EP2137106A2 - Polynary metal oxide phosphate - Google Patents
Polynary metal oxide phosphateInfo
- Publication number
- EP2137106A2 EP2137106A2 EP08717696A EP08717696A EP2137106A2 EP 2137106 A2 EP2137106 A2 EP 2137106A2 EP 08717696 A EP08717696 A EP 08717696A EP 08717696 A EP08717696 A EP 08717696A EP 2137106 A2 EP2137106 A2 EP 2137106A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- sub
- metal
- vanadium
- metal oxide
- phase
- 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.)
- Withdrawn
Links
- -1 metal oxide phosphate Chemical class 0.000 title claims abstract description 46
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 39
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 39
- 239000010452 phosphate Substances 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 230000003647 oxidation Effects 0.000 claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 238000000634 powder X-ray diffraction Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 37
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 37
- 229910052720 vanadium Inorganic materials 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 21
- 238000003746 solid phase reaction Methods 0.000 claims description 15
- 238000010671 solid-state reaction Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- 235000011180 diphosphates Nutrition 0.000 claims description 13
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 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 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- 150000004679 hydroxides Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical class [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002927 oxygen compounds Chemical class 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 abstract description 30
- 150000001875 compounds Chemical class 0.000 abstract description 15
- 230000011514 reflex Effects 0.000 abstract description 12
- 239000012071 phase Substances 0.000 description 29
- 239000000843 powder Substances 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 239000007858 starting material Substances 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 10
- 229940048084 pyrophosphate Drugs 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000004279 X-ray Guinier Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000007669 thermal treatment Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- YFYPIGDMLIHXSK-UHFFFAOYSA-K [O--].[V+5].[O-]P([O-])([O-])=O Chemical class [O--].[V+5].[O-]P([O-])([O-])=O YFYPIGDMLIHXSK-UHFFFAOYSA-K 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000001177 diphosphate Substances 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012458 free base Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 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
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical compound CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-N 0.000 description 1
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 1
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241001120493 Arene Species 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000396922 Pontia daplidice Species 0.000 description 1
- 101100532456 Rattus norvegicus Slc28a2 gene Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 239000008139 complexing agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 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
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- LIAWOTKNAVAKCX-UHFFFAOYSA-N hydrazine;dihydrochloride Chemical compound Cl.Cl.NN LIAWOTKNAVAKCX-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003041 laboratory chemical Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- KFAFTZQGYMGWLU-UHFFFAOYSA-N oxo(oxovanadiooxy)vanadium Chemical compound O=[V]O[V]=O KFAFTZQGYMGWLU-UHFFFAOYSA-N 0.000 description 1
- DKCWBFMZNUOFEM-UHFFFAOYSA-L oxovanadium(2+);sulfate;hydrate Chemical compound O.[V+2]=O.[O-]S([O-])(=O)=O DKCWBFMZNUOFEM-UHFFFAOYSA-L 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
- 238000012856 packing Methods 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000008262 pumice Substances 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
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- WWDQUBKFDJXHAH-UHFFFAOYSA-B vanadium(4+);tetraphosphate Chemical class [V+4].[V+4].[V+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WWDQUBKFDJXHAH-UHFFFAOYSA-B 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910021489 α-quartz Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- B01J35/612—Surface area less than 10 m2/g
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/16—Reducing
Definitions
- the present invention relates to a polynary metal oxide phosphate containing vanadium and optionally at least one other metal, a process for its preparation and its use in heterogeneously catalyzed gas phase oxidations, preferably heterogeneously catalyzed gas phase oxidations of a hydrocarbon having at least four carbon atoms.
- VPO catalysts Heterogeneous catalysts based on vanadyl pyrophosphate (VO) 2P2 ⁇ 7 (so-called VPO catalysts) are used in the industrial oxidation of n-butane to maleic anhydride as well as in a series of further oxidation reactions of hydrocarbons.
- VO vanadyl pyrophosphate
- the vanadyl pyrophosphate catalysts are usually prepared as follows: (1) Synthesis of a vanadyl hydrogen phosphate hemihydrate precursor (VOHPO 4 / 4H 2 O) from a pentavalent vanadium compound (eg, V 2 O 5), a trivalent or trivalent phosphorus Compound (eg ortho and / or pyrophosphoric acid, phosphoric acid ester or phosphorous acid) and a reducing alcohol (eg isobutanol), isolation of the precipitate, drying and optionally shaping (eg tableting) and (2) Preforming of the precursor to vanadyl pyrophosphate ((VO) 2 P2 ⁇ 7 ) by calcination. It is z. For example, see EP-A 0 520 972 and WO 00/72963.
- the object of the present invention was to provide new polynary vanadium oxide phosphates.
- a further object of the present invention was to provide novel polynary vanadium oxide phosphates with catalytic properties for heterogeneously catalyzed gas phase oxidations.
- a further object of the present invention was to provide novel polynary vanadium oxide phosphates, with the aid of which the catalytic properties of known heterogeneous catalysts based on vanadyl pyrophosphate can be modified.
- M is one or more metals selected from Ti, Zr, Hf, Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, Al, Ga and In,
- a has a value of 0 to 2.0
- b has a value of 2.0 to 4.0
- c has a value of 2.0 to 4.0
- the indication of the X-ray diffraction reflexes in this application takes place in the form of the lattice plane spacings d [A] independent of the wavelength of the X-ray radiation used.
- the wavelength ⁇ of the X-radiation used for the diffraction and the diffraction angle ⁇ are linked together via the Bragg relationship as follows:
- d is the respective diffraction reflex associated lattice spacing of the atomic space arrangement.
- the powder X-ray diffractogram of the metal oxide phosphate of the formula I according to the invention is characterized by the diffraction reflexes mentioned above.
- the diffraction reflections generally have the approximate relative intensities (l re ⁇ [%]) given in Table 1. Further, generally less intense diffraction reflexes of the powder X-ray diffractogram were not taken into account in Table 1.
- mixtures of the metal oxide phosphates according to the invention with other crystalline compounds have additional diffraction reflectances.
- Such mixtures of the metal oxide phosphate with other crystalline compounds can be prepared in a targeted manner by mixing the metal oxide phosphate according to the invention or can be formed in the preparation of the metal oxide according to the invention by incomplete reaction of the starting materials or formation of foreign phases with different crystal structure.
- a in formula I has the value 0. In other preferred embodiments, a has a value of 0.8 to 1.2.
- the formula I b has a value of 2.8 to 3.2.
- M is a metal selected from Ti, Zr, Hf, Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, Al, Ga and In or combinations of two or more of these metals. metals.
- M is a metal selected from Ti, Cr and Fe.
- metal oxide phosphates according to the invention have one of the following formulas:
- the metal oxide phosphates according to the invention are obtainable in various ways.
- the metal oxide phosphates according to the invention can be obtained on the one hand by a solid-state reaction in a closed system.
- at least two reactants selected from oxygen compounds of vanadium, phosphorus compounds of vanadium and mixed oxygen-phosphorus compounds of vanadium, elemental vanadium, oxygen compounds of metal M, phosphorus compounds of metal M and mixed oxygen-phosphorus compounds of metal M and elemental metal M are selected are.
- the reactants are generally selected such that (i) they provide the desired stoichiometry of the elements in formula I, and (ii) the sum of the products of valence times the abundance of non-oxygen elements in the reactants of the sum of the products of Valence times the frequency of elements other than oxygen in Formula I.
- the starting compounds can be selected so that all the elements other than oxygen have the same value as in Formula I. Alternatively, the starting compounds may be chosen such that some or all of the elements other than oxygen have a valency different from that which occurs in formula I.
- redox reactions for. For example, a synproportionation, during the solid state reaction, the elements other than oxygen get the value that they have in Formula I.
- a combination of equivalent amounts of vanadium (III) and vanadium (V) compounds can be used to form tetravalent vanadium in the solid state reaction.
- the required starting compounds in the form of oxides, phosphates, oxide phosphates, phosphides or the like are either commercially available or known from the literature or can easily be synthesized by the skilled person in analogy to known preparation methods.
- the starting materials are intimately mixed, for. B. by fine trituration.
- the solid state reaction is typically carried out at a temperature of at least 500 ° C, e.g. B. 650 to 1100 0 C, in particular about 800 0 C. Typical reaction times are z. 24 hours to 10 days.
- Suitable reaction vessels consist for. B. of quartz glass or corundum.
- a suitable mineralizer such as iodine or PtCb, in the solid-state reaction.
- metal oxide phosphates according to the invention by reacting
- a) produces a dry mixture of a vanadium source, optionally a source of the metal M and a phosphate source,
- a preferably intimate, preferably finely divided, dry mixture of the desired constituent stoichiometry is produced.
- the intimate mixing of the starting compounds can be carried out in dry or wet form.
- the starting compounds are expediently used as finely divided powders and subjected to the mixing and optionally compacting the calcination (thermal treatment).
- the intimate mixing is done in wet form, i. H. in dissolved or suspended form.
- the starting compounds are mixed together in the form of an aqueous solution (optionally with the concomitant use of complexing agents) and / or suspension.
- the aqueous solution or suspension is dried and calcined after drying.
- the drying can be carried out by evaporation in vacuo, by freeze-drying or by conventional evaporation. Preferably, however, the drying process is carried out by spray drying.
- the outlet temperatures are usually 70 to 150 0 C;
- the spray drying can be carried out in cocurrent or in countercurrent.
- Suitable vanadium sources are, for example, vanadyl sulfate hydrate, vanadyl acetylacetonate, vanadates such as ammonium metavanadate, vanadium oxides such as. B. vanadium dioxide (VO2) or divanadium trioxide (V2O3), Vanadiumhalogenide as z. As vanadium tetrachloride (VCU) and vanadyl halides such. B. VOCI3. Divanadium pentoxide and ammonium vanadate are preferred sources of vanadium.
- Possible sources of the metal M are all compounds of the elements which are capable of forming oxides and / or hydroxides upon heating (if appropriate in the presence of molecular oxygen, for example in air). Of course, oxides and / or hydroxides of the elemental constituents may also be used as such starting compounds or may be used exclusively. Oxides, hydroxides and oxide hydroxides of the metal M are preferred sources of the metal M.
- Suitable phosphate sources are phosphate group-containing compounds or compounds from which phosphate groups are formed by redox reactions and / or upon heating (optionally in the presence of molecular oxygen, eg in air).
- phosphoric acids in particular orthophosphoric acid, pyro- or metaphosphoric acids, phosphorous acid, hypophosphorous acid, phosphates or hydrogen phosphates, such as diammonium hydrogen phosphate, and elemental phosphorus, such as. B. white phosphorus.
- the phosphate source is at least partially formed by phosphorous acid or hypophosphorous acid, optionally in combination with orthophosphoric acid.
- vanadium source or metal source compounds are used in which the vanadium or the metal M have a higher valency than they have in formula I (ie, the formal valence of V and, if appropriate, M) the electroneutrality with the O 2 "and PO 4 3 " anions contained in formula I is required), reduction equivalents are preferably to be provided to convert the vanadium and / or metal M to the valence state associated with the vanadium and the metal M in the formula I belongs.
- the reduction equivalents are provided by a reducing agent capable of reducing the superior form of the vanadium and the metal M, respectively.
- the reduction can be carried out during the preparation of the dry mixture or at the latest when calcining.
- the preparation of the intimate dry mixture is preferably carried out under an inert gas atmosphere (eg N 2) in order to ensure better control over the oxidation stages.
- Preferred reducing agents for this purpose are selected from hypophosphorous acid, phosphorous acid, hydrazine (as free base or hydrate or in the form of its salts such as hydrazine dihydrochloride, hydrazine sulfate), hydroxylamine (as free base or in the form of its salts such as hydroxylamine hydrochloride), nitrosylamine, elemental vanadium , elemental phosphorus, borane (also in the form of complex borohydrides such as sodium borohydride) or oxalic acid.
- Phosphoric acid and / or hypophosphorous acid are preferred reducing agents. It will be understood that certain reducing agents, such as hypophosphorous acid or phosphorous acid, may simultaneously serve as the source of phosphate, or elemental vanadium may simultaneously serve as the vanadium source.
- the dry mixture is thermally treated at temperatures of at least 500 ° C., preferably 700 to 1000 ° C., in particular about 800 ° C.
- the thermal treatment can be carried out under oxidizing, reducing, as well as under inert atmosphere.
- As an oxidizing atmosphere z.
- air with molecular oxygen enriched air or oxygen-depleted air into consideration.
- the thermal treatment is preferably carried out under an inert atmosphere, ie, for example, under molecular nitrogen and / or noble gas.
- the thermal treatment is carried out at atmospheric pressure (1 atm).
- the thermal treatment can also be carried out under vacuum or under pressure.
- the thermal treatment takes place under a gaseous atmosphere, it can both stand and flow. Preferably, it flows. Overall, the thermal treatment can take up to 24 hours or more.
- the invention further relates to a gas phase oxidation catalyst which comprises at least one polynary metal oxide phosphate according to the invention.
- the metal oxide can be used as such, z.
- As a powder, or in the form of moldings are used as heterogeneous catalysts.
- the shaping is preferably carried out by tableting.
- a tabletting aid is generally added to the powder and intimately mixed.
- Tabletting aids are generally catalytically inert and improve the tabletting properties of the powder, for example by increasing the lubricity and flowability.
- a suitable and preferred Tablettierzkar is called graphite or boron nitride.
- the added tabletting aids usually remain in the activated catalyst.
- the powder can also be tabletted and then comminuted to chippings.
- the shaping of moldings can, for. B. by applying at least one metal oxide according to the invention or mixtures containing at least one metal oxide according to the invention, carried on a support body.
- the carrier bodies are preferably chemically inert. That is, they essentially do not interfere with the course of the catalytic gas-phase oxidation catalyzed by the metal oxide phosphates according to the invention.
- the material used for the support bodies are, in particular, alumina, silica, silicates such as clay, kaolin, steatite, pumice, aluminum silicate and magnesium silicate, silicon carbide, zirconium dioxide and thorium dioxide.
- the surface of the carrier body can be both smooth and rough.
- the surface of the support body is rough, since an increased surface roughness usually requires an increased adhesive strength of the applied active mass shell.
- the support material may be porous or non-porous.
- the carrier material is non-porous, d. H. the total volume of the pores is preferably less than 1 vol.%, Based on the volume of the carrier body.
- the thickness of the catalytically active layer is usually 10 to 1000 microns, z. B. 50 to 700 microns, 100 to 600 microns or 150 to 400 microns.
- carrier bodies with any geometric structure come into consideration. Their longest extent is usually 1 to 10 mm.
- balls or cylinders, in particular hollow cylinders, are used as carrier bodies.
- the preparation of the shell catalysts can be carried out in the simplest way by pretreating metal oxide phosphate compositions of the general formula (I), converting them into a finely divided form and finally applying them to the surface of the support body with the aid of a liquid binder.
- the surface of the carrier body is moistened in the simplest way with the liquid binder and, by contacting with the finely divided metal oxide phosphate mass, a layer of the active composition is attached to the moistened surface. Finally, the coated carrier body is dried. Needless to say you can repeat the process to achieve a greater layer thickness.
- the metal oxide phosphates according to the invention can also be used to modify the catalytic properties, in particular conversion and / or selectivity, of known catalysts, in particular based on vanadyl pyrophosphate.
- the metal oxide according to the invention z. B. can be used as a promoter phase in a catalyst based on vanadyl pyrophosphate.
- the catalyst then comprises a first phase and a second phase in the form of three-dimensionally extended regions that are different from their local environment by a different chemical composition.
- the first phase contains a catalytically active composition based on vanadyl pyrophosphate and the second phase contains at least one polynary metal oxide phosphate according to the invention.
- finely divided particles of the second phase may be dispersed in the first phase, or (ii) the first phase and the second phase relative to each other be distributed in a mixture of finely divided first phase and finely divided second phase.
- the preparation of these two-phase catalysts can, for. Example, by preparing a Vanadylhydrogenphosphat hemihydrate precursor (VOHPO 4/4 H2O), this is mixed with preformed particles of the second phase of metal oxide according to the invention, the resulting mass is deformed and calcined.
- the vanadyl hydrogenphosphate hemihydrate precursor can be prepared in a manner known per se from a compound of the pentavalent vanadium (for example V2O5), a compound with pentavalent or trivalent phosphorus (for example ortho and / or pyrophosphoric acid, Phosphoric acid ester or phosphorous acid) and a reducing alcohol (e.g., isobutanol) and isolation of the precipitate. It is z.
- a compound of the pentavalent vanadium for example V2O5
- a compound with pentavalent or trivalent phosphorus for example ortho and / or pyrophosphoric acid, Phosphoric acid ester or
- the catalysts according to the invention whose catalytically active composition comprises at least one metal oxide phosphate as defined above, can also be combined with catalysts based on vanadyl pyrophosphate in the form of a structured packing.
- a gas stream containing a hydrocarbon and molecular oxygen to be oxidized may be passed over a bed of first gas phase oxidation catalyst upstream in the gas flow direction and then via one or more downstream beds of second or further gas phase oxidation catalysts first or second or one of the further beds comprises a catalyst according to the invention.
- the invention further relates to a process for the partial gas phase oxidation or monoxidation, in which bringing a gas stream containing a hydrocarbon and molecular oxygen, with a catalyst according to the invention in contact.
- the gas stream additionally contains ammonia.
- ammoxidation is understood as meaning a heterogeneous catalytic process in which methyl-substituted alkenes, arenes and hetarenes are converted into nitriles by reaction with ammonia and oxygen in the presence of transition metal catalysts.
- the process for partial gas phase oxidation is used in preferred embodiments of the production of maleic anhydride, wherein the hydrocarbon used contains at least four carbon atoms.
- tube-bundle reactors are generally used.
- fluidized bed reactors are possible.
- hydrocarbons are generally aliphatic and aromatic, saturated and unsaturated hydrocarbons having at least four carbon atoms, such as 1, 3-butadiene, 1-butene, cis-2-butene, trans-2-butene, n-butane, C4 mixtures, 1, 3-pentadiene, 1,4-pentadiene, 1-pentene, cis-2-pentene, trans-2-pentene, n-pentane, cyclopentadiene, dicyclopentadiene, cyclopentene, cyclopentane, Cs-mixtures, hexenes, hexanes, xane, cyclohexane and benzene.
- Preference is given to using 1,3-butadiene, 1-butene, cis-2-butene
- n-butane and n-butane-containing gases and liquids are particularly preferred.
- the n-butane used can be derived, for example, from natural gas, steam crackers or FCC crackers.
- the addition of the hydrocarbon is generally quantity controlled, d. H. under constant specification of a defined amount per time unit.
- the hydrocarbon can be metered in liquid or gaseous form.
- the dosage in liquid form with subsequent evaporation before entering the reactor.
- oxygen-containing gases such as air, synthetic air, an oxygen-enriched gas or so-called "pure", d. H. z. B. originating from the air separation oxygen.
- the oxygen-containing gas is also preferably added in a controlled amount.
- the gas to be passed through the reactor generally contains a hydrocarbon concentration of 0.5 to 15% by volume and an oxygen concentration of 8 to 25% by volume.
- the proportion missing to one hundred% by volume consists of further gases such as nitrogen, noble gases, carbon monoxide, carbon dioxide, water vapor, oxygenated hydrocarbons (eg methanol, formaldehyde, formic acid, ethanol, acetaldehyde, acetic acid, propanol, propionaldehyde , Propionic acid, acrolein, cetonaldehyde) and mixtures thereof.
- oxygenated hydrocarbons eg methanol, formaldehyde, formic acid, ethanol, acetaldehyde, acetic acid, propanol, propionaldehyde , Propionic acid, acrolein, cetonaldehyde
- the n-butane content of the total amount of hydrocarbon is preferably more than 90%, and more preferably more than 95%.
- the gas is preferably fed to the gas in the process according to the invention a volatile phosphorus compound.
- Volatile phosphorus compounds are to be understood as meaning those phosphorus-containing compounds which are gaseous in the desired concentration under the conditions of use.
- suitable volatile phosphorus compounds for example, phosphines and phosphoric acid esters are mentioned.
- Particularly preferred are the C 1 to C 4 alkyl phosphoric esters, very particularly preferably trimethyl phosphate, triethyl phosphate and tripropyl phosphate, in particular triethyl phosphate.
- the process of the invention is generally carried out at a temperature of 300 to 500 0 C. Under the said temperature, the temperature of the catalyst bed located in the reactor is understood, which would be present in the practice of the process in the absence of a chemical reaction.
- the term means the number average of the temperatures along the reaction zone. In particular, this means that the true, present at the catalyst temperature due to the exothermicity of the oxidation reaction may also be outside the range mentioned.
- the process according to the invention is preferably carried out at a temperature of from 380 to 460 ° C., more preferably from 380 to 430 ° C.
- the process according to the invention can be carried out at a pressure below normal pressure (for example up to 0.05 MPa abs) or above normal pressure (for example up to 10 MPa abs). This is understood to mean the pressure present in the reactor unit. Preference is given to a pressure of 0.1 to 1.0 MPa abs, more preferably 0.1 to 0.5 MPa abs.
- the process according to the invention can be carried out in two preferred process variants, the "straight through” variant and the “recirculation” variant.
- the "straight pass” maleic anhydride and optionally oxygenated hydrocarbon by-products are removed from the reactor effluent and the remaining gas mixture is discharged and optionally thermally recovered.
- the “recycling” is also removed from the reactor effluent maleic anhydride and optionally oxygenated hydrocarbon by-products, the remaining gas mixture containing unreacted hydrocarbon, completely or partially recycled to the reactor.
- Another variant of the "recycling" is the removal of the unreacted hydrocarbon and its return to the reactor.
- n-butane is used as the starting hydrocarbon and the heterogeneously catalyzed gas phase oxidation is carried out in the "straight pass" on the catalyst according to the invention.
- Fig. 1 shows a Guinier technique of V 4 Os (PO 4 ) S, which was obtained by solid state reaction;
- Fig. 2 shows a Guinier recording of CrVsOs (PO 4 ) 3, which was obtained by solid state reaction;
- Fig. 3 shows a Guinier recording of FeVs ⁇ 3 (PO 4 ) 3, which was obtained by solid state reaction;
- Fig. 4 shows a Guinier recording of TiV3 ⁇ 3 (PO 4 ) 3, which was obtained by solid state reaction;
- Fig. 5 shows the powder X-ray diffractogram of V 4 O 3 (PO 4 ) 3 obtained by calcining a spray-dried precursor in air;
- Fig. 6 shows the powder X-ray diffractogram of FeV 3 O 3 (PO 4 ) 3 obtained by calcining a spray-dried precursor in air.
- V2O5 pa, Merck Eurolap GmbH, Darmstadt, Germany
- V2O3 from the reduction of V2O5 with hydrogen at 1073 K [G. Brauer, A. Simon in Handbuch der refparativen Inorganischen Chemie, G. Brauer ( Ed., Enke Verlag, Stuttgart 1981, p 1419]
- VPO 4 R.Glaum, R. Gruehn, Z. Kristallogr., 1992, 198, 41-47
- VO 2P2T7 were synthesized.
- the pyrophosphate was obtained by heating VO (HPO 4 ) V 2 H 2 O in the argon stream at 1073 K (JW Johnson, DC Johnston, AJ Jacobson, JF Brody, J. Amer. Chem. Soc., 1984, 106, 8123-8128). Vanadylhydro- dihydrogen phosphate hemihydrate was previously refluxing of V2O5 and HSPO (pa 85%, Merck Eurolap GmbH, Darmstadt, Germany) 4 in n-butanol was like.
- the title compound was obtained by reaction of 63.9 mg VO2, 12.4 mg VPO 4 and 237.0 mg (VO) 2P2Ü7.
- the starting materials were finely triturated in an agate dish, pressed into a tablet and heated for five days in a closed, evacuated silica glass ampoule at 1073 K. By using a corundum crucible, a reaction of the tablet with the ampoule wall was avoided.
- the table below shows selected X-ray diffraction reflexes as obtained by evaluating a Guinier image (FIG. 1).
- P-CrPO 4 was prepared by evaporation of an aqueous solution of stoichiometric amounts of Cr (N0S) 3 9 H2O (Sigma Aldrich Laboratory Chemicals GmbH, Riedel-de Haen fire, Seelze, Germany) and NH4H2PO4 (pa, Merck Eurolap GmbH, Darmstadt, Germany) and subsequent heating of the dry residue at 1273 K in air as described in J.-P. Attfield, PD Battle, AK Cheetham, J. Solid State Chem. 1985, 57, 357-361.
- the table below shows selected X-ray diffraction reflexes as obtained by evaluating a Guinier image ( Figure 2).
- FePO 4 was prepared by evaporation of an aqueous solution of stoichiometric amounts of Fe (NOs) 3 9 H 2 O (pa, Merck Eurolap GmbH, Darmstadt, Germany) and NH 4 H 2 PO 4 (pa, Merck Eurolap GmbH, Darmstadt, Germany) and subsequently heating the dry residue at 1273 K in air.
- TiP2Ü7 was prepared by thermal decomposition of Ti (HPO 4 ⁇ H2O at a temperature rising successively to 1073 K.
- Ti (HPO 4 ) 2 H 2 O was prepared by hydrolysis of TiO 2 (technically, Sigma Aldrich Laborchemikalien GmbH, Riedel-de Haen Brand , Seelze, Germany) in concentrated phosphoric acid (85% pure, Merck Eurolap GmbH, Darmstadt, Germany) as described in S. Bruque, Miguel AG Aranda, Enrique R. Losilla, Pascual O. Pastor and P. Maireles Torres, Inorg. Chem., 1995, 34, 893-899).
- the suspension thus prepared was dried over a spray dryer (Mobile Minor TM 2000, MM, from Niro A / S, Soborg, Denmark, inlet temperature: 330 ° C., outlet temperature: 107 ° C.).
- the resulting solid was calcined at 800 ° C for two hours in a nitrogen atmosphere in a quartz glass rotary tube having an inner volume of 1 liter.
- the resulting powder had a BET specific surface area of 3.0 m 2 / g. From the obtained powder, a powder X-ray diffractogram was taken. From the powder X-ray diffractogram (FIG. 5), the following 2 ⁇ values with the associated intensities I and wattage spacings d were determined.
- the resulting powder had a BET specific surface area of 1.0 m 2 / g. From the obtained powder, a powder X-ray diffractogram was taken. From the powder X-ray diffractogram, the following 2 ⁇ values with the associated intensities I and wattage spacings d were determined.
- the suspension thus prepared was dried over a spray dryer (Mobile Minor TM 2000, MM, from Niro A / S, Soborg, Denmark, inlet temperature: 330 ° C., outlet temperature: 107 ° C.).
- the resulting solid was calcined at 600 ° C for two hours and then at 800 ° C for two hours in a nitrogen atmosphere in a quartz rotary tube having an inner volume of 1 liter.
- the resulting powder had a BET specific surface area of 0.7 m 2 / g.
- a powder X-ray diffractogram (Fig. 6) was taken. From the powder X-ray diffractogram, the following 2 ⁇ values with the associated intensities I and wattage spacings d were determined.
- the catalysts A1, A2 and A3 were pressed into tablets in a tabletting machine and then comminuted to granules (chippings) with a diameter in the range of 1.6 to 2.0 mm.
- V ⁇ ataiysator bulk volume of the catalyst [L] t: time unit [h]
- Input gas mixture f volume of input gas mixture [NL] normalized to 0 ° C and 0.1013 MPa (calculated size) If the inlet gas mixture or a component thereof is in the liquid phase or solid under these conditions, then the ideal gas law is the hypothetical gas volume calculated.)
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Abstract
The invention relates to a novel polynary metal oxide phosphate of general formula M<SUB>a</SUB>V<SUB>4-a</SUB>O<SUB>b</SUB>(PO<SUB>4</SUB>)<SUB>c</SUB> (I), wherein M represents one or more metals selected from the group including Ti, Zr, Hf,Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, Al, Ga and In, a has a value of 0 to 2.0, b has a value of 2.0 to 4.0, c has a value of 2.0 to 4.0, said novel compound having a crystal structure and being characterized by defined diffraction reflexes in powder X-ray diffraction. Preferred representatives are V<SUB>4</SUB>O<SUB>3</SUB>(PO<SUB>4</SUB>)<SUB>3</SUB>, CrV<SUB>3</SUB>O<SUB>3</SUB>(PO<SUB>4</SUB>)<SUB>3</SUB>, FeV<SUB>3</SUB>O<SUB>3</SUB>(PO<SUB>4</SUB>)<SUB>3</SUB> and TiV<SUB>3</SUB>O<SUB>3</SUB>(PO<SUB>4</SUB>)<SUB>3</SUB>. The metal oxide phosphates are suitable as gas phase oxidation catalysts, e.g. for producing maleic anhydride from a hydrocarbon with at least four carbon atoms.
Description
Polynäres Metalloxidphosphat Polynary metal oxide phosphate
Beschreibungdescription
Die vorliegende Erfindung betrifft ein polynäres Metalloxidphosphat, das Vanadium und gegebenenfalls wenigstens ein weiteres Metall enthält, ein Verfahren zu dessen Herstellung und dessen Verwendung zu heterogenkatalytischen Gasphasenoxidationen, vorzugsweise heterogenkatalytischen Gasphasenoxidationen eines Kohlenwasserstoffs mit mindestens vier Kohlenstoffatomen.The present invention relates to a polynary metal oxide phosphate containing vanadium and optionally at least one other metal, a process for its preparation and its use in heterogeneously catalyzed gas phase oxidations, preferably heterogeneously catalyzed gas phase oxidations of a hydrocarbon having at least four carbon atoms.
Heterogene Katalysatoren auf der Basis von Vanadylpyrophosphat (VO)2P2θ7 (so genannte VPO-Katalysatoren) werden bei der industriellen Oxidation von n-Butan zu Maleinsäureanhydrid wie auch bei einer Reihe weiterer Oxidationsreaktionen von Kohlenwasserstoffen eingesetzt.Heterogeneous catalysts based on vanadyl pyrophosphate (VO) 2P2θ7 (so-called VPO catalysts) are used in the industrial oxidation of n-butane to maleic anhydride as well as in a series of further oxidation reactions of hydrocarbons.
Die Vanadylpyrophosphat-Katalysatoren werden in der Regel wie folgt hergestellt: (1 ) Synthese eines Vanadylhydrogenphosphat-Hemihydrat-Precursors (VOHPO4 /4 H2O) aus einer fünfwertigen Vanadium-Verbindung (z. B. V2O5), einer fünf- oder dreiwertigen Phosphor-Verbindung (z. B. Ortho- und/oder Pyrophosphorsäure, Phosphorsäureester oder Phosphorige Säure) und einem reduzierend wirkenden Alkohol (z. B. Isobutanol), Isolierung des Niederschlags, Trocknung und gegebenenfalls Formgebung (z. B. Tablettierung) und (2) Präformierung des Precursors zum Vanadylpyrophosphat ((VO)2P2θ7) durch Calcinierung. Es sei z. B. auf die EP-A 0 520 972 und WO 00/72963 verwiesen.The vanadyl pyrophosphate catalysts are usually prepared as follows: (1) Synthesis of a vanadyl hydrogen phosphate hemihydrate precursor (VOHPO 4 / 4H 2 O) from a pentavalent vanadium compound (eg, V 2 O 5), a trivalent or trivalent phosphorus Compound (eg ortho and / or pyrophosphoric acid, phosphoric acid ester or phosphorous acid) and a reducing alcohol (eg isobutanol), isolation of the precipitate, drying and optionally shaping (eg tableting) and (2) Preforming of the precursor to vanadyl pyrophosphate ((VO) 2 P2θ 7 ) by calcination. It is z. For example, see EP-A 0 520 972 and WO 00/72963.
Durch den Einsatz eines Alkohols als Reduktionsmittel verbleiben im Precusor im Allgemeinen mehrere Gew.-% an organischen Verbindungen eingeschlossen, welche sich auch durch sorgsames Waschen nicht entfernen lassen. Diese üben bei der weiteren Katalysatorherstellung, insbesondere bei der Calcinierung, einen negativen Effekt auf die katalytischen Eigenschaften des Katalysators aus. So besteht bei der anschließenden Calcinierung die Gefahr der Verdampfung beziehungsweise der thermischen Zersetzung dieser eingeschlossenen organischen Verbindung unter Bildung gasförmiger Komponenten, welche zu einem Druckanstieg im Inneren der Kristalle und somit zu einer Zerstörung der Katalysatorstruktur führen können. Dieser nachteilige Effekt ist besonders stark ausgeprägt bei der Calcinierung unter oxidierenden Bedingungen, da durch die Bildung der oxidierten Abbauprodukte, wie beispielsweise Kohlenmonoxid oder Kohlendioxid, eine wesentlich größere Gasmenge gebildet wird. Des Weiteren entstehen bei der Oxidation dieser organischen Verbindungen lokal sehr große Wärmemengen, welche zu einer thermischen Schädigung des Katalysators führen können.By using an alcohol as a reducing agent, several percent by weight of organic compounds, which can not be removed even by careful washing, generally remain in the precursor. These exert a negative effect on the catalytic properties of the catalyst in the further catalyst preparation, especially in the calcination. Thus, in the subsequent calcination the risk of evaporation or the thermal decomposition of this trapped organic compound to form gaseous components, which can lead to an increase in pressure inside the crystals and thus to a destruction of the catalyst structure. This disadvantageous effect is particularly pronounced in the case of calcination under oxidizing conditions, since a significantly larger amount of gas is formed by the formation of the oxidized decomposition products, such as, for example, carbon monoxide or carbon dioxide. Furthermore, in the oxidation of these organic compounds locally very large amounts of heat, which can lead to thermal damage to the catalyst.
Ferner besitzen die eingeschlossenen organischen Verbindungen auch einen signifikanten Einfluss auf die Einstellung der lokalen Oxidationsstufe des Vanadiums. So
belegen B. Kubias et al. in Chemie Ingenieur Technik 72 (3), 2000, Seiten 249-251 den reduzierenden Effekt organischen Kohlenstoffs bei der anaeroben Calcinierung (unter nicht-oxidierenden Bedingungen) eines aus isobutanolischer Lösung erhaltenen Vana- dylhydrogenphosphat-Hemihydrat-Precursors. Durch anaerobe Calcinierung wurde in dem genannten Beispiel eine mittlere Oxidationsstufe des Vanadiums von 3,1 erhalten, wohingegen durch aerobe Calcinierung (unter oxidierenden Bedingungen) eine mittlere Oxidationsstufe des Vanadiums von etwa 4 erhalten wird.Furthermore, the entrapped organic compounds also have a significant influence on the adjustment of the local oxidation state of the vanadium. So prove B. Kubias et al. in Chemie Ingenieur Technik 72 (3), 2000, pages 249-251 the reducing effect of organic carbon in the anaerobic calcination (under non-oxidizing conditions) of a obtained from isobutanolic solution Vana- dylhydrogenphosphat hemihydrate precursor. By anaerobic calcination in the example mentioned a mean oxidation state of the vanadium of 3.1 was obtained, whereas by aerobic calcination (under oxidizing conditions) a mean oxidation state of the vanadium of about 4 is obtained.
Zur Verbesserung des katalytischen Verhaltens ist vorgeschlagen worden, dem Vana- dylpyrophosphat in geringem Umfang Oxide zwei-, drei- oder vierwertiger Übergangsmetalle, so genannter Promotoren, zuzusetzen (vgl. G. J. Hutchings, J. Mater. Chem. 2004, 14, 3385-3395; K. V. Narayana et al., Z. Anorg. AIIg. Chem. 2005, 631 , 25-30). Die Wirkungsweise dieser Promotoren ist dabei bis heute weitgehend ungeklärt.To improve the catalytic behavior, it has been proposed to add to the vanadyl pyrophosphate to a small extent oxides of di-, trivalent or tetravalent transition metals, so-called promoters (cf GJ Hutchings, J. Mater. Chem. 2004, 14, 3385-3395 KV Narayana et al., Z. Anorg., Allg. Chem. 2005, 631, 25-30). The mode of action of these promoters is still largely unknown.
Über die Existenz und das katalytische Verhalten von einphasigen polynären Vanadi- um(IV)-phosphaten, die ein von Vanadium verschiedenes zwei-, drei- oder vierwertiges Übergangsmetall enthalten, liegen in der Literatur bislang keine Informationen vor.The existence and the catalytic behavior of single-phase polynary vanadium (IV) phosphates containing a divalent, trivalent or tetravalent transition metal other than vanadium are unknown in the literature.
Ein gemischtvalentes Vanadium(lll,IV)-diphosphat, Vm2(VlvO)(P2θ7)2, ist bereits länger bekannt und auch kristallographisch charakterisiert, vgl. J. W. Johnson et al., Inorg. Chem. 1988, 27, 1646-1648. Aus B. G. Golovkin, V. L. Volkov, Russ. J. Inorg. Chem. 1987, 32, 739-741 ist eine weitere Verbindung bekannt, die ebenfalls als Diphosphat V3θ4(P2Ü7) beschrieben ist; Angaben zu deren Charakterisierung fehlen jedoch vollständig.A mixed-valence vanadium (III, IV) diphosphate, V m 2 (V lv O) (P 2 O 7) 2, has been known for some time and is also characterized crystallographically, cf. JW Johnson et al., Inorg. Chem. 1988, 27, 1646-1648. From BG Golovkin, VL Volkov, Russ. J. Inorg. Chem. 1987, 32, 739-741 discloses another compound which is also described as diphosphate V3θ4 (P2Ü7); However, information on their characterization is missing completely.
Aufgabe der vorliegenden Erfindung war es, neue polynäre Vanadiumoxidphosphate bereitzustellen.The object of the present invention was to provide new polynary vanadium oxide phosphates.
Eine weitere Aufgabe der vorliegenden Erfindung war es, neue polynäre Vanadium- oxidphosphate mit katalytischen Eigenschaften für heterogenkatalytische Gasphasen- oxidationen bereitzustellen.A further object of the present invention was to provide novel polynary vanadium oxide phosphates with catalytic properties for heterogeneously catalyzed gas phase oxidations.
Eine weitere Aufgabe der vorliegenden Erfindung war es, neue polynäre Vanadiumoxidphosphate bereitzustellen, mit deren Hilfe die katalytischen Eigenschaften bekann- ter heterogener Katalysatoren auf der Basis von Vanadylpyrophosphat modifiziert werden können.A further object of the present invention was to provide novel polynary vanadium oxide phosphates, with the aid of which the catalytic properties of known heterogeneous catalysts based on vanadyl pyrophosphate can be modified.
Weitere Aufgaben der Erfindung betrafen die Bereitstellung von Verfahren zur Herstellung der neuen polynäre Vanadiumoxidphosphate und von Verfahren zur heterogenka- talytischen Gasphasenoxidation.
Demgemäß wurde ein polynäres Metalloxidphosphat der allgemeinen Formel I gefunden
Further objects of the invention were the provision of processes for the preparation of the novel polynary vanadium oxide phosphates and of processes for heterogeneous catalytic gas-phase oxidation. Accordingly, a polynary metal oxide phosphate of the general formula I was found
worinwherein
M für ein oder mehrere unter Ti, Zr, Hf, Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, AI, Ga und In ausgewählte Metalle steht,M is one or more metals selected from Ti, Zr, Hf, Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, Al, Ga and In,
a einen Wert von 0 bis 2,0 hat, b einen Wert von 2,0 bis 4,0 hat, c einen Wert von 2,0 bis 4,0 hat,a has a value of 0 to 2.0, b has a value of 2.0 to 4.0, c has a value of 2.0 to 4.0,
mit einer Kristallstruktur, deren Pulverröngtendiffraktogramm gekennzeichnet ist durch Beugungsreflexe bei den Netzebenenabständen d [Ä] = 3,30 ± 0,04, 3,16 ± 0,04, 2,57 ± 0,04, 2,02 ± 0,04, 1 ,65 ± 0,04, 1 ,59 ± 0,02, 1 ,58 ± 0,02.having a crystal structure whose powder X-ray diffraction pattern is characterized by diffraction reflectances at the interplanar spacings d [λ] = 3.30 ± 0.04, 3.16 ± 0.04, 2.57 ± 0.04, 2.02 ± 0.04, 1, 65 ± 0.04, 1, 59 ± 0.02, 1, 58 ± 0.02.
Die Angabe der Röntgenbeugungsreflexe erfolgt in dieser Anmeldung in Form der von der Wellenlänge der verwendeten Röntgenstrahlung unabhängigen Netzebenenab- stände d [A]. Die Wellenlänge λ der zur Beugung verwendeten Röntgenstrahlung und der Beugungswinkel θ (als Beugungsreflexlage wird in dieser Schrift der Scheitelpunkt eines Reflexes in der 2Θ-Auftragung verwendet) sind über die Bragg'sche Beziehung wie folgt miteinander verknüpft:The indication of the X-ray diffraction reflexes in this application takes place in the form of the lattice plane spacings d [A] independent of the wavelength of the X-ray radiation used. The wavelength λ of the X-radiation used for the diffraction and the diffraction angle θ (the diffraction reflex layer used in this document is the peak of a reflex in the 2Θ plot) are linked together via the Bragg relationship as follows:
2 sin θ = λ/d2 sin θ = λ / d
wobei d der zum jeweiligen Beugungsreflex gehörende Netzebenenabstand der atomaren Raumanordnung ist.where d is the respective diffraction reflex associated lattice spacing of the atomic space arrangement.
Das Pulverröntgendiffraktogramm des erfindungsgemäßen Metalloxidphosphats der Formel I ist durch die vorstehend aufgeführten Beugungsreflexe gekennzeichnet. Die Beugungsreflexe haben im Allgemeinen die in Tabelle 1 angegebenen ungefähren relativen Intensitäten (lreι [%]). Weitere, in der Regel weniger intensive Beugungsreflexe des Pulverröntgendiffraktogramms wurden in Tabelle 1 nicht berücksichtigt.The powder X-ray diffractogram of the metal oxide phosphate of the formula I according to the invention is characterized by the diffraction reflexes mentioned above. The diffraction reflections generally have the approximate relative intensities (l re ι [%]) given in Table 1. Further, generally less intense diffraction reflexes of the powder X-ray diffractogram were not taken into account in Table 1.
Tabelle 1Table 1
In Abhängigkeit vom Kristallinitätsgrad und der Texturierung der erhaltenen Kristalle des erfindungsgemäßen Metalloxidphosphats kann es allerdings zu einer Verstärkung oder Abschwächung der Intensität der Beugungsreflexe im Pulverröngtendiffrak- togramm kommen. Die Abschwächung kann soweit gehen, dass einzelne Beugungsreflexe im Pulverröngtendiffraktogramm nicht mehr detektierbar sind.Depending on the degree of crystallinity and the texturing of the resulting crystals of the metal oxide phosphate according to the invention, however, there may be a strengthening or weakening of the intensity of the diffraction reflexes in the powder X-ray diffractogram. The attenuation can go so far that individual diffraction reflections are no longer detectable in the powder X-ray diffractogram.
Es versteht sich für den Fachmann von selbst, dass Gemenge der erfindungsgemäßen Metalloxidphosphate mit anderen kristallinen Verbindungen zusätzliche Beugungsre- flexe aufweisen. Solche Gemenge des Metalloxidphosphats mit anderen kristallinen Verbindungen können gezielt durch Vermischen des erfindungsgemäßen Metalloxidphosphats hergestellt werden oder können bei der Herstellung der erfindungsgemäßen Metalloxidphosphate durch nicht vollständige Umsetzung der Ausgangsmaterialien oder Bildung von Fremdphasen mit abweichender Kristallstruktur entstehen.It is self-evident to the person skilled in the art that mixtures of the metal oxide phosphates according to the invention with other crystalline compounds have additional diffraction reflectances. Such mixtures of the metal oxide phosphate with other crystalline compounds can be prepared in a targeted manner by mixing the metal oxide phosphate according to the invention or can be formed in the preparation of the metal oxide according to the invention by incomplete reaction of the starting materials or formation of foreign phases with different crystal structure.
In einer bevorzugten Ausführungsform hat a in der Formel I den Wert 0. In anderen bevorzugten Ausführungsformen hat a einen Wert von 0,8 bis 1 ,2.In a preferred embodiment, a in formula I has the value 0. In other preferred embodiments, a has a value of 0.8 to 1.2.
Vorzugsweise hat in der Formel I b einen Wert von 2,8 bis 3,2.Preferably, in the formula I b has a value of 2.8 to 3.2.
Vorzugsweise hat in der Formel I c einen Wert von 2,8 bis 3,2.Preferably, in the formula I c has a value of 2.8 to 3.2.
In der Formel I steht M für ein unter Ti, Zr, Hf, Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, AI, Ga und In ausgewähltes Metall oder Kombinationen zweier oder mehrerer dieser Me- talle. Vorzugsweise steht M für ein unter Ti, Cr und Fe ausgewähltes Metall.In formula I, M is a metal selected from Ti, Zr, Hf, Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, Al, Ga and In or combinations of two or more of these metals. metals. Preferably, M is a metal selected from Ti, Cr and Fe.
Besonders bevorzugte erfindungsgemäße Metalloxidphosphate weisen eine der folgenden Formeln auf:Particularly preferred metal oxide phosphates according to the invention have one of the following formulas:
CrV3O3(PO4)3 oder
CrV 3 O 3 (PO 4 ) 3 or
Die erfindungsgemäßen Metalloxidphosphate sind auf verschiedene Weise erhältlich.
Die erfindungsgemäßen Metalloxidphosphate können zum einen durch eine Festkörperreaktion in einem geschlossenen System erhalten werden. Hierzu setzt man wenigstens zwei Reaktanden um, die unter Sauerstoffverbindungen von Vanadium, Phosphorverbindungen von Vanadium und gemischten Sauerstoff-Phosphorverbindungen von Vanadium, elementarem Vanadium, Sauerstoffverbindungen des Metalls M, Phosphorverbindungen des Metalls M und gemischten Sauerstoff-Phosphorverbindungen des Metalls M und elementarem Metall M ausgewählt sind.The metal oxide phosphates according to the invention are obtainable in various ways. The metal oxide phosphates according to the invention can be obtained on the one hand by a solid-state reaction in a closed system. For this purpose, at least two reactants selected from oxygen compounds of vanadium, phosphorus compounds of vanadium and mixed oxygen-phosphorus compounds of vanadium, elemental vanadium, oxygen compounds of metal M, phosphorus compounds of metal M and mixed oxygen-phosphorus compounds of metal M and elemental metal M are selected are.
Dabei wählt man die Reaktanden im Allgemeinen so aus, dass (i) sie die gewünschte Stöchiometrie der Elemente in der Formel I liefern und (ii) die Summe der Produkte von Wertigkeit mal Häufigkeit der von Sauerstoff verschiedenen Elemente in den Reaktanden der Summe der Produkte von Wertigkeit mal Häufigkeit der von Sauerstoff verschiedenen Elemente in der Formel I entspricht. Die Ausgangsverbindungen können so gewählt sein, dass darin allen von Sauerstoff verschiedenen Elementen bereits die Wertigkeit zukommt, die ihnen in der Formel I zukommt. Alternativ können die Ausgangsverbindungen so gewählt sein, dass darin einigen oder allen von Sauerstoff verschiedenen Elementen eine Wertigkeit zukommt, die von der abweicht, die ihnen in der Formel I zukommt. Durch Redoxreaktionen, z. B. eine Synproportionierung, während der Festkörperreaktion erhalten die von Sauerstoff verschiedenen Elemente die Wer- tigkeit, die ihnen in der Formel I zukommt. So kann man beispielweise eine Kombination äquivalenter Mengen von Vanadium(lll)- und Vanadium(V)-Verbindungen einsetzen, aus denen sich bei der Festkörperreaktion vierwertiges Vanadium bildet.The reactants are generally selected such that (i) they provide the desired stoichiometry of the elements in formula I, and (ii) the sum of the products of valence times the abundance of non-oxygen elements in the reactants of the sum of the products of Valence times the frequency of elements other than oxygen in Formula I. The starting compounds can be selected so that all the elements other than oxygen have the same value as in Formula I. Alternatively, the starting compounds may be chosen such that some or all of the elements other than oxygen have a valency different from that which occurs in formula I. By redox reactions, for. For example, a synproportionation, during the solid state reaction, the elements other than oxygen get the value that they have in Formula I. For example, a combination of equivalent amounts of vanadium (III) and vanadium (V) compounds can be used to form tetravalent vanadium in the solid state reaction.
Die Festkörperreaktion verläuft z. B. gemäß einer der folgenden Gleichungen (1 ) bis (3):The solid-state reaction proceeds z. B. according to one of the following equations (1) to (3):
(1 ) VO2 + MPO4 + (VO)2P2O7 > M111VV 3O3(PO4)S (z. B. M = Cr oder Fe)(1) VO 2 + MPO 4 + (VO) 2 P 2 O 7 > M 111 V V 3 O 3 (PO 4 ) S (eg M = Cr or Fe)
(2) V2O3 + MP2O7 + VOPO4 > M'"V'V 3O3(PO4)3 (z. B. M = Ti)(2) V 2 O 3 + MP 2 O 7 + VOPO 4 > M '"V' V 3 O 3 (PO 4 ) 3 (eg M = Ti)
(3) 0,5 V2O5 + 0,5 VP + 2,5 VOPO4 > VIMVIV 3O3(PO4)3 (3) 0.5 V 2 O 5 + 0.5 VP + 2.5 VOPO 4 > V IN V IV 3 O 3 (PO 4 ) 3
Die erforderlichen Ausgangsverbindungen in Form von Oxiden, Phosphaten, Oxidphosphaten, Phosphiden oder dergleichen sind entweder handelsüblich oder literatur- bekannt oder können vom Fachmann leicht in Analogie zu bekannten Herstellungsweisen synthetisiert werden.The required starting compounds in the form of oxides, phosphates, oxide phosphates, phosphides or the like are either commercially available or known from the literature or can easily be synthesized by the skilled person in analogy to known preparation methods.
Die Ausgangsstoffe werden innig vermischt, z. B. durch feines Verreiben. Die Festkörperreaktion erfolgt typischerweise bei einer Temperatur von wenigstens 500 0C, z. B. 650 bis 1100 0C, insbesondere etwa 800 0C. Typische Reaktionsdauern betragen z. B. 24 Stunden bis 10 Tage. Geeignete Reaktionsgefäße bestehen z. B. aus Quarzglas oder Korund.
Um Produkte mit einem hohen Kristallinitätsgrad oder Einkristalle zu erhalten, kann man bei der Festkörperreaktion zweckmäßigerweise einen geeigneten Mineralisator, wie lod oder PtCb, mitverwenden.The starting materials are intimately mixed, for. B. by fine trituration. The solid state reaction is typically carried out at a temperature of at least 500 ° C, e.g. B. 650 to 1100 0 C, in particular about 800 0 C. Typical reaction times are z. 24 hours to 10 days. Suitable reaction vessels consist for. B. of quartz glass or corundum. In order to obtain products with a high degree of crystallinity or single crystals, it is expedient to use a suitable mineralizer, such as iodine or PtCb, in the solid-state reaction.
Alternativ kann man erfindungsgemäße Metalloxidphosphate herstellen, indem manAlternatively, it is possible to prepare metal oxide phosphates according to the invention by reacting
a) ein Trockengemisch einer Vanadiumquelle, gegebenenfalls einer Quelle des Metalls M und einer Phosphatquelle herstellt,a) produces a dry mixture of a vanadium source, optionally a source of the metal M and a phosphate source,
b) dabei gegebenenfalls Reduktionsäquivalente bereitstellt, um das Vanadium und/oder das Metall M in den Wertigkeitszustand umzuwandeln, der dem Vanadium und dem Metall M in der Formel I zukommt, undb) optionally providing reduction equivalents to convert the vanadium and / or metal M to the valence state associated with the vanadium and metal M in formula I, and
c) das Trockengemisch bei wenigstens 500 0C calciniert.c) calcining the dry mixture at least 500 0 C.
Hierzu erzeugt man aus geeigneten Quellen der elementaren Konstituenten der Metalloxidphosphate ein möglichst inniges, vorzugsweise feinteiliges, Trockengemisch der gewünschten Konstituentenstöchiometrie.For this purpose, from suitable sources of the elemental constituents of the metal oxide phosphates, a preferably intimate, preferably finely divided, dry mixture of the desired constituent stoichiometry is produced.
Das innige Vermischen der Ausgangsverbindungen kann in trockener oder in nasser Form erfolgen.The intimate mixing of the starting compounds can be carried out in dry or wet form.
Erfolgt es in trockener Form, werden die Ausgangsverbindungen zweckmäßigerweise als feinteilige Pulver eingesetzt und nach dem Mischen und gegebenenfalls Verdichten der Calcinierung (thermischen Behandlung) unterworfen.If it is carried out in dry form, the starting compounds are expediently used as finely divided powders and subjected to the mixing and optionally compacting the calcination (thermal treatment).
Vorzugsweise erfolgt das innige Vermischen jedoch in nasser Form, d. h. in gelöster oder suspendierter Form. Üblicherweise werden die Ausgangsverbindungen dabei in Form einer wässrigen Lösung (gegebenenfalls unter Mitverwendung komplexbildender Mittel) und/oder Suspension miteinander vermischt. Anschließend wird die wässrige Lösung oder Suspension getrocknet und nach der Trocknung calciniert.Preferably, however, the intimate mixing is done in wet form, i. H. in dissolved or suspended form. Usually, the starting compounds are mixed together in the form of an aqueous solution (optionally with the concomitant use of complexing agents) and / or suspension. Subsequently, the aqueous solution or suspension is dried and calcined after drying.
Das Trocknen kann durch Eindampfen im Vakuum, durch Gefriertrocknung oder durch konventionelles Eindampfen erfolgen. Vorzugsweise erfolgt der Trocknungsprozess jedoch durch Sprühtrocknung. Die Austrittstemperaturen betragen in der Regel 70 bis 150 0C; die Sprühtrocknung kann im Gleichstrom oder im Gegenstrom durchgeführt werden.The drying can be carried out by evaporation in vacuo, by freeze-drying or by conventional evaporation. Preferably, however, the drying process is carried out by spray drying. The outlet temperatures are usually 70 to 150 0 C; The spray drying can be carried out in cocurrent or in countercurrent.
Geeignete Vanadiumquellen sind z.B. Vanadylsulfathydrat, Vanadylacetylacetonat, Vanadate wie Ammoniummetavanadat, Vanadiumoxide wie z. B. Divanadiumpentoxid (V2O5), Vanadiumdioxid (VO2) oder Divanadiumtrioxid (V2O3), Vanadiumhalogenide wie
z. B. Vanadiumtetrachlorid (VCU) und Vanadylhalogenide wie z. B. VOCI3. Divanadium- pentoxid und Ammoniumvanadat sind bevorzugte Vanadiumquellen.Suitable vanadium sources are, for example, vanadyl sulfate hydrate, vanadyl acetylacetonate, vanadates such as ammonium metavanadate, vanadium oxides such as. B. vanadium dioxide (VO2) or divanadium trioxide (V2O3), Vanadiumhalogenide as z. As vanadium tetrachloride (VCU) and vanadyl halides such. B. VOCI3. Divanadium pentoxide and ammonium vanadate are preferred sources of vanadium.
Als Quellen für das Metall M kommen alle Verbindungen der Elemente in Betracht, die beim Erhitzen (gegebenenfalls in Gegenwart von molekularem Sauerstoff, z. B. an Luft) Oxide und/oder Hydroxide zu bilden vermögen. Selbstredend können als solche Ausgangsverbindungen auch bereits Oxide und/oder Hydroxide der elementaren Konstituenten mitverwendet oder ausschließlich verwendet werden. Oxide, Hydroxide und Oxidhydroxide des Metalls M sind bevorzugte Quellen des Metalls M.Possible sources of the metal M are all compounds of the elements which are capable of forming oxides and / or hydroxides upon heating (if appropriate in the presence of molecular oxygen, for example in air). Of course, oxides and / or hydroxides of the elemental constituents may also be used as such starting compounds or may be used exclusively. Oxides, hydroxides and oxide hydroxides of the metal M are preferred sources of the metal M.
Geeignete Phosphatquellen sind Phosphatgruppen enthaltende Verbindungen oder Verbindungen, aus denen sich durch Redoxreaktionen und/oder beim Erhitzen (gegebenenfalls in Gegenwart von molekularem Sauerstoff, z. B. an Luft) Phosphatgruppen bilden. Hierzu zählen Phosphorsäuren, insbesondere Orthophosphorsäure, Pyro- oder Metaphosphorsäuren, Phosphorige Säure, Hypophosphorige Säure, Phosphate oder Hydrogenphosphate, wie Diammoniumhydrogenphosphat, und elementarer Phosphor, wie z. B. weißer Phosphor. Vorzugsweise wird die Phosphatquelle zumindest teilweise von Phosphoriger Säure oder Hypophosphoriger Säure gebildet, gegebenenfalls in Kombination mit Orthophosphorsäure.Suitable phosphate sources are phosphate group-containing compounds or compounds from which phosphate groups are formed by redox reactions and / or upon heating (optionally in the presence of molecular oxygen, eg in air). These include phosphoric acids, in particular orthophosphoric acid, pyro- or metaphosphoric acids, phosphorous acid, hypophosphorous acid, phosphates or hydrogen phosphates, such as diammonium hydrogen phosphate, and elemental phosphorus, such as. B. white phosphorus. Preferably, the phosphate source is at least partially formed by phosphorous acid or hypophosphorous acid, optionally in combination with orthophosphoric acid.
Kommen als Vanadiumquelle bzw. Quelle für das Metall M Verbindungen zum Einsatz, in denen das Vanadium bzw. das Metall M eine höhere Wertigkeit aufweisen, als ihnen in der Formel I zukommt (d. h. als die formale Wertigkeit von V und gegebenenfalls M, die zur Erlangung der Elektroneutralität mit den in Formel I enthaltenen O2"- und PO43"- Anionen erforderlich ist), so sind vorzugsweise Reduktionsäquivalente bereitzustellen, um das Vanadium und/oder das Metall M in den Wertigkeitszustand umzuwandeln, der dem Vanadium und dem Metall M in der Formel I zukommt.For the vanadium source or metal source, compounds are used in which the vanadium or the metal M have a higher valency than they have in formula I (ie, the formal valence of V and, if appropriate, M) the electroneutrality with the O 2 "and PO 4 3 " anions contained in formula I is required), reduction equivalents are preferably to be provided to convert the vanadium and / or metal M to the valence state associated with the vanadium and the metal M in the formula I belongs.
Die Reduktionsäquivalente werden von einem Reduktionsmittel bereitgestellt, das in der Lage ist, die höherwertige Form des Vanadiums bzw. des Metalls M zu reduzieren. Die Reduktion kann bei der Zubereitung des Trockengemisches oder spätestens beim Calcinieren erfolgen. Vorzugsweise erfolgt die Präparation des innigen Trockenge- mischs unter Inertgasatmosphäre (z. B. N2) um eine bessere Kontrolle über die Oxida- tionsstufen zu gewährleisten.The reduction equivalents are provided by a reducing agent capable of reducing the superior form of the vanadium and the metal M, respectively. The reduction can be carried out during the preparation of the dry mixture or at the latest when calcining. The preparation of the intimate dry mixture is preferably carried out under an inert gas atmosphere (eg N 2) in order to ensure better control over the oxidation stages.
Bevorzugte Reduktionsmittel zu diesem Zweck sind ausgewählt unter Hypophosphoriger Säure, Phosphoriger Säure, Hydrazin (als freie Base oder Hydrat oder in Form seiner Salze wie Hydrazindihydrochlorid, Hydrazinsulfat), Hydroxylamin (als freie Base oder in Form seiner Salze wie Hydroxylaminhydrochlorid), Nitrosylamin, elementarem Vanadium, elementarem Phosphor, Boran (auch in Form komplexer Borhydride wie Natriumborhydrid) oder Oxalsäure. Phosphorige Säure und/oder Hypophosphorige Säure sind bevorzugte Reduktionsmittel.
Es versteht sich, dass bestimmte Reduktionsmittel, wie Hypophosphorige Säure oder Phosphorige Säure, gleichzeitig als Phosphatquelle dienen können, oder elementares Vanadium gleichzeitig als Vanadiumquelle dient.Preferred reducing agents for this purpose are selected from hypophosphorous acid, phosphorous acid, hydrazine (as free base or hydrate or in the form of its salts such as hydrazine dihydrochloride, hydrazine sulfate), hydroxylamine (as free base or in the form of its salts such as hydroxylamine hydrochloride), nitrosylamine, elemental vanadium , elemental phosphorus, borane (also in the form of complex borohydrides such as sodium borohydride) or oxalic acid. Phosphoric acid and / or hypophosphorous acid are preferred reducing agents. It will be understood that certain reducing agents, such as hypophosphorous acid or phosphorous acid, may simultaneously serve as the source of phosphate, or elemental vanadium may simultaneously serve as the vanadium source.
Das Trockengemisch wird bei Temperaturen von wenigstens 500 0C, vorzugsweise 700 bis 1000 0C, insbesondere etwa 800 0C, thermisch behandelt. Die thermische Behandlung kann sowohl unter oxidierender, reduzierender, als auch unter inerter Atmosphäre erfolgen. Als oxidierende Atmosphäre kommt z. B. Luft, mit molekularem Sau- erstoff angereicherte Luft oder an Sauerstoff abgereicherte Luft in Betracht. Vorzugsweise wird die thermische Behandlung jedoch unter inerter Atmosphäre, d.h. z. B. unter molekularem Stickstoff und/oder Edelgas, durchgeführt. Üblicherweise erfolgt die thermische Behandlung bei Normaldruck (1 atm). Selbstverständlich kann die thermische Behandlung auch unter Vakuum oder unter Überdruck erfolgen.The dry mixture is thermally treated at temperatures of at least 500 ° C., preferably 700 to 1000 ° C., in particular about 800 ° C. The thermal treatment can be carried out under oxidizing, reducing, as well as under inert atmosphere. As an oxidizing atmosphere z. As air, with molecular oxygen enriched air or oxygen-depleted air into consideration. However, the thermal treatment is preferably carried out under an inert atmosphere, ie, for example, under molecular nitrogen and / or noble gas. Usually, the thermal treatment is carried out at atmospheric pressure (1 atm). Of course, the thermal treatment can also be carried out under vacuum or under pressure.
Erfolgt die thermische Behandlung unter gasförmiger Atmosphäre, kann diese sowohl stehen als auch fließen. Vorzugsweise fließt sie. Insgesamt kann die thermische Behandlung bis zu 24 h oder mehr in Anspruch nehmen.If the thermal treatment takes place under a gaseous atmosphere, it can both stand and flow. Preferably, it flows. Overall, the thermal treatment can take up to 24 hours or more.
Die Erfindung betrifft ferner einen Gasphasenoxidations-Katalysator, der wenigstens ein erfindungsgemäßes polynäres Metalloxidphosphat umfasst. Die Metalloxidphosphate können als solche, z. B. als Pulver, oder in Gestalt von Formkörpern als heterogene Katalysatoren eingesetzt werden.The invention further relates to a gas phase oxidation catalyst which comprises at least one polynary metal oxide phosphate according to the invention. The metal oxide can be used as such, z. As a powder, or in the form of moldings are used as heterogeneous catalysts.
Bevorzugt erfolgt die Formgebung durch Tablettierung. Zur Tablettierung wird dem Pulver im Allgemeinen ein Tablettierhilfsmittel zugesetzt und innig vermischt.The shaping is preferably carried out by tableting. For tabletting, a tabletting aid is generally added to the powder and intimately mixed.
Tablettierhilfsmittel sind in der Regel katalytisch inert und verbessern die Tablettiereigenschaften des Pulvers, beispielsweise durch Erhöhung der Gleit- und Rieselfähig- keit. Als geeignetes und bevorzugtes Tablettierhilfsmittel sei Graphit oder Bornitrid genannt. Die zugesetzten Tablettierhilfsmittel verbleiben in der Regel im aktivierten Katalysator.Tabletting aids are generally catalytically inert and improve the tabletting properties of the powder, for example by increasing the lubricity and flowability. As a suitable and preferred Tablettierhilfsmittel is called graphite or boron nitride. The added tabletting aids usually remain in the activated catalyst.
Das Pulver kann auch tablettiert und anschließend zu Splitt zerkleinert werden.The powder can also be tabletted and then comminuted to chippings.
Die Formung zu Formkörpern kann z. B. auch durch Aufbringen wenigstens eines erfindungsgemäßen Metalloxidphosphats oder von Gemischen, die wenigstens ein erfindungsgemäßes Metalloxidphosphat enthalten, auf einen Trägerkörper erfolgen.The shaping of moldings can, for. B. by applying at least one metal oxide according to the invention or mixtures containing at least one metal oxide according to the invention, carried on a support body.
Die Trägerkörper sind vorzugsweise chemisch inert. D. h., sie greifen in den Ablauf der katalytischen Gasphasenoxidation, die durch die erfindungsgemäßen Metalloxidphosphate katalysiert wird, im Wesentlichen nicht ein.
Als Material für die Trägerkörper kommen insbesondere Aluminiumoxid, Siliciumdioxid, Silicate wie Ton, Kaolin, Steatit, Bims, Aluminiumsilicat und Magnesiumsilicat, Silicium- carbid, Zirkondioxid und Thoriumdioxid in Betracht.The carrier bodies are preferably chemically inert. That is, they essentially do not interfere with the course of the catalytic gas-phase oxidation catalyzed by the metal oxide phosphates according to the invention. The material used for the support bodies are, in particular, alumina, silica, silicates such as clay, kaolin, steatite, pumice, aluminum silicate and magnesium silicate, silicon carbide, zirconium dioxide and thorium dioxide.
Die Oberfläche des Trägerkörpers kann sowohl glatt als auch rau sein. Mit Vorteil ist die Oberfläche des Trägerkörpers rau, da eine erhöhte Oberflächenrauhigkeit in der Regel eine erhöhte Haftfestigkeit der aufgebrachten Aktivmassenschale bedingt.The surface of the carrier body can be both smooth and rough. Advantageously, the surface of the support body is rough, since an increased surface roughness usually requires an increased adhesive strength of the applied active mass shell.
Ferner kann das Trägermaterial porös oder unporös sein. Zweckmäßigerweise ist das Trägermaterial unporös, d. h. das Gesamtvolumen der Poren beträgt vorzugsweise weniger als 1 Vol.%, bezogen auf das Volumen des Trägerkörpers.Furthermore, the support material may be porous or non-porous. Conveniently, the carrier material is non-porous, d. H. the total volume of the pores is preferably less than 1 vol.%, Based on the volume of the carrier body.
Die Dicke der katalytisch aktiven Schicht beträgt üblicherweise 10 bis 1000 μm, z. B. 50 bis 700 μm, 100 bis 600 μm oder 150 bis 400 μm.The thickness of the catalytically active layer is usually 10 to 1000 microns, z. B. 50 to 700 microns, 100 to 600 microns or 150 to 400 microns.
Prinzipiell kommen Trägerkörper mit beliebiger geometrischer Struktur in Betracht. Ihre Längstausdehnung beträgt in der Regel 1 bis 10 mm. Vorzugsweise werden jedoch Kugeln oder Zylinder, insbesondere Hohlzylinder, als Trägerkörper angewendet.In principle, carrier bodies with any geometric structure come into consideration. Their longest extent is usually 1 to 10 mm. Preferably, however, balls or cylinders, in particular hollow cylinders, are used as carrier bodies.
Die Herstellung der Schalenkatalysatoren kann in einfachster weise so erfolgen, dass man Metalloxidphosphatmassen der allgemeinen Formel (I) vorbildet, sie in eine fein- teilige Form überführt und abschließend mit Hilfe eines flüssigen Bindemittels auf die Oberfläche des Trägerkörpers aufbringt. Dazu wird die Oberfläche des Trägerkörpers in einfachster weise mit dem flüssigen Bindemittel befeuchtet und durch Inkontaktbrin- gen mit der feinteiligen Metalloxidphosphatmasse eine Schicht der Aktivmasse auf der befeuchteten Oberfläche angeheftet. Abschließend wird der beschichtete Trägerkörper getrocknet. Selbstredend kann man zur Erzielung einer größeren Schichtdicke den Vorgang wiederholen.The preparation of the shell catalysts can be carried out in the simplest way by pretreating metal oxide phosphate compositions of the general formula (I), converting them into a finely divided form and finally applying them to the surface of the support body with the aid of a liquid binder. For this purpose, the surface of the carrier body is moistened in the simplest way with the liquid binder and, by contacting with the finely divided metal oxide phosphate mass, a layer of the active composition is attached to the moistened surface. Finally, the coated carrier body is dried. Needless to say you can repeat the process to achieve a greater layer thickness.
Die erfindungsgemäßen Metalloxidphosphate können auch verwendet werden, um die katalytischen Eigenschaften, insbesondere Umsatz und/oder Selektivität, bekannter Katalysatoren, insbesondere auf der Basis von Vanadylpyrophosphat, zu modifizieren. Dazu können die erfindungsgemäßen Metalloxidphosphate z. B. als Promotorphase in einem Katalysator auf der Basis von Vanadylpyrophosphat eingesetzt werden. Zweckmäßigerweise umfasst der Katalysator dann eine erste Phase und eine zweite Phase in Form dreidimensional ausgedehnter Bereiche, die sich von ihrer lokalen Umgebung durch eine unterschiedliche chemische Zusammensetzung abgrenzen. Dabei enthält die erste Phase eine katalytisch aktive Masse auf der Basis von Vanadylpyrophosphat und die zweite Phase wenigstens ein erfindungsgemäßes polynäres Metalloxidphosphat. Dabei können (i) feinteilige Partikel der zweiten Phase in der ersten Phase dispergiert sein, oder (ii) die erste Phase und die zweite Phase relativ zueinander wie
in einem Gemenge aus feinteiliger erster Phase und feinteiliger zweiter Phase verteilt sein.The metal oxide phosphates according to the invention can also be used to modify the catalytic properties, in particular conversion and / or selectivity, of known catalysts, in particular based on vanadyl pyrophosphate. For this purpose, the metal oxide according to the invention z. B. can be used as a promoter phase in a catalyst based on vanadyl pyrophosphate. Conveniently, the catalyst then comprises a first phase and a second phase in the form of three-dimensionally extended regions that are different from their local environment by a different chemical composition. The first phase contains a catalytically active composition based on vanadyl pyrophosphate and the second phase contains at least one polynary metal oxide phosphate according to the invention. In this case, (i) finely divided particles of the second phase may be dispersed in the first phase, or (ii) the first phase and the second phase relative to each other be distributed in a mixture of finely divided first phase and finely divided second phase.
Die Herstellung dieser zweiphasigen Katalysatoren kann z. B. erfolgen, indem man einen Vanadylhydrogenphosphat-Hemihydrat-Precursor (VOHPO4 /4 H2O) herstellt, diesen mit vorgebildeten Teilchen der zweiten Phase aus erfindungsgemäßem Metalloxidphosphat versetzt, die erhaltene Masse verformt und calciniert. Der Vanadylhydro- genphosphat-Hemihydrat-Precursor kann in an sich bekannter Weise aus einer Verbindung des fünfwertigen Vanadiums (z. B. V2O5), einer Verbindung mit fünf- oder drei- wertigem Phosphor (z. B. Ortho- und/oder Pyrophosphorsäure, Phosphorsäureester oder phosphorige Säure) und einem reduzierend wirkenden Alkohol (z. B. Isobutanol) und Isolierung des Niederschlags erhalten werden. Es sei z. B. auf die EP-A 0 520 972 und WO 00/72963 verwiesen.The preparation of these two-phase catalysts can, for. Example, by preparing a Vanadylhydrogenphosphat hemihydrate precursor (VOHPO 4/4 H2O), this is mixed with preformed particles of the second phase of metal oxide according to the invention, the resulting mass is deformed and calcined. The vanadyl hydrogenphosphate hemihydrate precursor can be prepared in a manner known per se from a compound of the pentavalent vanadium (for example V2O5), a compound with pentavalent or trivalent phosphorus (for example ortho and / or pyrophosphoric acid, Phosphoric acid ester or phosphorous acid) and a reducing alcohol (e.g., isobutanol) and isolation of the precipitate. It is z. For example, see EP-A 0 520 972 and WO 00/72963.
Die erfindungsgemäßen Katalysatoren, deren katalytisch aktive Masse wenigstens ein oben definiertes Metalloxidphosphat umfasst, können mit Katalysatoren auf der Basis von Vanadylpyrophosphat auch in Form einer strukturierten Packung kombiniert werden. So kann man einen Gasstrom, der einen zu oxidierenden Kohlenwasserstoff und molekularen Sauerstoff enthält, über eine stromaufwärts in Strömungsrichtung des Gasstroms gelegene Schüttung eines ersten Gasphasenoxidations-Katalysators und dann über eine oder mehrere stromabwärts gelegene Schüttung eines zweiten oder weiterer Gasphasenoxidations-Katalysatoren leiten, wobei die erste oder zweite oder eine der weiteren Schüttungen einen erfindungsgemäßen Katalysator umfasst.The catalysts according to the invention, whose catalytically active composition comprises at least one metal oxide phosphate as defined above, can also be combined with catalysts based on vanadyl pyrophosphate in the form of a structured packing. Thus, a gas stream containing a hydrocarbon and molecular oxygen to be oxidized may be passed over a bed of first gas phase oxidation catalyst upstream in the gas flow direction and then via one or more downstream beds of second or further gas phase oxidation catalysts first or second or one of the further beds comprises a catalyst according to the invention.
Die Erfindung betrifft ferner ein Verfahren zur partiellen Gasphasenoxidation oder Am- monoxidation, bei dem man einen Gasstrom, der einen Kohlenwasserstoff und molekularen Sauerstoff enthält, mit einem erfindungsgemäßen Katalysator in Kontakt bringt. Im Falle der Ammonoxidation enthält der Gasstrom zusätzlich Ammoniak. Unter der Ammonoxidation versteht man im Rahmen der vorliegenden Erfindung einen hetero- gen-katalytischer Prozess, bei dem methylsubstituierte Alkene, Arene und Hetarene durch Umsetzung mit Ammoniak und Sauerstoff in Gegenwart von Übergangsmetall- Katalysatoren in Nitrile umgewandelt werden.The invention further relates to a process for the partial gas phase oxidation or monoxidation, in which bringing a gas stream containing a hydrocarbon and molecular oxygen, with a catalyst according to the invention in contact. In the case of ammoxidation, the gas stream additionally contains ammonia. For the purposes of the present invention, ammoxidation is understood as meaning a heterogeneous catalytic process in which methyl-substituted alkenes, arenes and hetarenes are converted into nitriles by reaction with ammonia and oxygen in the presence of transition metal catalysts.
Das Verfahren zur partiellen Gasphasenoxidation dient in bevorzugten Ausführungs- formen der Herstellung von Maleinsäureanhydrid, wobei der eingesetzte Kohlenwasserstoff mindestens vier Kohlenstoffatomen enthält.The process for partial gas phase oxidation is used in preferred embodiments of the production of maleic anhydride, wherein the hydrocarbon used contains at least four carbon atoms.
Beim erfindungsgemäßen Verfahren zur partiellen Gasphasenoxidation oder Ammonoxidation werden im Allgemeinen Rohrbündelreaktoren eingesetzt. Alternativ ist auch der Einsatz von Wirbelbettreaktoren möglich.
Als Kohlenwasserstoffe sind im Allgemeinen aliphatische und aromatische, gesättigte und ungesättigte Kohlenwasserstoffe mit mindestens vier Kohlenstoffatomen, wie beispielsweise 1 ,3-Butadien, 1 -Buten, cis-2-Buten, trans-2-Buten, n-Butan, C4-Gemische, 1 ,3-Pentadien, 1 ,4-Pentadien, 1-Penten, cis-2-Penten, trans-2-Penten, n-Pentan, Cyc- lopentadien, Dicyclopentadien, Cyclopenten, Cyclopentan, Cs-Gemische, Hexene, He- xane, Cyclohexan und Benzol geeignet. Bevorzugt eingesetzt werden 1 ,3-Butadien, 1- Buten, cis-2-Buten, trans-2-Buten, n-Butan, Benzol oder deren Mischungen.In the process according to the invention for partial gas-phase oxidation or ammoxidation, tube-bundle reactors are generally used. Alternatively, the use of fluidized bed reactors is possible. As hydrocarbons are generally aliphatic and aromatic, saturated and unsaturated hydrocarbons having at least four carbon atoms, such as 1, 3-butadiene, 1-butene, cis-2-butene, trans-2-butene, n-butane, C4 mixtures, 1, 3-pentadiene, 1,4-pentadiene, 1-pentene, cis-2-pentene, trans-2-pentene, n-pentane, cyclopentadiene, dicyclopentadiene, cyclopentene, cyclopentane, Cs-mixtures, hexenes, hexanes, xane, cyclohexane and benzene. Preference is given to using 1,3-butadiene, 1-butene, cis-2-butene, trans-2-butene, n-butane, benzene or mixtures thereof.
Besonders bevorzugt ist der Einsatz von n-Butan und n-Butan-haltigen Gasen und Flüssigkeiten. Das verwendete n-Butan kann beispielsweise aus Erdgas, aus Steamc- rackern oder FCC-Crackern stammen.Particularly preferred is the use of n-butane and n-butane-containing gases and liquids. The n-butane used can be derived, for example, from natural gas, steam crackers or FCC crackers.
Die Zugabe des Kohlenwasserstoffs erfolgt im Allgemeinen mengengeregelt, d. h. unter stetiger Vorgabe einer definierten Menge pro Zeiteinheit. Der Kohlenwasserstoff kann in flüssiger oder gasförmiger Form dosiert werden. Bevorzugt ist die Dosierung in flüssiger Form mit anschließender Verdampfung vor Eintritt in den Reaktor.The addition of the hydrocarbon is generally quantity controlled, d. H. under constant specification of a defined amount per time unit. The hydrocarbon can be metered in liquid or gaseous form. Preferably, the dosage in liquid form with subsequent evaporation before entering the reactor.
Als Oxidationsmittel werden Sauerstoff enthaltende Gase, wie beispielsweise Luft, synthetische Luft, ein mit Sauerstoff angereichertes Gas oder auch sogenannter "reiner", d. h. z. B. aus der Luftzerlegung stammender Sauerstoff eingesetzt. Auch das Sauer- stoff-enthaltende Gas wird vorzugsweise mengengeregelt zugegeben.As the oxidizing agent are oxygen-containing gases, such as air, synthetic air, an oxygen-enriched gas or so-called "pure", d. H. z. B. originating from the air separation oxygen. The oxygen-containing gas is also preferably added in a controlled amount.
Das durch den Reaktor zu leitende Gas enthält im Allgemeinen eine Kohlenwasserstoff-Konzentration von 0,5 bis 15 Vol.-% und eine Sauerstoff-Konzentration von 8 bis 25 Vol.-%. Der zu einhundert Vol. -% fehlende Anteil setzt sich aus weiteren Gasen wie beispielsweise Stickstoff, Edelgasen, Kohlenmonoxid, Kohlendioxid, Wasserdampf, oxygenierte Kohlenwasserstoffe (z. B. Methanol, Formaldehyd, Ameisensäure, Etha- nol, Acetyaldehyd, Essigsäure, Propanol, Propionaldehyd, Propionsäure, Acrolein, Cro- tonaldehyd) und deren Mischungen zusammen. Im Falle der Selektivoxidation von n- Butan beträgt der n-Butan-Anteil an der Gesamtmenge an Kohlenwasserstoff vorzugsweise mehr als 90 % und besonders bevorzugt mehr als 95 %.The gas to be passed through the reactor generally contains a hydrocarbon concentration of 0.5 to 15% by volume and an oxygen concentration of 8 to 25% by volume. The proportion missing to one hundred% by volume consists of further gases such as nitrogen, noble gases, carbon monoxide, carbon dioxide, water vapor, oxygenated hydrocarbons (eg methanol, formaldehyde, formic acid, ethanol, acetaldehyde, acetic acid, propanol, propionaldehyde , Propionic acid, acrolein, cetonaldehyde) and mixtures thereof. In the case of selective oxidation of n-butane, the n-butane content of the total amount of hydrocarbon is preferably more than 90%, and more preferably more than 95%.
Zur Gewährung einer langen Katalysatorstandzeit und weiteren Erhöhung von Umsatz, Selektivität, Ausbeute, Katalysator-Belastung und Raum/Zeit-Ausbeute wird dem Gas beim erfindungsgemäßen Verfahren bevorzugt eine flüchtige Phosphorverbindung zugeführt.To provide a long catalyst life and further increase in conversion, selectivity, yield, catalyst loading and space / time yield, the gas is preferably fed to the gas in the process according to the invention a volatile phosphorus compound.
Ihre Konzentration beträgt zu Beginn, d. h. am Reaktoreingang, mindestens 0,2 VoIu- men-ppm, d. h. 0,2 10"6 Volumenanteile der flüchtigen Phosphorverbindungen bezo- gen auf das Gesamtvolumen des Gases am Reaktoreingang. Bevorzugt ist ein Gehalt von 0,2 bis 20 Volumen-ppm, besonders bevorzugt von 0,5 bis 10 Volumen-ppm.
Als flüchtige Phosphorverbindungen sind all jene Phosphor-enthaltende Verbindungen zu verstehen, welche in der gewünschten Konzentration unter den Einsatzbedingungen gasförmig vorliegen. Als geeignete flüchtige Phosphorverbindungen sind beispielsweise Phosphine und Phosphorsäureester genannt. Besonders bevorzugt sind die d- bis C4-Alkyl-Phosphorsäureester, ganz besonders bevorzugt Trimethylphosphat, Triethylphosphat und Tripropylphosphat, insbesondere Triethylphosphat.Its concentration at the beginning, ie at the reactor inlet, at least 0.2 ppm by volume, ie 0.2 10 "6 volume of the volatile phosphorus compounds Relative to the total volume of the gas at the reactor inlet. Preferably, a content of 0.2 to 20 ppm by volume, more preferably from 0.5 to 10 ppm by volume. Volatile phosphorus compounds are to be understood as meaning those phosphorus-containing compounds which are gaseous in the desired concentration under the conditions of use. As suitable volatile phosphorus compounds, for example, phosphines and phosphoric acid esters are mentioned. Particularly preferred are the C 1 to C 4 alkyl phosphoric esters, very particularly preferably trimethyl phosphate, triethyl phosphate and tripropyl phosphate, in particular triethyl phosphate.
Das erfindungsgemäße Verfahren wird im Allgemeinen bei einer Temperatur von 300 bis 500 0C durchgeführt. Unter der genannten Temperatur wird die Temperatur der im Reaktor befindlichen Katalysatorschüttung verstanden, welche bei Ausübung des Verfahrens in Abwesenheit einer chemischen Reaktion vorliegen würde.The process of the invention is generally carried out at a temperature of 300 to 500 0 C. Under the said temperature, the temperature of the catalyst bed located in the reactor is understood, which would be present in the practice of the process in the absence of a chemical reaction.
Ist diese Temperatur nicht an allen Stellen exakt gleich, so meint der Begriff den Zahlenmittelwert der Temperaturen längs der Reaktionszone. Insbesondere bedeutet dies, dass die wahre, am Katalysator vorliegende Temperatur aufgrund der Exothermie der Oxidationsreaktion auch außerhalb des genannten Bereichs liegen kann. Bevorzugt wird das erfindungsgemäße Verfahren bei einer Temperatur von 380 bis 460 0C, besonders bevorzugt 380 bis 430 0C durchgeführt.If this temperature is not exactly the same at all points, then the term means the number average of the temperatures along the reaction zone. In particular, this means that the true, present at the catalyst temperature due to the exothermicity of the oxidation reaction may also be outside the range mentioned. The process according to the invention is preferably carried out at a temperature of from 380 to 460 ° C., more preferably from 380 to 430 ° C.
Das erfindungsgemäße Verfahren kann bei einem Druck unterhalb von Normaldruck (z. B. bis 0,05 MPa abs) als auch oberhalb von Normaldruck (z. B. bis 10 MPa abs) ausgeübt werden. Darunter ist der in der Reaktor-Einheit vorliegende Druck zu verstehen. Bevorzugt ist ein Druck von 0,1 bis 1 ,0 MPa abs, besonders bevorzugt 0,1 bis 0,5 MPa abs.The process according to the invention can be carried out at a pressure below normal pressure (for example up to 0.05 MPa abs) or above normal pressure (for example up to 10 MPa abs). This is understood to mean the pressure present in the reactor unit. Preference is given to a pressure of 0.1 to 1.0 MPa abs, more preferably 0.1 to 0.5 MPa abs.
Das erfindungsgemäße Verfahren kann in zwei bevorzugten Verfahrensvarianten, der Variante mit "geradem Durchgang" und der Variante mit "Rückführung" durchgeführt werden. Beim "geraden Durchgang" wird aus dem Reaktoraustrag Maleinsäureanhydrid und gegebenenfalls oxygenierte Kohlenwasserstoff-Nebenprodukte entfernt und das verbleibende Gasgemisch ausgeschleust und gegebenenfalls thermisch verwertet. Bei der "Rückführung" wird aus dem Reaktoraustrag ebenfalls Maleinsäureanhydrid und gegebenenfalls oxygenierte Kohlenwasserstoff-Nebenprodukte entfernt, das verbleibende Gasgemisch, welches nicht-umgesetzten Kohlenwasserstoff enthält, ganz oder teilweise zum Reaktor rückgeführt. Eine weitere Variante der "Rückführung" ist die Entfernung des nicht-umgesetzten Kohlenwasserstoffs und dessen Rückführung zum Reaktor.The process according to the invention can be carried out in two preferred process variants, the "straight through" variant and the "recirculation" variant. In the "straight pass", maleic anhydride and optionally oxygenated hydrocarbon by-products are removed from the reactor effluent and the remaining gas mixture is discharged and optionally thermally recovered. In the "recycling" is also removed from the reactor effluent maleic anhydride and optionally oxygenated hydrocarbon by-products, the remaining gas mixture containing unreacted hydrocarbon, completely or partially recycled to the reactor. Another variant of the "recycling" is the removal of the unreacted hydrocarbon and its return to the reactor.
In einer besonders bevorzugten Ausführungsform zur Herstellung von Maleinsäureanhydrid setzt man n-Butan als Ausgangs-Kohlenwasserstoff ein und führt die heterogen- katalytische Gasphasenoxidation im "geraden Durchgang" an dem erfindungsgemäßen Katalysator durch.
Die vorliegende Erfindung wird durch die beigefügten Zeichnungen und die nachfolgenden Beispiele näher veranschaulicht.In a particularly preferred embodiment for the preparation of maleic anhydride, n-butane is used as the starting hydrocarbon and the heterogeneously catalyzed gas phase oxidation is carried out in the "straight pass" on the catalyst according to the invention. The present invention is further illustrated by the accompanying drawings and the following examples.
Fig. 1 zeigt eine Guinieraufnahme von V4Os(PO4)S, das durch Festkörperreaktion erhalten wurde;Fig. 1 shows a Guinieraufnahme of V 4 Os (PO 4 ) S, which was obtained by solid state reaction;
Fig. 2 zeigt eine Guinieraufnahme von CrVsOs(PO4)3, das durch Festkörperreaktion erhalten wurde;Fig. 2 shows a Guinier recording of CrVsOs (PO 4 ) 3, which was obtained by solid state reaction;
Fig. 3 zeigt eine Guinieraufnahme von FeVsθ3(PO4)3, das durch Festkörperreaktion erhalten wurde;Fig. 3 shows a Guinier recording of FeVsθ3 (PO 4 ) 3, which was obtained by solid state reaction;
Fig. 4 zeigt eine Guinieraufnahme von TiV3θ3(PO4)3, das durch Festkörperreaktion erhalten wurde;Fig. 4 shows a Guinier recording of TiV3θ3 (PO 4 ) 3, which was obtained by solid state reaction;
Fig. 5 zeigt das Pulverröngtendiffraktogramm von V4θ3(PO4)3, das durch Calcinieren eines sprühgetrockneten Vorläufers an Luft erhalten wurde;Fig. 5 shows the powder X-ray diffractogram of V 4 O 3 (PO 4 ) 3 obtained by calcining a spray-dried precursor in air;
Fig. 6 zeigt das Pulverröngtendiffraktogramm von FeV3θ3(PO4)3, das durch Calcinieren eines sprühgetrockneten Vorläufers an Luft erhalten wurde.Fig. 6 shows the powder X-ray diffractogram of FeV 3 O 3 (PO 4 ) 3 obtained by calcining a spray-dried precursor in air.
Für die Röntgenbeugungsuntersuchungen nach der Guinier-Technik wurde eine Kame- ra FR-552 (Fa. Nonius, Delft) unter Verwendung von Image Plate-Folie (Y. Amemiya, J. Miyahara, NATURE 1988, 336, 89-90) benutzt (CuKαi-Strahlung, λ=1 , 54051 Ä, α- Quarz Monochromator, α-Siθ2 als interner Standard). Vgl. K. Maaß, R. Glaum, R. Gruehn, Z. anorg. AIIg. Chem. 2002, 628, 1663-1672.For the X-ray diffraction studies according to the Guinier technique, a camera FR-552 (Nonius, Delft) was used using Image Plate film (Y. Amemiya, J. Miyahara, NATURE 1988, 336, 89-90) ( CuKαi radiation, λ = 1, 54051 Å, α-quartz monochromator, α-SiO 2 as internal standard). See K. Maass, R. Glaum, R. Gruehn, Z. anorg. AIIg. Chem. 2002, 628, 1663-1672.
Alle übrigen Röntgenbeugungsuntersuchungen gehen zurück auf unter Anwendung von Cu-Kα-Strahlung (λ = 1 ,54178 Ä) als Röntgenstrahlung erzeugte Röntgendiffrak- togramme (Siemens-Diffraktometer Theta-Theta D-5000, Röhrenspannung: 40 kV, Röhrenstrom: 40 mA, Aperturblende V20 (variabel), Streustrahlblende V20 (variabel), Sekundärmonochromatorblende (0,1 mm), Deterktorblende (0,6 mm), Messintervall (2Θ): 0,02 [°], Messzeit je Schritt: 2,4 s, Detektor: Scintillationszählrohr).
A. Herstellung der Metalloxidphosphate der Formel IAll other X-ray diffraction studies are based on X-ray diffraction patterns generated using Cu-Kα radiation (λ = 1, 54178 Å) (Siemens Theta-Theta D-5000 diffractometer, tube voltage: 40 kV, tube current: 40 mA, aperture stop V20 (variable), diffuser aperture V20 (variable), secondary monochromator aperture (0.1 mm), detector aperture (0.6 mm), measuring interval (2Θ): 0.02 [°], measuring time per step: 2.4 s, detector: Scintillationszählrohr). A. Preparation of the metal oxide phosphates of the formula I.
Beispiel 1 : Herstellung von V4Os(PO4)S durch FestkörperreaktionExample 1: Preparation of V 4 Os (PO 4 ) S by solid-state reaction
Zunächst wurde VO2 durch Synproportionierung von V2O5 (p. a., Merck Eurolap GmbH, Darmstadt, Deutschland) und V2O3 (aus der Reduktion von V2O5 mit Wasserstoff bei 1073 K [G. Brauer, A. Simon in Handbuch der Präparativen Anorganischen Chemie, G. Brauer (Hrsg.), Ferd. Enke Verlag, Stuttgart 1981 , S. 1419]) in geschlossenen Kieselglasampullen bei 1073 K unter Zugabe von 80 mg lod als Mineralisator dargestellt. Als weitere Edukte wurden VPO4 (R. Glaum, R. Gruehn, Z. Kristallogr. 1992, 198, 41-47) und (VO)2P2Ü7 synthetisiert. Das Pyrophosphat wurde durch Erhitzen von VO(HPO4) V2 H2O im Argonstrom bei 1073 K erhalten (J. W. Johnson, D. C. Johnston, A. J. Jacobson, J. F. Brody, J. Amer. Chem. Soc. 1984, 106, 8123-8128). Vanadylhydro- genphosphat-Hemihydrat war zuvor durch Kochen unter Rückfluss von V2O5 und HsPO4 (85% p. a., Merck Eurolap GmbH, Darmstadt, Deutschland) in n-Butanol gefällt worden.First, VO2 was synthesized by synproportionation of V2O5 (pa, Merck Eurolap GmbH, Darmstadt, Germany) and V2O3 (from the reduction of V2O5 with hydrogen at 1073 K [G. Brauer, A. Simon in Handbuch der Präparativen Inorganischen Chemie, G. Brauer ( Ed., Enke Verlag, Stuttgart 1981, p 1419]) in closed silica glass ampoules at 1073 K with the addition of 80 mg of iodine shown as a mineralizer. As further starting materials, VPO 4 (R.Glaum, R. Gruehn, Z. Kristallogr., 1992, 198, 41-47) and (VO) 2P2T7 were synthesized. The pyrophosphate was obtained by heating VO (HPO 4 ) V 2 H 2 O in the argon stream at 1073 K (JW Johnson, DC Johnston, AJ Jacobson, JF Brody, J. Amer. Chem. Soc., 1984, 106, 8123-8128). Vanadylhydro- dihydrogen phosphate hemihydrate was previously refluxing of V2O5 and HSPO (pa 85%, Merck Eurolap GmbH, Darmstadt, Germany) 4 in n-butanol was like.
Schließlich wurde die Titelverbindung durch Umsetzung von 63,9 mg VO2, 1 12,4 mg VPO4 und 237,0 mg (VO)2P2Ü7 erhalten. Die Edukte wurden dazu in einer Achatschale fein verrieben, zu einer Tablette gepresst und fünf Tage in einer geschlossenen, evakuierten Kieselglasampulle bei 1073 K erhitzt. Durch Verwendung eines Korundtiegels wurde eine Reaktion der Tablette mit der Ampullenwand vermieden.Finally, the title compound was obtained by reaction of 63.9 mg VO2, 12.4 mg VPO 4 and 237.0 mg (VO) 2P2Ü7. The starting materials were finely triturated in an agate dish, pressed into a tablet and heated for five days in a closed, evacuated silica glass ampoule at 1073 K. By using a corundum crucible, a reaction of the tablet with the ampoule wall was avoided.
In der nachstehenden Tabelle sind ausgewählte charakteristische Röntgenbeugungs- reflexe angegeben, wie sie durch Auswertung einer Guinieraufnahme (Fig. 1 ) erhalten wurden.The table below shows selected X-ray diffraction reflexes as obtained by evaluating a Guinier image (FIG. 1).
Mittels DTA wurde der Schmelzpunkt der Titelverbindung zu 1180 K bestimmt. Isothermes Erhitzen von Eduktgemengen aus VO2, VPO4 und (VO)2P2Ü7 knapp unterhalb des Schmelzpunkts der Titelverbindung, unter Zusatz von wenigen mg PtCb als Mineralisator führte zur Bildung schwarzer, isometrischer Kristalle mit Kantenlängen bis zu
0,2 mm. Anhand von Einkristalldaten wurde die Raumgruppe F2dd (Nr. 43) Z = 24, a = 7,2596(8) Ä, b = 21 ,786(2) Ä, c = 38,904(4) Ä ermittelt.The melting point of the title compound was determined to be 1180 K by means of DTA. Isothermal heating of starting material mixtures of VO2, VPO 4 and (VO) 2P2Ü7 just below the melting point of the title compound, with the addition of a few mg of PtCb as mineralizer led to the formation of black, isometric crystals with edge lengths up to 0.2 mm. From single crystal data, the space group F2dd (# 43) Z = 24, a = 7.2596 (8) λ, b = 21, 786 (2) λ, c = 38.904 (4) λ was determined.
Beispiel 2: Herstellung von CrVsOs(PO4)S durch FestkörperreaktionExample 2: Preparation of CrVsOs (PO 4 ) S by solid-state reaction
Zunächst wurde P-CrPO4 durch Eindampfen einer wässrigen Lösung stöchiometrischer Mengen Cr(N0s)3 9 H2O (Sigma Aldrich Laborchemikalien GmbH, Riedel-de Haen Brand, Seelze, Deutschland) und NH4H2PO4 (p. a., Merck Eurolap GmbH, Darmstadt, Deutschland) und nachfolgendes Erhitzen des Trockenrückstands bei 1273 K an der Luft gemäß den Angaben in J.-P. Attfield, P. D. Battle, A. K. Cheetham, J. Solid State Chem. 1985, 57, 357-361 hergestellt.First, P-CrPO 4 was prepared by evaporation of an aqueous solution of stoichiometric amounts of Cr (N0S) 3 9 H2O (Sigma Aldrich Laboratory Chemicals GmbH, Riedel-de Haen fire, Seelze, Germany) and NH4H2PO4 (pa, Merck Eurolap GmbH, Darmstadt, Germany) and subsequent heating of the dry residue at 1273 K in air as described in J.-P. Attfield, PD Battle, AK Cheetham, J. Solid State Chem. 1985, 57, 357-361.
Danach wurden 45,8 mg VO2, 81 ,2 mg ß-CrPO4 und 170 mg (VO)2P2O7 in einer Achatschale fein verrieben, zu einer Tablette gepresst und 24 Stunden in einer geschlossenen, evakuierten Kieselglasampulle bei 753 K und anschließend fünf Tage bei 1073 K erhitzt.Thereafter, 45.8 mg of VO 2 , 81, 2 mg of β-CrPO 4 and 170 mg of (VO) 2 P 2 O 7 were finely triturated in an agate dish, pressed into a tablet and left in a closed, evacuated silica glass vial at 753 K for 24 hours and then heated at 1073 K for five days.
In der nachstehenden Tabelle sind ausgewählte charakteristische Röntgenbeugungs- reflexe angegeben, wie sie durch Auswertung einer Guinieraufnahme (Fig. 2) erhalten wurden.The table below shows selected X-ray diffraction reflexes as obtained by evaluating a Guinier image (Figure 2).
Beispiel 3: Herstellung von FeVsOs(PO4)S durch FestkörperreaktionExample 3: Production of FeVsOs (PO 4 ) S by Solid-State Reaction
Zunächst wurde FePO4 durch Eindampfen einer wässrigen Lösung stöchiometrischer Mengen Fe(NOs)3 9 H2O (p. a., Merck Eurolap GmbH, Darmstadt, Deutschland) und NH4H2PO4 (p. a., Merck Eurolap GmbH, Darmstadt, Deutschland) und nachfolgendes Erhitzen des Trockenrückstands bei 1273 K an der Luft hergestellt.First, FePO 4 was prepared by evaporation of an aqueous solution of stoichiometric amounts of Fe (NOs) 3 9 H 2 O (pa, Merck Eurolap GmbH, Darmstadt, Germany) and NH 4 H 2 PO 4 (pa, Merck Eurolap GmbH, Darmstadt, Germany) and subsequently heating the dry residue at 1273 K in air.
Danach wurden 71 ,0 mg VO2, 132,9 mg FePO4 und 263,8 mg (VO)2P2O7 in einer A- chatschale fein verrieben, zu einer Tablette gepresst und 24 Stunden in einer ge-
schlossenen, evakuierten Kieselglasampulle bei 753 K und anschließend sechs Tage bei 1000 K erhitzt.Thereafter, 71.0 mg of VO 2 , 132.9 mg of FePO 4 and 263.8 mg of (VO) 2 P 2 O 7 were finely triturated in an acetone dish, pressed into a tablet and left to stand for 24 hours. closed, evacuated silica glass ampule at 753 K and then heated at 1000 K for six days.
In der nachstehenden Tabelle sind ausgewählte charakteristische Röntgenbeugungs- reflexe angegeben, wie sie durch Auswertung einer Guinieraufnahme (Fig. 3) erhalten wurden.In the following table, selected characteristic X-ray diffraction reflexes are obtained, as obtained by evaluating a Guinier image (FIG. 3).
Beispiel 4: Herstellung von TiVsOs(PO4)S durch FestkörperreaktionExample 4: Preparation of TiVsOs (PO 4 ) S by Solid-State Reaction
Zunächst wurde TiP2Ü7 durch thermischen Abbau von Ti(HPO4^ H2O bei sukzessiv bis 1073 K ansteigender Temperatur hergestellt. Die Herstellung von Ti(HPO4)2 H2O erfolgte durch Hydrolyse von TiÜ2 (technisch, Sigma Aldrich Laborchemikalien GmbH, Riedel-de Haen Brand, Seelze, Deutschland) in konzentrierter Phosphorsäure (85 % reinst, Merck Eurolap GmbH, Darmstadt, Deutschland) gemäß den Angaben in S. Bru- que, Miguel A. G. Aranda, Enrique R. Losilla, Pascual O. -Pastor und P. Maireles- Torres, Inorg. Chem., 1995, 34, 893-899).Initially, TiP2Ü7 was prepared by thermal decomposition of Ti (HPO 4 ^ H2O at a temperature rising successively to 1073 K. Ti (HPO 4 ) 2 H 2 O was prepared by hydrolysis of TiO 2 (technically, Sigma Aldrich Laborchemikalien GmbH, Riedel-de Haen Brand , Seelze, Germany) in concentrated phosphoric acid (85% pure, Merck Eurolap GmbH, Darmstadt, Germany) as described in S. Bruque, Miguel AG Aranda, Enrique R. Losilla, Pascual O. Pastor and P. Maireles Torres, Inorg. Chem., 1995, 34, 893-899).
Zur Herstellung der Titelverbindung wurden 75,9 mg ΗP2O7, 52,3 mg V2O3 und 55,9 mg VOPO4 in einen kleinen Korundtiegel gegeben. Dieser wurde zusammen mit 25 mg PtCb als Mineralisator in eine evakuierte Ampulle eingeschmolzen und 24 Stunden bei 753 K und anschließend sechs Tage bei 1000 K erhitzt.For the preparation of the title compound, 75.9 mg of ΗP2O7, 52.3 mg of V2O3 and 55.9 mg of VOPO 4 were placed in a small corundum crucible. This was melted together with 25 mg of PtCb as a mineralizer in an evacuated ampoule and heated at 753 K for 24 hours and then at 1000 K for six days.
In der nachstehenden Tabelle sind ausgewählte charakteristische Röntgenbeugungs- reflexe angegeben, wie sie durch Auswertung einer Guinieraufnahme (Fig. 4) erhalten wurden.The table below shows selected X-ray diffraction reflexes as obtained by evaluating a Guinier image (Figure 4).
Beispiel 5: Herstellung von V4Os(PO4)S (Katalysator A1 )Example 5: Preparation of V 4 Os (PO 4 ) S (Catalyst A1)
In einen mit strömenden Stickstoff gespülten Glasreaktor gab man 2,5 L Wasser, 727,5 g V2O5 [> 99 %, 8 Mol, berechnet als V] (GfE Umwelttechnik GmbH, Nürnberg, Deutschland), 1 15,3 g H3PO4 [85 %, 1 Mol, berechnet als P] (Sigma Aldrich, Seelze, Deutschland) und 820,0 g H3PO3 [50 %, 5 Mol, berechnet als P] (Sigma Aldrich, Seelze, Deutschland). Man erwärmte die Mischung unter kräftigem Rühren auf 90 °C und rührte bei dieser Temperatur 2 Stunden. Unter einer Stickstoffatmosphäre wurde die so hergestellte Suspension über einen Sprühtrockner (Mobile Minor™ 2000, MM, der Fa. Niro A/S, Soborg, Dänemark, Eintrittstemperatur: 330 °C, Austrittstemperatur: 107 °C) getrocknet. Der erhaltene Feststoff wurde bei 800 °C zwei Stunden in Stickstoff- Atmosphäre in einem Quarzglasdrehrohr mit einem inneren Volumen von 1 L calciniert.Into a glass reactor purged with flowing nitrogen was added 2.5 L of water, 727.5 g of V 2 O 5 [> 99%, 8 mol, calculated as V] (GfE Umwelttechnik GmbH, Nuremberg, Germany), 1 15.3 g H 3 PO 4 [85%, 1 mole, calculated as P] (Sigma Aldrich, Seelze, Germany) and 820.0 g of H 3 PO 3 [50%, 5 mol, calculated as P] (Sigma Aldrich, Seelze, Germany ). The mixture was heated with vigorous stirring to 90 ° C and stirred at this temperature for 2 hours. Under a nitrogen atmosphere, the suspension thus prepared was dried over a spray dryer (Mobile Minor ™ 2000, MM, from Niro A / S, Soborg, Denmark, inlet temperature: 330 ° C., outlet temperature: 107 ° C.). The resulting solid was calcined at 800 ° C for two hours in a nitrogen atmosphere in a quartz glass rotary tube having an inner volume of 1 liter.
Das erhaltene Pulver hatte eine spezifische Oberfläche nach BET von 3,0 m2/g. Vom erhaltenen Pulver wurde ein Pulverröntgendiffraktogramm aufgenommen. Aus dem Pulverröntgendiffraktogramm (Fig. 5) wurden die folgenden 2Θ-Werte mit den dazugehörigen Intensitäten I und Netzebenabständen d ermittelt.The resulting powder had a BET specific surface area of 3.0 m 2 / g. From the obtained powder, a powder X-ray diffractogram was taken. From the powder X-ray diffractogram (FIG. 5), the following 2Θ values with the associated intensities I and wattage spacings d were determined.
Beispiel 6: Herstellung von CrV3O3(PO4)3 (Katalysator A2)Example 6: Preparation of CrV 3 O 3 (PO 4 ) 3 (catalyst A2)
In einen mit strömenden Stickstoff gespülten Glasreaktor gab man 2,5 L Wasser, 272,8 g V2O5 [> 99 %, 3 Mol, berechnet als V] (GfE Umwelttechnik GmbH, Nürnberg, Deutschland), 100,0 g CrO3 [>99%, 1 Mol, berechnet als Cr] (Sigma Aldrich, Seelze, Deutschland) und 492,0 g H3PO3 [50 %, 3 Mol, berechnet als P] (Sigma Aldrich, Seelze, Deutschland). Man erwärmte diese Mischung unter kräftigem Rühren auf 90 °C und
rührte bei dieser Temperatur 2 Stunden. Unter einer Stickstoffatmosphäre wurde die so hergestellte Suspension über einen Sprühtrockner (Mobile Minor™ 2000, MM, der Fa. Niro A/S, Soborg, Dänemark, Eintrittstemperatur: 330 0C, Austrittstemperatur: 107 0C) getrocknet. Der erhaltene Feststoff wurde bei 775 0C zwei Stunden in Stickstoff- Atmosphäre in einem Quarzdrehrohr mit einem inneren Volumen von 1 L calciniert.Into a glass reactor purged with flowing nitrogen was added 2.5 L of water, 272.8 g of V 2 O 5 [> 99%, 3 mol, calculated as V] (GfE Umwelttechnik GmbH, Nuremberg, Germany), 100.0 g of CrO 3 [> 99%, 1 mole, calculated as Cr] (Sigma Aldrich, Seelze, Germany) and 492.0 g H 3 PO 3 [50%, 3 mol, calculated as P] (Sigma Aldrich, Seelze, Germany). This mixture was heated with vigorous stirring to 90 ° C and stirred at this temperature for 2 hours. The suspension thus prepared with a dryer under a nitrogen atmosphere (. Mobile Minor ™ 2000, MM, from Niro A / S, Soborg, Denmark, inlet temperature: 330 0 C, outlet temperature: 107 0 C). The solid obtained was calcined at 775 0 C for two hours in nitrogen atmosphere in a rotary quartz tube having an internal volume of 1 L.
Das erhaltene Pulver hatte eine spezifische Oberfläche nach BET von 1 ,0 m2/g. Vom erhaltenen Pulver wurde ein Pulverröntgendiffraktogramm aufgenommen. Aus dem Pulverröntgendiffraktogramm wurden die folgenden 2Θ-Werte mit den dazugehörigen Intensitäten I und Netzebenabständen d ermittelt.The resulting powder had a BET specific surface area of 1.0 m 2 / g. From the obtained powder, a powder X-ray diffractogram was taken. From the powder X-ray diffractogram, the following 2Θ values with the associated intensities I and wattage spacings d were determined.
Beispiel 7: Herstellung von FeV3O3(PO4)S (Katalysator A3)Example 7: Preparation of FeV 3 O 3 (PO 4 ) S (Catalyst A3)
In einen mit strömenden Stickstoff gespülten Glasreaktor gab man 6,0 L Wasser, 750,0 g V2O5 [> 99 %, 8,25 Mol, berechnet als V] (GfE Umwelttechnik GmbH, Nürnberg, Deutschland), 257,1 g FeOOH [95%, 2,75 Mol, berechnet als Fe] (Sicopur® Gelb, BASF, Deutschland) und 475,4 g H3PO4 [85 %, 4,12 Mol, berechnet als P] (Sigma Aldrich, Seelze, Deutschland) und 676,2 g H3PO3 [50 %, 4,12 Mol, berechnet als P] (Sigma Aldrich, Seelze, Deutschland). Man erwärmte diese Mischung unter kräftigem Rühren auf 90 °C und rührte bei dieser Temperatur 2 Stunden. Unter einer Stickstoffatmosphäre wurde die so hergestellte Suspension über einen Sprühtrockner (Mobile Minor™ 2000, MM, der Fa. Niro A/S, Soborg, Dänemark, Eintrittstemperatur: 330 °C, Austrittstemperatur: 107 °C) getrocknet. Der erhaltene Feststoff wurde zwei Stunden bei 600 °C und danach zwei Stunden bei 800 °C in Stickstoff-Atmosphäre in einem Quarzdrehrohr mit einem inneren Volumen von 1 L calciniert.In a glass reactor purged with flowing nitrogen was added 6.0 L of water, 750.0 g of V 2 O 5 [> 99%, 8.25 mol, calculated as V] (GfE Umwelttechnik GmbH, Nuremberg, Germany), 257.1 g FeOOH [95%, 2.75 mol, calculated as Fe] (Sicopur® Yellow, BASF, Germany) and 475.4 g H 3 PO 4 [85%, 4.12 mol, calculated as P] (Sigma Aldrich, Seelze, Germany) and 676.2 g H 3 PO 3 [50%, 4.12 mol, calculated as P] (Sigma Aldrich, Seelze, Germany). The mixture was heated with vigorous stirring to 90 ° C and stirred at this temperature for 2 hours. Under a nitrogen atmosphere, the suspension thus prepared was dried over a spray dryer (Mobile Minor ™ 2000, MM, from Niro A / S, Soborg, Denmark, inlet temperature: 330 ° C., outlet temperature: 107 ° C.). The resulting solid was calcined at 600 ° C for two hours and then at 800 ° C for two hours in a nitrogen atmosphere in a quartz rotary tube having an inner volume of 1 liter.
Das erhaltene Pulver hatte eine spezifische Oberfläche nach BET von 0,7 m2/g. Vom erhaltenen Pulver wurde ein Pulverröntgendiffraktogramm (Fig. 6) aufgenommen. Aus dem Pulverröntgendiffraktogramm wurden die folgenden 2Θ-Werte mit den dazugehörigen Intensitäten I und Netzebenabständen d ermittelt.
The resulting powder had a BET specific surface area of 0.7 m 2 / g. From the obtained powder, a powder X-ray diffractogram (Fig. 6) was taken. From the powder X-ray diffractogram, the following 2Θ values with the associated intensities I and wattage spacings d were determined.
B Katalysatortest der Katalysatoren A1 , A2 und A3 mittels selektiver Oxidation von n-Butan bzw. 1 -Buten in der GasphaseB catalyst test of the catalysts A1, A2 and A3 by means of selective oxidation of n-butane or 1-butene in the gas phase
Die Katalysatoren A1 , A2 bzw. A3 wurden in einer Tablettiermaschine zu Tabletten gepresst und anschließend zu Granalien (Splitt) mit einem Durchmesser im Bereich von 1 ,6 bis 2,0 mm zerkleinert.The catalysts A1, A2 and A3 were pressed into tablets in a tabletting machine and then comminuted to granules (chippings) with a diameter in the range of 1.6 to 2.0 mm.
Von unten nach oben wurden jeweils in einen Reaktor, bestehend aus einem Reaktionsrohr mit einer lichten Weite von 13 mm und einer Länge von 100 cm eine Vorschüttung von 5 cm Steatitkugeln mit einem Durchmesser von 2 mm und 85 cm SpNt des Katalysators A1 , A2 bzw. A3 eingefüllt. Bei den Versuchen zur Oxidation von 1 -Buten wurde der Katalysator mit 88 Vol.-% (A1), 75 Vol.-% (A2) bzw. 50 Vol.-% (A3) Inertma- terial (Steatitkugeln) abgemischt. Das Reaktionsrohr war zur Temperaturregelung mit einem Elektroheizmantel umgeben. Außerdem enthielt das Reaktionsrohr ein integriertes Thermoelement mit einem Durchmesser von 3,17 mm zur Temperaturmessung am Katalysator. Durch das Rohr wurde jeweils von oben nach unten ein Gasgemisch der Zusammensetzung n-Butan bzw. 1 -Buten - Luft (1 Vol.-% in Luft) geleitet. Die Gaspha- senoxidation erfolgte bei der in der nachstehenden Tabelle angegebenen Temperatur. Direkt nach dem Reaktor wurde gasförmiges Produkt entnommen und gaschroma- tographisch analysiert. Die erhaltenen Ergebnisse sind wie folgt:From bottom to top, in each case in a reactor consisting of a reaction tube with a clear width of 13 mm and a length of 100 cm, a feed of 5 cm steatite balls with a diameter of 2 mm and 85 cm SpNt of the catalyst A1, A2 or A3 filled. In the experiments on the oxidation of 1-butene, the catalyst was mixed with 88% by volume of (A1), 75% by volume (A2) or 50% by volume (A3) of inert material (steatite spheres). The reaction tube was surrounded for temperature control with a Elektroheizmantel. In addition, the reaction tube contained an integrated thermocouple with a diameter of 3.17 mm for temperature measurement on the catalyst. A gas mixture of composition n-butane or 1-butane-air (1 vol .-% in air) was passed through the tube from top to bottom. The gas phase oxidation took place at the temperature indicated in the table below. Directly after the reactor gaseous product was taken and analyzed by gas chromatography. The results obtained are as follows:
Selektivoxidation von 1 -ButenSelective oxidation of 1-butene
Selektivoxidation von n-Butan Selective oxidation of n-butane
Definitionen:definitions:
GHSV (GaS HoUrly Space VelθCity)= VEιngangsgasmιschungf/(VKatalysator t)GHSV (gas hourly space VelθCity) = V E ιngangsgasmιschungf / (V K atalysator t)
Umsatz X - (nκW,Reaktor eιn " fi KW, Reaktor aus)/n KW, Reaktor einSales X - (nκW, reactor ein "fi KW, reactor off) / n KW, reactor
Selektivität S - nMSA, Reaktor aus /(nκW,Reaktor eιn " fi KW, Reaktor aus)Selectivity S - nMSA, reactor off / (nκW, reactor eιn "fi KW, reactor off)
Ausbeute Y= X SY yield = X s
nMSA: Stoffmenge an produziertem Maleinsäureanhydrid [mol]nMSA: amount of produced maleic anhydride [mol]
ΠKW: Stoffmenge Kohlenwasserstoff am Reaktoreingang bzw. Reaktorausgang [mol]ΠKW: amount of hydrocarbon at the reactor inlet or reactor outlet [mol]
Vκataiysator: Schüttvolumen des Katalysators [L] t: Zeiteinheit [h]Vκataiysator: bulk volume of the catalyst [L] t: time unit [h]
VEingangsgasmischungf: auf 0 °C und 0,1013 MPa normiertes Volumen der Eingangsgasmi- schung [NL] (Rechnerische Größe. Liegt die Einganggasmischung oder ein Bestandteil davon unter diesen Bedingungen in der Flüssigphase oder fest vor, so wird über das ideale Gasgesetz das hypothetische Gasvolumen berechnet.)
Input gas mixture f: volume of input gas mixture [NL] normalized to 0 ° C and 0.1013 MPa (calculated size) If the inlet gas mixture or a component thereof is in the liquid phase or solid under these conditions, then the ideal gas law is the hypothetical gas volume calculated.)
Claims
1. Polynäres Metalloxidphosphat der allgemeinen Formel 1. Polynary metal oxide phosphate of the general formula
worinwherein
M für ein oder mehrere unter Ti, Zr, Hf, Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, AI, Ga und In ausgewählte Metalle steht,M is one or more metals selected from Ti, Zr, Hf, Cr, Fe, Co, Ni, Ru, Rh, Pd, Cu, Zn, B, Al, Ga and In,
a einen Wert von 0 bis 2,0 hat, b einen Wert von 2,0 bis 4,0 hat, c einen Wert von 2,0 bis 4,0 hat,a has a value of 0 to 2.0, b has a value of 2.0 to 4.0, c has a value of 2.0 to 4.0,
mit einer Kristallstruktur, deren Pulverröngtendiffraktogramm gekennzeichnet ist durch Beugungsreflexe bei den Netzebenenabständen d [Ä] = 3,30 ± 0,04, 3,16 ± 0,04, 2,57 ± 0,04, 2,02 ± 0,04, 1 ,65 ± 0,04, 1 ,59 ± 0,02, 1 ,58 ± 0,02.having a crystal structure whose powder X-ray diffraction pattern is characterized by diffraction reflectances at the interplanar spacings d [λ] = 3.30 ± 0.04, 3.16 ± 0.04, 2.57 ± 0.04, 2.02 ± 0.04, 1, 65 ± 0.04, 1, 59 ± 0.02, 1, 58 ± 0.02.
2. Metalloxidphosphat nach Anspruch 1 , wobei die Beugungsreflexe folgende relative Intensitäten aufweisen:2. Metal oxide phosphate according to claim 1, wherein the diffraction reflections have the following relative intensities:
3. Metalloxidphosphat nach Anspruch 1 oder 2, worin3. Metal oxide according to claim 1 or 2, wherein
a den Wert 0 oder einen Wert von 0,8 bis 1 ,2 hat, b einen Wert von 2,8 bis 3,2 hat, c einen Wert von 2,8 bis 3,2 hat.a is 0 or 0.8 to 1.2, b is 2.8 to 3.2, c is 2.8 to 3.2.
4. Metalloxidphosphat nach einem der Ansprüche 1 bis 3, worin M für ein unter Ti, Cr und Fe ausgewähltes Metall steht. The metal oxide phosphate according to any one of claims 1 to 3, wherein M is a metal selected from Ti, Cr and Fe.
5. Metalloxidphosphat nach Anspruch 4, der Formel5. Metal oxide according to claim 4, of the formula
CrV3O3(PO4)3 oder CrV 3 O 3 (PO 4 ) 3 or
6. Verfahren zur Herstellung eines polynären Metalloxidphosphats nach einem der Ansprüche 1 bis 5, bei dem man in einer Festkörperreaktion in einem geschlos- senen System wenigstens zwei Reaktanden umsetzt, die unter Sauerstoffverbindungen von Vanadium, Phosphorverbindungen von Vanadium und gemischten Sauerstoff-Phosphorverbindungen von Vanadium, elementarem Vanadium, Sauerstoffverbindungen des Metalls M, Phosphorverbindungen des Metalls M und gemischten Sauerstoff-Phosphorverbindungen des Metalls M und elementarem Metall M ausgewählt sind.6. A process for the preparation of a polynary metal oxide phosphate according to any one of claims 1 to 5, comprising reacting in a solid state reaction in a closed system at least two reactants selected from oxygen compounds of vanadium, phosphorus compounds of vanadium and mixed oxygen-phosphorus compounds of vanadium, elemental vanadium, oxygen compounds of the metal M, phosphorus compounds of the metal M and mixed oxygen-phosphorus compounds of the metal M and elemental metal M are selected.
7. Verfahren zur Herstellung eines polynären Metalloxidphosphats nach einem der Ansprüche 1 bis 5, bei dem man7. A process for the preparation of a polynary metal oxide according to any one of claims 1 to 5, wherein
a) ein Trockengemisch einer Vanadiumquelle, gegebenenfalls einer Quelle des Metalls M und einer Phosphatquelle herstellt,a) produces a dry mixture of a vanadium source, optionally a source of the metal M and a phosphate source,
b) dabei gegebenenfalls Reduktionsäquivalente bereitstellt, um das Vanadium und/oder das Metall M in den Wertigkeitszustand umzuwandeln, der dem Vanadium und dem Metall M in der Formel I zukommt, undb) optionally providing reduction equivalents to convert the vanadium and / or metal M to the valence state associated with the vanadium and metal M in formula I, and
c) das Trockengemisch bei wenigstens 500 0C calciniert.c) calcining the dry mixture at least 500 0 C.
8. Verfahren nach Anspruch 7, wobei die Reduktionsäquivalente von einem Reduk- tionsmittel bereitgestellt werden, das ausgewählt ist unter Hypophosphoriger8. The method of claim 7, wherein the reduction equivalents are provided by a reducing agent selected from hypophosphorous
Säure, Phosphoriger Säure, Hydrazin, Hydroxylamin, Nitrosylamin, elementarem Vanadium, elementarem Phosphor, Boran und Oxalsäure.Acid, phosphorous acid, hydrazine, hydroxylamine, nitrosylamine, elemental vanadium, elemental phosphorus, borane and oxalic acid.
9. Verfahren nach Anspruch 7 oder 8, wobei man das Trockengemisch herstellt, indem man die Vanadiumquelle, gegebenenfalls die Quelle des Metalls M, die9. The method of claim 7 or 8, wherein the dry mixture is prepared by the vanadium source, optionally the source of the metal M, the
Phosphatquelle und gegebenenfalls ein Reduktionsmittel in gelöster oder suspendierter Form mischt und die gemischte Lösung zum Trockengemisch trocknet.Phosphate source and optionally a reducing agent in dissolved or suspended form and the mixed solution is dried to dry mixture.
10. Verfahren nach Anspruch 9, wobei die Vanadiumquelle unter Divanadiumpent- oxid und Ammoniumvanadat ausgewählt ist. 10. The method of claim 9, wherein the vanadium source is selected from divanadium pentoxide and ammonium vanadate.
1 1. Verfahren nach Anspruch 9 oder 10, wobei die Quelle des Metalls M unter Oxiden, Hydroxiden und Oxidhydroxiden des Metalls M ausgewählt ist.A process according to claim 9 or 10, wherein the source of the metal M is selected from oxides, hydroxides and oxide hydroxides of the metal M.
12. Verfahren nach einem der Ansprüche 9 bis 1 1 , wobei die Phosphatquelle zumin- dest teilweise von Phosphoriger Säure oder Hypophosphoriger Säure gebildet wird.12. The method according to any one of claims 9 to 1 1, wherein the phosphate source is at least partially formed by phosphorous acid or hypophosphorous acid.
13. Verfahren nach einem der Ansprüche 9 bis 12, wobei das Trocknen zum Trockengemisch durch Sprühtrocknung erfolgt.13. The method according to any one of claims 9 to 12, wherein the drying is carried out to the dry mixture by spray drying.
14. Gasphasenoxidations-Katalysator, umfassend ein polynäres Metalloxidphosphat nach einem der Ansprüche 1 bis 5.14. A gas phase oxidation catalyst comprising a polynary metal oxide phosphate according to any one of claims 1 to 5.
15. Katalysator nach Anspruch 14, umfassend eine erste Phase und eine zweite Phase in Form dreidimensional ausgedehnter, abgegrenzter Bereiche, wobei die erste Phase eine katalytisch aktive Masse auf der Basis von Vanadylpyro- phosphat enthält und die zweite Phase ein polynäres Metalloxidphosphat nach einem der Ansprüche 1 bis 5 enthält.15. Catalyst according to claim 14, comprising a first phase and a second phase in the form of three-dimensionally extended, delimited areas, wherein the first phase contains a catalytically active composition based on vanadyl pyrophosphate and the second phase comprises a polynary metal oxide according to any one of claims 1 to 5 contains.
16. Katalysator nach Anspruch 15, wobei (i) feinteilige Partikel der zweiten Phase in der ersten Phase dispergiert sind, oder (ii) die erste Phase und die zweite Phase relativ zueinander wie in einem Gemenge aus feinteiliger erster Phase und fein- teiliger zweiter Phase verteilt sind.16. Catalyst according to claim 15, wherein (i) finely divided particles of the second phase are dispersed in the first phase, or (ii) the first phase and the second phase relative to each other as in a mixture of finely divided first phase and finely divided second phase are distributed.
17. Verfahren zur partiellen Gasphasenoxidation oder Ammonoxidation, bei dem man einen Gasstrom, der einen Kohlenwasserstoff und molekularen Sauerstoff enthält, mit einem Katalysator nach einem der Ansprüche 14 bis 16 in Kontakt bringt.17. A process for partial gas phase oxidation or ammoxidation, in which bringing a gas stream containing a hydrocarbon and molecular oxygen, with a catalyst according to any one of claims 14 to 16 in contact.
18. Verfahren nach Anspruch 17, zur Herstellung von Maleinsäureanhydrid, wobei der Kohlenwasserstoff mindestens vier Kohlenstoffatomen enthält. 18. The method of claim 17 for the preparation of maleic anhydride, wherein the hydrocarbon contains at least four carbon atoms.
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DE102007012725A DE102007012725A1 (en) | 2007-03-16 | 2007-03-16 | Polynary metal oxide phosphate |
PCT/EP2008/052950 WO2008113731A2 (en) | 2007-03-16 | 2008-03-12 | Polynary metal oxide phosphate |
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US8652988B2 (en) * | 2011-04-27 | 2014-02-18 | Celanese International Corporation | Catalyst for producing acrylic acids and acrylates |
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 |
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 |
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 |
GB201223473D0 (en) * | 2012-12-28 | 2013-02-13 | Faradion Ltd | Metal-containing compounds |
DE102017106912A1 (en) | 2017-03-30 | 2018-10-04 | Chemische Fabrik Budenheim Kg | Process for the preparation of Fe (II) P / Fe (II) MetP compounds |
DE102017106911A1 (en) | 2017-03-30 | 2018-10-04 | Chemische Fabrik Budenheim Kg | Use of water-free Fe (II) compounds as radiation absorbers |
DE102017106913A1 (en) | 2017-03-30 | 2018-10-04 | Chemische Fabrik Budenheim Kg | Process for the production of electrically conductive structures on a carrier material |
CN107617444A (en) * | 2017-09-30 | 2018-01-23 | 常熟理工学院 | Microwave-hydrothermal method prepares the multicomponent catalyst of pyromellitic acid dianhydride |
CN108479824A (en) * | 2018-03-08 | 2018-09-04 | 中触媒新材料股份有限公司 | A method of with Solid phase synthesis vpo catalyst |
CN109046412B (en) * | 2018-08-23 | 2021-05-25 | 常州新日催化剂股份有限公司 | Catalyst for preparing maleic anhydride by oxidizing n-butane and preparation method thereof |
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Publication number | Publication date |
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DE102007012725A1 (en) | 2008-09-18 |
WO2008113731A3 (en) | 2009-01-15 |
US20100105926A1 (en) | 2010-04-29 |
JP2010521402A (en) | 2010-06-24 |
WO2008113731A2 (en) | 2008-09-25 |
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