CN111135829B - Ammonia oxidation catalyst and preparation method and application thereof - Google Patents
Ammonia oxidation catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN111135829B CN111135829B CN202010003447.XA CN202010003447A CN111135829B CN 111135829 B CN111135829 B CN 111135829B CN 202010003447 A CN202010003447 A CN 202010003447A CN 111135829 B CN111135829 B CN 111135829B
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- Prior art keywords
- catalyst
- ammoxidation
- reaction
- xylene
- arsenic
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 39
- 230000003647 oxidation Effects 0.000 title claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000008096 xylene Substances 0.000 claims abstract description 29
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 4
- 229910052745 lead Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 78
- 238000000034 method Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 29
- 235000006408 oxalic acid Nutrition 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 21
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- OEYOHULQRFXULB-UHFFFAOYSA-N arsenic trichloride Chemical compound Cl[As](Cl)Cl OEYOHULQRFXULB-UHFFFAOYSA-N 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 claims description 3
- ZSRZHCIWJJKHAU-UHFFFAOYSA-N pentachloro-$l^{5}-arsane Chemical compound Cl[As](Cl)(Cl)(Cl)Cl ZSRZHCIWJJKHAU-UHFFFAOYSA-N 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 claims description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- CQXADFVORZEARL-UHFFFAOYSA-N Rilmenidine Chemical compound C1CC1C(C1CC1)NC1=NCCO1 CQXADFVORZEARL-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 2
- RGSYEFMEEJRHBT-UHFFFAOYSA-D [V+5].[V+5].OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O Chemical compound [V+5].[V+5].OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O RGSYEFMEEJRHBT-UHFFFAOYSA-D 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 claims description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 2
- 229940045105 silver iodide Drugs 0.000 claims description 2
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 2
- 229910000161 silver phosphate Inorganic materials 0.000 claims description 2
- 229940019931 silver phosphate Drugs 0.000 claims description 2
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000004364 calculation method Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000002431 foraging effect Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000012847 fine chemical Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- YOLNUNVVUJULQZ-UHFFFAOYSA-J iridium;tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ir] YOLNUNVVUJULQZ-UHFFFAOYSA-J 0.000 description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- -1 aromatic nitriles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides an ammonia oxidation catalyst and a preparation method and application thereof, wherein the ammonia oxidation catalyst comprises a carrier and active components, and the active components satisfy the following structure in atomic ratio calculation: v 1.0 Ag a As b D c E d G e O x Wherein D is selected from one or more of Mn, Zn, Ca, Ba and Pb, E is selected from one or more of Cs, Zr, La, Ce and Pr, and G is selected from one or more of Rh, Ru, Ir, Pt and Au; a is 0.01-3, b is 0.01-3, c is 0.01-2, d is 0.001-1, e is 0.001-0.6, and 0.3 < b/(1+ a) < 1.2, 0.1 < (b + e)/(c + d) < 15; x is determined by the degree of oxidation of the other elements of formula I; the catalyst has high conversion rate and selectivity and good stability when fed at a low ammonia/xylene ratio, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of catalysts, and relates to an ammoxidation catalyst, a preparation method thereof and application of the catalyst in preparation of phthalonitrile through ammoxidation of xylene.
Background
Phthalonitrile (isophthalonitrile (IPN), Terephthalonitrile (TPN), phthalodinitrile (OPN)) and other aromatic nitriles are widely used fine chemical intermediates, the cyano group of which has extremely high chemical activity, and can be synthesized into a series of fine chemical products through hydrolysis, hydrogenation, addition, condensation, polymerization, halogenation and other reactions, and the fine chemical products are important raw materials for producing pesticides, medicines, dyes, perfumes, oil products, fuel additives and the like, and are also commonly used for producing polyester resin and polyester fiber, and the latter is an important intermediate for building materials, insulating materials and textile assistants.
The method for synthesizing the isophthalonitrile or the isomer thereof by carrying out ammoxidation on xylene, ammonia and air through one-step reaction is the simplest and most economical production method. At present, the relatively advanced technology at home and abroad applies a fine particle catalyst and a fluidized bed ammoxidation reaction process, and has the characteristics of safe production, simple process and high once-through yield. The ammoxidation process has been developed rapidly in recent years, and the core technology of the process is the development of catalysts.
At present, a dimethylbenzene ammoxidation catalyst mainly comprises four systems of V-Cr, V-P, V-Sb and Sb-Fe, wherein the V-Cr system catalyst is widely applied due to the characteristics of easy industrial scale-up production, good batch stability and higher ammoxidation activity. However, the feed to the present xylene ammoxidation process needs to maintain a higher ammonia/xylene ratio to increase conversion and selectivity.
Patent CN1500775A discloses a V-Cr-B-Ti fluidized bed catalyst, which is prepared by adding Li, Na, K, Cs, Mn, Ca, Fe, Mo, W or rare earth elements, and the molar ratio of the raw materials is ammonia: 5-10: 1 of m-xylene; patent CN1490309A discloses a V-Cr-Ti fluidized bed catalyst, which is prepared by adding P, B, Bi, Sb, As, alkali metal or/and alkaline earth metal, Mn, Ni, Co, Pb, Fe, Mo, W or rare earth element, and the molar ratio of raw materials is ammonia: 5-10: 1 of p-xylene; patent CN102219711A discloses a V-Sb fluidized bed catalyst, which is prepared by adding alkali metal, Ca, Cr, Mo, Mn, Fe, Co, Ni, B, and P, and the molar ratio of raw materials is ammonia: and (3) m-xylene to 10: 1.
The applicant finds in research that the problem of excessively high ammonia/xylene ratio exists in the feed of the existing xylene ammoxidation process, a good reaction effect can be obtained only when the ammonia/xylene ratio is higher than 6, and meanwhile, a large amount of ammonia in the raw material is not reacted to cause waste, so that the raw material cost is increased; in addition, mixing of a large amount of unreacted raw material ammonia in the reaction tail gas causes difficulty in separation and increase in cost, and also causes increase in three-waste treatment and environmental protection cost. Currently, reducing the ammonia/xylene ratio in the feed to ameliorate the above problems results in a reduction in xylene conversion, target product phthalonitrile selectivity and yield.
In summary, there is a need for an ammoxidation catalyst with optimized structure, which can reduce the ammonia/xylene ratio in the reaction feed and improve the conversion rate of xylene, the selectivity and yield of the target product phthalonitrile, so as to reduce the raw material waste and reduce the environmental protection cost.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides an ammoxidation catalyst, a preparation method and an application thereof, wherein the catalyst has the characteristics of high conversion rate and selectivity, good stability and suitability for large-scale industrial production when fed at a low ammonia/xylene ratio.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the invention provides an ammonia oxidation catalyst, which comprises a carrier and active components, wherein the active components satisfy the following structure shown in the formula I in terms of atomic ratio:
V 1.0 Ag a As b D c E d G e O x formula I
In the formula I, D is selected from one or more of Mn, Zn, Ca, Ba and Pb, E is selected from one or more of Cs, Zr, La, Ce and Pr, and G is selected from one or more of Rh, Ru, Ir, Pt and Au;
wherein a is 0.01-3, b is 0.01-3, c is 0.01-2, d is 0.001-1, e is 0.001-0.6, and 0.3 < b/(1+ a) < 1.2, 0.1 < (b + e)/(c + d) < 15; x is determined by the degree of oxidation of the other elements of formula I.
In some embodiments, in the structure shown in formula i, a is 0.1 to 2, b is 0.05 to 2, c is 0.05 to 1.5, d is 0.005 to 0.8, and e is 0.005 to 0.5.
In the ammoxidation catalyst provided by the invention, the ratio of main elements V, Ag and As in the catalyst is accurately adjusted to form an active site of the high-efficiency multi-element composite oxide, so that the reaction activation energy in the catalytic process is reduced, the usage amount of ammonia in the raw material is reduced, and the higher conversion rate of xylene can be ensured under the condition of lower ammonia concentration.
According to the ammonia oxidation catalyst provided by the invention, the D-type metal element is introduced as an active assistant, so that the reaction activity is further improved; meanwhile, the introduction of the metal element E regulates the selectivity of the catalyst under lower ammonia concentration, and reduces CO and CO 2 Formation of deep ammoxidation by-products such as HCN; the G-type elements in the catalyst regulate the stability of the catalyst and ensure the stability of the catalyst in the long-period operation process.
In a specific embodiment of the invention, the mass percentage of the active component is 20-80% of the total mass of the ammoxidation catalyst, and the balance is a carrier;
the carrier is selected from silica or alumina.
In a second aspect, the present invention provides a process for preparing the above ammonia oxidation catalyst, using a process comprising the steps of:
1) adding the first reaction solution into an oxalic acid aqueous solution to form a first mixed solution;
2) adding a component containing a carrier and a reaction solution II into the mixed solution I to obtain a mixed solution II;
3) aging the mixed solution II, evaporating the obtained solution to obtain slurry with the solid content of 45-80%, and drying the slurry to obtain catalyst precursor powder;
4) roasting the catalyst precursor powder at 400-750 ℃ for 3-15 h to obtain an ammonia oxidation catalyst;
in the step 1), the first reaction solution is an aqueous solution of a vanadium-containing compound, a silver-containing compound and an arsenic-containing compound; the molar ratio of the vanadium-containing compound to oxalic acid contained in the oxalic acid aqueous solution is 1: 0.01-50;
in the step 2), the reaction solution two contains compounds of other metal elements in the active component, and the other metal elements in the active component are metal elements represented by D, E, G in the structure shown in the formula I;
the amount of the mixed liquid I and the amount of the mixed liquid II meet the proportion of each element in the structure shown in the formula I.
In step 1) of the preparation method, the vanadium-containing compound is selected from one or more of vanadium pentoxide, vanadium oxalate, vanadium tartrate, ammonium metavanadate and vanadium sulfate; preferably vanadium pentoxide or vanadium oxalate; the silver-containing compound is selected from one or more of silver nitrate, silver chloride, silver iodide, silver carbonate, silver phosphate and silver acetate, and is preferably silver nitrate or silver chloride; the arsenic-containing compound is one or more selected from arsenic pentoxide, arsenic trioxide, arsenic pentafluoride, arsenic trifluoride, arsenic pentachloride and arsenic trichloride, and is preferably arsenic pentachloride or arsenic trichloride.
In the specific implementation process of the invention, in order to increase the solubility of oxalic acid, oxalic acid can be added into water heated to 70-90 ℃, and an oxalic acid aqueous solution is formed under the stirring of the rotation speed of 200-400 rpm; for example, water is heated to 85 ℃, oxalic acid is added thereto and stirred at 250rpm to obtain an oxalic acid aqueous solution.
In step 2) of the specific preparation method of the present invention, the support-containing component is selected from a silicon source or an aluminum source, preferably selected from one or more of silica sol, nano silica, silica prepared from silicate by a sol-gel method, or alumina sol; as is well known to those skilled in the art, the amount of the support-containing component added during the preparation of a particular catalyst may be determined based on the amount of active component in the ammonia oxidation catalyst to ensure that the active component and the support in the resulting ammonia oxidation catalyst meet the above requirements.
The compounds of other metal elements in the active component are respectively selected from one or more of nitrate, chloride, carbonate or acetate of other metal elements; in some embodiments, hydrated metal salts may be used if nitrates, chlorides, carbonates, and acetates of the above-mentioned other metal elements are present; for example, the compound containing the other metal element D in the active component may be selected from manganese nitrate, lead nitrate, zinc nitrate; the compound containing other metal elements E in the active component can be selected from cerium nitrate, lanthanum nitrate hexahydrate and praseodymium chloride; the compound containing other metal element G in the active component can be selected from aurous chloride, ruthenium nitrate and iridium trichloride hydrate.
In the step 3) of the specific preparation method, the mixed solution II is stirred for 30-450 min at 45-100 ℃, and then heated to 100-125 ℃ for aging treatment; preferably, the aging treatment is performed for 30 to 600 min.
In a specific embodiment of the invention, the drying treatment is to spray-dry the slurry at an inlet temperature of 250 to 300 ℃ and an outlet temperature of 105 to 140 ℃. As is well known to those skilled in the art, spray drying is a systematic technique applied to material drying, in which a slurry is atomized in a drying chamber and then contacted with hot air, and moisture is rapidly vaporized to obtain a dried product.
In the step 4) of the specific preparation method, the catalyst precursor powder is heated to 120-200 ℃ at the speed of 0.5-6 ℃/min and is kept warm for 10-30 h; and then heating to 400-750 ℃ at the speed of 0.5-8 ℃/min, and then roasting.
In the third aspect of the invention, in the presence of a catalyst, after the ammoxidation reaction of xylene, ammonia gas and oxygen-containing gas, the isophthalonitrile or an isomer thereof is obtained; the catalyst adopts the ammonia oxidation catalyst or the ammonia oxidation catalyst prepared by the method;
wherein the molar ratio of the xylene to the ammonia to the oxygen in the oxygen-containing gas is 1: 1-2.9: 3.7-12.5, preferably 1: 2-2.5: 5.2-11.5;
in some preferred embodiments, the conversion of xylene is 99% or more and the selectivity of phthalonitrile is 98% or more.
The ammoxidation catalyst obtained by the invention is used for ammoxidation reaction, so that the molar ratio of the dimethylbenzene to the ammonia gas reaches 1-2.9, preferably 2-2.5, the usage amount of the raw material ammonia is greatly reduced, and the efficiency of the ammoxidation reaction is improved.
In the practice of the present invention, the oxygen-containing gas may be pure oxygen or air containing about 21% by volume.
In the specific method, the temperature of the ammoxidation reaction is 280-500 ℃, preferably 300-450 ℃; the gauge pressure of the ammoxidation reaction is 1-350 kPa; preferably 10 to 150 kPa. In some embodiments, the xylene as feedstock may be selected from ortho-xylene, meta-xylene, and para-xylene.
More preferably, the reaction raw materials are gasified, uniformly mixed and introduced into a reactor for carrying out the ammoxidation reaction, and the weight load of the catalyst in the reactor is 0.01-0.3 h -1 Preferably 0.02 to 0.18h -1 。
By adopting the technical scheme, the method has the following technical effects:
in the ammoxidation catalyst provided by the invention, the high-efficiency multi-element composite oxide active site is formed by adjusting the proportion of the main catalytic elements V, Ag and As, so that the reaction activation energy can be effectively reduced in the ammoxidation reaction, a higher xylene conversion rate can be ensured when the ammonia concentration is lower, and the use amount of ammonia in the raw material is greatly reduced.
Meanwhile, the D-type element introduced into the ammoxidation catalyst provided by the invention is an active assistant, which is beneficial to further improving the reaction activity; the E element is beneficial to regulating selectivity under lower ammonia concentration and reducing CO and CO 2 And the generation of byproducts of deep oxidation such as HCN and the like, and G elements are beneficial to regulating the stability of the catalyst and ensuring the long-period stable operation of the catalyst.
In the application process of the ammoxidation catalyst provided by the invention, the ammoxidation catalyst is subjected to ammoxidation reaction under the concentration of xylene, oxygen-containing gas and lower ammonia raw material to obtain (ortho-, meta-and para-) phthalonitrile, and the reaction has higher conversion rate, selectivity and stability, and is beneficial to large-scale industrial application.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The raw materials used in the examples are conventional in the art, and the purity specifications used are technical grade.
The calculation formula of the conversion rate of the raw material xylene and the selectivity of the target product m (o, m, p) phthalonitrile is as follows:
xylene conversion (%). times.100% (moles of xylene reacted/moles of xylene fed)
Phthalonitrile selectivity (%) - (moles of phthalonitrile formed/moles of xylene reacted) × 100%
Example 1
1) 2500g of water was heated to 85 ℃ and 1950g of oxalic acid (H) was added with stirring at 250rpm 2 C 2 O 4 ) Adding water to form an oxalic acid aqueous solution; adding 455g of vanadium pentoxide, 680g of silver nitrate and 1360g of arsenic trichloride into 680g of water to form a first reaction solution;
adding the first reaction solution into an oxalic acid aqueous solution under stirring to form a first mixed solution;
2) 1074g of manganese nitrate, 1073g of zirconium nitrate pentahydrate and 8.7g of rhodium nitrate were dissolved in 3918.3g of water to form a reaction solution II;
adding 2750g of silica sol with the mass percentage of 40% and the reaction liquid II into the mixed liquid I to obtain mixed liquid II;
3) stirring the mixed solution II at 90 ℃ for 200min at the rotating speed of 350rpm, then heating to 105 ℃, standing for 60min for aging treatment, and evaporating the aged solution to slurry with the solid content of 45%;
spray-drying the obtained slurry at the inlet temperature of 285 ℃ and the outlet temperature of 125 ℃ to obtain catalyst precursor powder;
4) heating the obtained catalyst precursor powder to 120 ℃ at the speed of 1.5 ℃/min and preserving heat for 13 h; then heating to 670 ℃ at the speed of 1 ℃/min for roasting for 6h, and finally cooling to room temperature at the speed of 3 ℃/min to obtain the ammoxidation catalyst 1.
The active component proportion of the ammoxidation catalyst 1 is detected to be V 1.0 Ag 0.8 As 1.5 Mn 1.2 Zr 0.5 Rh 0.006 O x 。
The obtained ammoxidation catalyst 1 is filled in a fluidized bed reactor for ammoxidation, the molar ratio of m-xylene, ammonia gas and oxygen in the raw materials is 1:2:9.4, the temperature of the ammoxidation is 380 ℃, the reaction pressure (gauge pressure) is 20kPa, and the weight load of the catalyst in the reactor is 0.06h -1 。
After the reactor was operated for 1000 hours, the conversion of m-xylene was 99.9% and the selectivity of m-phthalonitrile was 98.9%.
Example 2
1) 2550g of water are heated to 75 ℃ and 2000g of oxalic acid (H) are stirred at 350rpm 2 C 2 O 4 ) Adding water to form an oxalic acid aqueous solution; adding 455g of vanadium pentoxide, 765g of silver nitrate and 1269g of arsenic trichloride into 780g of water to form a reaction liquid I;
adding the first reaction solution into an oxalic acid aqueous solution under stirring to form a first mixed solution;
2) 1988g of lead nitrate, 293g of cesium nitrate and 12.4g of iridium trichloride hydrate were dissolved in 4594.6g of water to form a reaction liquid II;
adding 2800g of silica sol with the mass percentage of 40% and the reaction liquid II into the mixed liquid I to obtain mixed liquid II;
3) stirring the mixed solution II at 85 ℃ for 180min at the rotating speed of 300rpm, then heating to 108 ℃, standing for 75min for aging treatment, and evaporating the aged solution to slurry with the solid content of 48%;
spray-drying the obtained slurry at the inlet temperature of 275 ℃ and the outlet temperature of 135 ℃ to obtain catalyst precursor powder;
4) heating the obtained catalyst precursor powder to 130 ℃ at the speed of 1 ℃/min and preserving heat for 15 h; then heating to 680 ℃ at the speed of 1.5 ℃/min for roasting for 6h, and finally cooling to room temperature at the speed of 5 ℃/min to obtain the ammoxidation catalyst 2.
The active component proportion of the ammoxidation catalyst 2 is V through detection 1.0 Ag 0.9 As 1.4 Pb 1.2 Cs 0.3 Ir 0.007 O x 。
The obtained ammoxidation catalyst 2 is filled in a fluidized bed reactor for ammoxidation reaction, the molar ratio of m-xylene, ammonia gas and oxygen in the reaction raw materials is 1:2.1:10, the ammoxidation reaction temperature is 360 ℃, the reaction pressure (gauge pressure) is 15kPa, and the weight load of the catalyst in the reactor is 0.06h -1 。
After the reactor was operated for 1000 hours, the conversion of m-xylene was 99.8% and the selectivity of m-phthalonitrile was 99.1%.
Example 3
1) 2600g of water are heated to 80 ℃ and 2100g of oxalic acid (H) are stirred at 300rpm 2 C 2 O 4 ) Adding water to form an oxalic acid aqueous solution; adding 455g of vanadium pentoxide, 510g of silver nitrate and 998g of arsenic trichloride into 800g of water to form a first reaction solution;
adding the first reaction solution into an oxalic acid aqueous solution under stirring to form a first mixed solution;
2) 1190g of zinc nitrate hexahydrate, 1519g of cerium nitrate hexahydrate and 16.85g of platinum chloride are dissolved in 3513.15g of water to form reaction liquid II;
adding 3000g of 40 mass percent silica sol and the reaction solution II into the mixed solution I to obtain mixed solution II;
3) stirring the mixed solution II at 90 ℃ for 150min at the rotating speed of 310rpm, then heating to 110 ℃, standing for 180min for aging treatment, and evaporating the aged solution to slurry with the solid content of 45%;
spray-drying the obtained slurry at the inlet temperature of 280 ℃ and the outlet temperature of 130 ℃ to obtain catalyst precursor powder;
4) heating the obtained catalyst precursor powder to 135 ℃ at the speed of 2 ℃/min and preserving the temperature for 12 hours; then heating to 650 ℃ at the speed of 3 ℃/min for roasting for 8h, and finally cooling to room temperature at the speed of 5 ℃/min to obtain the ammoxidation catalyst 3.
The active component proportion of the ammoxidation catalyst 3 is detected to be V 1.0 Ag 0.6 As 1.1 Zn 0.8 Ce 0.7 Pt 0.01 O x 。
The ammoxidation catalyst 3 obtained above is filled in a fluidized bed reactor for ammoxidation, the molar ratio of m-xylene, ammonia gas and oxygen in the reaction raw materials is 1:2.1:8.6, the ammoxidation temperature is 315 ℃, the reaction pressure (gauge pressure) is 18kPa, and the catalyst weight load in the reactor is 0.03h -1 。
After the reactor was operated for 1000 hours, the conversion of m-xylene was 99.9% and the selectivity of m-phthalonitrile was 99.5%.
Example 4
1) 2650g of water are heated to 75 ℃ and 2050g of oxalic acid (H) are stirred at 350rpm 2 C 2 O 4 ) Adding water to form an oxalic acid aqueous solution; adding 455g of vanadium pentoxide, 1020g of silver nitrate and 726g of arsenic trichloride into 900g of water to form a first reaction solution;
adding the first reaction solution into an oxalic acid aqueous solution under stirring to form a first mixed solution;
2) 722g of calcium chloride, 1299g of lanthanum nitrate hexahydrate and 12.68g of ruthenium nitrate are dissolved in 3568.32g of water to form a reaction solution II;
adding 2900g of silica sol with the mass percentage of 40% and the reaction liquid II into the mixed liquid I to obtain mixed liquid II;
3) stirring the mixed solution II at 95 ℃ for 250min at the rotating speed of 320rpm, then heating to 120 ℃, standing for 85min for aging treatment, and evaporating the aged solution to slurry with the solid content of 48%;
spray-drying the obtained slurry at the inlet temperature of 285 ℃ and the outlet temperature of 135 ℃ to obtain catalyst precursor powder;
4) heating the obtained catalyst precursor powder to 150 ℃ at the speed of 1 ℃/min and preserving heat for 15 h; then heating to 610 ℃ at the speed of 2 ℃/min for 7h for roasting, and finally cooling to room temperature at the speed of 6 ℃/min to obtain the ammoxidation catalyst 4.
The active component proportion of the ammoxidation catalyst 4 is V through detection 1.0 Ag 1.2 As 0.8 Ca 1.3 La 0.6 Ru 0.008 O x 。
The ammoxidation catalyst 4 obtained above was charged in a fluidized bed reactor to conduct ammoxidation, the molar ratio of p-xylene, ammonia gas and oxygen in the reaction raw material was 1:2.3:10.7, the ammoxidation temperature was 362 ℃, the reaction pressure (gauge pressure) was 20kPa, and the catalyst weight load in the reactor was 0.05h -1 。
After the reactor was operated for 1000 hours, the conversion of p-xylene was 99.7% and the selectivity to terephthalonitrile was 99.3%.
Example 5
1) 2700g of water are heated to 85 ℃ and 1980g of oxalic acid (H) are stirred at 350rpm 2 C 2 O 4 ) Adding water to form an oxalic acid aqueous solution; adding 455g of vanadium pentoxide, 850g of silver nitrate and 1541g of arsenic trichloride into 980g of water to form a first reaction solution;
adding the first reaction solution into an oxalic acid aqueous solution under stirring to form a first mixed solution;
2) 1700g of barium nitrate, 742g of praseodymium chloride and 6.97g of aurous chloride are dissolved in 4301.03g of water to form a reaction solution II;
adding 2980g of silica sol with the mass percentage of 40% and the reaction liquid II into the mixed liquid I to obtain mixed liquid II;
3) stirring the mixed solution II at 85 ℃ for 150min at the rotating speed of 280rpm, then heating to 108 ℃, standing for 120min for aging treatment, and evaporating the aged solution to slurry with the solid content of 48%;
spray-drying the obtained slurry at the inlet temperature of 275 ℃ and the outlet temperature of 125 ℃ to obtain catalyst precursor powder;
4) heating the obtained catalyst precursor powder to 180 ℃ at the speed of 2 ℃/min and preserving heat for 10 hours; then heating to 650 ℃ at the speed of 1 ℃/min for roasting for 10h, and finally cooling to room temperature at the speed of 5 ℃/min to obtain the ammoxidation catalyst 5.
The active component proportion of the ammoxidation catalyst 5 is V through detection 1.0 Ag 1 As 1.7 Ba 1.3 Pr 0.6 Au 0.006 O x 。
The obtained ammoxidation catalyst 5 is filled in a fluidized bed reactor for ammoxidation, the molar ratio of p-xylene, ammonia gas and oxygen in the reaction raw material is 1:2:7.9, the ammoxidation temperature is 365 ℃, the reaction pressure (gauge pressure) is 21kPa, and the weight load of the catalyst in the reactor is 0.06h -1 。
After the reactor was operated for 1000 hours, the conversion of p-xylene was 99.9%, and the selectivity to terephthalonitrile was 99.8%.
Comparative example 1
The preparation of V according to the method of example 1 in patent publication CN1490309A 1.00 Cr 0.95 Ti 0.15 B 0.50 P 0.10 Mn 0.2 K 0.05 /SiO 2 1-1 parts of an ammoxidation catalyst;
the ammoxidation catalyst 1-1 obtained above was charged in a fluidized bed reactor to carry out an ammoxidation reaction under the same conditions as in example 1 of the present application;
after the reactor was operated for 1000 hours, the conversion of m-xylene was 65.3% and the selectivity of m-phthalonitrile was 72.1%.
Comparative example 2
The preparation of V was carried out according to the method of example 1 of patent publication CN1500775A 1.0 Cr 0. 9 B 0.5 Ti 0.1 P 0.05 Mo 0.1 Na 0.05 /SiO 2 2-1 of an ammonia oxidation catalyst;
the ammoxidation catalyst 2-1 obtained above was charged in a fluidized bed reactor to carry out an ammoxidation reaction under the same conditions as in example 2 of the present application;
after the reactor was operated for 1000 hours, the conversion of m-xylene was 73.9% and the selectivity to m-phthalonitrile was 62.8%.
Comparative example 3
This comparative example differs from example 3 in that: during the preparation of the catalyst, silver nitrate is not added to obtain the ammoxidation catalyst 3-1, and the active component proportion is V 1.0 As 1.1 Zn 0.8 Ce 0.7 Pt 0.01 O x 。
The ammoxidation catalyst 3-1 obtained above was charged in a fluidized bed reactor, and an ammoxidation reaction was carried out by the method of example 3, and after 1000 hours of operation of the reactor, the conversion of m-xylene was 91.8% and the selectivity for m-phthalonitrile was 83.7%.
Comparative example 4
This comparative example differs from example 4 in that: in the preparation process of the catalyst, arsenic trichloride is not added to obtain an ammoxidation catalyst 4-1, and the active component proportion is V 1.0 Ag 1.2 Ca 1.3 La 0.6 Ru 0.008 O x 。
The ammoxidation catalyst 4-1 obtained above was charged in a fluidized bed reactor, and the ammoxidation was carried out by the method of example 4, and after 1000 hours of operation of the reactor, the conversion of m-xylene was 92.5% and the selectivity for m-phthalonitrile was 81.3%.
Claims (19)
1. An ammoxidation catalyst, comprising a carrier and an active component satisfying a structure represented by the following formula I in terms of atomic ratio:
V 1.0 Ag a As b D c E d G e O x formula I
In the formula I, D is selected from one or more of Mn, Zn, Ca, Ba and Pb, E is selected from one or more of Cs, Zr, La, Ce and Pr, and G is selected from one or more of Rh, Ru, Ir, Pt and Au;
wherein a is 0.01-3, b is 0.01-3, c is 0.01-2, d is 0.001-1, e is 0.001-0.6, and 0.3 < b/(1+ a) < 1.2, 0.1 < (b + e)/(c + d) < 15; x is determined by the degree of oxidation of the other elements of formula I.
2. The ammoxidation catalyst according to claim 1, wherein in the formula I, a is 0.1 to 2, b is 0.05 to 2, c is 0.05 to 1.5, d is 0.005 to 0.8, and e is 0.005 to 0.5.
3. The ammoxidation catalyst according to claim 1, wherein the active component is contained in an amount of 20 to 80% by mass, and the balance is a carrier, based on the total mass of the ammoxidation catalyst;
the carrier is selected from silica or alumina.
4. A process for preparing the ammoxidation catalyst according to any one of claims 1 to 3, wherein the process comprises the steps of:
1) adding the first reaction solution into an oxalic acid aqueous solution to form a first mixed solution;
2) adding a component containing a carrier and a reaction solution II into the mixed solution I to obtain a mixed solution II;
3) aging the mixed solution II, evaporating the obtained solution to obtain slurry with the solid content of 45-80%, and drying the slurry to obtain catalyst precursor powder;
4) roasting the catalyst precursor powder at 400-750 ℃ for 3-15 h to obtain an ammonia oxidation catalyst;
in the step 1), the first reaction solution is an aqueous solution of a vanadium-containing compound, a silver-containing compound and an arsenic-containing compound; the molar ratio of the vanadium-containing compound to oxalic acid contained in the oxalic acid aqueous solution is 1: 0.01-50;
in the step 2), the reaction solution two contains compounds of other metal elements in the active component, wherein the other metal elements in the active component are metal elements expressed by D, E, G in the structure shown in the formula I in the claim 1;
the amount of the mixed solution I and the mixed solution II meets the proportion of each element in the structure shown in the formula I in claim 1.
5. The method according to claim 4, wherein in step 1), the vanadium-containing compound is selected from one or more of vanadium pentoxide, vanadium oxalate, vanadium tartrate, ammonium metavanadate or vanadium sulfate;
the silver-containing compound is selected from one or more of silver nitrate, silver chloride, silver iodide, silver carbonate, silver phosphate or silver acetate;
the arsenic-containing compound is one or more selected from arsenic pentoxide, arsenic trioxide, arsenic pentafluoride, arsenic trifluoride, arsenic pentachloride or arsenic trichloride.
6. The method of claim 5, wherein in step 2), the support-containing component is selected from the group consisting of a silicon source or an aluminum source;
the compounds of other metal elements in the active component are respectively selected from one or more of nitrate, chloride, carbonate or acetate of other metal elements.
7. The method according to claim 6, wherein the support-containing component is selected from one or more of silica sol, nano silica or alumina sol.
8. The method according to claim 6, wherein in the step 3), the aging treatment is performed by stirring the second mixed solution at 45 to 100 ℃ for 30 to 450min and then heating the mixture to 100 to 125 ℃.
9. The method according to claim 8, wherein the aging treatment is performed for 30 to 600 min.
10. The method according to claim 8, wherein in the step 3), the drying is carried out by performing spray drying on the slurry under the conditions that the inlet temperature is 250-300 ℃ and the outlet temperature is 105-140 ℃.
11. The method according to claim 10, wherein in the step 4), the catalyst precursor powder is heated to 120-200 ℃ at a speed of 0.5-6 ℃/min and is kept at the temperature for 10-30 h; and then heating to 400-750 ℃ at the speed of 0.5-8 ℃/min, and then roasting.
12. A process for producing phthalonitrile, characterized in that a process comprising the steps of: in the presence of a catalyst, carrying out ammoxidation reaction on xylene, ammonia gas and oxygen-containing gas to obtain phthalonitrile; the catalyst is the ammonia oxidation catalyst as described in any one of claims 1 to 3 or the ammonia oxidation catalyst prepared by the method as described in any one of claims 4 to 11;
wherein the molar ratio of the xylene to the ammonia to the oxygen in the oxygen-containing gas is 1: 1-2.9: 3.7-12.5.
13. The method of claim 12, wherein the molar ratio of the xylene, the ammonia gas, and the oxygen in the oxygen-containing gas is from 1:2 to 2.5:5.2 to 11.5.
14. The method according to claim 12, wherein the conversion of xylene is 99% or more and the selectivity of phthalonitrile is 98% or more.
15. The method according to claim 12, wherein the ammoxidation reaction temperature is 280 to 500 ℃; the gauge pressure of the ammoxidation reaction is 1 to 350 kPa.
16. The method of claim 15, wherein the ammoxidation reaction is carried out at a temperature of 300 to 450 ℃.
17. The method of claim 15, wherein the ammoxidation reaction is at a gauge pressure of 10 to 150 kPa.
18. The method of claim 15, wherein the reaction raw materials are gasified, uniformly mixed and introduced into a reactor for the ammoxidation reaction, and the weight load of the catalyst in the reactor is 0.01 to 0.3h -1 。
19. The method of claim 18, wherein the weight loading of the catalyst in the reactor is 0.02 to 0.18h -1 。
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| CN112675847B (en) * | 2021-01-12 | 2022-07-12 | 万华化学集团股份有限公司 | Wear-resistant isophthalonitrile catalyst, preparation method and method for preparing isophthalonitrile by using wear-resistant isophthalonitrile catalyst |
| CN112961075B (en) * | 2021-02-04 | 2023-01-24 | 鞍山七彩化学股份有限公司 | Synthetic method of terephthalonitrile |
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