前驱体硅溶胶与铝氧化物前驱体Al-MOF材料、拟薄水铝石、薄水铝石和铝溶胶中的至少一种混合均匀;
2)将转化形成为催化剂活性组分VFebTicDdEeOx的各前驱体溶解、混合并与上述作载体用的硅、铝氧化物前驱体均匀混合成悬浮液或浆料;
3)通过高速离心式喷雾干燥器喷雾成型;
4)干燥后高温活化而成微米级的硅铝复合氧化物载体负载的多组分无机氧化物微球型催化剂;所述高温活化的温度为623~973K,活化时间为2~15小时;
所述催化剂活性组分前驱体是指含有V、Fe、Ti、D和E中的至少一种元素的化合物,各前驱体中V的物质的量的和、Fe的物质的量的和、Ti的物质的量的和、D的物质的量的和、E的物质的量的和的比值为1:b:c:d:e;d为零时,则任一前驱体都不含D元素;e为零时,则任一前驱体都不含E元素。
7.根据权利要求6所述的催化剂的制备方法,其特征在于:所述高温活化的温度为673~873K,活化时间为3~8小时。
8.根据权利要求6或7所述的催化剂的制备方法,其特征在于:所述催化剂活性组分前驱体为至少含有V、Fe、Ti、D和E中的一种元素的氧化物、盐、酸或碱。
9.根据权利要求8所述的催化剂的制备方法,其特征在于:所述催化剂活性组分前驱体为V2O5或NH4VO3;FeCl3、Fe2O3、Fe3O4、Fe(NO3)3·9H2O、Fe(OAc)2、FeC2O4·2H2O或Fe2(C2O4)3·6H2O;TiCl4、TiCl3或TiO2;H3BO3、B2O3;稀土的硝酸盐、乙酸盐、硫酸盐、苯磺酸盐或对甲苯磺酸盐、氯化物、氧化物;Cr(NO3)3·9H2O、Cr2O3、CrO3或(NH4)2Cr2O7;MoO3、(NH4)6Mo7O24;Bi(NO3)3、BiCl3、Bi2O3;WO3、WCl6、WOCl4、WO2Cl2、H2WO4或(NH4)2WO4;ZrCl4、ZrO2或乙酰丙酮锆;MnO2、MnCl2、Mn(NO3)2;Co(OAc)2、Co(NO3)2·6H2O、Co3O4或CoCl2;NiCl2·6H2O或Ni(NO3)2·6H2O;ZnO、ZnCl2、Zn(NO3)2或Zn(OAc)2·2H2O;Li2O、LiCl、LiNO3或Li2CO3;Na2CO3、NaHCO3、NaOH、NaCl、NaNO3、Na2SO4、NaOAc或Na2C2O4;KOH、KCl、KNO3、K2CO3、K2SO4、KOAc或K2C2O4;RbCl、RbNO3、Rb2CO3、Rb2SO4、RbOAc或Rb2C2O4;CsCl、CsNO3、Cs2CO3、Cs2SO4、CsOAc或Cs2C2O4;MgO、MgCl2或Mg(NO3)2·6H2O;CaCl2·6H2O、Ca(OH)2或Ca(NO3)2;SrCl2、Sr(OH)2或Sr(NO3)2;BaCl2、Ba(OH)2或Ba(NO3)2。
10.权利要求1至5任一项所述的催化剂的用途,其特征在于:所述催化剂用于2,4-二氯甲苯氨氧化法制备2,4-二氯苯甲腈。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310127785.8A CN116351434B (zh) | 2023-02-17 | 2023-02-17 | 用于制备2,4-二氯苯腈的催化剂及制备方法和用途 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310127785.8A CN116351434B (zh) | 2023-02-17 | 2023-02-17 | 用于制备2,4-二氯苯腈的催化剂及制备方法和用途 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116351434A CN116351434A (zh) | 2023-06-30 |
CN116351434B true CN116351434B (zh) | 2024-05-03 |
Family
ID=86930959
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310127785.8A Active CN116351434B (zh) | 2023-02-17 | 2023-02-17 | 用于制备2,4-二氯苯腈的催化剂及制备方法和用途 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116351434B (zh) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6187943B1 (en) * | 1996-10-24 | 2001-02-13 | Mitsubishi Rayon Co., Ltd. | Process for preparing carbocyclic or heterocyclic nitriles by vapor phase ammoxidation |
CN1328874A (zh) * | 2000-06-20 | 2002-01-02 | 武汉大学 | 氨氧化法制备2,4-二氯苯腈的方法及专用催化剂 |
CN101670291A (zh) * | 2009-09-24 | 2010-03-17 | 河北工业大学 | 用于环己酮氨氧化一步合成己内酰胺的催化剂及其制备和应用方法 |
EP2428267A1 (en) * | 2010-09-08 | 2012-03-14 | Leibniz-Institut für Katalyse e.V. an der Universität Rostock | Catalyst, its preparation and use for the preparation of nitriles from alkyl aromatic or heteroaromatic compounds |
CN108200762A (zh) * | 2015-10-26 | 2018-06-22 | 国际壳牌研究有限公司 | 强催化剂及催化剂载体、其制备和其用途 |
CN109847772A (zh) * | 2018-12-17 | 2019-06-07 | 中南民族大学 | 氨氧化法制备对氯苯腈的专用催化剂及制备方法与用途 |
CN109912453A (zh) * | 2017-12-13 | 2019-06-21 | 中南民族大学 | 制备2,5-二氯苯腈的方法和专用催化剂及其制备方法 |
CN111569924A (zh) * | 2020-04-22 | 2020-08-25 | 中南民族大学 | 氨氧化法制备2,6-二氯苯腈的专用催化剂及其制备方法和用途 |
CN113289629A (zh) * | 2021-04-27 | 2021-08-24 | 中汽研(天津)汽车工程研究院有限公司 | 一种用于柴油车尾气净化的三维复合烧绿石氨氧化催化剂 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010143690A1 (ja) * | 2009-06-11 | 2010-12-16 | 三菱瓦斯化学株式会社 | アンモ酸化触媒及びそれを用いたニトリル化合物の製造方法 |
-
2023
- 2023-02-17 CN CN202310127785.8A patent/CN116351434B/zh active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6187943B1 (en) * | 1996-10-24 | 2001-02-13 | Mitsubishi Rayon Co., Ltd. | Process for preparing carbocyclic or heterocyclic nitriles by vapor phase ammoxidation |
CN1328874A (zh) * | 2000-06-20 | 2002-01-02 | 武汉大学 | 氨氧化法制备2,4-二氯苯腈的方法及专用催化剂 |
CN101670291A (zh) * | 2009-09-24 | 2010-03-17 | 河北工业大学 | 用于环己酮氨氧化一步合成己内酰胺的催化剂及其制备和应用方法 |
EP2428267A1 (en) * | 2010-09-08 | 2012-03-14 | Leibniz-Institut für Katalyse e.V. an der Universität Rostock | Catalyst, its preparation and use for the preparation of nitriles from alkyl aromatic or heteroaromatic compounds |
CN108200762A (zh) * | 2015-10-26 | 2018-06-22 | 国际壳牌研究有限公司 | 强催化剂及催化剂载体、其制备和其用途 |
CN109912453A (zh) * | 2017-12-13 | 2019-06-21 | 中南民族大学 | 制备2,5-二氯苯腈的方法和专用催化剂及其制备方法 |
CN109847772A (zh) * | 2018-12-17 | 2019-06-07 | 中南民族大学 | 氨氧化法制备对氯苯腈的专用催化剂及制备方法与用途 |
CN111569924A (zh) * | 2020-04-22 | 2020-08-25 | 中南民族大学 | 氨氧化法制备2,6-二氯苯腈的专用催化剂及其制备方法和用途 |
CN113289629A (zh) * | 2021-04-27 | 2021-08-24 | 中汽研(天津)汽车工程研究院有限公司 | 一种用于柴油车尾气净化的三维复合烧绿石氨氧化催化剂 |
Non-Patent Citations (3)
Title |
---|
A novel approach to synthesize dichlorobenzonitriles by selective ammoxidation;Yunzhao Dong et al.;《Research on Chemical Intermediates》;20220108;第48卷;1151-1158 * |
Mixed oxides with rutile type structure active in ammoxidation to acrylonitrile;Stefania Albonetti et al.;《Studies in Surface Science and Catalysis》;19981231;第121卷;79-84 * |
SiO2载体对二氯甲苯氨氧化钒磷复合氧化物催化剂性能的影响;许龙龙 等;《武汉大学学报( 理学版)》;20181106;第64卷(第5期);540-548 * |
Also Published As
Publication number | Publication date |
---|---|
CN116351434A (zh) | 2023-06-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102066001B (zh) | 用于通过甘油的脱水反应制造丙烯醛和丙烯酸的催化剂及其制造方法 | |
US4049575A (en) | Process of producing antimony-containing oxide catalysts | |
JP5491037B2 (ja) | アクリロニトリルの製造用触媒及びアクリロニトリルの製造方法 | |
KR20090127310A (ko) | 담체 본체 및 담체 본체의 표면에 도포된 촉매적 활성 매스로 이루어진 촉매의 제조 방법 | |
CN101990460A (zh) | 包含含钼、铋和铁的多金属氧化物的涂覆催化剂 | |
JP6621569B2 (ja) | アンモ酸化用触媒、及び、その製造方法、並びにアクリロニトリルの製造方法 | |
CN103721722B (zh) | 复合氧化物催化剂及其制备方法 | |
KR20120093853A (ko) | 글리세린의 탈수 반응에 의한 아크롤레인 및/또는 아크릴산의 제조용 촉매 및 방법 | |
JP2020157301A (ja) | 酸化的脱水素化反応用触媒、その製造方法及びそれを用いた酸化的脱水素化方法 | |
CN103934000A (zh) | 丙烯醛催化剂及其制备方法 | |
CN103097024A (zh) | 用于制造不饱和醛和/或不饱和羧酸的催化剂和使用该催化剂的不饱和醛和/或不饱和羧酸的制造方法 | |
CN110420643A (zh) | 一种蛋壳型复合金属催化剂的制备方法及其应用 | |
CN103769161A (zh) | 丙烯醛催化剂及其制备方法 | |
JP2023101553A (ja) | 触媒及びその製造方法 | |
US4264476A (en) | Catalyst for producing acrylonitrile in a fluidized bed reactor | |
CN116351434B (zh) | 用于制备2,4-二氯苯腈的催化剂及制备方法和用途 | |
CN111569925B (zh) | 制备3,4-二氯苯甲腈的催化剂及制备方法和用途 | |
US20220002233A1 (en) | Ammoxidation catalyst for propylene, manufacturing method of the same catalyst, ammoxidation method using the same catalyst | |
CN111569924B (zh) | 氨氧化法制备2,6-二氯苯腈的专用催化剂及其制备方法和用途 | |
US20150045581A1 (en) | Method for producing acrolein and acrylic acid with a fixed-bed multitubular reactor | |
CN104105544B (zh) | 用于烃脱氢的催化剂 | |
CN116273099A (zh) | 硅铝复合氧化物载体负载型催化剂及其制备方法和用途 | |
CN104437526B (zh) | 丙烯醛氧化制丙烯酸催化剂及其制备方法 | |
CN116237038A (zh) | 氨氧化法制备对溴苯腈的催化剂及制备方法与用途 | |
CN111203251A (zh) | 一种低碳烃氨氧化合成不饱和腈的耐磨混合金属氧化物催化剂及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |