CN112439435A - Catalyst for preparing maleic anhydride by benzene oxidation, preparation method and application - Google Patents
Catalyst for preparing maleic anhydride by benzene oxidation, preparation method and application Download PDFInfo
- Publication number
- CN112439435A CN112439435A CN201910801277.7A CN201910801277A CN112439435A CN 112439435 A CN112439435 A CN 112439435A CN 201910801277 A CN201910801277 A CN 201910801277A CN 112439435 A CN112439435 A CN 112439435A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- compound
- nickel
- maleic anhydride
- heating rate
- 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.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 134
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 126
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 230000003647 oxidation Effects 0.000 title claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title 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 46
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000005470 impregnation Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000011068 loading method Methods 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 52
- 238000010438 heat treatment Methods 0.000 claims description 47
- 239000011148 porous material Substances 0.000 claims description 32
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 28
- 229940010552 ammonium molybdate Drugs 0.000 claims description 28
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 28
- 239000011609 ammonium molybdate Substances 0.000 claims description 28
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000001488 sodium phosphate Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 12
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 12
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000003682 vanadium compounds Chemical class 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000005078 molybdenum compound Substances 0.000 claims description 8
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 7
- 150000002816 nickel compounds Chemical class 0.000 claims description 7
- -1 phosphorus compound Chemical class 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000003388 sodium compounds Chemical class 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium 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
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 241000219793 Trifolium Species 0.000 claims description 3
- 230000003213 activating effect Effects 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
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 3
- 239000011733 molybdenum Substances 0.000 claims 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 3
- 229910052750 molybdenum Inorganic materials 0.000 claims 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- 150000003018 phosphorus compounds Chemical class 0.000 claims 1
- 239000013543 active substance Substances 0.000 abstract description 10
- 238000012546 transfer Methods 0.000 abstract description 5
- 238000005507 spraying Methods 0.000 abstract description 4
- 239000000428 dust Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 42
- 239000012018 catalyst precursor Substances 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000001994 activation Methods 0.000 description 14
- 238000002791 soaking Methods 0.000 description 14
- 239000012452 mother liquor Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000005696 Diammonium phosphate Substances 0.000 description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 8
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 8
- 235000019838 diammonium phosphate Nutrition 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 6
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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Abstract
The invention discloses a catalyst for preparing maleic anhydride by benzene oxidation, a preparation method and application. The catalyst comprises a carrier and an active component, wherein the carrier is macroporous alumina. The preparation method adopts an impregnation method to prepare the catalyst, so that a large amount of dust generated in the traditional high-temperature spraying is avoided, the possibility of fire hazard is reduced, the preparation process is more environment-friendly, the active substance loading capacity of the catalyst is low, and the cost is reduced; the invention adopts macroporous alumina as a carrier, utilizes the structural characteristics of macropores and large specific surface area of the macroporous alumina, and improves the mass transfer process of the raw material benzene and the product maleic anhydride, thereby improving the performance of the catalyst.
Description
Technical Field
The invention relates to the field of catalysts, and relates to a catalyst for preparing maleic anhydride through benzene oxidation, a preparation method and application.
Background
Maleic anhydride (maleic anhydride) is a very important organic chemical raw material, and at present, it has become the second largest organic anhydride which is second only to phthalic anhydride. The method is mainly used for producing 1, 4-butanediol, gamma-butyrolactone, tetrahydrofuran, fumaric acid, unsaturated polyester resin and the like, and can also be used for producing medicines and pesticides. Unsaturated Polyester Resin (UPR) is the largest downstream consumer product of maleic anhydride, and 1, 4-butanediol, and the consumption of the two can account for more than 60% of the consumption of the maleic anhydride.
The production of maleic anhydride is mainly based on the benzene and n-butane process, depending on the source of the raw materials. In recent years, the productivity of the domestic n-butane oxidation method device is continuously expanded, the development momentum is fast, but the process for preparing maleic anhydride by the n-butane method is more complex than that of the benzene method, and the operation is relatively difficult, so that the process using the benzene as the raw material still can account for 50 percent of the total production energy of the maleic anhydride. In addition, the price of benzene is gradually lowered since 2019, the price of n-butane is not changed greatly, the market price of n-butane is currently 4000 yuan/ton, the price of benzene is 4500 yuan/ton, the price difference between the two is very small, and according to feedback of manufacturers, when the price difference between the raw material benzene and the ton price of n-butane is within 1500 yuan, the comprehensive cost advantage of the benzene method is higher than that of the n-butane method.
In areas with relatively rich coal resources and relatively deficient petroleum resources, such as Shanxi province, the maleic anhydride device using the coking benzene as the raw material still serves as the mainstream device. At present, the production of a maleic anhydride device has great competition, manufacturers reduce the production cost as much as possible in order to improve the economic benefit, the raw material cost of benzene occupies more than 80 percent of the production cost of maleic anhydride, the benzene consumption is reduced, and the utilization rate of benzene is improved, so that the economic benefit can be obviously improved.
At present, patents for preparing maleic anhydride by benzene oxidation mainly focus on screening of auxiliaries and optimization of a formula, for example, patent CN103816931A proposes a preparation method of a catalyst for preparing maleic anhydride by benzene oxidation, in which molybdenum compounds and vanadium compounds are dissolved in hydrochloric acid, then a solution containing compounds such as phosphorus, sodium, nickel, copper and the like is added into the active mother liquor, the obtained mother liquor is sprayed on an inert talc ceramic carrier, and activation is performed at 350-. However, the method uses hydrochloric acid as a reducing agent and a solvent, and the hydrochloric acid is a very volatile and corrosive acid, so that not only can equipment be corroded and the cost of the equipment be increased, but also the health of workers can be damaged, and a series of problems such as environmental pollution are caused. Patent 105536837a also discloses a catalyst for preparing maleic anhydride by benzene oxidation, which is prepared by using rare earth metal oxide as a main additive, such as one or more of lanthanum, cerium, terbium and europium, and silicon carbide as a carrier by an impregnation method or a spraying method.
Disclosure of Invention
The macroporous alumina carrier has the advantages of large specific surface area, high pore volume and large average pore diameter, is applied to the catalyst for preparing maleic anhydride by benzene oxidation, is beneficial to the diffusion of raw materials and the desorption of products, reduces the retention time of the products and avoids deep oxidation.
On the basis of earlier-stage formula optimization, macroporous alumina is used as a carrier, and an impregnation method is used to improve the performance of the catalyst, so that the benzene conversion rate can reach 98.4%, the mass yield of maleic anhydride can reach 94.9%, and the mass yield can be improved by 2.7% compared with that of a common alumina carrier.
The invention aims to solve the technical problem of improving the mass transfer problem in the prior art, and adopts the characteristics of large pore channels and large specific surface area of the large pore alumina to strengthen the mass transfer process of raw materials and products, thereby improving the performance of the catalyst.
The invention provides a catalyst for preparing maleic anhydride by benzene oxidation, which comprises a carrier and an active component, wherein the carrier is macroporous alumina.
According to some embodiments of the invention, the macroporous alumina has an average pore diameter of 10 to 80m and a pore volume of 0.4 to 1.5g/cm3Specific surface area of 160-450m2/g。
According to some embodiments of the invention, the macroporous alumina has an average pore diameter of 20 to 50nm and a pore volume of 0.6 to 1.1g/cm3The specific surface area is 200-420m2/g。
According to some embodiments of the invention, the carrier has a shape of any one of a sphere, a cylinder, a ring, a clover.
According to some embodiments of the invention, the carrier is annular in shape.
According to some embodiments of the invention, the active component comprises a primary catalyst and a secondary catalyst; the main catalyst includes a vanadium compound, a molybdenum compound, a sodium compound, a phosphorus compound, and a nickel compound.
According to some embodiments of the invention, the promoter is selected from one or more of the elements rubidium, cesium, cerium, niobium, chromium, tungsten, iron, ruthenium, cobalt, rhodium, gallium, indium, thallium, antimony, bismuth, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
According to some embodiments of the invention, the loading of the active component is 6% to 18% by weight.
According to some embodiments of the invention, the loading of the active component is 8% to 12% by weight.
The insufficient load of the active component can affect the activity of the catalyst, so that the benzene conversion rate is too low, the excessive load of the active component can cause severe deep oxidation of the catalyst, more byproducts are produced, and the weight yield of the maleic anhydride is reduced, so that the load of the active component is very important for the performance of the catalyst.
According to some embodiments of the invention, the vanadium compound is selected from one or more of ammonium metavanadate, vanadium pentoxide and sodium vanadate.
According to some embodiments of the invention, the vanadium compound is ammonium metavanadate.
According to some embodiments of the invention, the molybdenum compound is selected from one or more of ammonium molybdate, molybdenum trioxide, calcium molybdate, and the like.
According to some embodiments of the invention, the molybdenum compound is ammonium molybdate.
According to some embodiments of the invention, the sodium compound is selected from one or more of monosodium phosphate and trisodium phosphate.
According to some embodiments of the invention, the sodium compound is trisodium phosphate.
According to some embodiments of the invention, the phosphorus compound is selected from one or more of monoammonium phosphate, 85% -115% phosphoric acid and phosphorus pentoxide.
According to some embodiments of the invention, the phosphorus compound is ammonium dihydrogen phosphate.
According to some embodiments of the invention, the nickel compound is selected from one or more of nickel nitrate, nickel sulfate, nickel chloride and nickel oxide.
According to some embodiments of the invention, the nickel compound is nickel oxide.
According to some embodiments of the invention, V is2O5Calculated as MoO, of a vanadium compound3Calculated as Na, of a molybdenum compound2Sodium compound calculated as O, in terms of P2O5The phosphorus compound and the nickel compound calculated as NiO are mixed according to the molar ratio of the promoter to the vanadium compound: a molybdenum compound: sodium compound: phosphorus compound: nickel compound (b): the cocatalyst is 1 (0.2-0.90): (0.001-0.2): 0.005-0.25): 0.0001-0.05).
A second aspect of the present invention provides a method for preparing the catalyst of the first aspect, comprising the steps of:
s1, adding the main catalyst and the auxiliary catalyst into the reducing agent solution to obtain a catalyst active component mixture;
s2, impregnating the macroporous alumina with the catalyst active component mixture to obtain a catalyst; preferably multiple impregnations; and/or, preferably, the support is dried before impregnation or the impregnated support is dried before re-impregnation;
and optionally step S3, subjecting the catalyst to high temperature activation to obtain an active catalyst; preferably, the high-temperature activation is that the catalyst is heated from room temperature to 150 ℃ at the heating rate of 70-150 ℃/h, kept for 5-30 minutes, then heated to 250 ℃ at the heating rate of 60-120 ℃/h, kept for 5-30 minutes, then heated to 350 ℃ at the heating rate of 50-100 ℃/h, kept for 10-60 minutes, finally heated to 420-480 ℃ at the heating rate of 40-90 ℃/h, kept for 5-10 hours, and then cooled to room temperature at the heating rate of 40-80 ℃/h; and/or preferably the activating atmosphere is closed, nitrogen, helium, a mixture of nitrogen and helium.
According to some embodiments of the invention, the reducing agent is oxalic acid;
oxalic acid as the reducer of ammonium metavanadate is first oxidized and reduced in solution to produce one kind of complex (NH)4)2[V2O2(C2O4)3]Wherein the valence state of the vanadium is +4, the complex can be further heated and decomposed in the activation process, and then an active phase V is generated2MoO8. The reduction degree of ammonium metavanadate can be controlled by controlling the addition of oxalic acid, the influence on the mother solution is very important, and finally the active phase V in the catalyst can be influenced2MoO8The composition and content of (a) affect the final catalytic performance of the catalyst.
According to some embodiments of the invention, the molar ratio of the reducing agent to the vanadium compound is (1.8-3): 1.
According to some embodiments of the invention, the molar ratio of the reducing agent to the vanadium compound is (1.9-2.0): 1.
According to some embodiments of the invention, the impregnation is performed a plurality of times.
According to some embodiments of the invention, the impregnated support is dried before impregnation or dried before re-impregnation.
According to some embodiments of the present invention, the high temperature activation is raising the temperature of the catalyst from room temperature to 150 ℃ at a temperature raising rate of 70-150 ℃/h for 5-30 minutes, then raising the temperature to 250 ℃ at a temperature raising rate of 60-120 ℃/h for 5-30 minutes, then raising the temperature to 350 ℃ at a temperature raising rate of 50-100 ℃/h for 10-60 minutes, finally raising the temperature to 420-480 ℃ at a temperature raising rate of 40-90 ℃/h for 5-10 hours, and then lowering the temperature to room temperature at a rate of 40-80 ℃/h. The catalyst can be better protected and the performance of the catalyst can be improved by gradually reducing the heating rate.
According to some embodiments of the invention, the activating atmosphere is a closed, nitrogen, helium, a mixture of nitrogen and helium.
A third aspect of the present invention is to provide a process for producing maleic anhydride using the catalyst of the first aspect or the catalyst produced by the process of the second aspect, wherein maleic anhydride is produced by oxidizing a mixed gas of benzene and air through a fixed bed reactor packed with the catalyst.
According to some embodiments of the present invention, the concentration of benzene in the mixed gas is 40 to 55g/Nm in order to prevent the risk of excessive benzene concentration3。
According to some embodiments of the invention, the volume space velocity of the mixed gas is 1500--1。
According to some embodiments of the invention, the volume space velocity of the mixed gas is 2000-h-1。
According to some embodiments of the invention, the heating and removing heat is performed using a molten salt bath.
According to some embodiments of the invention, the molten salt temperature is 340-.
According to some embodiments of the invention, the reaction pressure is negative, normal or elevated.
According to some embodiments of the invention, the reaction pressure is atmospheric.
According to some embodiments of the invention, there is provided a catalyst according to the invention, the catalyst is activated in a closed vessel. The closed container is a cylindrical or square activation furnace body, the upper part of the furnace body is sealed by a flange, so that the inner space is isolated from the outside, electric furnace wires are wound around the outer wall of the furnace body, heat-preservation cloth or heat-preservation tiles are arranged outside the electric furnace wires, and the heating temperature of the furnace body is controlled by an automatic digital temperature control meter; the furnace body is equipped with the blow vent from top to bottom, and lower blow vent is as the gas inlet port, goes up the blow vent and as gas outlet, and gaseous velocity of flow is controlled through gas mass flowmeter.
According to some embodiments of the invention, the process uses a fixed bed reactor, and the heating and heat removal is performed using a molten salt bath. In the evaluation reaction process, the temperatures of all positions in the catalyst bed layer from top to bottom are inconsistent, wherein the highest value of the temperature area is called the hot spot temperature of the catalyst, the corresponding bed layer height is the position of the hot spot of the catalyst, and the thermocouple is used for measuring by means of the temperature of the broaching layer. The benzene concentration is the number of grams of benzene contained in a unit volume of air, and a higher number indicates a higher benzene content in air.
A fourth aspect of the present invention provides the use of a catalyst according to the first aspect or a catalyst prepared by the process of the second aspect in the production of maleic anhydride.
The invention has the beneficial effects that:
(1) the catalyst is prepared by adopting an impregnation method, so that a large amount of dust generated in the traditional high-temperature spraying is avoided, the possibility of fire hazard is reduced, the preparation process is more environment-friendly, the loading capacity of active substances of the catalyst is low, the traditional spraying method is more than 15%, the lowest loading capacity of the catalyst can be 6%, and the cost is obviously reduced;
(2) the invention adopts macroporous alumina as a carrier, utilizes the structural characteristics of macropores and large specific surface area of the macroporous alumina, and improves the mass transfer process of the raw material benzene and the product maleic anhydride, thereby improving the performance of the catalyst.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples. The raw materials or components used in the present invention can be commercially or conventionally prepared unless otherwise specified, and the quantitative tests in the following examples are set up in three repeated experiments, and the results are averaged.
Example 1
Step A: dissolving 49g of oxalic acid in 175mL of water at room temperature, adding 33.8g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is completely dissolved to form a dark green solution; dissolving 14.4g of ammonium molybdate into 25mL of ammonium molybdate, uniformly dissolving the ammonium molybdate and the ammonium molybdate-oxalic acid solution, and adding the solution into the ammonium metavanadate-oxalic acid solution; 2.1g of trisodium phosphate, 1.0g of diammonium phosphate, 0.8g of nickel nitrate, 0.6g of cerium nitrate and 0.9g of indium nitrate are added in turn under stirring, and a catalyst active component mixture is prepared after mixing.
And B: 300g of annular macroporous alumina carrier is put into an oven, the average pore diameter of the macroporous alumina carrier is 21nm, the pore volume is 0.62g/ml, and the specific surface area is 255m2G, and dried at 120 ℃ for 12 hours, then cooled to elevated temperature and stored in a desiccator. And (2) soaking 200g of macroporous alumina carrier in the solution for 30 minutes, then placing the catalyst in an oven, drying at 120 ℃ for 5 hours until the weight is constant, then placing the catalyst in mother liquor for re-soaking, repeating the steps for 3 times, finally obtaining a precursor catalyst, and weighing to obtain 218g of catalyst precursor, wherein the content of active substances is 8.2% of the total mass of the catalyst.
And C: 200g of the above catalyst precursor was placed in an activation furnace, sealed, heated from room temperature to 160 ℃ at a heating rate of 160 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 120 ℃/h for 10 minutes, heated to 350 ℃ at a heating rate of 100 ℃/h for 20 minutes at 350 ℃, then heated to 420 ℃ at a heating rate of 90 ℃/h for 4 hours at that temperature, and then gradually cooled to room temperature to obtain catalyst A.
Catalyst a was loaded in the fixed bed reactor and tested using a molten salt temperature of 350 ℃, the results are shown in table 1.
Example 2
Step A: dissolving 49g of oxalic acid in 175mL of water at room temperature, adding 33.8g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is completely dissolved to form a dark green solution; dissolving 14.4g of ammonium molybdate into 25mL of ammonium molybdate, uniformly dissolving the ammonium molybdate and the ammonium molybdate-oxalic acid solution, and adding the solution into the ammonium metavanadate-oxalic acid solution; 2.1g of trisodium phosphate, 1.0g of diammonium phosphate, 0.8g of nickel nitrate, 0.6g of cesium nitrate and 1.2g of erbium oxide are added in turn under stirring and mixed to prepare a catalyst active component mixture.
And B: 300g of cloverleaf macroporous alumina carrier is put into an oven, the average pore diameter of the macroporous alumina carrier is 39.8nm, the pore volume is 1.01g/ml, and the specific surface area is 405m2G, and dried at 120 ℃ for 12 hours, then cooled to elevated temperature and stored in a desiccator. And (2) soaking 200g of macroporous alumina carrier in the solution for 30 minutes, then placing the catalyst in an oven, drying at 120 ℃ for 5 hours to constant weight, then placing the catalyst in mother liquor for re-soaking, repeating the steps for 4 times, finally obtaining a precursor catalyst, and weighing to obtain 227g of catalyst precursor, wherein the content of active substances is 11.9% based on the total mass of the catalyst.
And C: 200g of the above catalyst precursor was placed in an activation furnace, sealed, heated from room temperature to 180 ℃ at a heating rate of 160 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 130 ℃/h for 10 minutes, heated to 360 ℃ at a heating rate of 100 ℃/h for 20 minutes at 360 ℃, heated to 440 ℃ at a heating rate of 90 ℃/h for 5 hours, and then gradually cooled to room temperature to obtain catalyst B.
Catalyst B was loaded in the fixed bed reactor and tested using a molten salt temperature of 350 c, the results are shown in table 1.
Example 3
Step A: dissolving 49g of oxalic acid in 175mL of water at room temperature, adding 33.8g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is completely dissolved to form a dark green solution; dissolving 14.4g of ammonium molybdate into 25mL of ammonium molybdate, uniformly dissolving the ammonium molybdate and the ammonium molybdate-oxalic acid solution, and adding the solution into the ammonium metavanadate-oxalic acid solution; 2.1g of trisodium phosphate, 1.0g of diammonium phosphate, 0.8g of nickel nitrate, 0.6g of rubidium nitrate and 1.2g of ferric nitrate are added in turn under stirring, and a catalyst active component mixture is prepared after mixing.
And B: 300g of clover-shaped macroporous alumina carrier is put into an oven, the average pore diameter of the macroporous alumina carrier is 31nm, the pore volume is 0.75g/ml, and the specific surface area is 304m2G, and dried at 120 ℃ for 12 hours, then cooled to elevated temperature and stored in a desiccator. And (2) soaking 200g of macroporous alumina carrier in the solution for 30 minutes, then placing the catalyst in an oven, drying at 120 ℃ for 5 hours until the weight is constant, then placing the catalyst in mother liquor for soaking again, repeating the steps for 3 times, finally obtaining a precursor catalyst, and weighing to obtain 220g of catalyst precursor, wherein the content of active substances is 9.1% of the total mass of the catalyst.
And C: 200g of the above catalyst precursor was placed in an activation furnace, sealed, heated from room temperature to 180 ℃ at a heating rate of 130 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 140 ℃/h for 10 minutes, heated to 360 ℃ at a heating rate of 100 ℃/h for 20 minutes at 360 ℃, heated to 450 ℃ at a heating rate of 90 ℃/h for 5 hours, and then gradually cooled to room temperature to obtain catalyst C.
Catalyst C was loaded in the fixed bed reactor and tested using a molten salt temperature of 350℃, the results are shown in table 1.
Example 4
Step A: dissolving 49g of oxalic acid in 175mL of water at room temperature, adding 33.8g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is completely dissolved to form a dark green solution; dissolving 14.4g of ammonium molybdate into 25mL of ammonium molybdate, uniformly dissolving the ammonium molybdate and the ammonium molybdate-oxalic acid solution, and adding the solution into the ammonium metavanadate-oxalic acid solution; 2.1g of trisodium phosphate, 1.0g of diammonium phosphate, 0.8g of nickel nitrate, 0.6g of cesium nitrate and 1.2g of erbium oxide are added in turn under stirring and mixed to prepare a catalyst active component mixture.
And B: a 300g cylinder is putPlacing the macroporous alumina carrier into an oven, wherein the average pore diameter of the macroporous alumina carrier is 50nm, the pore volume is 0.68g/ml, and the specific surface area is 205m2G, and dried at 120 ℃ for 12 hours, then cooled to elevated temperature and stored in a desiccator. And (2) soaking 200g of macroporous alumina carrier in the solution for 30 minutes, then placing the catalyst in an oven, drying at 120 ℃ for 5 hours until the weight is constant, then placing the catalyst in mother liquor for re-soaking, repeating the steps for 3 times, and finally obtaining a precursor catalyst, and weighing 224g of catalyst precursor, wherein the content of active substances is 10.7% of the total mass of the catalyst.
And C: 200g of the above catalyst precursor was placed in an activation furnace, sealed, heated from room temperature to 180 ℃ at a heating rate of 130 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 140 ℃/h for 10 minutes, heated to 360 ℃ at a heating rate of 100 ℃/h for 20 minutes at 360 ℃, heated to 450 ℃ at a heating rate of 90 ℃/h for 5 hours, and then gradually cooled to room temperature to obtain catalyst D.
Catalyst D was loaded in the fixed bed reactor and tested using a molten salt temperature of 350 c, the results are shown in table 1.
Example 5
Step A: dissolving 49g of oxalic acid in 175mL of water at room temperature, adding 33.8g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is completely dissolved to form a dark green solution; dissolving 14.4g of ammonium molybdate into 25mL of ammonium molybdate, uniformly dissolving the ammonium molybdate and the ammonium molybdate-oxalic acid solution, and adding the solution into the ammonium metavanadate-oxalic acid solution; 2.1g of trisodium phosphate, 1.0g of diammonium phosphate, 0.8g of nickel nitrate, 0.6g of rubidium nitrate and 1.2g of ferric nitrate are added in turn under stirring, and a catalyst active component mixture is prepared after mixing.
And B: 300g of cloverleaf macroporous alumina carrier is put into an oven, the average pore diameter of the macroporous alumina carrier is 70nm, the pore volume is 0.73g/ml, and the specific surface area is 185m2G, and dried at 120 ℃ for 12 hours, then cooled to elevated temperature and stored in a desiccator. 200g of macroporous alumina carrier is dipped in the solutionAnd (3) the reaction time is 30 minutes, then the catalyst is placed in an oven, dried at 120 ℃ for 5 hours until the weight is constant, then the catalyst is placed in mother liquor to be soaked again, the operation is repeated for 3 times, finally, a precursor catalyst is obtained, and 225g of catalyst precursor is weighed, wherein the content of active substances is 11.1% of the total mass of the catalyst.
And C: 200g of the above catalyst precursor was placed in an activation furnace, sealed, heated from room temperature to 180 ℃ at a heating rate of 130 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 140 ℃/h for 10 minutes, heated to 360 ℃ at a heating rate of 100 ℃/h for 20 minutes at 360 ℃, heated to 450 ℃ at a heating rate of 90 ℃/h for 5 hours, and then gradually cooled to room temperature to obtain catalyst E.
Catalyst E was loaded in the fixed bed reactor and tested using a molten salt temperature of 350 c, the results are shown in table 1.
Comparative example 1 using ordinary alumina as a carrier
Step A: dissolving 49g of oxalic acid in 175mL of water at room temperature, adding 33.8g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is completely dissolved to form a dark green solution; dissolving 14.4g of ammonium molybdate into 25mL of ammonium molybdate, uniformly dissolving the ammonium molybdate and the ammonium molybdate-oxalic acid solution, and adding the solution into the ammonium metavanadate-oxalic acid solution; 2.1g of trisodium phosphate, 1.0g of diammonium phosphate, 0.8g of nickel nitrate, 0.6g of cerium nitrate and 0.9g of indium nitrate are added in turn under stirring, and a catalyst active component mixture is prepared after mixing.
And B: 300g of ordinary annular alumina carrier is put into an oven, the average pore diameter of the alumina carrier is 7nm, the pore volume is 0.31g/ml, and the specific surface area is 100m2G, and dried at 120 ℃ for 12 hours, then cooled to elevated temperature and stored in a desiccator. Soaking 200g of macroporous alumina carrier in the solution for 30 minutes, then placing the catalyst in an oven, drying at 120 ℃ for 5 hours to constant weight, then placing the catalyst in mother liquor for re-soaking, repeating the steps for 3 times to finally obtain a precursor catalyst, weighing to obtain 218g of catalyst precursor, and preparing the catalyst precursor by using the catalyst precursorThe content of active substance was 8.3% by mass.
And C: 200g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 160 ℃ at a heating rate of 160 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 120 ℃/h for 10 minutes, subsequently heated to 350 ℃ at a heating rate of 100 ℃/h for 20 minutes at 350 ℃, then heated to 420 ℃ at a heating rate of 90 ℃/h for 4 hours at that temperature, and then gradually cooled to room temperature, to obtain catalyst A1.
The catalyst a1 was loaded into the fixed bed reactor and tested using a molten salt temperature of 350 ℃ and the results are shown in table 1.
Comparative example 2 use ordinary alumina as a support
Step A: dissolving 49g of oxalic acid in 175mL of water at room temperature, adding 33.8g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is completely dissolved to form a dark green solution; dissolving 14.4g of ammonium molybdate into 25mL of ammonium molybdate, uniformly dissolving the ammonium molybdate and the ammonium molybdate-oxalic acid solution, and adding the solution into the ammonium metavanadate-oxalic acid solution; 2.1g of trisodium phosphate, 1.0g of diammonium phosphate, 0.8g of nickel nitrate, 0.6g of cesium nitrate and 1.2g of erbium oxide are added in turn under stirring and mixed to prepare a catalyst active component mixture.
And B: 300g of common clover-shaped macroporous alumina carrier is put into an oven, the average pore diameter of the alumina carrier is 4nm, the pore volume is 0.35g/ml, and the specific surface area is 110m2G, and dried at 120 ℃ for 12 hours, then cooled to elevated temperature and stored in a desiccator. And (2) soaking 200g of macroporous alumina carrier in the solution for 30 minutes, then placing the catalyst in an oven, drying at 120 ℃ for 5 hours to constant weight, then placing the catalyst in mother liquor for re-soaking, repeating the steps for 4 times, finally obtaining a precursor catalyst, and weighing to obtain 227g of catalyst precursor, wherein the content of active substances is 11.7% by total mass of the catalyst.
And C: 200g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 180 ℃ at a heating rate of 160 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 130 ℃/h for 10 minutes, subsequently heated to 360 ℃ at a heating rate of 100 ℃/h for 20 minutes at 360 ℃, then heated to 440 ℃ at a heating rate of 90 ℃/h for 5 hours, and then gradually cooled to room temperature, to obtain catalyst B1.
Catalyst B1 was loaded into the fixed bed reactor and tested using a molten salt temperature of 350 ℃ and the results are shown in Table 1.
Comparative example 3 use of ordinary alumina as support
Step A: dissolving 49g of oxalic acid in 175mL of water at room temperature, adding 33.8g of ammonium metavanadate, and stirring while adding until the ammonium metavanadate is completely dissolved to form a dark green solution; dissolving 14.4g of ammonium molybdate into 25mL of ammonium molybdate, uniformly dissolving the ammonium molybdate and the ammonium molybdate-oxalic acid solution, and adding the solution into the ammonium metavanadate-oxalic acid solution; 2.1g of trisodium phosphate, 1.0g of diammonium phosphate, 0.8g of nickel nitrate, 0.6g of rubidium nitrate and 1.2g of ferric nitrate are added in turn under stirring, and a catalyst active component mixture is prepared after mixing.
And B: 300g of common clover-shaped macroporous alumina carrier is put into an oven, the average pore diameter of the alumina carrier is 2nm, the pore volume is 0.25g/ml, and the specific surface area is 88m2G, and dried at 120 ℃ for 12 hours, then cooled to elevated temperature and stored in a desiccator. And (2) soaking 200g of macroporous alumina carrier in the solution for 30 minutes, then placing the catalyst in an oven, drying at 120 ℃ for 5 hours until the weight is constant, then placing the catalyst in mother liquor for soaking again, repeating the steps for 3 times, finally obtaining a precursor catalyst, and weighing to obtain 220g of catalyst precursor, wherein the content of active substances is 9.1% of the total mass of the catalyst.
And C: 200g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 180 ℃ at a heating rate of 130 ℃/h for 5 minutes, subsequently heated to 250 ℃ at a heating rate of 140 ℃/h for 10 minutes, subsequently heated to 360 ℃ at a heating rate of 100 ℃/h for 20 minutes at 360 ℃, then heated to 450 ℃ at a heating rate of 90 ℃/h for 5 hours, and then gradually cooled to room temperature, to obtain catalyst C1.
Catalyst C1 was loaded into the fixed bed reactor and tested using a molten salt temperature of 350℃, the results are shown in table 1.
Catalyst evaluation
And (3) respectively filling the activated catalyst into a 120ml bubbling molten salt circulating reactor, wherein the bottom of the reactor is supported by a base, and the upper part of the catalyst is provided with a carrier with a certain height. When the molten salt is heated to the reaction temperature, air is fed, benzene is fed, after the benzene concentration reaches the required working condition concentration, sampling analysis is started after 1 hour of stabilization, and the sampling evaluation results of the catalysts are shown in table 1. The calculation method of each index is as follows:
benzene conversion (%) — amount of substance of benzene at the inlet of the reactor per unit time-amount of substance of benzene at the outlet of the reactor per unit time)/amount of substance of benzene at the inlet of the reactor per unit time × 100%
Maleic anhydride yield (%). the amount of benzene converted to maleic anhydride per unit time/the amount of benzene at the reactor inlet per unit time. times.100%
TABLE 1120 mL Single tube Activity evaluation results
As can be seen from Table 1, the catalyst of the invention has higher reaction performance, the mass yield of maleic anhydride can reach 94.9% optimally, and the comparative example is only 92.1% optimally, and the mass yield is 2.7% higher, which shows that compared with the alumina carrier with small pores, the large pore channel of the large pore alumina has large specific surface area and is more beneficial to mass transfer, thereby improving the conversion rate of benzene and having higher weight yield of maleic anhydride, and when the pore diameter is continuously improved to more than 50nm, the activity of the catalyst can be further improved, but the selectivity of the catalyst is reduced, and the yield is reduced to about 92%.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A catalyst for preparing maleic anhydride by benzene oxidation comprises a carrier and an active component, wherein the carrier is macroporous alumina; preferably, the macroporous alumina has an average pore diameter of 10 to 80m and a pore volume of 0.4 to 1.5g/cm3Specific surface area of 160-450m2(ii)/g; further preferably, the average pore diameter of the macroporous alumina is 20-50nm, and the pore volume is 0.6-1.1g/cm3The specific surface area is 200-420m2/g。
2. The catalyst according to claim 1, wherein the shape of the carrier is any one of a spherical shape, a cylindrical shape, an annular shape, a clover shape and a clover shape, preferably an annular shape.
3. The catalyst of claim 1 or 2, wherein the active component comprises a primary catalyst and a secondary catalyst;
the main catalyst comprises vanadium, molybdenum, sodium, phosphorus and nickel;
and/or the promoter is selected from one or more of rubidium, cesium, cerium, niobium, chromium, tungsten, iron, ruthenium, cobalt, rhodium, gallium, indium, thallium, antimony, bismuth, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium elements.
4. A catalyst according to any one of claims 1 to 3, characterised in that the loading of the active component is 6% to 18%, preferably 8% to 12% by weight.
5. The catalyst according to any one of claims 1 to 4, wherein V is2O5Calculated as MoO of vanadium3Calculated as Na, molybdenum2Sodium in terms of O, in terms of P2O5The molar ratio of phosphorus calculated, nickel calculated as NiO and the cocatalyst is vanadium: molybdenum: sodium: phosphorus: nickel: the cocatalyst is 1 (0.2-0.90): (0.001-0.2): 0.005-0.25): 0.0001-0.05).
6. A process for preparing a catalyst according to any one of claims 1 to 5, comprising the steps of:
s1, adding a main catalyst raw material and an auxiliary catalyst raw material into the reducing agent solution to obtain a catalyst active component mixture; preferably, the reducing agent is oxalic acid; and/or, preferably, the molar ratio of the reducing agent to the vanadium in the main catalyst raw material is (1.8-3) to 1, more preferably (1.9-2.0) to 1;
s2, impregnating the macroporous alumina with a catalyst active component mixture to obtain a catalyst; preferably multiple impregnations; and/or, preferably, the support is dried before impregnation or the impregnated support is dried before re-impregnation;
and optionally step S3, subjecting the catalyst to high temperature activation to obtain an active catalyst; preferably, the high temperature activation is that the temperature of the catalyst is raised from room temperature to 160 ℃ at a heating rate of 70-150 ℃/h, kept for 5-30 minutes, then raised from 230 ℃ to 260 ℃ at a heating rate of 60-120 ℃/h, kept for 5-30 minutes, then raised from 330 ℃ at a heating rate of 50-100 ℃/h, kept for 10-60 minutes, finally raised from 420 ℃ at a heating rate of 40-90 ℃/h, kept for 5-10 hours, and then lowered to room temperature at a heating rate of 40-80 ℃/h; and/or preferably the activating atmosphere is closed, nitrogen, helium, a mixture of nitrogen and helium.
7. The method of claim 6, wherein the procatalyst feed comprises a vanadium compound, a molybdenum compound, a sodium compound, a phosphorous compound, and a nickel compound;
preferably, the vanadium compound is selected from one or more of ammonium metavanadate, vanadium pentoxide and sodium vanadate, and further preferably ammonium metavanadate;
preferably, the molybdenum compound is selected from one or more of ammonium molybdate, molybdenum trioxide and calcium molybdate, and further preferably ammonium molybdate;
preferably, the sodium compound is selected from one or more of sodium dihydrogen phosphate and trisodium phosphate, further preferably trisodium phosphate;
preferably, the phosphorus compound is selected from one or more of ammonium dihydrogen phosphate, 85% -115% phosphoric acid and phosphorus pentoxide, and further preferably ammonium dihydrogen phosphate;
preferably, the nickel compound is selected from one or more of nickel nitrate, nickel sulfate, nickel chloride and nickel oxide, and is further preferably nickel oxide.
8. A process for producing maleic anhydride by using the catalyst according to any one of claims 1 to 6 or the catalyst prepared by the process according to claim 7, characterized in that a mixed gas of benzene and air is contacted with the catalyst.
9. The method of claim 8, wherein the concentration of benzene in the mixed gas is 40-55g/Nm3；
And/or the volume space velocity of the mixed gas is 1500--1Preferably 2000-h-1；
And/or, heating and removing heat by using a molten salt bath, wherein the temperature of the molten salt is preferably 340-360 ℃ pressure.
10. Use of a catalyst according to any one of claims 1 to 6 or prepared according to the process of claim 8 or 9 in the production of maleic anhydride.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115518683A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Supported catalyst, preparation method and application thereof, and method for synthesizing pyromellitic anhydride by durene gas-phase oxidation |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106714A (en) * | 1994-07-05 | 1995-08-16 | 化学工业部北京化工研究院 | Maleic anhydride catalyst with heavy rare earth oxide and its application |
| CN1258567A (en) * | 1998-12-30 | 2000-07-05 | 中国石油化工集团公司 | Macroporous Alpha-alumina and its preparation and application |
| US6180557B1 (en) * | 1998-08-13 | 2001-01-30 | Council Of Scientific & Industrial Research | Supported catalyst useful for Friedel-Crafts reactions and process for the preparation of aralkylated aromatic compounds using the catalyst |
| CN1733748A (en) * | 2005-09-05 | 2006-02-15 | 中国人民解放军军事医学科学院毒物药物研究所 | Cyclohexenone analog bicyclo (condensed ring) compound and preparation method thereof and purposes |
| CN102040235A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Three-dimensional ordered macroporous alumina and preparation method thereof |
| CN104383922A (en) * | 2013-07-18 | 2015-03-04 | 中国石油大学(北京) | Heavy oil hydrogenation iron-based catalyst and application thereof |
| CN104437580A (en) * | 2014-10-24 | 2015-03-25 | 大连瑞克科技有限公司 | Supported VPO catalyst for preparing maleic anhydride by employing butane oxidation and preparation method |
| CN106807419A (en) * | 2017-03-09 | 2017-06-09 | 武汉凯迪工程技术研究总院有限公司 | The method that infusion process prepares hydrotreating catalyst |
| CN106861766A (en) * | 2017-02-28 | 2017-06-20 | 山西大学 | A kind of alumina support and preparation method and application |
| CN109201095A (en) * | 2017-07-04 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of benzene oxidatoin catalyst for preparing cis-anhydride and the preparation method and application thereof |
-
2019
- 2019-08-28 CN CN201910801277.7A patent/CN112439435A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106714A (en) * | 1994-07-05 | 1995-08-16 | 化学工业部北京化工研究院 | Maleic anhydride catalyst with heavy rare earth oxide and its application |
| US6180557B1 (en) * | 1998-08-13 | 2001-01-30 | Council Of Scientific & Industrial Research | Supported catalyst useful for Friedel-Crafts reactions and process for the preparation of aralkylated aromatic compounds using the catalyst |
| CN1258567A (en) * | 1998-12-30 | 2000-07-05 | 中国石油化工集团公司 | Macroporous Alpha-alumina and its preparation and application |
| CN1733748A (en) * | 2005-09-05 | 2006-02-15 | 中国人民解放军军事医学科学院毒物药物研究所 | Cyclohexenone analog bicyclo (condensed ring) compound and preparation method thereof and purposes |
| CN102040235A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Three-dimensional ordered macroporous alumina and preparation method thereof |
| CN104383922A (en) * | 2013-07-18 | 2015-03-04 | 中国石油大学(北京) | Heavy oil hydrogenation iron-based catalyst and application thereof |
| CN104437580A (en) * | 2014-10-24 | 2015-03-25 | 大连瑞克科技有限公司 | Supported VPO catalyst for preparing maleic anhydride by employing butane oxidation and preparation method |
| CN106861766A (en) * | 2017-02-28 | 2017-06-20 | 山西大学 | A kind of alumina support and preparation method and application |
| CN106807419A (en) * | 2017-03-09 | 2017-06-09 | 武汉凯迪工程技术研究总院有限公司 | The method that infusion process prepares hydrotreating catalyst |
| CN109201095A (en) * | 2017-07-04 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of benzene oxidatoin catalyst for preparing cis-anhydride and the preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIN QIN ET AL.: "Progress in catalysis in China during 1982–2012: Theory and", 《CHINESE JOURNAL OF CATALYSIS》 * |
| 丁巍等: "高分子模板剂在大孔氧化铝纳米材料中的脱除", 《精细石油化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115518683A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Supported catalyst, preparation method and application thereof, and method for synthesizing pyromellitic anhydride by durene gas-phase oxidation |
| CN115518683B (en) * | 2021-06-24 | 2024-02-02 | 中国石油化工股份有限公司 | Supported catalyst, preparation method and application thereof, and method for synthesizing pyromellitic dianhydride by gas-phase oxidation of durene |
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