WO2002034387A1 - Katalysator und verfahren zur herstellung von maleinsäureanhydrid - Google Patents
Katalysator und verfahren zur herstellung von maleinsäureanhydrid Download PDFInfo
- Publication number
- WO2002034387A1 WO2002034387A1 PCT/EP2001/012445 EP0112445W WO0234387A1 WO 2002034387 A1 WO2002034387 A1 WO 2002034387A1 EP 0112445 W EP0112445 W EP 0112445W WO 0234387 A1 WO0234387 A1 WO 0234387A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- vanadium
- phosphorus
- maleic anhydride
- temperature
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 66
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 64
- 239000011574 phosphorus Substances 0.000 claims abstract description 64
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 44
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 43
- 230000003647 oxidation Effects 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 29
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 25
- 238000000634 powder X-ray diffraction Methods 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 230000005855 radiation Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 57
- 239000012298 atmosphere Substances 0.000 claims description 43
- 239000012018 catalyst precursor Substances 0.000 claims description 42
- -1 phosphorus compound Chemical class 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 238000001354 calcination Methods 0.000 claims description 28
- 239000011261 inert gas Substances 0.000 claims description 25
- 239000003638 chemical reducing agent Substances 0.000 claims description 21
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 15
- 229910001882 dioxygen Inorganic materials 0.000 claims description 15
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 15
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000010586 diagram Methods 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000002955 isolation Methods 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 235000011007 phosphoric acid Nutrition 0.000 claims description 6
- 229910016523 CuKa Inorganic materials 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 125000002015 acyclic group Chemical group 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000005496 tempering Methods 0.000 claims description 3
- 241001026509 Kata Species 0.000 claims 2
- 210000003608 fece Anatomy 0.000 claims 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 abstract 1
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000843 powder Substances 0.000 description 16
- 150000003682 vanadium compounds Chemical class 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 13
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000007493 shaping process Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- 150000003018 phosphorus compounds Chemical class 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 235000011180 diphosphates Nutrition 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229940048084 pyrophosphate Drugs 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052756 noble gas Inorganic materials 0.000 description 3
- 150000002835 noble gases Chemical class 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- 239000011733 molybdenum Substances 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
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- 239000010452 phosphate Substances 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
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- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
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- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- GWEFHNYDRUAGGI-UHFFFAOYSA-N ethanolate silicon(4+) Chemical compound [Si+4].CC[O-].CC[O-].CC[O-].CC[O-] GWEFHNYDRUAGGI-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZSSVQAGPXAAOPV-UHFFFAOYSA-K molybdenum trichloride Chemical compound Cl[Mo](Cl)Cl ZSSVQAGPXAAOPV-UHFFFAOYSA-K 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- QHMGFQBUOCYLDT-RNFRBKRXSA-N n-(diaminomethylidene)-2-[(2r,5r)-2,5-dimethyl-2,5-dihydropyrrol-1-yl]acetamide Chemical compound C[C@@H]1C=C[C@@H](C)N1CC(=O)N=C(N)N QHMGFQBUOCYLDT-RNFRBKRXSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- PRCNQQRRDGMPKS-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O.CC(=O)CC(C)=O PRCNQQRRDGMPKS-UHFFFAOYSA-N 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
Definitions
- the present invention relates to a vanadium, phosphorus and oxygen-containing catalyst for the production of maleic anhydride by heterogeneous gas phase oxidation of a hydrocarbon offs with at least four carbon atoms and a method for the production thereof.
- the present invention relates to a process for the production of maleic anhydride by heterogeneously catalyzed gas-phase oxidation of a hydrocarbon with at least four carbon atoms using the catalyst according to the invention.
- Maleic anhydride is an important intermediate in the synthesis of ⁇ -butyrolactone, tetrahydrofuran and 1,4-butanediol, which in turn are used as solvents or are further processed, for example, into polymers such as polytetrahydrofuran or polyvinylpyrrolidone.
- VPO catalysts vanadium, phosphorus and oxygen-containing catalysts
- VHPO 4 • Vz H 2 O ⁇ from a pentavalent vanadium compound (eg V 2 O 5 ), a pentavalent phosphorus compound (eg H 3 P0) and a reducing agent Alcohol (eg isobutanol), isolation of the precipitate and drying, optionally shaping (eg tableting); and
- US 4,567,158 also discloses a two-stage calcination, in which calcination was first carried out in air at 350 to 400 ° C. and then in a nitrogen / steam atmosphere at 330 to 500 ° C.
- No. 4,996,179 teaches the calcination of the catalyst precursor in an inert atmosphere at a temperature of 343 to 704 ° C. before contact with an oxygen-containing atmosphere at an elevated temperature.
- US Pat. No. 5,137,860 teaches the preforming of the vanadylphosphate hemihydrate precursor by calcination in an atmosphere containing oxygen, water vapor and, if appropriate, inert gas at a temperature of up to 300.degree. C., a subsequent increase in temperature to above 350.degree. C. and below 550 ° C to set the vanadium oxidation level and continue the temperature treatment under a non-oxidizing, steam-containing atmosphere with a water content of 25 to 75 mol%.
- WO 97/12674 describes the preparation of molybdenum-modified vanadyl pyrophosphate catalysts, the precursors of which are calcined under conditions as previously described in US Pat. No. 5,137,860. Finally, the catalysts are activated in an atmosphere containing air and n-butane. The catalysts contain a substantial proportion of crystalline vanadyl pyrophosphate.
- EP-A 0 799 795 describes the production of a VPO catalyst with a more precisely defined X-ray diffraction diagram, in which the catalyst precursor is initially in an oxygen-containing atmosphere in a temperature range from 350 to 600 ° C. and then under an inert gas atmosphere at 600 calcined up to 800 ° C or under a hydrocarbon / air atmosphere at 350 to 600 ° C.
- the object of the present invention was to find a catalyst for the production of maleic anhydride by heterogeneous catalytic gas-phase oxidation of a hydrocarbon with at least four carbon atoms, which compared to the catalysts according to the prior art with at least activity with a higher selectivity and a higher yield of maleic anhydride. Another object was to find a process for the preparation of the catalyst mentioned which is technically simple to carry out. Furthermore, it was an object to find a process for the preparation of maleic anhydride by heterogeneously catalytic gas-phase oxidation of a hydrocarbon with at least four carbon atoms using the catalyst mentioned.
- composition is understood to mean all components of the catalyst, including active and non-active components.
- a powder sample is used to record the powder X-ray diffraction pattern. When measuring the catalyst, the particles must therefore be pulverized in the present case.
- the powder X-ray diffraction diagram is recorded with a so-called powder diffractometer with variable aperture and scattered aperture diaphragm, with measurements being taken in reflection.
- the signal / background ratio of the individual diffraction lines ("peaks") can be determined from the powder X-ray diffraction diagram as follows:
- the "proximity of the diffraction signal” means a value of + 2 ° in the 2 ⁇ range, starting from the 2 ⁇ ⁇ value of the intensity maximum.
- Correct assignment of the individual diffraction lines is important in the evaluation, since the labeling with respect to the signal / background ratio only affects those diffraction lines in the 2 ⁇ range from 10 ° to 70 ° which are due to a phase containing vanadium and phosphorus are. Suitable for this purpose are, for example, the files and databases known to the person skilled in the art, such as the "PDF 2" data file from the International Center for Diffraction.
- the intensity fraction of the diffraction line is to be calculated from the remaining diffraction pattern of this phase according to the usual methods.
- the quantity of the diffraction signal of interest "to use this value.
- the above-mentioned marking according to the invention in relation to the signal / background ratio relates to all diffraction lines in the 2 ⁇ range from 10 ° to 70 °, which are due to a phase containing vanadium and phosphorus, preferably a phase containing vanadium, phosphorus and oxygen , In normal parlance, such a phase can be referred to as an "amorphous VPO phase” or an "essentially amorphous VPO phase".
- the term "essentially amorphous VPO phase” indicates that within the characteristic signal / background ratio also contain crystalline components and phases of a compound containing vanadium and phosphorus, for example crystalline vanadyl pyrophosphate (VO) 2 Py0 7 could be.
- the catalyst according to the invention can additionally contain phases which are essentially free of vanadium and / or essentially free of phosphorus, regardless of the signal / background ratio of their diffraction lines in the powder X-ray diffraction diagram.
- the term “essentially free” is to be understood as meaning a content of ⁇ 0.1% by weight, preferably ⁇ 0.01% by weight, in the respective phase.
- the phases mentioned can be, for example, phases containing a promoter, phases of a so-called adjuvant or phases containing vanadium or phosphorus (e.g. vanadium pentoxide or vanadium tetroxide).
- a promoter is generally understood to mean additives which improve the catalytic properties of the catalyst.
- the elements of the 1st to 15th group of the periodic table and their compounds are mentioned as suitable promoters for the catalyst according to the invention.
- the catalyst contains promoters, these are preferably compounds of the elements cobalt, molybdenum, iron, zinc, hafnium, zirconium, lithium, titanium, chromium, manganese, nickel, copper, boron, silicon, antimony, tin, niobium and bismuth, particularly preferred Molybdenum, iron, zinc, antimony, bismuth, lithium.
- the catalyst according to the invention can contain one or more promoters.
- the total amount of promoters in the finished catalyst is generally no more than about 5% by weight, preferably not more than about 2% by weight, each calculated as the oxide.
- An auxiliary is generally understood to mean additives which have a positive influence on the production and / or the mechanical-physical properties of the catalyst. Tableting aids and pore formers may be mentioned as non-limiting examples.
- Tableting aids are generally added when the shaping of the catalysts according to the invention is carried out by tableting.
- Tableting aids are generally catalytically inert and improve the tabletting properties of the so-called precursor powder, an intermediate stage in catalyst production, for example by increasing the sliding and free-flowing ability.
- Graphite may be mentioned as a suitable and preferred tabletting aid.
- the tabletting aids added generally remain in the activated catalyst.
- the content of tabletting aid in the finished catalyst is typically about 2 to 6% by weight.
- Pore formers are substances that are used for the targeted adjustment of the pore structure in the macroporous area. In principle, they can be used regardless of the molding process. As a rule, these are compounds containing carbon, hydrogen, oxygen and / or nitrogen, which are added before the catalyst is shaped and are largely removed during the subsequent activation of the catalyst with sublimation, decomposition and / or evaporation. The finished catalyst can nevertheless contain residues or decomposition products of the pore former.
- the catalyst according to the invention can contain the active composition containing vanadium, phosphorus and oxygen, for example in pure, undiluted form as a so-called “full catalyst” or diluted with a preferably oxidic support material as a so-called “mixed catalyst".
- Suitable support materials for the mixed catalysts are, for example, aluminum oxide, silicon dioxide, aluminum silicates, zirconium dioxide, titanium dioxide or a mixture thereof.
- the unsupported and mixed catalysts are preferred, with particular preference the unsupported catalysts.
- the molar phosphorus / vanadium ratio in the catalyst according to the invention is 0.9 to 1.5, preferably 0.95 to 1.2, particularly preferably 0.95 to 1.1, in particular 1.0 to 1.05 ,
- the sow Substance / vanadium ratio is generally ⁇ 5.5 and is preferably in the range 4 to 5.
- the average oxidation state of the vanadium is preferably +3.9 to +4.4 and particularly preferably +4.0 to +4.3.
- the catalyst according to the invention preferably has a BET surface area of 10 to 50 m / g and particularly preferably 15 to 30 m 2 / g. It preferably has a pore volume of 0.1 to 0.5 ml / g and particularly preferably 0.1 to 0.3 ml / g.
- the bulk density of the catalyst according to the invention is preferably 0.5 to 1.5 kg / 1.
- the catalyst according to the invention has particles with an average diameter of at least 2 mm, preferably at least 3 mm.
- the mean diameter of a particle is the mean of the smallest and the largest dimension between two plane-parallel plates.
- Particles are understood to mean both randomly shaped particles and geometrically shaped particles, so-called shaped bodies.
- the catalyst according to the invention preferably has shaped bodies.
- suitable moldings are tablets, cylinders, hollow cylinders, balls, strands, wagon wheels or extrudates. Special shapes such as “Trilobes” and “Tristars” (see EP-A-0 593 646) or shaped bodies with at least one notch on the outside (see US Pat. No. 5,168,090) are also possible.
- the catalyst according to the invention particularly preferably has shaped bodies with an essentially hollow cylindrical structure.
- An essentially hollow-cylindrical structure is to be understood as a structure which essentially comprises a cylinder with an opening passing between the two cover surfaces.
- the cylinder is characterized by two essentially parallel cover surfaces and a lateral surface, the cross section of the cylinder, i.e. parallel to the cover surfaces, is essentially circular in structure.
- the cross section of the through opening, i.e. parallel to the top surfaces of the cylinder is also essentially circular in structure.
- the through opening is in the middle of the lid, whereby other spatial arrangements are not excluded.
- the term "essentially” indicates that deviations from the ideal geometry, such as slight deformations of the circular structure, non-plane-parallel top surfaces, chipped corners and edges, surface roughness or notches in the lateral surface, the cover surfaces or the inner surface of the bore passing through are also included in the catalyst according to the invention.
- circular cover surfaces, a circular cross section of the bore passing through, parallel cover surfaces and macroscopically smooth surfaces are preferred.
- the essentially hollow cylindrical structure can be described by an outer diameter di, a height h as the distance between the two cover surfaces and a diameter of the inner hole (through opening) d.
- the outer diameter d of the catalyst according to the invention is preferably 3 to 10 mm, particularly preferably 4 to 8 mm, very particularly preferably 5 to 6 mm.
- the height h is preferably 1 to 10 mm, particularly preferably 2 to 6 mm, very particularly preferably 2 to 3 mm.
- the diameter of the opening d 2 passing through is preferably 1 to 8 mm, particularly preferably 2 to 6 mm, very particularly preferably 2 to 3 mm.
- the hollow cylindrical catalyst comprises vanadium, phosphorus and oxygen as well as graphite as a tabletting aid.
- FIG. 1 shows an example of a possible powder X-ray diffraction diagram of such a catalyst according to the invention.
- a high-intensity diffraction signal with a 2 ⁇ value of approximately 26.6 ° is clearly recognizable. It is due to the graphite used as a tablet animal aid. Furthermore, a wide maximum intensity can be seen at about 27 °.
- the signal / background ratio of all diffraction lines which can be attributed to a phase containing vanadium and phosphorus is ⁇ 0.5.
- the invention furthermore relates to a process for the preparation of a catalyst for the production of maleic anhydride by heterogeneously catalyzed gas-phase oxidation of a hydrocarbon having at least four carbon atoms, which comprises a catalytically active composition comprising vanadium, phosphorus and oxygen and in which the molar phosphorus / vanadium
- the ratio is 0.9 to 1.5 due to (i) reaction of a pentavalent vanadium compound with a reducing agent and a phosphorus compound, (ii) isolation of the catalyst precursor formed and (iii) calcination of the catalyst precursor , which is characterized in that the calcination comprises the following steps: (a) Annealing in an oxidizing atmosphere with a molecular oxygen content of> 3 vol. -% and of hydrogen oxide of ⁇ 5 vol. -% at a temperature of 300 to 450 ° C;
- (b) annealing is in an inert gas atmosphere having a molecular oxygen content of ⁇ 2 vol .-% and of hydrogen oxide content of ⁇ 2 vol .-% at a temperature of 350 to 500 ° C over ei ⁇ NEN period of time effective to set an atomic spatial order in the composition, which can be achieved using
- a powder X-ray diffraction ⁇ chart shows the in 2 ⁇ range from 10 ° to 70 °, a signal / background ratio for all diffraction lines which a vanadium and phosphorus containing phase can be attributed to ⁇ 10 t.
- the process according to the invention for producing the catalyst can roughly be divided into the three process steps
- the catalyst precursor contains vanadium, phosphorus and oxygen and is generally present as a fine to coarse particulate solid, for example as a powder or as a shaped body, before the calcination step (iii) begins.
- the catalyst precursor is preferably present as a shaped body, particularly preferably as a shaped body with an average diameter of at least 2 mm.
- the catalyst precursor is in an oxidizing atmosphere with a molecular oxygen content of> 3 vol .-% and hydrogen oxide of ⁇ 5 vol. -% annealed at a temperature of 300 to 450 ° C.
- the molecular oxygen content is preferably> 5 vol. -%, particularly preferably at> 10 vol. -%.
- the maximum content of molecular oxygen is generally ⁇ 50% by volume, preferably ⁇ 30% by volume and particularly preferably ⁇ 25% by volume.
- the hydrogen oxide content is preferably ⁇ 3% by volume, particularly preferably ⁇ 2% by volume. -% and in particular at ⁇ 1% by volume.
- step (a) uses mixtures of oxygen and inert gases (e.g. nitrogen or argon), mixtures of oxygen and air, mixtures of air and inert gases (e.g. nitrogen or argon) or air.
- the use of air is preferred. It is advantageous if a certain gas exchange in the calcining furnace is ensured during step (a), so that the gases released by the catalyst precursor, such as water vapor, are removed and the required minimum content of molecular oxygen is maintained.
- step (a) a temperature of 300 to 400 ° C. is preferred, particularly preferably 325 to 390 ° C.
- the temperature can be kept constant during the calcining step, it can rise or fall or fluctuate in the middle. Since step (a) is generally preceded by a heating-up phase, the temperature will generally rise first and then level off at the desired end value.
- the period of time over which the heat treatment in step (a) is maintained should preferably be selected in the process according to the invention in such a way that an average oxidation state of the vanadium is from +3.9 to +4.4, preferably from +4 , 0 to +4.3.
- the average oxidation state of the vanadium is determined by potentiometric titration. A description of the method can be found in the example under "Determination of the Average Oxidation Level of Vanadium".
- the required period of time can advantageously be determined experimentally in preliminary tests.
- a series of measurements is used for this, in which heat treatment is carried out under defined conditions, the samples being removed from the system after different times, cooled and loaded. analyzed with regard to the average oxidation state of the vanadium.
- the period in step (a) extends over a period of over 5 minutes, preferably over 10 minutes and particularly preferably over 15 minutes.
- a period of at most 2 hours, preferably at most 1 hour is sufficient to set the desired average oxidation state.
- a period of over 2 hours is also possible under correspondingly set conditions (e.g. lower range of the temperature interval and / or low molecular oxygen content).
- inert gas atmosphere is to be understood as a gas atmosphere which is characterized by a content of molecular oxygen of ⁇ 2% by volume and of hydrogen oxide (H 2 0) of ⁇ 2% by volume.
- the molecular oxygen content is preferably ⁇ 1% by volume, particularly preferably ⁇ 0.5% by volume.
- the hydrogen oxide content is preferably ⁇ 1.5 vol. -% and in particular at ⁇ 1% by volume.
- the inert gas atmosphere generally contains predominantly nitrogen and / or noble gases, such as argon, which is not to be understood as a restriction. Gases such as carbon dioxide are also suitable in principle.
- the inert gas atmosphere preferably contains> 90 vol. ⁇ % and particularly preferably> 95 vol. -% nitrogen.
- step (b) a temperature of 350 to 450 ° C. is preferred, particularly preferably 375 to 450 ° C.
- the temperature can be kept constant during the calcining step, it can rise or fall on average or fluctuate.
- the temperature of step (b) is preferably at the same level or higher than in step (a), particularly preferably 40 to 80 ° C., in particular 40 to 60 ° C. higher than in step (a).
- the required period of time can advantageously be determined experimentally in preliminary experiments.
- a series of measurements is used for this, in which heat treatment is carried out under defined conditions, the samples being removed from the system after different times, cooled and measured with respect to the powder X-ray diffraction diagram.
- the period in step (b) extends over a period of at least 0.5 hours, preferably over 1 hour and particularly preferably over 2 hours. In general, a period of at most 10 hours, preferably at most 6 hours, is sufficient to set the desired atomic spatial order.
- the calcination (iii) contains, as a further step (c) to be carried out after step (b), cooling in an inert gas atmosphere with a molecular oxygen content of ⁇ 2% by volume and hydrogen oxide of ⁇ 2% by volume. -% to a temperature of ⁇ 300 ° C, preferably of ⁇ 200 ° C and particularly preferably of ⁇ 150 ° C.
- the inert gas atmosphere to be used in step (c) may differ from that in step (b) within the limits of molecular oxygen and hydrogen oxide. For practical reasons, however, it is advantageous to use the same gas atmosphere as in step (b).
- the inert gas atmosphere to be used in step (c) is mainly intended to prevent a change in the atomic spatial order to such an extent that the required signal / background ratio of the above-mentioned diffraction lines in the powder X-ray diffraction diagram is observed.
- the catalyst precursor generally has a temperature of ⁇ 100 ° C. before the beginning of the calcination, it is usually to be heated before step (a).
- the heating can be carried out using different gas atmospheres.
- the heating is preferably carried out in an oxidizing atmosphere, as defined in step (a), or in an inert gas atmosphere, as defined in step (b).
- a change of the gas atmosphere during the heating phase is also possible. Heating in the oxidizing atmosphere, which is also used in step (a), is particularly preferred, in particular in an air atmosphere.
- the average heating rate is generally in the range of about 0.2 to about 10 ° C / min, and preferably about 0.5 to about 5 ° C / min.
- the average heating rate is determined by determining the start and end point using the generally used tangent method and then calculating from these two pairs of values.
- the upper limit of the average heating rate is mainly determined by the apparatus to be used, the lower limit by the time required for the entire heating process, which should advantageously be within an economically reasonable range.
- the current heating rate that is to say the heating rate present at a certain time, can be very different within the heating process.
- the heating rate in the first half of the heating process is usually higher than in the second half. Typical values for the first half are generally in the range from 2 to 10 ° C./min, preferably from 5 to 10 ° C./min, and for the second half in general in the range from 0.2 to 5 ° C./min ,
- step (b) preferably follows directly on the tempering of step (a), the gas atmosphere of course having to be changed from an oxidizing atmosphere to an inert gas atmosphere in accordance with the above-mentioned information.
- the temperature of step (b) is preferably at a temperature higher than that of step (a).
- cooling is preferably carried out as described in step (c).
- the calcining process step (iii) can be carried out in various apparatuses which are suitable for setting the required parameters (e.g. temperature, gas atmosphere).
- suitable apparatus are shaft furnace, tray furnace, muffle furnace, tube furnace or rotary tube furnace.
- a pentavalent vanadium compound with a reducing agent and a phosphorus compound are combined and reacted.
- the catalyst precursor can be produced, for example, as described in US Pat. Nos. 5,275,996 and 5,641,722 or in WO 97/12674.
- the oxides, the acids and the inorganic and organic salts which contain pentavalent vanadium or mixtures thereof can be used as pentavalent vanadium compounds in the process according to the invention.
- the pentavalent vanadium compounds present as solids are used in the form of a powder, preferably in a particle size range from 50 to 500 ⁇ m. If significantly larger particles are present, the solid is crushed and, if necessary, sieved. Suitable devices are, for example, ball mills or planetary mills.
- phosphorus compounds which can be used are both phosphorus compounds having a reducing action, such as, for example, phosphorous acid, and pentavalent phosphorus compounds, such as, for example, phosphorus pentoxide (P0s), orthophosphoric acid (H 3 P0 4 ), pyrophosphoric acid (H 4 P 2 ⁇ ), polyphosphoric acids of the general formula H n + P n 0 3n + 1 with n> 3 or mixtures thereof.
- pentavalent phosphorus compounds is preferred.
- the content of the compounds and mixtures mentioned is usually given in% by weight, based on H 3 PO 4 .
- the use of 80 to 110% H 3 P0 4 is preferred, particularly preferred added from 95 to 110% H 3 P0 4 and very particularly preferably from 100 to 105% H 3 P0 4 .
- Both inorganic compounds such as, for example, reducing phosphorus compounds (for example phosphorous acid) or organic compounds, such as, for example, alcohols, can be used as the reducing agent.
- reducing phosphorus compounds for example phosphorous acid
- organic compounds such as, for example, alcohols
- Suitable examples are methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 1-butanol, 2-butanol (sec-butanol), 2-methyl-l-propanol (isobutanol), 1-pentanol ( Amyl alcohol), 3-methyl-1-butanol (isoamyl alcohol), 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol and 1-dodecanol.
- 1-Butanol and 2-methyl-l-propanol (isobutanol) are particularly preferred, in particular 2-methyl-l-propanol (isobutanol).
- vanadium pentoxide as the pentavalent vanadium compound, an unsubstituted or substituted, acyclic or cyclic C ⁇ ⁇ to C ⁇ 2 alkanol as the reducing agent, and orthophosphoric acid, pyrophosphoric acid, polyphosphoric acids or mixtures thereof as the phosphorus compound.
- the components of the pentavalent vanadium compound, phosphorus compound and reducing agent can be joined together in the method according to the invention in different ways.
- the assembly is carried out in the reaction apparatus suitable for the subsequent reaction, for example a stirred tank, in a temperature range from 0 to 50 ° C., preferably ambient temperature. Temperature increases are possible through the release of heat from the mixture.
- the reducing agent is placed in the reactor and the pentavalent vanadium compound is added, preferably with stirring. Then the phosphorus compound, which can optionally be diluted with a further subset of the reducing agent, is added. If the entire amount of the reducing agent has not yet been added, the part still missing can also be added to the reaction apparatus.
- the reducing agent and the phosphorus compound are placed in the reactor and the pentavalent vanadium compound is added, preferably with stirring.
- another liquid diluent can also be added. Examples include alcohols and small amounts of water. The process according to the invention is preferably carried out without the addition of a diluent.
- the relative molar ratio of the phosphorus compound to be added to the pentavalent vanadium compound to be added is generally adjusted in accordance with the desired ratio in the catalyst precursor.
- the amount of the reducing agent to be added should be above the amount required for the reduction of the vanadium from the oxidation level +5 to an oxidation level in the range +3.5 to +4.5 stoichiologically fresh. If, as in the preferred variant, no so-called liquid diluent is added, the amount of the reducing agent to be added is to be dimensioned at least in such a way that a slurry can be formed with the pentavalent vanadium compound which mixes it intimately of the phosphorus compound to be added. If alcohols are used as the reducing agent, the molar alcohol / vanadium ratio is generally 5 to 15 and preferably 6 to 9.
- the slurry is heated to react the compounds mentioned and form the catalyst precursor.
- the temperature range to be selected depends on various factors, in particular the reduction effect and the boiling point of the components. In general, a temperature of 50 to 200 ° C, preferably 100 to 200 ° C is set.
- the volatile compounds such as water or, in the preferred use of an alcohol, the reducing alcohol and its degradation products, such as aldehyde or carboxylic acid, evaporate from the reaction and can either be removed or partially or completely condensed and recycled. Partial or complete recycling by heating under reflux is preferred. Complete recycling is particularly preferred.
- the reaction at elevated temperature generally takes several hours and is dependent on many factors, such as the type of components added, the temperature.
- the properties of the catalyst precursor can also be set and influenced in a certain range via the temperature and the selected heating time.
- the parameters Temperature and time can easily be optimized for an existing system with just a few tests.
- the promoter is generally added when the pentavalent vanadium compound, the phosphorus compound and the reducing agent are combined in the form of an inorganic or organic salt.
- Suitable promoter compounds are, for example, the acetates, acetylacetonates, oxalates, oxides or alkoxides of the aforementioned promoter metals, such as cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (II) chloride, molybdenum ( VI) oxide, molybdenum (III) chloride, iron (III) acetylacetonate, iron (III) chloride, zinc (II) oxide, zinc (II) acetylacetonate, lithium chloride, lithium oxide, bismuth (III) Chloride, bismuth (III) ethyl hexanoate, Nikkei (II) ethyl
- the catalyst precursor formed is isolated, it being possible for a cooling phase and a storage or aging phase of the cooled reaction mixture to be interposed before the isolation.
- the solid catalyst precursor is separated from the liquid phase. Suitable methods are, for example, filtering, decanting or centrifuging.
- the catalyst precursor is preferably isolated by filtration.
- process step (ii) further includes intermediate steps, such as washing, drying the catalyst precursor and, if appropriate, also shaping it.
- the isolated catalyst precursor can be processed unwashed or washed.
- the isolated catalyst precursor is preferably washed with a suitable solvent in order, for example, to remove adhering reducing agent (for example alcohol) or its degradation products.
- suitable solvents are, for example, alcohols (e.g. methanol, ethanol, 1-propanol, 2-propanol), aliphatic and / or aromatic hydrocarbons (e.g. pentane, hexane, benzine, benzene, toluene, xylenes), ketones (e.g.
- the solid is generally dried.
- the drying can be carried out under different conditions. They are generally carried out at a pressure of 0.0 ("vacuum") to 0.1 MPa abs ("atmospheric pressure").
- the drying temperature is generally 30 to 250 ° C, whereby drying under vacuum compared to drying under atmospheric pressure can often use lower temperatures.
- the gas atmosphere which may protrude during drying can contain oxygen, hydrogen vapor and / or inert gases such as nitrogen, carbon dioxide or noble gases.
- the drying is preferably carried out at a pressure of 1 to 30 kPa abs and a temperature of 50 to 200 ° C. under an oxygen-containing or oxygen-free residual gas atmosphere, such as, for example, air or nitrogen.
- the dried catalyst precursor powder obtained is converted into moldings before the calcination (iii), even if this is not essential for the process according to the invention.
- the shaping can be carried out in various ways, such as, for example, the extrusion of the pasted catalyst precursor powder or the tableting. Tableting is preferred. Suitable moldings are, for example, tablets, cylinders, hollow cylinders, balls, strands, wagon wheels or extrudates. Tablets and hollow cylinders, in particular hollow cylinders, are preferred.
- auxiliaries Before shaping the catalyst precursor, it is often advantageous to mix in so-called auxiliaries into the catalyst precursor powder.
- Tableting aids such as graphite and pore formers may be mentioned as non-limiting examples. Reference is made here to the explanations and definitions given in the description of the catalyst.
- the catalyst precursor powder is intensively mixed with about 2 to 4% by weight of graphite and precompressed in a tablet press.
- the pre-compressed particles are ground in a mill to form granules with a particle diameter of about 0.2 to 1.0 mm and shaped into rings in a ring tablet press.
- the catalyst precursor powder is mixed intensively with about 2 to 4% by weight of graphite and additionally with 5 to 20% by weight of a pore former and is further treated as described above and shaped into rings.
- the desired amounts of vanadium pentoxide powder and isobutanol are placed in a stirred tank and the reactor contents are slurried by stirring. Now the desired amount of phosphoric acid, which is preferably mixed with further isobutanol, is added to the stirred slurry. The resulting vanadium, phosphorus and alcohol-containing slurry is heated under reflux and held at the desired temperature for several hours. The reaction mixture is then cooled with further stirring and placed on a suction filter.
- the filtered-off catalyst precursor is then washed with methanol and dried at a reduced pressure of 1 to 30 kPa abs, preferably 1 to 2 kPa abs at 50 to 200 ° C., preferably 50 to 100 ° C.
- About 2 to 4% by weight of graphite as a tabletting aid is then mixed into the catalyst precursor powder and the mixture is then tabletted in a tablet press into tablets or hollow cylinders.
- the moldings obtained are then heated in an air atmosphere to a temperature in the range from 300 to 450 ° C. and are left under these conditions for a period of about 5 minutes to a maximum of 2 hours in order to set the desired average oxidation state of the vanadium.
- the temperature is preferably increased by 40 to 80 ° C. and the moldings are left under these conditions for a further 0.5 to 10 hours until the desired atomic spatial order has been established.
- the shaped bodies are cooled to a temperature of ⁇ 100 ° C. under a nitrogen atmosphere.
- a catalyst for the production of maleic anhydride by heterogeneously catalyzed gas-phase oxidation of a hydrocarbon with at least four carbon atoms the catalyst containing vanadium, phosphorus and oxygen, the molar phosphorus / vanadium ratio being 0.9 to 1.5, and which particle with has an average diameter of at least 2 mm, which can be obtained by the process according to the invention described above.
- the catalyst according to the invention enables the production of maleic anhydride by heterogeneous catalytic gas phase oxidation of a hydrocarbon with at least four carbon atoms with a higher activity, a higher selectivity to and a higher yield of maleic anhydride than the prior art catalysts.
- the process according to the invention for producing the catalyst can be carried out industrially simply by reacting a pentavalent vanadium compound with a reducing agent and a phosphorus compound, isolating the catalyst precursor formed and calcining the catalyst precursor under defined conditions.
- the invention furthermore relates to a process for the preparation of maleic anhydride by heterogeneously catalytic gas-phase oxidation of a hydrocarbon having at least four carbon atoms with gases containing oxygen, which is characterized in that the catalyst according to the invention is used as described above.
- tube-bundle reactors In the process according to the invention for the production of maleic anhydride, tube-bundle reactors are generally used.
- a tube bundle reactor in turn consists of at least one reactor tube which is surrounded by a heat transfer medium for heating and / or cooling.
- the tube bundle reactors used industrially contain a few hundred to several tens of thousands of reactor tubes connected in parallel.
- the hydrocarbons in the process according to the invention are aliphatic and aromatic, saturated and unsaturated hydrocarbons with at least four carbon atoms, such as 1,3-butadiene, 1-butene, 2-cis-butene, 2-trans-butene, n-butane, C 4 - Mixture, 1, 3-pentadiene, 1, 4-pentadiene, 1-pentene, 2-cis-pentene, 2-trans-pentene, n-pentane, cyclopentadiene, dicyclopentadiene, cyclopentene, cyclopentane, Cs-Ge isch, hexenes , Hexanes, cyclohexane and benzene.
- n-butane 1-Butene, 2-cis-butene, 2-trans-butene, n-butane, benzene or mixtures thereof are preferably used.
- the use of n-butane and n-butane-containing gases and liquids is particularly preferred.
- the n-butane used can originate, for example, from natural gas, steam crackers or FCC crackers.
- the addition of the hydrocarbon generally takes place in a quantity-controlled manner, that is to say under constant specification of a defined quantity per unit of time.
- the hydrocarbon can be metered in liquid or gaseous form. Dosing in liquid form with subsequent evaporation before entry into the tube bundle reactor is preferred. Gases containing oxygen, such as, for example, air, synthetic air, an oxygen-enriched gas or so-called “pure”, ie, oxygen that originates from air separation, are used as oxidizing agents.
- the oxygen-containing gas is also added in a quantity-controlled manner.
- the gas to be passed through the tube bundle reactor generally contains inert gas.
- the proportion of inert gas is usually 50 to 95% by volume at the start.
- Inert gases are all gases that do not directly contribute to the formation of maleic anhydride, such as nitrogen, noble gases, carbon monoxide, carbon dioxide, water vapor, oxygenated and non-oxygenated hydrocarbons with less than four carbon atoms (e.g. methane, ethane, propane, Methanol, formaldehyde, formic acid, ethanol, acetyaldehyde, acetic acid, propanol, propionaldehyde, propionic acid, acrolein, crotonaldehyde) and their mixtures.
- maleic anhydride such as nitrogen, noble gases, carbon monoxide, carbon dioxide, water vapor, oxygenated and non-oxygenated hydrocarbons with less than four carbon atoms (e.g. methane, ethane, propane, Methanol, formaldehyde,
- the inert gas is introduced into the system via the oxygen-containing gas.
- further inert gases separately. Enrichment with further inert gases, which can originate, for example, from the partial oxidation of the hydrocarbons, is possible via a partial recycling of the reaction effluent that may have been prepared.
- a volatile phosphorus compound is preferably added to the gas in the process according to the invention.
- Their concentration at the beginning, ie at the reactor inlet is at least 0.2 ppm by volume, ie 0.2-10 ⁇ 6 parts by volume of the volatile phosphorus compounds, based on the total volume of the gas at the reactor inlet.
- a content of 0.2 to 20 ppm by volume is preferred, particularly preferably 0.5 to 10 ppm by volume.
- Volatile phosphorus compounds are understood to be all those phosphorus-containing compounds which are gaseous in the desired concentration under the conditions of use. Examples of compounds of the general formulas (i) and (II) are mentioned
- R 1 , R 2 and R 3 independently of one another are hydrogen, C C ⁇ to C 6 alkyl, C 3 - to C 6 ⁇ cycloalkyl and Cg- to C ⁇ o-aryl.
- Particularly preferred are the compounds of formula (II) in which R 1 , R 2 and R 3 independently of one another are C ⁇ ⁇ to C 4 alkyl, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl , 2-methylpropyl and 1, 1-dimethylethyl.
- Tri ethyl phosphate, triethyl phosphate and tri-propyl phosphate, in particular triethyl phosphate are very particularly preferred.
- the inventive method is generally conducted at a temperature Tem ⁇ carried out 350-480 ° C.
- Tem ⁇ carried out 350-480 ° C.
- the temperature of the catalyst bed present in the Rorbündelreaktor is understood that would be present in practice the procedure in the absence of a chemical reaction. If this temperature is not exactly the same at all points, the term means the number average of the temperatures along the reaction zone. In particular, this means that the true temperature present on the catalyst can also lie outside the stated range due to the exothermic nature of the oxidation reaction.
- the process according to the invention is preferably carried out at a temperature of 380 to 460 ° C., particularly preferably 380 to 430 ° C.
- the process according to the invention can be carried out at a pressure below normal pressure (e.g. up to 0.05 MPa abs) as well as above normal pressure (e.g. up to 10 MPa abs).
- a pressure of 0.1 to 1.0 MPa abs is preferred, particularly preferably 0.1 to 0.5 MPa abs.
- the process according to the invention can be carried out in two preferred process variants, the variant with "straight passage” and the variant with "return”.
- the "straight pass” maleic anhydride and possibly oxygenated hydrocarbon by-products are removed from the reactor discharge and the remaining gas mixture is discharged and added. otherwise thermally utilized.
- maleic anhydride and optionally oxygenated hydrocarbon by-products are also removed from the reactor discharge, and the remaining gas mixture, which contains unreacted hydrocarbon, is wholly or partly returned to the reactor.
- Another variant of the "recycling” is the removal of the unreacted hydrocarbon and its recycling to the reactor.
- n-butane is used as the starting hydrocarbon and the heterogeneous catalytic gas phase oxidation is carried out “straight through” on the catalyst according to the invention.
- Air as gas containing oxygen and inert gas is fed into the feed unit in a quantity-controlled manner.
- the quantity of n-butane is also regulated, but is preferably supplied in a liquid form via a pump and evaporated in the gas stream.
- the ratio between the amounts of n-butane and oxygen supplied is generally adjusted according to the exothermic nature of the reaction and the desired space / time yield and is therefore dependent, for example, on the type and amount of the catalyst.
- trialkyl phosphate is preferably added to the gas stream as a volatile phosphorus compound in a quantity-controlled manner.
- the volatile phosphorus compound can be added, for example, undiluted or diluted in a suitable solvent, for example water.
- the required amount of the phosphorus compound depends on various parameters, for example the type and amount of the catalyst or the temperatures and pressures in the system, and must be adapted for each system.
- the gas stream is passed through a static mixer for thorough mixing and through a heat exchanger for heating.
- the mixed and preheated gas stream is now passed to the tube bundle reactor in which the catalyst according to the invention is located.
- the tube bundle reactor is advantageously heated by a molten salt circuit.
- the temperature is set such that a conversion of 75 to 90% per reactor pass is preferably achieved.
- the product gas stream originating from the tube bundle reactor is cooled down in a heat exchanger and fed to the unit for separating the maleic anhydride.
- the unit contains at least one apparatus for the absorptive removal of the maleic anhydride and optionally the oxygenated hydrocarbon by-products. Suitable apparatus are, for example, coated with an absorption liquid. filled containers through which the cooled discharge gas is passed or apparatus in which the absorption liquid is sprayed into the gas stream.
- the maleic anhydride-containing solution is discharged from the plant for further processing or for isolation of the valuable product.
- the remaining gas stream is also discharged from the plant and, if necessary, fed to a unit for recovering the unreacted n-butane.
- the process according to the invention using the catalysts according to the invention enables a high hydrocarbon load on the catalyst with a high conversion as a result of high activity.
- the process according to the invention also enables high selectivity, a high yield and therefore also a high space / time yield of maleic anhydride.
- the catalysts were pulverized and measured in an X-ray powder diffractometer of the type "D5000 from Siemens Theta / Theta".
- the measurement parameters were as follows: Circle diameter 435 mm
- the signal / background ratio of the diffraction lines of the powder X-ray diffraction pattern was determined as described in the text.
- the average oxidation state of the vanadium was determined by potentiometric titration using the method described below.
- the solution does not contain V 5+ , which means that the entire vanadium was measured by titration.
- the amount of V 3+ and V + is calculated from the consumption of the 0.1 molar potassium permanganate solution and the position of the two stages. The weighted average then gives the average oxidation state.
- the amount of V + can be calculated from the consumption of the 0.1 molar potassium permanganate solution.
- the total V 5+ of the solution obtained with a 0.1 molar ammonium iron (II) sulfate solution and re-oxidation with 0.1 molar potassium permanganate solution can be used to calculate the total amount of vanadium.
- the difference between the total amount of vanadium and the amount of V + gives the original amount of V 5+ .
- the weighted average then gives the average oxidation state e.
- the test facility was equipped with a feed metering unit and an electrically heated reactor tube.
- the reaction tube length was 30 cm, the inside diameter of the reactor tube was 11 mm.
- 12 g of catalyst in the form of a grit of grain size 0.7 to 1.0 mm were mixed with the same volume of inert material (steatite balls) and filled into the reaction tube. The remaining empty volume was filled with further inert material (steatite balls).
- the reactor was operated in a "straight pass”.
- the reactor pressure was 0.1 MPa abs. Air was used as the oxidizing gas.
- n-Butane was evaporated and gaseous, narrowly metered.
- the test facility was operated with a GHSV of 2000 tr 1 , an n-butane concentration of 2.0 vol. -% and a water content of 1.0 vol. -% operated.
- the resulting product gas was analyzed by gas chromatography.
- Example 1 (Catalyst A, According to the Invention)
- the catalyst obtained was by a molar phosphorus / Vana ⁇ dium ratio of 1.05, an average vanadium oxidation state of from +4.15 and a BET surface area of 17 m 2 / g are characterized.
- the powder X-ray diffraction diagram showed in the 2 ⁇ range from 10 ° to 70 ° a broad intensity maximum at 27 ° and a signal / background for all diffraction lines
- the catalytic test was carried out in the test facility under the specified conditions at a temperature of 400 ° C. A conversion of 85.3% and a selectivity of 69.3% were achieved. The yield obtained was 59.1%.
- the catalyst precursor, including the shaping, was produced analogously to Example 1.
- the moldings were then heated in air in a muffle furnace at a heating rate of 7.5 ° C./min initially to 250 ° C., then at a heating rate of 2 ° C./min to 285 ° C. and left at this temperature for 10 minutes.
- the gas atmosphere was then switched from air to nitrogen / water vapor (molar ratio 1: 1), heated to 425 ° C. and left under these conditions for 3 hours. Finally, the mixture was cooled to room temperature under nitrogen. Characterization of the catalyst:
- the catalyst obtained could be characterized by a molar phosphorus / vanadium ratio of 1.04, an average oxidation state of the vanadium of +4.18 and a BET surface area of 19 m 2 / g.
- the powder X-ray diffraction pattern is shown in Figure 2.
- An evaluation of the line pattern showed that the catalyst essentially consisted of crystalline vanadyl pyrophosphate (VO) P0, the line with the highest intensity having a 2 ⁇ value of 28.5 ° having a signal / background ratio of 17.
- the catalytic test was carried out in the test facility under the specified conditions at a temperature of 410 ° C. A conversion of 84.5% and a selectivity of 66.0% were achieved. The yield obtained was 55.8%.
- Examples 1 and 2 show that even at a temperature which is 10 ° C lower, the catalyst according to the invention leads to a conversion which is approximately 1% by rel.% And a yield of maleic anhydride which is approximately 6%.% Higher.
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Abstract
Description
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Priority Applications (5)
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US10/399,153 US20040014990A1 (en) | 2000-10-27 | 2001-10-26 | Preparation of maleic anhydride and catalyst for this purpose |
KR10-2003-7005829A KR20030061381A (ko) | 2000-10-27 | 2001-10-26 | 말레산 무수물 제조용 촉매 및 제조 방법 |
JP2002537428A JP2004512167A (ja) | 2000-10-27 | 2001-10-26 | 無水マレイン酸を製造するための触媒及び方法 |
AU2002221768A AU2002221768A1 (en) | 2000-10-27 | 2001-10-26 | Catalyst and method for producing maleic anhydride |
EP01988623A EP1337332A1 (de) | 2000-10-27 | 2001-10-26 | Katalysator und verfahren zur herstellung von maleinsäureanhydrid |
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DE10053494A DE10053494A1 (de) | 2000-10-27 | 2000-10-27 | Katalysator und Verfahren zur Herstellung von Maleinsäureanhydrid |
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WO2003078057A1 (de) * | 2002-03-15 | 2003-09-25 | Basf Aktiengesellschaft | Katalysator und verfahren zur herstellung von maleinsäureanhydrid |
US7345167B2 (en) | 2003-07-28 | 2008-03-18 | Basf Aktiengesellschaft | Method for the production of maleic anhydride |
WO2010072723A3 (de) * | 2008-12-22 | 2010-09-10 | Basf Se | Katalysator und verfahren zur herstellung von maleinsäureanhydrid |
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GB0816703D0 (en) * | 2008-09-12 | 2008-10-22 | Johnson Matthey Plc | Shaped heterogeneous catalysts |
GB0816705D0 (en) * | 2008-09-12 | 2008-10-22 | Johnson Matthey Plc | Shaped heterogeneous catalysts |
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KR20130102589A (ko) * | 2010-09-10 | 2013-09-17 | 헌츠만 페트로케미칼 엘엘씨 | 말레산 무수물 제조를 위한, 낮은 바나듐 산화 상태를 갖는 개선된 vpo 촉매 |
US9573119B2 (en) | 2011-09-16 | 2017-02-21 | Eastman Chemical Company | Process for preparing V—Ti—P catalysts for synthesis of 2,3-unsaturated carboxylic acids |
US8883672B2 (en) | 2011-09-16 | 2014-11-11 | Eastman Chemical Company | Process for preparing modified V-Ti-P catalysts for synthesis of 2,3-unsaturated carboxylic acids |
US8765629B2 (en) | 2011-09-16 | 2014-07-01 | Eastman Chemical Company | Process for preparing V-Ti-P catalysts for synthesis of 2,3-unsaturated carboxylic acids |
US8993801B2 (en) | 2011-09-16 | 2015-03-31 | Eastman Chemical Company | Process for preparing V-Ti-P catalysts for synthesis of 2,3-unsaturated carboxylic acids |
EP2781262B1 (de) * | 2013-03-22 | 2020-05-27 | Clariant International Ltd | Entfernbare Schutzbeschichtung für die Aufnahme eines staubfreien Katalysators |
CN103551175A (zh) * | 2013-11-06 | 2014-02-05 | 兰州理工大学 | 磷酸氧钒催化剂及其制备方法与用途 |
US9675966B2 (en) * | 2015-07-16 | 2017-06-13 | Ineos Europe Ag | Catalyst for n-butane oxidation to maleic anhydride |
US11289700B2 (en) | 2016-06-28 | 2022-03-29 | The Research Foundation For The State University Of New York | KVOPO4 cathode for sodium ion batteries |
CN109395755A (zh) * | 2018-10-24 | 2019-03-01 | 中南大学 | 一种导热材料掺杂钒磷氧催化剂及制备和在正丁烷选择性催化氧化合成顺酐中的应用 |
CN112705233A (zh) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | 一种钒磷氧催化剂及其制备方法和应用 |
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US4392986A (en) * | 1981-10-08 | 1983-07-12 | Exxon Research & Engineering Co. | Catalyst for carboxylic anhydride production |
US4795818A (en) * | 1984-09-04 | 1989-01-03 | Scientific Design Company, Inc. | Optimizing the yield of maleic anhydride catalyst |
DE19645066A1 (de) * | 1996-10-31 | 1998-05-07 | Consortium Elektrochem Ind | Verfahren zur Herstellung von Katalysatoren für die Gasphasenoxidation von C¶4¶-Kohlenwasserstoffen zu Maleinsäureanhydrid |
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2000
- 2000-10-27 DE DE10053494A patent/DE10053494A1/de not_active Withdrawn
-
2001
- 2001-10-26 US US10/399,153 patent/US20040014990A1/en not_active Abandoned
- 2001-10-26 JP JP2002537428A patent/JP2004512167A/ja not_active Withdrawn
- 2001-10-26 AU AU2002221768A patent/AU2002221768A1/en not_active Abandoned
- 2001-10-26 EP EP01988623A patent/EP1337332A1/de not_active Withdrawn
- 2001-10-26 WO PCT/EP2001/012445 patent/WO2002034387A1/de not_active Application Discontinuation
- 2001-10-26 KR KR10-2003-7005829A patent/KR20030061381A/ko not_active Application Discontinuation
- 2001-10-26 CN CNA018180159A patent/CN1471430A/zh active Pending
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US4795818A (en) * | 1984-09-04 | 1989-01-03 | Scientific Design Company, Inc. | Optimizing the yield of maleic anhydride catalyst |
DE19645066A1 (de) * | 1996-10-31 | 1998-05-07 | Consortium Elektrochem Ind | Verfahren zur Herstellung von Katalysatoren für die Gasphasenoxidation von C¶4¶-Kohlenwasserstoffen zu Maleinsäureanhydrid |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003078057A1 (de) * | 2002-03-15 | 2003-09-25 | Basf Aktiengesellschaft | Katalysator und verfahren zur herstellung von maleinsäureanhydrid |
US7345167B2 (en) | 2003-07-28 | 2008-03-18 | Basf Aktiengesellschaft | Method for the production of maleic anhydride |
WO2010072723A3 (de) * | 2008-12-22 | 2010-09-10 | Basf Se | Katalysator und verfahren zur herstellung von maleinsäureanhydrid |
US9138729B2 (en) | 2008-12-22 | 2015-09-22 | Basf Se | Catalyst and method for producing maleic anhydride |
US10022714B2 (en) | 2008-12-22 | 2018-07-17 | Basf Se | Catalyst and method for producing maleic anhydride |
Also Published As
Publication number | Publication date |
---|---|
US20040014990A1 (en) | 2004-01-22 |
EP1337332A1 (de) | 2003-08-27 |
DE10053494A1 (de) | 2002-05-02 |
AU2002221768A1 (en) | 2002-05-06 |
WO2002034387A8 (de) | 2002-05-23 |
CN1471430A (zh) | 2004-01-28 |
JP2004512167A (ja) | 2004-04-22 |
KR20030061381A (ko) | 2003-07-18 |
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