AU617387B2 - Metallic oxide powders, their mixtures, systems of mixed metallic oxide powders, their mixtures and their use for catalytic dehydration of hydrocarbons - Google Patents
Metallic oxide powders, their mixtures, systems of mixed metallic oxide powders, their mixtures and their use for catalytic dehydration of hydrocarbons Download PDFInfo
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- AU617387B2 AU617387B2 AU26193/88A AU2619388A AU617387B2 AU 617387 B2 AU617387 B2 AU 617387B2 AU 26193/88 A AU26193/88 A AU 26193/88A AU 2619388 A AU2619388 A AU 2619388A AU 617387 B2 AU617387 B2 AU 617387B2
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- 239000000843 powder Substances 0.000 title claims description 59
- 239000000203 mixture Substances 0.000 title claims description 52
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 23
- 230000018044 dehydration Effects 0.000 title claims description 17
- 238000006297 dehydration reaction Methods 0.000 title claims description 17
- 230000003197 catalytic effect Effects 0.000 title claims description 15
- 229930195733 hydrocarbon Natural products 0.000 title description 13
- 150000002430 hydrocarbons Chemical class 0.000 title description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 235000010215 titanium dioxide Nutrition 0.000 claims description 13
- 238000001725 laser pyrolysis Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- -1 vanadyl chloride Chemical compound 0.000 claims description 11
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- AHXGRMIPHCAXFP-UHFFFAOYSA-L chromyl dichloride Chemical compound Cl[Cr](Cl)(=O)=O AHXGRMIPHCAXFP-UHFFFAOYSA-L 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- 239000007767 bonding agent Substances 0.000 claims 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 40
- 238000004458 analytical method Methods 0.000 description 29
- 239000011651 chromium Substances 0.000 description 26
- 239000001282 iso-butane Substances 0.000 description 21
- 235000013847 iso-butane Nutrition 0.000 description 21
- 229940035415 isobutane Drugs 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 15
- 239000012159 carrier gas Substances 0.000 description 12
- 238000011084 recovery Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 230000009466 transformation Effects 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 235000013849 propane Nutrition 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- 229910010066 TiC14 Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 101100497923 Viola odorata Voc1 gene Proteins 0.000 description 2
- 238000004279 X-ray Guinier Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- 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
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
- 241001136792 Alle Species 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- 229910019929 CrO2Cl2 Inorganic materials 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 244000182067 Fraxinus ornus Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010218 electron microscopic analysis Methods 0.000 description 1
- JYLMMZCUGDOOEV-UHFFFAOYSA-N ethane ethene methane Chemical compound C.CC.C=C JYLMMZCUGDOOEV-UHFFFAOYSA-N 0.000 description 1
- AEFWNQIKCMUAQU-UHFFFAOYSA-N ethane ethene propane Chemical compound CC.C=C.CCC AEFWNQIKCMUAQU-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- KOKKJWHERHSKEB-UHFFFAOYSA-N vanadium(3+) Chemical compound [V+3] KOKKJWHERHSKEB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- B01J35/613—
Description
1 K OPI DATE 14/06/89 APPLN. ID 26193 88 V q Pm'
WEI
J DP 0 89 PCT NUMBER PCT/DE88/00683 INTERNATIONALE ANME INTERNATIONALE ZUSA? N E AqF t an 1 y t v wcomma gr w (51) Internationale Patentklassifikation 4 (11) Internationale Veriffentlichungsnumnmer: WO 89/ 04717 B01J 37/34, 37/02, C07C 5/32 Al (42) Internationales Verdffentlichungsdatum: 1. Juni 1989 (01.06.89) (21) Internationales Aktenzeichen: PCT/DE88/00683 D-4650 Gelsenkirchen (DE).
(22) Internationales Anmeldedatum: (74) Anwalt: LINDNER, Wolfgang; Alexander-von-Hum- November 1988 (05.11.83) boldt-Strage, D-4650 Gelsenkirchen (DE).
(31) Prioritiitsaktenzeichen: P37 39 002.3 (81) Bestimmungsstaaten: AT (europaisches Patent), AU, BE (europaisches Patent), CH (europhisches Patent), (32) Priorititsdatum: 17. November 1987 (17.11.87) DE (europtiisches Patent), FI, FR (europqisches Patent), GB (europdisches Patent), IT (europdisches Pa- (33) Prioritlitsland: DE tent), JP, LU (europHisches Patent), NL (europiisches Patent), NO, SE (europAisches Patent), US.
(71) Anmelder (fiur alle Bestimmungsstaaten ausser US): VE- BA OEL AKTIENGESELLSCHAFT [DE/DE]; Ale- Veriiffentlicht xander-von-Humboldt-Strage, D-4650 Gelsenkirchen Mit internationalem Recherchenbericht.
(DE).
(72) Erfinder;und Erfinder/ALimelder (nur fir US) SCHRAMM, Bernhard [DE/DE]; Langgewann 33, D-6900 Heidelberg KERN, Jilrgen [DE/DE]; Teichweg 10, D-6919 Bammental SCHWAHN, Harald [DE/DE]; Schlogstrage 68, D-6908 Wiesloch PREUSS, August-Wilhelm [DE/DE]; Riedweg 22, D-4270 Dorsten GOTYLIEB, Klaus [DE/DE]; Alte StraBe 59, D-5804 Herdecke BRUDERRECK, Hartmut [DE/DE]; Bdrenkampstraae (54) Title: METALLIC OXIDE POWDERS, THEIR MIXTURES, SYSTEMS OF MIXED METALLIC OXIDE POW- DERS, THEIR MIXTURES AND THEIR USE FOR CATALYTIC DEHYDRATION OF HYDROCAR-
BONS
(54) Bezeichnung: METALLOXIDPULVER, DEREN GEMISCHE, METALLMISCHOXIDPULVER, DEREN GEMI- SCHE UND DEREN VERWENDUNG BEI DER KATALYTISCHEN DEHYDRIERUNG VON KOH' ENWASSERSTOFFEN (57) Abstract Metallic ixide powders from the group chromium (III), titanium (IV) oxide, vanadium oxide, their mixtures or systems of mixed metallic oxide powders composed of two representatives'of the above-mentioned group, their mixtures and their use for the catalytic dehydration of hydrocarbons. The invention concerns new metallic oxide powders or their mixtures, new systems of mixed metallic oxides or their mixtures having advantageous properties, such as BET surface areas of 5 to 50 m 2 /g and particle diameters of 25 to 350 nm. These compounds hulp to increase the yield and selectivity of the manufacture of mono-olefines during catalytic dehydration of saturated hydrocarbons. The metallic oxide powders are produced by laser pyrolysis of mixtures of the vaporized metallic compounds chromyl chloride, titanium tetrachloride or vanadium tetrachloride in the presence of certain gases. The catalytic strength of the new metallic oxides has been investigated for uxample in the dehydration of isobutane.
(57) Zusammenfassung Metalloxidpulver aus der Gruppe Chrom(III)-oxid, Titan(IV)-oxid, Vanadin(V)-oxid, deren Gemische oder Metallmischoxidpulver aus 2 Vertretern der vorgenannten Gruope sowie deren Gemischen und deren Verwondung bei der katalytischen Dehydrierung von Koblenwasserstoffen. Es sollen neue Metalloxidpulver oder deren Gemischen, neue Metallmischoxide oder deren Gemische mit vorteilhaften Eigenschaften, u.a. BET Oberflichen von 5 bis 50 m 2 /g und Teilchendurchmessern von 25 bis 350 nm, zur Verfilgung gestcllt werden. Mit Hilfe der vorgenanaten Verbindungen sollen Umsatz und Selektivitat der Herstellung von Monoolefinen bei der katalytischen Dehydrierung gesdttigter Kohlenwasserstoffe gesteigert werden. Die Metalloxidpulver werden aus Gemischen der verdampften Metallverbindungen Chromylchlorid, Titantetrachlorid bzw. Vanadylchlorid in Gegenwart bestimmter Gase durch Laserpyrolyse hergesteilt. Die katalytische Wirksamkeit der neuen Metalloxide wurde am Beispiel der Dehydrierung von Isobutan untersucht.
j I I I I *T VERIFIED TRANSLATION OiV 9 1 Metallic Mixed Oxide Powders, their Mixtures, Metallic Oxide Powders and their Use in the Catalytic Dehydration of Hydrocarbons This invention relates to metallic mixed oxide powders as well as their mixtures, metallic oxide powders as well as their mixtures and their use ia the catalytic dehydration of branch-chain or branchless'saturated and unsaturated hydrocarbons with 2 to 6 carbon atoms or their mixtures at a temperature of 300 to 700 °C and a pressure of 0.1 to 20 bar, if necessary in the presence of hydrogen, S Q steam, oxygen or mixtures thereof.
The catalytic dehydration of hydrocarbons, particularly of short-chain hydrocarbons with 2 to 6 carbon atoms, is carried out in accordance with the standard method by means of adiabeticly feeding the hydrocarbons, which are pure or diluted with inert gas, through fixed bed reactors, which can be parallel-connected in groups.
Dehydration catalysers generally consist of aluminium oxide and additives such as for example chromic oxide or other metallic oxides or their mixtures (comp. DE- 36 14 2Q 854, DE 36 20 481, US 2,934,067 and US 2,419,997).
The preparation of this type of metallic oxides is carried out according to the standard method by means of evaporating the metallic nitrite solutions or by means of precipitating them, a ul ";SUBSTITUTE
PAGE
2 for example with aqueous ammonia solution. Suitable solutions of the metallic salts are frequently applied to support materials such as aluminium oxide.
For about 8 years various working groups have been involved in the analysis of ceramic powders which are prepared by means of a modern method; suitable gaseous parent compounds react under CO2 laser treatment with powdered solids.
The constituted powders have the following propertiessmall particle diameter, regular form, narrow distribution of particle sizes, high degree of purity, low degree of agglomeration and high surface activity (comp. Journal of the American Ceramic Society, Vol. 65, No. 7, 324 ff.).
In US 4,343,687, among other things, theepreparation of metallic oxide powders is described wherein suitable parent ccxpounds are treated with a pulsed IR-laser at a frequency which is not absorbed by the reaction mixture.
The thereby obtained products are to be suitable for catalytic purposes. According to this method a Cr 2 0 3 powder, for example, is prepared in a closed static cell on a support by means of a laser-induced reaction between chromyl chloride (Cr0 2 C12) as oxidizing agent and hydrogen as reactant, under reduced pressure by means of a chain reaction, generated by at least one laser impulse of 2 Joule/cm 2 STITUTEIP|GEi l-U SUBSTITUTE PACE ii AIT L
I
x: k PP: One object of the present invention consists in making available new metallic mixed oxides from chromic(III) o'xide and titanium(IV) oxide, chromic(III) oxide and vanadium(V) pentoxide or titanium(IV) oxide and vanadium(V) pentoxide or their mixtures and new metallic oxide powders or their mixtures with advantageous properties. Another object consists in increasing the transformation and selectivity in the preparation of mono-olefines in the catalytic dehydration of saturated hydrocarbons by means of the above mentioned compounds or their mixtures.
This tasks have been so.ved with the metallic mixed oxide powders according to the invention or their mixtures according to claim 1 or the metallic oxide powder according to claim 4 or their mixtures and their use as dehydration catalysts.
Qspec t The present invention 'i orne concerns metallic mixed oxide powders from' chromic(III) oxide and titanium(IV) oxide, chromic(III) oxide and vanadium(V) pentoxide, titanium('IV) oxide and vandium(V) pentoxide or their no+ ony mixtures. These new metallic mixed oxide powders differAfrom the basic mixtures of commercially available single oxides, but also from the mixtures of the metallic oxide powders, another aspec o-F which are included inAthe invention,too, namely chromic(I'II) oxide, titanium(IV) oxide, vanadium(V) pentoxide powders with a BET-surface of between 5 and m'/g and average particle d.iameters of between 25 and 350 nm.
SUBSTITUTE PAGE 4 ro« L^*si7 i., _II i_ The new metallic mixed oxide powders are prepared from mixtures of the evaporated metallic compounds, namely chromyl chloride and titanium tetrachloride, chromyl chloride and vanadyl chloride or titanium tetrachloride and vanadyl chloride (claim 1) and the new metallic oxide powders, namely chromic(III) oxide, titaniua(IV) oxide, vanadium(V) pentoxide powders,are prepared from each of the above mentioned separately evaporated volatile metallic compounds (claim 4).
The preparation of the metallic mixed oxide powders or metallic oxide powders from the above mentioned evaporated volatile metallic compounds is carried out in the presence of an inert gas, hydro en, nitrogen, .sulphur hexafluoride, oxygen or a mixture thereof by means of continuous laser pyrolysis at a pressure of 10 to 1000 mbar.
The invention is further concerned with the use of the above mentioned metallic mixed oxide powders or their mixtures as well as the use of a compound or a mixture of compounds selected_from.the group consisting of.-chromic (III) oxide, titanium(IV) oxide and vanadium(V) pentoxide powders for the catalytic dehydration of branched or straight chained, saturated or unsaturated hydrocarbons with 2 to 6 carbon atoms or mixtures thereof, at a temperature of between 300 and 700 OC' and a pressure of 0.1 to 20 bar.
T
0 SUBSTITUTE PAGE It is preferable to carry out the catalytic dehydration in the presence of hydrogen, steam, oxygen or of mixtures of them.
It is also preferable to apply the metallic mixed oxide powders, prescribed in the invention, or their mixtures in the presence of up to 90 weight per cent aluminium hydroxide powder in the form of formed bodies, prepared by means of a bonding for the catalytic dehydration of the listed hydrocarbons.
esl 0 The apparatus(depicted in Fig.l) used for the decomposition of the,gaseous parent compounds and the precipitation of the obtained solid products such as titanium(IV) oxide (TiO2), vanadium(V) pentoxide (V 2 0 5 as well as chromic(III) oxide (Cr 2 0 3 or metallic mixed oxide powders, consists of glass.
The laser beam enter the cell through NaCl-windows (1) and leaves the cell the same way, too, ending at a detector with a performance gauge The applied
CO
2 laser shows an emission spectrum with over 100 lines.
C02/ The applied permanent line laser shows a performance of 15 and generates 75 to 86 watt on the line at 984 cm 1 -l about 100 watt on the line at 945 cm and about 75 watt -1 on the line at 1042 cm At an overall performance of watt witho'ut focussing,the power density is about 3 2 4 2 3 x 10 watt/cm and with focussing about 3 x 10 watt/cm 2 'I .E (jjl SUBSTITUTE PAGE L i 'IIIII~L--~P~a-~ The gaseous educts pass from a slit-sha.ped or a perforated nozzle vertical to the laser beam.
Before the reaction the parent compounds in the reserve flask are cooled with dry ice/methanol to prevent premature evaporation. During the reaction the reserve flask has to be heated up slightly. The supply pipe to the -nozzle is heated up with a heating wire to prevent the condensation of the parent compound.
Without focussing the laser beam has a diameter of about 2 mm, with focussing a diameter of 0.5 to 0.7 mm.
A gas flow, consisting of an inert gas, hydrogen, nitrogen, sulphur hexafluoride or oxygen or a mixture of the above mentioned gases, is passed around the nozzle to maintain a laminar flow of the educts and products or to influence the reaction. At the NaCl-windows each additional gas is passed through leads and (10) to prevent the windows from collecting dirt from powders developing during the laser pyrolysis. According to the standard method, the total pressure is held at 50 mbar by means of regulating the rate of pumping and is checked on the pressure gauge (11).
At a total pressure in the range of between 10 and 1000 mbar a reaction can be obtained.
SUBSTITUTE PAGE TO^ The powder is collected on a membrane filter or in a fibre filter Condensable gases and un'transformed educt are frozen outin cooling ducts (13) fitted downstealm, and later rejected or used again after being recycled.
The laser beam is focussed with a ZnSe-convex lens with a focal distance of f 30 cm or a NaCl-convex lens with a focal distance of f 20 chi on one point over the nozzle.
In order to increase the output, a multipass cell is used in which the parent compound flo% passes the laser beam vertically several times. To the same end a cell is employed in which the laser beam passes through four places.of entry arranged in cross-shaped fashion,altgetheiour times in a horizontal plane through the same field over the nozzle.
In the following description the invention is further explained and the experiments for the preparation of Cr203, Ti0 2 as well as V 2 0 5 are described.
The breakdown of titanium tetrachloride (TiCI 4 in (he passage of) the argon-oxygenS aKs place in the above -1 described apparatus. TiCI 4 absorbs at 984 cm 1 However, the absorption of TiCI 4 on this line and in the whole emission spectrum of the CO 2 laser is low. A reaction with powder formation and a light pinkish violet flame' is obtained with the application of more heat to the.storage flask.
The recovery amounts to a few percent only.
a SUBSTITUTE PAGE ZV O The catalyst layer consisted of pellets which prepared as follows;
I
j o An X-ray diffractometer analysis demonstratedthat.the reaction product consists of both titanium dioxide modifica'tions, rutile and anatase.
TEM recordings show- that the developed particles are on-'an average 25 nm large and have a very narrow size distribution.
The breakdown of vanadyl chloride (VOC1 3 also takes place in the above .described apparatus. The ilradiation -i is carried out on a p-line of the laser at 1042 cm.
VOC1 3 absorbs the CO 2 laser beams better than TiC14, but still absorbs far less than CrO 2 C1 2 In the argon-oxygen str.eInm a continuous reaction with powder development and a fallow flame is possible.
The recovery of yellowish brown V205, however, only amounts to a few per cent.
Diffractometer analyses demonstrate that the developed V205 s X-ray amorphous. Disintegration on other lines is not possible.
Up to now, no continuous reaction iocLbe. obtained in the argon-hydrogen passage. A weak reaction with a small fallow flame supplied only a little black vanadium (III) than/ oxide with a .discovery of 1(ss:- one per cent.
CrO 2 C1 2 which can easily be evaporated, proved to be the most suitable chromium compound for the preparation of Cr203 as a catalyst. With conventional methods SUBSTITUTE PAGE i at temperatures of up to 380 C, the thermal breakdown of CrO 2 C1 leads mainly to the development of chromic (IV) oxide. A rise in temperature to over 400 0 C results in stable chromic (III) oxide and release of oxygen.
The CO2 laser line at 984 cm- is the most suitable one for the decomposition of CrO 2 C1 2 Pyrolysis is also possible on neighbouring lines.
If sulphur hexafluoride (SF is used as carrier gas the radiation for the development of Cr 20 3 can also be carried out on the absorption band of SF6 at 945 -i cm However, CrO 2 C1 2 does not break down under irradiation with CO 2 laser light with a wave number of 945 cm when a carrier gas different to SF is applied.
The CrO 2 Cl vapour absorbs 2 to 8 watt of the applied laser output.
The CrO 2 C1 2 partial pressure is 2 to 10 mbar.
Depending on the experimental conditions, 1.5 to 12 g Cr ?03 can be synthesised per hour.
SUBSTITUTE PAGE i( 1 During the decomposition of Cr0 2 C1 2 with an inert gas, nitrogen, oxygen, or SF, as carrier gas, the flame was orange and, depending on the experimental conditions, had a size of 3 to 20 mm and started 2 to 4 mm above the nozzle.
In experiments with pure hydrogen, the flame only burnt very irregularly, was a bright light yellow shade and started immediately at the opening of the nozzle or already in the nozzle. This made a longer continuous experimental run with the powder product difficult.
By means of diluting hydrogen with argon to a volume ratio of 1 8, a steady operation was possible.
In experiments with hydrogen and argon, it was possible, to transform nearly 100% of the Cr, 2 0; during experiments with argon alone, only 45 to of the nitrogen or oxygen could be transformed. During the experiments with SF, as carrier gas and absorber of the laser beams, only 30% of the CrO,C1 2 was transformed. Helium as carrier gas reduced recovery to about Constant wave laser irradiation of, eg., 100 to 1000 W is absorbed continuously in the gaseous metallic compounds, eg., CrO 2 Cl 2 or in an energy transmission gas, eg., SF 6 thereby producing a chemical reaction to the new oxides or mixed oxides.
Since the chemical reaction is maintained via the laser irradiation, the course of the reaction can be controlled in this manner that finer or coarser powder could be produced at will or more or fewer defects can also be achieved in the crystal lattice of the metallic oxide or metallic oxide mixture.
The analysis of the specific surface of the prepared Cr 2 0 3 powders was carried out in accordance with the BET-method. Commercial Cr, 2 0 has a surface of about 2 to 3 m2/g. All powders synthesised according to the present procedure showed increases in their specific surfaces by a factor of between 5 and SUBSTITUTE PAGE 11 The Cr, 2 0 obtained was characterized by means of Guinier's method of radiographic analysis. The lines of the film strip show the same elementary cell as commercial CrO, with the same measurements at the same line intensity ratio. According to a transmission electron microscopic analysis (TEM), the samples from the experiments with hydrogen and/or argon showed particle sizes significantly below 100 nm. This is also the reason, why broadened and diffuse lines were visible in the Guinier spectrum.
X-ray diffractrometric analysis and X-ray fluorescence analysis proved that the prepared powders consist of very pure Cr 2 0 3 Only the element chlorine was detectable in small quantities of 400 to 1500 ppm. The experiments with SF, as carrier and absorber gas only contained traces of sulphur ppm).
Also, by prepared (see fig.
means of IR-spectroscopy, it could be product, as prescribed in the invention, 2).
demonstrated that the was a very pure Cr 2 0s Scanning electron microscopic experiments (SEM) and transmission electron microscopic analyses (TEM) proved the narrow size distribution of the particles. The average particle sizes of various CrO, powders were between 50 and 350 nm.
OA
SUBSTITUTE PAGE i In comparison, commercial Cr203 was found to have an average particle size of 800 nm.
In ESR-experiments (electron spin resonance)' all synthesised powders, as prescribed in the invention, show different magnetic behaviour compared with commerci.lly available Cr 2 0 3 The mixed oxides, as prescribed in the invention, are prepared according to the following method:- The evaporated parent compounds are X-rayed with a
CO
2 permanent line laser, variable in frequence, while either the parent compound itself or SF 6 as auxiliary gas absorb the laser energy. The transformation lasting/ can be performed in a continuous operation st everal hours.
To this end, the formed. gases are continuously e.vacuatedi and the foaed.- powders are absorbed by filters.
In the experiments for the demonstration of mixed oxides a reserve flask, separated into b o chambers, is used.
Each chamb.er can be heated up separately to give the required partial pressure of each parent compound; and as a result, the mixing ratio of the gases can be freely chosen.
During the reaction, the reserve flask has to be heated up strealm/ slightly. Again, both evaporated compounds e from a shared nozzle through the laser beam.
SUBSTITUTE PAGE I According to this method, for the preparation of a mixed 'oxide from, 3 /Ti02, CrO 2 Cl2 and TiC]I are evaporated at the same time with an inert gas as carrier gas and transformed in the laser beam. The use of other carrier gases such as for example nitrogen, oxygen or hydrogen is also possible. Cr02Cl2 is the oxygen supplier for the development of Ti0 2 Ihe irradiation is carried out on the combined absorption line of Cr0 2
C
I 2 and TiC 1 at 98 cm" Pyrolysis is also possible on neighbouring lines.
Under these conlitions, a continuous reaction with a production of powder and .a flame is possible, which corresponds to the reaction during the decomposition of pure CrO 2 Cl2. No reaction is possible on other lines of the"CO 2 laser.
Lae to the optionally adjustable gas compound, oxides with a broad mixing ratio can be prepared. At a mixing ratio of for example CrO2Cl2 to TiC14 of 3 to 17 a mixed oxide with a total recovery of about is obtained.
An X-ray fluorescence analysis has shown chromium and main components.
The IR-spectrum (pee fig. 3) shows the characteristic and 300 cm"1 and clearly demonstrates.
titanium to be the bands between 1200 SUBSTITUTE PAGE
I
that the new Cr 2
OQ
3 /TiO 2 mixed oxide has .a dif ferei~t structure to the commercial mixture of Cr 2 0 3 and Ti 9 2 or even to the mixture of Cr 0 and TiO as p r e zc riJb e d fA\i.~ I Vrxe. O~her OjSer-'rc e ereJ 2 3. 21 i--th- invention.
The.
X-ray diff ractometer analysis see f ig 4) clearly shows broadened bands whic .h are attributable to Cr 23 Bands of a Tio2 modification cannot be iscerned!nt to the fact that titanium atoms have replaced the position occupied by the ciircmi9. atcrns in the Cr 2 0j structure.
For. the preparation of Cr 203/2 05 itrsC 2 Cl2 and VOCl 3 are simultaneously transformed in the laser beam, whereby an inert gas also serves as carrier gas.
As prescribed in the inveiition, both' transformation and recbvery iii the dehydration of saturated ,Showed an increase hydrocarbons/with a low number of carbon using metallic mixed oxide powders, prepared by means of laser pyrolysis,or using mixtures of metallic mixed oxide powders as'well as metallic oxide powders or their mixtures.
In. the fo-iloying it. is shown that. from~ the comoleted formed bodies.
rTepared.- from CRB 2 0 3 in accordance with the invention, higher* recovery and transforn~ti~i- values are obtained, for exaniple, in_..he dehran of. Isobutane in..cpmzparison with. the application of.- conmercia~ly acqiuired C.R. as the. catal-yst.
SUBSTITE PAGE L a) At a temperature of 593 OC and a pressure of 300 mbar, isobutane was passed through a tube reactor, in which a catalyst was fixed in position.' In each case the reaction time was 10 minutes. The load was 2 g isobutane per gramme catalyst and hour.
The catalyst layer consisted of a given quantity of 3 x Limm.large. catalyst pellets, which were prepared as follows; units of weight of sodium potassium silicate are added to 97.5 units of weight of Cr 2 0 3 out of which, by means of adding water, a readily.spreadable: paste is prepared. From this paste formed bodies of 3 x 4 mm are prepared. These pell-ts are dried at 150 °C for several hours and subsequently calcined at 550 OC'for 3 hours.
After the reaction a spraying with nitrogen follows, then the regeneration of the catalyser by means of burning it down in a nitrogen/oxygen mixture.
The reaction products were gas-chromatographically analyzed at the reactor exit. By means of burning down the catalyser with air, the carbon, deposited on the.
catalyseri was analyzed as CO 2 on the infrared analyzer.
SUBSTITUTE PAGE A. Commercial,conventionally prepared Cr 2 0 3 (Comparative test) Application isobutane 99.9 weight per cent Result of the GC and infrared-analysis at the reactor exit GC-Analysis Methane 0.09 weight per cent Propane 0.01 weight per cent Propene 0.20 weight per cent Isobutane 99.09 weight per cent n-Butane 0.01 weight per cent Isobutylene 0.57 weight per cent
H
2 0.02 weight per cent Infrared-Analysis Carbon 0 weight per cent Transformation (mol 1 Selectivity (mol 73 0utput (Recovery) (mol 1 B. Preparation of Cr 2 0 3 by means of laser pyrolysis in a hydrogen inert gas mixture as carrier gas Application Isobutane 99.9 weight per 'cent Result of the GC and infrared analysis at the ieactor exit SUBSTITUTE PAGE i t~ GC-Analysis Methane Ethane Ethene Propane Propene Isobutane n-Butane Butylene-1 Isobutylene t-Butylene-2 c-Butylene-2 Butadiene-1,3 Hydrocarbons
C
5
H
2
CO
0.92 0.28 0.16 0.41 1.11 58.23 0.09 0.15 33.84 0.28 0.19 0.14 0.12 1.88 0.7 weight weight weight weight weight weight weight weight weight weight weight weight weight weight weight per per per per per per per per per per per per per per per cent qent cent cent cent .'cent cent cent cent cent cent cent cent cent cent Ifrared Analysis Carbon 1.53 weight per cent Transformation (mol Selectivity (mol Output (Recovery) (mol b) In the same apparatus as used in isobutane was dehydrated at a temperature of 593 OC and a pressure of 300 mbar. Again, the reaction time was 10 minutes, whilst the catalyst load was only 0.5. g isobutane per gramme catalyst and hour.
SSUBSTITUTE
PAGE
i i The catalyst layer consisted of pellets, which where prepared as follows; units of weight of chromic oxide powder are well mixed with 85 units of weight of aluminium hydroxide.
units of weight of sodium potassium silicate are added to 97.5 units of weight of the above mixture and an,easy-to-spread paste,. is prepared by S adding more water.
From this paste formed bodies of 3 x 4 mm are prepared. These pellets are dried at 150 OCfor several hours and then calcined at 550 OC for 3 hours.
The regeneration of the catalyst, as well as the analysis of the reaction products were carried out in a manner analogous to a).
A. Commercial,conventionally prepared Cr203 (Comparative test) Application Isobutane 99.9 weight per cent Result of the GC and infrared analysis at the reactor exit i S TI SUBSTITUTE PAGE
II
GC-Analysis Ethene Methane Propane Propene Iso butane Butylene-1 Isobutylene t-Butylene-2 c-lButylene-2 00 2 Butad-: ene-1.*3 0.*18 2 .83 0.11 1.87 84. 65 0.11 7.4 0.08 0.06 1.82 0.36 0.1 0.04 weight WE, i g h t.
we ight we ight we:.ght weight weight weight weight weight we ig ft we i. g h t weipht per cent ppr cent per cent per cent per cent per cent per cent per cent per cent per-cent per cent per cent Der cent Infrared Analysis Carbon Transformation Selectivit y Output (Recovery) 0.44 weight per cent B. Preparation of Cr 2 0 3 by means of laser pyrolysis in argon as carrier gas Application Isobutane 99.9 weight per cent Result of the GC and infrared analysis at the reactor exit SUBSTITUTE PAGE i I. GC-Analysis Methane 1.27 weight per cent Ethane 0.28 weight per cent Ethene 0.15 weight per cent Propane 0.5 weight per cent Propene 1.95 weight per cent Isobutane 53.89 weight per cent n-Butane 0.11 weight per cent Butylene-1 0.21 weight per cent Isobutylene 36.50 weight per cnt t- Butylene-2 0.29 weight per cent c-Butylene-2 0.20 weight per cent Butadiene-1.3 0.16 weight per cent Hydrocarbons C 5 0.03 weight per cent
H
2 2.74 weight per cent CO 0.3 weight per cent Infrared Analysis Carbon 1.93 weight per cent Transformation 46 0 Selectivity 82 Output (Recovery) 38 c) In the same apparatus as used in isobutane was dehydrated at a temperature of 566 OC and a pressure of 300 mbar. The reaction time was 10 minutes and the catalyser load 1 g isobutane per gramme catalyser and hour.
SUBSTITUTE PAGE IN§ i' r The catalyst layer consisted of pellets which prepared as folxows; The applied materials Cr 2 0 3 (61.5 weight per cent) 'and melamine (0.5 weight per cent) as pore forming materials and boehmite (3 weight per cent) (Pural SB, Fa. Condea) as bonding ,agent--- are intimately mixed dry in the weight ratios listed in the enclosure.
Under continuous stirring 1 M formic acid (35 weight per cent) is added to this'mixture until a well kneadable substance is obtained, from which the catalyst pellets, which are initially moistened with water, are prepared in a suitable mould.
The obtained formed bodies are dried in the nitrogen stream at 50 °C for 2 to 5 hours, then calcined at 550 °C for 5 hours and finally consist of weight per cent Cr203 and 5 weight per cent boehmite.
The regeneration of the catalyst as well as the analysis of the reaction product were carried out analogous o a).
A. Commercial,conventionally prepared Cr203 (Comparative test) Application Isobutane 99.9 weight per cent Result of the GC and infrared analysis at the reactor exit SUBSTITUTE PAGE I *1 GC-Analysis Methane Ethane Ethene, Pro pane Propene Isobu tane n-Butane Isobutylene t-Butylene-2 c-Butylene-2 0.22,weight 0.02 wei-ght 0. 02 w'eight 0.08 weight 0.35 weight 77.73 weight 0.02 weight 19.97 weight 0.07 weight 0.04 weight 1.22 weight 0.03 weight per per per per per per per per per per.
per per cent cent cent cent rent cent cent cent cent cent cent cent Infrared Analysis Carbon 0.25 weieht Der cent Transformation (rnol Selectivity (moJ. O u t put (Mecovery) (xnoJ B. Preparation of Cr 2 O0 3 by means of laser pyrolysis in nitrogen as carrier gas Application Isobutane 99.9 weight per cent Result of the GC and infrared analysis at the reactor exit
E
SUBSTITUTE PAC
SUBSTITUTE-PAGE
rr. ~'1 GC-Analysis Methane Ethane Ethene Pro pane Pro pene Isobutane n-Bu tane Butylene-1 Isobutylene t-]3utylene- 2 c-Butylene-2 Butadiene-1 .3.
Hydrocarbons >C 5 112
CO
Inf rared Analy-sis 0.88 weight per cent 0.22 weigh't per cent 0.12 weight iier cent 0.38 weight per cent 0.87 weight per cent 60.68 weight per cent 0.28 weight per cent 0.43 weight per cent 31.38 weight per cent 0.58 weight per cent 0.40 weight per cent 0.19 weight per cent 0.04 weight per cent 1.90 weight per cent 0.28 weight per cent 1.45 wigt percent Carbon Tran~formation (mol Selectivity (mol Output (Recoveiy) (mol C. Cr 2 0 3 prepared by means of laser pyrolysis in oxyge,n as carrier -ac Application I 'sobutane 99.9 weight per cent Result of the GC and infrared analysis at the reactor exit C SUBSTITUTE PAGE
V
GO-Analysis Me thane Ethane Ethene Pro pane Pro pene Isobutane n-Butane Butylene-1 Isobutylene t-Butylene-2 c-Butylene-2 Butadiene-1,3 Hydrocarbons H 2 C 2
CO
1.91 0. 56 0.15 0.93 1.17 46.51 0.30 0 .30 39 .37 0 .40 0.27 0.10 0.03 3.15 0.04 1 .08 weight per weigh t per weight per weight per weight per weight per weight per weight per weight per weight per weight per weight per weight per weight per weight per weight per cent cent rcent cent cent cent cent cent cent -cen t cent cent cent cent cent cent Infrared Analysis Carbon 4.02 wei54ht )er cent Transformation (mol Selectivity (mol Output '(Recovery. (ml %I ISUBSTITUTE PACE ~NTO Y r D. Cr 2 0 3 prepared by means of laser pyrolysis in oxygen as carrier gas' Pellets as under however saturated in.
KHCO
3 solution Application Isobutane 99.9 weight per cent Result of the:GC and infrared analysis at the reactor exit GC-Analysis Methane 1.20 weight per cent Ethane 0.79 weight per cent Ethene 0.08 weight per cent Propane 0.67 weight per cent Propene 0.96 weight per cent Isobutane, 46.44 weight per cent n-Butane 0.24 weight per cent Isobutylene 44.30 weight per cent t-Butylene-2 0.30 weight per cent c-Butylene-2 0.21 weight per cent Butadiene-1.3 0.10 weight per cent Hydrocarbons
C
5 0.03 weight per cent
H
2 2.56 weight per cent
CO
2 0.14 weight per cent CO- 0.48 weight per cent Infrared Analysis Carbon 2.05'weight per cent Transformation (mol 53 Selectivity (mol 86 Output (Recovery) (mol 46 SUBSTITUTE PAGE i
Claims (6)
1. Metallic mixed oxide powders from chromic(III) oxide, and titanium(IV) oxide, chromic(III) oxide and vanadium(V) pentoxide, titanium(IV) oxide and vanadiuia(V) pentoxide or their mixtures with a BET surface of between 5 and 50 m'/g and average particle diameters of between 25 and 350 nm, prepared from mixtures of the evaporated metallic compounds, namely chromyl chloride and titanium tetr.achloride, chromyl chloride and vanadyl chloride or titanium tetrachloride and vanadyl chloride in the presence of hydrogen, nitrogen, sulphur .hexafluoride', oxygen, a mixture of one of the above mentioned gases with an inert gas or of an-inertgasby means of continuous laser pyrolysis at a pressure of between and 1000 mbar.
2. Use of metallic mixed oxide powders or their mixtures according- to claim 1 for the catalytic dehydration of branched-chain or branchless saturated or unsaturated hydrocarbons with 2 to 6 carbon atoms or their mixtures at a temperature of 300 to 700 OC and a pressure of 0.1 to bar, if necessary in the presence of hydrogen, steam, oxygen or mixtures of them.
3. Use of metallic mixed oxide powders or their mixtures according to claim 2 in the presenct of up to 90 weight per cent alumin.ium hydroxide powder in the form of formed bodies, prepared by means of a bonding agent, qI, Ea SUBSTITUTE PAGE SL i ~fC' 2
4. Metallic oxide powders, namely chromic(III) oxide, titanium(IV) oxide, vanadium pentoxide powders with a BET surface of.5 to 50 m'/g and average particle diameters of 25 to 350 nm, prepared from evaporated chromyl chloride titanium tetrachloride or vanadyl chloride.in the presence of hydrogen, nitrogen, sulphur hexafluoride, oxygen, a mixture of one of the above mentioned gases with an inert gas or of an inert gas by means of continuous laser pyrolysis at a pressure of 10 to 1000 mbar.
Use of a representative or of a mixture of representatives of the group of chromic(III) oxide, titanium(IV) oxide, vanadium(V) pentoxide powders in accordance with claim 4 for the catalytic dehydration of branch-chain or branchless saturated or unsaturated hydrocarbons with 2 to 6 carbon atoms or their mixtures at .a temperature of 300 to 700 OC and a pressure of 0.1 to 20 bar, if necessary in the presence of hydrogen, steam, oxygen or of a mixture of them.
6. Use of a representative or a mixture of representatives of the group of chromic(III) oxide, titanium(IY) oxide, vanadium.(V) pentoxide powders in accordance with claim in the presence of up to 90 weight per cent aluminium hydroxide powder in the form of formed bodies, prepared by means of a bonding agent. 4P;E I- i
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873739002 DE3739002A1 (en) | 1987-11-17 | 1987-11-17 | METAL MIXED OXIDE POWDER, THEIR MIXTURES, METAL OXIDE POWDER AND THEIR USE IN THE CATALYTIC DEHYDRATION OF HYDROCARBONS |
| DE3739002 | 1987-11-17 | ||
| PCT/DE1988/000683 WO1989004717A1 (en) | 1987-11-17 | 1988-11-05 | Metallic oxide powders, their mixtures, systems of mixed metallic oxide powders, their mixtures and their use for catalytic dehydration of hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2619388A AU2619388A (en) | 1989-06-14 |
| AU617387B2 true AU617387B2 (en) | 1991-11-28 |
Family
ID=25861898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU26193/88A Ceased AU617387B2 (en) | 1987-11-17 | 1988-11-05 | Metallic oxide powders, their mixtures, systems of mixed metallic oxide powders, their mixtures and their use for catalytic dehydration of hydrocarbons |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU617387B2 (en) |
| NO (1) | NO174837C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4468474A (en) * | 1983-05-16 | 1984-08-28 | Allied Corporation | Iron/silicon-based catalyst exhibiting high selectivity to C2 -C62 Fischer-Tropsch reactions |
| US4668647A (en) * | 1985-05-20 | 1987-05-26 | Exxon Research And Engineering Company | Iron carbide-based catalyst produced in the presence of laser radiation |
| US4788222A (en) * | 1985-05-20 | 1988-11-29 | Exxon Research And Engineering Company | Method for the production of hydrocarbons using iron-carbon-based catalysts |
-
1988
- 1988-11-05 AU AU26193/88A patent/AU617387B2/en not_active Ceased
-
1989
- 1989-03-22 NO NO891268A patent/NO174837C/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4468474A (en) * | 1983-05-16 | 1984-08-28 | Allied Corporation | Iron/silicon-based catalyst exhibiting high selectivity to C2 -C62 Fischer-Tropsch reactions |
| US4668647A (en) * | 1985-05-20 | 1987-05-26 | Exxon Research And Engineering Company | Iron carbide-based catalyst produced in the presence of laser radiation |
| US4788222A (en) * | 1985-05-20 | 1988-11-29 | Exxon Research And Engineering Company | Method for the production of hydrocarbons using iron-carbon-based catalysts |
Also Published As
| Publication number | Publication date |
|---|---|
| NO174837B (en) | 1994-04-11 |
| NO891268L (en) | 1989-06-01 |
| AU2619388A (en) | 1989-06-14 |
| NO891268D0 (en) | 1989-03-22 |
| NO174837C (en) | 1994-07-20 |
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