CN101743059A - 用于由氯化氢的气相氧化制备氯气的催化剂和方法 - Google Patents
用于由氯化氢的气相氧化制备氯气的催化剂和方法 Download PDFInfo
- Publication number
- CN101743059A CN101743059A CN200880024513A CN200880024513A CN101743059A CN 101743059 A CN101743059 A CN 101743059A CN 200880024513 A CN200880024513 A CN 200880024513A CN 200880024513 A CN200880024513 A CN 200880024513A CN 101743059 A CN101743059 A CN 101743059A
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- China
- Prior art keywords
- catalyst
- uranium
- active component
- oxide
- hydrogen chloride
- Prior art date
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- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims abstract description 28
- 230000003647 oxidation Effects 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000460 chlorine Substances 0.000 title claims abstract description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 13
- 239000007789 gas Substances 0.000 title description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 23
- 239000012876 carrier material Substances 0.000 claims abstract description 15
- 150000003671 uranium compounds Chemical class 0.000 claims abstract description 13
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 claims abstract 3
- WZECUPJJEIXUKY-UHFFFAOYSA-N [O-2].[O-2].[O-2].[U+6] Chemical compound [O-2].[O-2].[O-2].[U+6] WZECUPJJEIXUKY-UHFFFAOYSA-N 0.000 claims description 24
- 229910000439 uranium oxide Inorganic materials 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 150000001224 Uranium Chemical class 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- -1 anatases) Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
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- 230000004044 response Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000007138 Deacon process reaction Methods 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000931705 Cicada Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 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
- 239000007788 liquid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229960002668 sodium chloride Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical compound [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- HPICRATUQFHULE-UHFFFAOYSA-J uranium(4+);tetrachloride Chemical compound Cl[U](Cl)(Cl)Cl HPICRATUQFHULE-UHFFFAOYSA-J 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/12—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/04—Preparation of chlorine from hydrogen chloride
-
- 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
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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Abstract
本发明涉及用于由氯化氢的催化氧化制备氯气的催化剂和方法。该催化剂包括活性组分和载体材料,该活性组分至少包括铀或铀化合物。该催化剂的特点在于高稳定性和活性以及与贵金属相比更低的成本。
Description
本发明涉及用于由氯化氢的催化氧化制备氯气的催化剂和方法。该催化剂包括活性组分和载体材料,其中该活性组分至少包括铀或铀化合物。该催化剂的特点在于高稳定性和活性以及与贵金属相比更低的成本。
大工业关注的反应是由Deacon在1868年开发的用氧气催化氧化氯化氢的方法:
过去,氯碱电解强烈排挤迪肯制氯法。几乎所有氯气的制备都是通过氯化钠水溶液的电解进行的[Ullmann Encyclopedia of industrialchemistry,seventh release,2006,第3页]。然而,近年来迪肯制氯法的吸引力再次升高,因为全球对氯气的需求比对氢氧化钠水溶液的需求增加得更快。这种发展非常有利于通过氯化氢氧化制备氯气的方法,其与氢氧化钠水溶液的制备是分开的。此外,氯化氢作为例如光气化反应中(例如异氰酸酯制备中)的联产物而大量获得。
氯化氢到氯气的氧化是平衡反应。随着温度的升高,该平衡位置向不利于所需的最终产物方向移动。因此有利的是使用具有尽可能高活性的催化剂,这使得该反应能在低温下进行。
在早至1965年的DE 1567788中描述了具有钌的催化活性组分的第一种用于氯化氢氧化的催化剂,在该实例中从RuCl3出发。
在DE-A 19748299中已经描述了具有由钌氧化物或混合钌氧化物构成的活性组分的其它的Ru基催化剂。在这种情况中,钌氧化物的含量为0.1重量%~20重量%,钌氧化物的平均粒径为1.0nm~100nm。
从DE-A 19734412中已知了其它的负载在钛氧化物或锆氧化物上的Ru催化剂。为了制备此处所述的包括选自二氧化钛和二氧化锆的至少一种化合物的氯化钌催化剂,列举了一系列Ru原料化合物,例如钌-羰基配合物、无机酸的钌盐、钌-亚硝酰基配合物、钌-胺配合物、有机胺的钌配合物或钌-乙酰丙酮化物配合物。在优选实施方式中,使用金红石形式的二氧化钛作为载体。
尽管已知的Ru催化剂已经具有相当高的活性,但对于在氯化氢氧化中的工业应用,希望进一步提高的活性和同时好的长期稳定性。反应温度的提高尽管会能够提高该Ru催化剂的活性,但在这些较高的温度下其容易烧结以及甚至由此失活。
已知铀氧化物适用作用于一系列完全和选择性氧化的氧化催化剂。使用铀基催化剂的典型实例是CO氧化为CO2,如例如由Campbell等人在J.Mollec.Cat.A:Chem.,(2006),245(1-2),62-68中所述。其它由含铀混合氧化物催化氧化的反应例如是异丁烯到丙烯醛的反应(Corberan等人,Ind.Eng.Chem.Prod.Res.Dev.,(1984),24,546,和1985,24,62)和丙烯到丙烯醛和丙烯腈的反应(US 3308151和US 3198750)。此外,VOC(挥发性有机化合物)在U3O8上的完全氧化也是已知的,其特别已经由Hutchings等人(Nature,(1996),384,第341页)进行了研究。然而,在这一点上,还没有公开铀化合物对于用氧气催化氧化氯化氢的适用性。
DE 1078100公开了包括存在于由高岭土、硅胶、硅藻土或浮石构成的惰性载体上的银、铀或钍的盐或氧化物的催化剂。其未公开煅烧该所得到的催化剂,因此预计所公开的催化剂具有低稳定性。其公开的组合物总是需要银和稀土元素的盐或氧化物存在。因此,由于缺乏进一步的公开,必须假定该技术教导是实现了共催化效果,该共催化效果以各个催化活性成分的相互作用才使得能实现反应。
这是有缺点的,因为银和稀土元素的盐或氧化物的同时使用导致该催化剂与没有这些组分的替代方式相比具有经济上不利的银。特别地,考虑到该贵金属连续提高的成本,银的使用在此处能够被认为是特别不利的。
因此本发明的目的是提供以高活性与好的长期稳定性和尽可能低成本实现氯化氢的氧化的催化剂。本发明的另一目的是提供使用这种催化剂用氧气催化气相氧化氯化氢的方法。
现在已经令人惊奇地发现铀基催化剂具有针对将氯化氢氧化到氯气的高活性和同时好的长期稳定性。同时,铀基催化剂提供了经济优点,因为其比现有技术中通常使用的物质更廉价。
因此本发明提供了用于氯化氢的催化氧化的催化剂,其特征在于其至少包括作为催化活性组分的铀或铀化合物和载体材料。
适用于该催化剂的载体材料是例如二氧化硅、氧化铝(例如α或γ-变体)、二氧化钛(以金红石、锐钛矿等形式)、二氧化锡、二氧化锆、二氧化铈、碳纳米管或它们的混合物。
适合的铀化合物例如是铀氧化物、氯化铀和氧氯化铀。适合的铀氧化物例如-但不局限于-UO3、UO2、UO或由混合产生的非化学计量相,例如U3O5、U2O5、U3O7、U3O8、U4O9和/或U13O34。
优选铀氧化物或具有UO2.1~UO2.9的化学计量组成的铀氧化物的混合物。
这些包括铀氧化物或铀氧化物的混合物作为催化剂的优选的催化剂是特别有利的,因为其令人惊奇地具有未曾预期的针对氧化反应的高活性和适用性。
在优选实施方式中,铀氧化物的前体也可以是氯化物化合物或氧氯化物化合物(UOxCly)。
该铀或铀化合物能够单独使用或与其它催化活性组分一起使用。适合的其它催化活性组分是选自包括以下的列表的那些:钌、锇、铑、铱、钯、铂、铜、银、金、铼、铋、钴、铁、锑、锡、锰和铬。同样适合的是其混合物或包括上述列表中的至少一种元素的化学化合物。在优选实施方式中,使用钌、金、铋、铈或Zr及其化合物。在非常优选的实施方式中,使用氧化形式的钌或作为氯化物化合物或作为氧氯化物化合物。
典型地,基于活性组分和载体材料的总质量,该活性组分的比例为0.1~90重量%范围,优选为1~60重量%范围,更优选为1~50重量%范围。
能够通过多种方法将该活性组分施加到该载体材料上。能够使用例如用存在于溶液中的适合的原料化合物或液体或胶体形式的原料化合物水法和湿法浸渍载体材料、沉淀和共沉淀方法、以及离子交换和气相涂覆(CVD、PVD)。能够通过例如将铀或铀化合物施加到该载体材料上并然后干燥或干燥和煅烧而得到适合的催化剂。
优选其中将活性组分以水溶液或悬浮液的形式施加到该载体材料上并然后除去该溶剂的催化剂。
特别优选用浸渍和随后的干燥/煅烧或用还原物质(优选氢气、氢化物或肼化合物)或碱性物质(优选NaOH、KOH或氨)沉淀的组合。
在另一实施方式中,能够将该活性组分以非氧化形式施加到该载体上并在反应过程中转化为氧化形式。
特别优选的是这样的催化剂,其特征在于将该催化活性组分作为在各种情况下单独或以任意混合物的铀的卤化物、氧化物、氢氧化物或氧卤化物、卤化铀酰、氧化物、氢氧化物、氧卤化物、硝酸盐、乙酸盐或乙酰丙酮化物的水溶液或悬浮液施加到该载体上并然后除去溶剂。
该催化剂可以包括促进剂作为其它组分。适合的促进剂包括碱性金属(例如碱金属、碱土金属和稀土金属);优选碱金属,特别是Na和Cs,和碱土金属;特别优选碱土金属,特别是Sr、Ba,和稀土金属Ce。该促进剂可以但并不限定于通过浸渍和CVD方法施加到该催化剂上;优选浸渍,特别优选在施加该催化主要组分之后。
该催化剂可以包括用于稳定活性组分的分散体的化合物作为其它组分。适合的分散体稳定剂例如是钪化合物、氧化锰和氧化镧。优选通过浸渍和/或沉淀和该活性组分一起施加该用于稳定该分散体的化合物。
该催化剂可以在标准压力下(或优选在降低压力下)在氮气、氩气或空气气氛中在40~200℃温度干燥。干燥时间优选为10min~6h。
能够使用未煅烧或煅烧形式的催化剂。该煅烧能够在还原、氧化或惰性相中进行;优选在空气流或氮气流中进行煅烧。典型地用在150~100℃(优选在200~1100℃的范围内)的温度范围在隔绝氧的条件下实现该煅烧。在存在氧化性气体的情况下,在150~1500℃,优选200~1100℃的温度范围进行煅烧。
在本发明的优选其它扩展方案中,可以将该包含铀或铀化合物的催化剂经过预处理。
该预处理典型地是在该反应物所用的工艺条件下的预处理。由于此处公开的催化剂优选用于用氧气对HCl的氧化中,因此优选用氧气和HCl的化学计量混合物进行预处理。特别优选用HCl和氧气的化学计量混合物在至少400℃,优选至少500℃进行预处理。该预处理典型地进行至少10h,优选至少50h,更优选至少100h。
该预处理能够在任何温度下进行任意长的时间。已经发现较长的和较热的预处理比较短的和较冷的预处理更好。较短的和较冷的预处理也是可以考虑的。问题是考虑反映在提高的活性上的在该预处理中支出的提高程度能够被这种活性提高再次弥补。因此,由此列举的该温度范围和持续时间应当被理解为是切合实际的建议而不是技术限制。
上述得到的催化剂的特点在于在低温下在氯化氢氧化中的高活性。在不束缚到某一理论的情况下,假定该铀氧化物形成“氧缺陷晶格位”,因此能够有效促进氧化还原循环。同时,铀氧化物对氯化氢具有高的稳定性。对于特别优选的铀氧化物或具有UO2.1~UO2.9的化学计量组成的铀氧化物混合物,这是特别正确的。
本发明进一步提供了在包括活性组分和载体材料的催化剂的存在下由氯化氢的催化氧化制备氯气的方法,其特征在于该活性组分包括铀或铀化合物。
当进行依照本发明的方法时,在上面已经描述的催化剂的存在下,在放热平衡反应中,用氧气将氯化氢氧化为氯气,其中产生水蒸气。该反应温度典型地为150~750℃,常规反应压力为1~25巴。由于这是平衡反应,因此合乎目的地在该催化剂仍具有足够活性的尽可能低温度下工作。而且,合乎目的地使用相对于氯化氢超化学计量量的氧气。例如,通常氧过量两倍到四倍。因为没有任何选择性损失的风险,因此在相对高的压力以及因此相对于标准压力较长的滞留时间工作是经济有利的。
该催化氯化氢氧化能够以以下方式进行:绝热或优选等温或近似等温;间歇但优选连续作为流化床或固定床方法,优选作为固定床方法,更优选在管束式反应器中在多相催化剂上;在180~750℃,优选200~650℃,更优选220~600℃的反应器温度下,在1~25巴(1000~25000hPa),优选1.2~20巴,更优选1.5~17巴,尤其2.0~15巴的压力下。
在其中进行该催化氯化氢氧化的常规反应装置包括固定床或流化床反应器。该催化氯化氢氧化优选也能在多阶段中进行。
在该绝热、等温或近似等温的操作模式下,也可以使用具有中间冷却的多个(即2~10个,优选2~6个,更优选2~5个,尤其2~3个)串联连接的反应器。该氯化氢能够全部与该第一反应器上游的氧气一起添加或者经不同反应器分开添加。各个反应器的这种串联连接也可组合在一个装置中。
适用于该方法的装置的另一种优选实施方式是使用其中该催化剂活性在流动方向上升高的结构化催化剂填料。催化剂填料的这种结构化能够通过用活性组分对催化剂载体进行不同浸渍或用惰性材料对该催化剂进行不同稀释而实现。所用的该惰性材料可以为例如二氧化钛、二氧化锆或它们的混合物、氧化铝、皂石、陶瓷、玻璃、石墨或不锈钢的环、圆筒或球。在优选使用催化剂成型体的情况下,该惰性材料应当优选具有相似的外部尺寸。
适合的催化剂成型体包括任何形状的成型体;优选片状、环状、圆柱形、星形、车轮形或球形;特别优选球形、环形、圆柱形或星形挤出物作为其形状。
能够在浸渍载体材料之后或优选之前将该催化剂成型。
单次通过中氯化氢的转化率能够优选限制为15~90%,优选40~85%,更优选50~70%。未转化的氯化氢在分离出来之后能够部分或全部循环到该催化氯化氢氧化中。在反应器入口处氯化氢与氧气的体积比优选为1∶1~20∶1,优选2∶1~8∶1,更优选2∶1~5∶1。
能够有利地使用该催化氯化氢氧化的反应热来产生高压水蒸气。这能够用于操作光气化反应器和/或蒸馏塔,尤其是异氰酸酯蒸馏塔。
后面的实施例解释本发明,但并不限制于此。
实施例
实施例1:在锡(IV)载体上的铀氧化物催化剂
在烧杯中,通过喷雾和随后的称重用二水合乙酸双氧铀(获自Riedel-de-Haen公司)的约10重量%水溶液浸渍2g氧化锡(IV)球体(获自Saint-Gobain公司,BET表面积44.6m2/g),以经计算得到在该载体上的2重量%U的载量。在等待时间60min之后,在空气流中在80℃将该催化剂干燥2h。在800℃在空气流中随后煅烧4小时,这提供了负载在氧化锡(IV)上的铀氧化物催化剂。
实施例2:在TiO2载体上的铀氧化物催化剂
在烧杯中,与实施例1类似地用二水合乙酸双氧铀(获自Riedel-de-Haen)的约10重量%水溶液浸渍2g二氧化钛(BET表面积8.8m2/g,获自Saint-Gobain),以经计算得到在该载体上的2重量%U的载量。在等待时间60min之后,在空气流中在80℃将该催化剂干燥2h。在800℃在空气流中随后煅烧4小时,这提供了负载在氧化钛(IV)上的铀氧化物催化剂。
实施例3:在α-Al2O3载体上的铀氧化物催化剂
在烧杯中,与实施例1类似地用二水合乙酸双氧铀(获自Riedel-de-Haen)的约10重量%水溶液浸渍2g α-Al2O3(BET为0.02m2/g,获自Saint-Gobain),以经计算得到在该载体上的2重量%U的载量。在等待时间60min之后,在空气流中在80℃将该催化剂干燥2h。在800℃在空气流中随后煅烧4小时,这提供了负载在α-氧化铝上的铀氧化物催化剂。
实施例4:在γ-Al2O3载体上的铀氧化物催化剂
在烧杯中,与实施例1类似地用二水合乙酸双氧铀(获自Riedel-de-Haen)的10重量%水溶液浸渍2gγ-Al2O3成型体(BET为260m2/g,获自Saint-Gobain)。在作用时间1h之后,在空气流中在80℃除去残余水达2h。重复该程序,直至在该成型体上存在12重量%的铀为止。
随后将该成型体在空气流中在800℃下煅烧4小时。
实施例5:在800℃煅烧的在Al2O3载体上的铀氧化物催化剂及分析
与实施例4类似,用铀浸渍40gγ-Al2O3成型体(BET为200m2/g,获自Saint-Gobain)并煅烧。
借助于XRD(SIEMENS D 5000θ/θ反射衍射仪)显示存在γ-Al2O3和U3O8。
实施例6-8:来自实施例1-3的催化剂在500℃用于HCl氧化中
将0.2g依照实施例1-3得到的催化剂磨碎并作为与1g石英砂(100-200μm)的混合物加入石英反应管(直径~10mm)中。
将该石英反应管加热到500℃,并然后在该温度下操作。
将80ml/min的HCl和80ml/min的氧气的气体混合物通过该石英反应管。在30分钟之后,将产物气流通入16重量%的碘化钾溶液中10分钟,用0.1N的硫代硫酸盐溶液返滴定由此生成的碘,以确定引入的氯气量。
这样给出了表1中所示的该催化剂在500℃的生产率。
实施例9:来自实施例4的催化剂在540℃用于HCl氧化中
对依照实施例4的催化剂进行类似实施例6-8的实验,只是现在将该石英反应管加热到540℃,并然后在该温度下操作。
这样给出了表2中所示的该催化剂在540℃的生产率。
实施例10:来自实施例4的催化剂在600℃用于HCl氧化中
对依照实施例4的催化剂进行类似实施例6-8的实验,只是现在将该石英反应管加热到600℃,并然后在该温度下操作。
这样给出了表2中所示的该催化剂在600℃的生产率。
表1:
实施例 | 依照实施例的催化剂 | 在500℃的生产率[kgCl2/kg催化剂*h] |
6 | 1 | 2.28 |
7 | 2 | 0.72 |
8 | 3 | 3.83 |
表2:
实施例 | 依照实施例的催化剂 | 在540℃的生产率[kgCl2/kg催化剂*h] | 在600℃的生产率[kgCl2/kg催化剂*h] |
9、10 | 4 | 5.93 | 9.53 |
Claims (13)
1.用于氯化氢的催化氧化的催化剂,其特征在于其至少包括作为催化活性组分的铀或铀化合物和载体材料。
2.权利要求1的催化剂,其特征在于该载体包括UO3、UO2、UO,或由这些物质的混合物得到的非化学计量相,例如U3O5、U2O5、U3O7、U3O8、U4O9、U13O34。
3.权利要求1或2的催化剂,其特征在于该铀或铀化合物以铀氧化物或具有UO2.1~UO2.9的化学计量组成的铀氧化物混合物的形式存在。
4.权利要求1~3中任一项的催化剂,其特征在于另外包括选自包括以下的列表的用作其它催化活性组分的物质:钌、锇、铑、铱、钯、铂、铜、银、金、铼、铋、钴、铁、锑、锡、锰和铬,或它们的混合物或包括上述列表中的至少一种元素的化学化合物。
5.权利要求1~4中任一项的催化剂,其特征在于该载体材料选自包括以下的列表:二氧化硅、氧化铝、二氧化钛、二氧化锡、二氧化锆、二氧化铈、碳纳米管或它们的混合物。
6.在包括活性组分和载体材料的催化剂的存在下由氯化氢的催化氧化制备氯气的方法,其特征在于该活性组分包括铀或铀化合物。
7.权利要求6的方法,其特征在于该铀或铀化合物以铀氧化物或具有UO2.1~UO2.9的化学计量组成的铀氧化物混合物的形式存在。
8.权利要求6或7的方法,其特征在于基于活性组分和载体材料的总质量,该活性组分的比例为0.1~90重量%范围。
9.权利要求6~8中任一项的方法,其特征在于反应温度为150~750℃。
10.权利要求6~9中任一项的方法,其特征在于反应压力为1~25巴。
11.权利要求6~10中任一项的方法,其特征在于其是等温或绝热地、连续和作为固定床方法进行的。
12.权利要求6~11中任一项的方法,其特征在于其是在具有中间冷却的串联的2~10个,优选2~6个,更优选2~5个,尤其为2~3个反应器中以多阶段进行的。
13.权利要求6~12中任一项的方法,其特征在于反应器入口处氯化氢与氧气的体积比为1∶1~20∶1,优选2∶1~8∶1,更优选2∶1~5∶1。
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DE102007033114A DE102007033114A1 (de) | 2007-07-13 | 2007-07-13 | Verfahren zur Herstellung von Chlor durch Gasphasenoxidation von Chlorwasserstoff |
DE200710033113 DE102007033113A1 (de) | 2007-07-13 | 2007-07-13 | Temperaturstabiler Katalysator für die Chlorwasserstoffgasphasenoxidation |
DE102007033113.6 | 2007-07-13 | ||
PCT/EP2008/005353 WO2009010182A1 (de) | 2007-07-13 | 2008-07-01 | Katalysator und verfahren zur herstellung von chlor durch gasphasenoxidation von chlorwasserstoff |
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CN200880024513A Pending CN101743059A (zh) | 2007-07-13 | 2008-07-01 | 用于由氯化氢的气相氧化制备氯气的催化剂和方法 |
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EP (2) | EP2178636A1 (zh) |
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CN112675834A (zh) * | 2021-01-12 | 2021-04-20 | 万华化学集团股份有限公司 | 一种铀基催化剂的制备方法、由其制备的催化剂和在氯化氢氧化制备氯气中的应用 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102000583A (zh) * | 2010-11-18 | 2011-04-06 | 烟台万华聚氨酯股份有限公司 | 一种氯化氢氧化制氯气的催化剂及其制备方法 |
CN102000583B (zh) * | 2010-11-18 | 2012-08-15 | 烟台万华聚氨酯股份有限公司 | 一种氯化氢氧化制氯气的催化剂及其制备方法 |
CN112675834A (zh) * | 2021-01-12 | 2021-04-20 | 万华化学集团股份有限公司 | 一种铀基催化剂的制备方法、由其制备的催化剂和在氯化氢氧化制备氯气中的应用 |
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US20100183498A1 (en) | 2010-07-22 |
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WO2009010182A1 (de) | 2009-01-22 |
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US7985395B2 (en) | 2011-07-26 |
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US20100202959A1 (en) | 2010-08-12 |
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