WO2011124824A1 - Procede d'oxydation selective de monoxyde de carbone - Google Patents
Procede d'oxydation selective de monoxyde de carbone Download PDFInfo
- Publication number
- WO2011124824A1 WO2011124824A1 PCT/FR2011/050692 FR2011050692W WO2011124824A1 WO 2011124824 A1 WO2011124824 A1 WO 2011124824A1 FR 2011050692 W FR2011050692 W FR 2011050692W WO 2011124824 A1 WO2011124824 A1 WO 2011124824A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrocarbon
- carbon monoxide
- catalyst
- reaction
- temperature
- Prior art date
Links
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 73
- 230000003647 oxidation Effects 0.000 title claims abstract description 58
- 230000008569 process Effects 0.000 title claims abstract description 53
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 51
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 90
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 90
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 76
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 26
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 239000011949 solid catalyst Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 96
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 239000007789 gas Substances 0.000 claims description 50
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 45
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 44
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 43
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 30
- 239000001294 propane Substances 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- 239000001301 oxygen Substances 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 20
- 229910052697 platinum Inorganic materials 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000008246 gaseous mixture Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- RLFXJQPKMZNLMP-UHFFFAOYSA-N 2-phenylprop-2-enenitrile Chemical compound N#CC(=C)C1=CC=CC=C1 RLFXJQPKMZNLMP-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 230000010354 integration Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 229910001868 water Inorganic materials 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 8
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- -1 acetic acid Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000001282 iso-butane Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 101100043112 Homo sapiens SERPINB3 gene Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 102100036383 Serpin B3 Human genes 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 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
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021065 Pd—Fe Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical class [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- 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
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14833—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds
- C07C7/14841—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/12—Liquefied petroleum gas
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the invention relates generally to the field of production of hydrocarbon derivatives from hydrocarbons in the gas phase in the presence of oxygen or an oxygen-containing gas. More specifically, the invention relates to a process for the selective oxidation of carbon monoxide to carbon dioxide present in a gaseous mixture comprising at least one hydrocarbon or a hydrocarbon derivative, and to its integration into a process for producing carbon monoxide. hydrocarbon derivatives.
- hydrocarbon derivatives are produced industrially by partial oxidation of a suitable hydrocarbon in the gas phase in the presence of molecular oxygen or a molecular oxygen-containing gas and a suitable catalyst.
- the main process for producing acrylic acid is based on the oxidation of propylene and / or propane.
- the synthesis of acrylic acid by oxidation of propylene has two stages, the first is the oxidation of propylene to acrolein and the second the oxidation of acrolein to acrylic acid. This synthesis is generally carried out in two reactors using two specific catalyst systems for each of the oxidation steps, the two stages being carried out in the presence of oxygen or an oxygen-containing gas.
- methacrolein and methacrylic acid are industrially produced by catalytic oxidation of isobutene and / or tert-butanol.
- Anhydrides such as maleic anhydride or phthalic anhydride, may be produced by catalytic oxidation of aromatic hydrocarbons such as benzene or ⁇ -xylene or straight chain hydrocarbons such as n-butane or butene.
- Acrylonitrile is produced by catalytic gas phase oxidation of propylene or propane by air in the presence of ammonia, such a reaction being known as ammoxidation.
- ammoxidation of isobutane / isobutene or methylstyrene leads to methacrylonitrile and atroponitrile, respectively.
- the selective oxidation catalyst for CO 2 in CO 2 is chosen from non-oxidizing catalysts with respect to the unreacted hydrocarbon present in the stream gaseous, generally catalysts based on mixed oxides copper-manganese or platinum-nickel, optionally supported on silica or alumina.
- the examples illustrating this process are carried out with a CO converter comprising a fixed bed of catalyst.
- the tests indicate a rate of 80% for the conversion of CO, but also a conversion of a part of propylene and propane, thus generating losses. of reagent in the process.
- Catalysts that can be used in this case for the selective oxidation of CO 2 in CO 2 are, for example, made of supported precious metal, such as platinum, rhodium, ruthenium , palladium.
- the CO converter is preferably of the tubular type in a fixed bed.
- Document EP 1 434 833 proposes, as a catalyst for the selective oxidation of CO 2 in CO 2 in a gaseous stream comprising at least one alkane, a catalyst substrate, such as Pt, Pd, Pt-Fe or Pd-Fe on a support.
- a catalyst substrate such as Pt, Pd, Pt-Fe or Pd-Fe on a support.
- silica provided with a substantially continuous coating of a molecular sieve material.
- the selective oxidation of CO is carried out in fixed bed at a chosen temperature so that the catalyst has no effect on the alkane.
- the selective oxidation of CO to C0 2 is carried out either at low space velocities SV (generally less than 10,000 h "l), the space velocity being defined as the ratio between reagent flow rate and catalyst volume, or as the inverse of "contact time", ie for low concentrations of CO input, in some cases it also leads to a simultaneous conversion of the hydrocarbon present in the gas.
- SV space velocities
- the space velocity being defined as the ratio between reagent flow rate and catalyst volume, or as the inverse of "contact time", ie for low concentrations of CO input, in some cases it also leads to a simultaneous conversion of the hydrocarbon present in the gas.
- hydrocarbon-based hydrocarbon-based hydrocarbon-based hydrocarbon-based hydrocarbon derivatives processes generally operate with low hydrocarbon levels to maintain the hydrocarbon content. reaction gas mixture outside the flammability range.
- EP 293 224 It has thus been proposed in EP 293 224 to add from 5 to 70% by volume of a saturated aliphatic hydrocarbon of 1 to 5 carbon atoms, such as methane, ethane or propane, for the reaction of propylene oxidation leading to acrolein in a process for producing acrylic acid by catalytic oxidation in two steps, the second step of oxidizing acrolein to acrylic acid.
- a saturated aliphatic hydrocarbon of 1 to 5 carbon atoms such as methane, ethane or propane
- this gaseous ballast has several advantages over a ballast of inert gases such as nitrogen or carbon dioxide.
- inert gases such as nitrogen or carbon dioxide.
- Cp specific heat
- it has a certain chemical inertness under the conditions where the propylene oxidation reaction is carried out and its possible reaction products are of a nature very similar to those of propylene.
- it makes it easier to satisfy the constraints of composition of the mixture related to the question of flammability by placing the reaction mixture above the upper limit of flammability.
- the feedstock supplying the propylene oxidation reactor may be larger in volume fraction, which increases the productivity of the conversion while controlling the hot spots within the catalyst bed and promoting thus the selectivity of the reaction.
- the problem that the present invention proposes to solve is to carry out the conversion of CO to CO 2 in a stream rich in hydrocarbons or a mixture of hydrocarbons, without, however, oxidizing these hydrocarbons.
- a start of selective CO conversion is possible, but soon a runaway of the reaction can occur which greatly increases the temperature of the catalyst and causes the conversion of other compounds present in the flow.
- the large amounts of CO present lead to an adiabatic increase in temperature, such that the conversion start temperatures (ignition temperatures) of all the constituents are exceeded.
- the exothermicity of the conversion reaction of CO to C0 2 is characterized by AHr of 283 kJ / mol.
- AHr is 341 kJ / mol for the conversion of propylene to acrolein
- the kinetics of the combustion reaction is much faster.
- a "conventional" technology of the multi-tubular reactor type does not then make it possible to properly control the catalyst temperature. Under conditions where the temperature can be controlled, the conversion of CO to CO 2 can be at a lower temperature than the oxidation temperature of the hydrocarbon, and thus it can be carried out selectively.
- the following table 1 illustrates the increase in the temperature of the gas during the combustion of 1000 ppm impurity in air.
- the Applicant has discovered that the use of a fluidized bed for converting CO to C0 2 in a hydrocarbon-rich stream makes it possible to solve the various problems mentioned above and to optimally satisfy the needs for the use of ballast. thermal and / or recycling of a reaction gas containing an excessively high CO content, in processes for the production of hydrocarbon derivatives by selective oxidation of hydrocarbons in the gas phase in the presence of oxygen, and more generally in the processes of production of hydrocarbon derivatives from hydrocarbons in the gas phase in the presence of oxygen.
- the subject of the present invention is therefore a process for the selective oxidation of carbon monoxide present in a gaseous mixture comprising at least one hydrocarbon or a hydrocarbon derivative, said process comprising the step of bringing said gas mixture into contact with a solid catalyst capable of oxidizing carbon monoxide to carbon dioxide at a chosen temperature, characterized in that said step is carried out in a fluidized bed.
- the fluidized bed technology ensures a mixing of the solid and the gaseous mixture, and thus a homogenization of the catalyst temperature. By obtaining a homogeneous temperature, it is possible to control the selectivity of the oxidation reaction carbon monoxide, and no longer destroy the valuable molecules. This homogeneity gives the fluidized bed an undeniable advantage over fixed beds which are generally subjected to a strong temperature gradient. The escape of the calories from the reaction can be provided by cooling pins arranged in the fluid bed. The heat transfer coefficient between the suspension and the exchanger tubes is very high, and allows to heat or cool the equipment effectively.
- the method of selective oxidation of CO according to the invention can be integrated in all industrial processes requiring a purge of CO 2 and / or CO for chemical reasons (inhibition of the reaction), physical (decrease in the Cp of the gas reaction), or for safety reasons (flammability limits).
- the invention also relates to a process for producing a hydrocarbon derivative comprising at least one step of selective oxidation of carbon monoxide present in a gaseous mixture comprising at least one hydrocarbon or a hydrocarbon derivative at the using a fluidized bed comprising a solid catalyst capable of oxidizing carbon monoxide to carbon dioxide at a selected temperature.
- the gaseous mixture subjected to the CO selective oxidation process according to the invention comprises at least one hydrocarbon or a hydrocarbon derivative.
- the hydrocarbons are saturated or mono or diunsaturated linear or branched hydrocarbons containing from 2 to 6 carbon atoms or aromatic hydrocarbons which may be substituted and contain from 6 to 12 carbon atoms.
- hydrocarbons examples include, for example, ethylene, propane, propylene, n-butane, isobutane, isobutene, butene, butadiene, isopentene, benzene, ⁇ -xylene. , methyl-styrene, naphthalene.
- the hydrocarbon is chosen from propylene or propane, alone or as a mixture.
- the hydrocarbon derivative may be a partial oxidation product of a hydrocarbon, and may be selected from anhydrides, such as phthalic anhydride and maleic anhydride, aldehydes such as acrolein or methacrolein, unsaturated carboxylic acids such as acrylic acid or methacrylic acid, unsaturated nitriles such as acrylonitrile, methacrylonitrile, atroponitrile or mixtures thereof.
- the hydrocarbon derivative is acrolein and / or acrylic acid.
- the hydrocarbon derivative may also be an oxygen adduct or a halogenated compound on an unsaturated hydrocarbon, for example, ethylene oxide, propylene oxide or 1,2-dichloroethane.
- Well-adapted catalysts are, for example, solids slightly loaded with platinum or palladium (for example of the order of 2%) on a support of silicalite or sodium silicate type.
- the catalyst used in the process according to the invention is in the form of solid particles having a particle size ranging from 20 to 1000 microns, preferably from 40 to 500 microns, more particularly from 60 to 200 microns.
- the particle size distribution can be done according to many methods, in particular according to a simple method such as sieving with a succession of sieves of decreasing mesh size, or laser diffraction determination for example with devices of the brand MALVERN.
- the temperature of the fluidized bed is between 20 ° C and 400 ° C, preferably between 70 ° C and 300 ° C, more preferably between 100 ° C and 230 ° C.
- a temperature below the temperature is chosen
- propylene there is generally at least about 20 ° C, and preferably at least 30 ° C, difference between the ignition temperature of the CO (start of CO combustion) and the ignition temperature of propylene. This gap is sufficient to ensure combustion of CO without having propylene combustion. If the ignition temperature of propylene is reached, the reaction becomes difficult to control because of the high oxygen content and propylene gas to be treated.
- the fluidized bed can operate in discontinuous (batch) or continuous (semi-batch or open) mode.
- the process according to the invention is carried out continuously. Indeed, given the ease of sampling and addition of solid particles in the fluidized bed during its operation, the solid phase can be renewed continuously if necessary.
- the catalyst bed can maintain a constant activity over time, if deactivated catalyst is continuously withdrawn and replaced with fresh catalyst.
- the emptying and cleaning of the fluidized beds is very easy as for a water tank.
- the rackings can be carried out continuously or with a certain periodicity.
- the deactivated catalyst can optionally be reactivated ex-situ by any appropriate technique, and then be reinjected into the reactor. Non-limiting catalyst reactivation techniques include redispersion of the catalyst metals by a reducing treatment, washing the catalyst to remove pollutants, or re-impregnating the catalyst with a fresh charge of the active metals of the catalyst.
- mild oxidation conditions are used, that is to say a combination of a weakly active catalyst (weakly charged with active metal), a moderate temperature (for example from 80 ° C. to 180 ° C.) and a short contact time (for example less than a second).
- a short residence time makes it possible to envisage a higher temperature for a given catalyst.
- a moderate pressure is used in the fluidized bed reactor, for example between 1 and 3 bars, and a relatively short residence time resulting in high space velocities.
- the linear velocity of the gaseous mixture in the fluidized bed can range from 0.1 to 80 cm / s. For fluidized beds of industrial size, it can go from 50 to 80 cm / s. In the case of fluidized beds of lower height, in particular fluidized laboratory beds, the linear velocity of the gases is most often between 0.1 and 10 cm / s.
- the flow rate of the gas flow will be adapted to the catalyst volume, therefore to the size of the reactor, so as to achieve very high SV space velocities, expressed in hourly volume volume of reactants relative to the volume of the reactor. catalyst.
- the process according to the invention is advantageously carried out with high SV space velocities, for example ranging from 1000 h -1 to 30000 h -1 , preferably greater than 10000 h -1 , or better still from 10000 h -1 to 30000 h "1.
- the process according to the invention is particularly suitable for gas streams containing more than 0.5 mol% of carbon monoxide entry into, and preferably more than 1 mol% of carbon monoxide.
- Another subject of the invention is a process for producing a hydrocarbon derivative comprising at least the following stages:
- At least one hydrocarbon and oxygen or oxygen-containing gas are contacted with a suitable catalyst leading to a gaseous mixture containing at least one hydrocarbon derivative, the unconverted hydrocarbon, the oxygen and carbon monoxide,
- the carbon monoxide present in the gaseous stream is converted into carbon dioxide by means of a fluidized bed comprising a solid catalyst capable of oxidizing carbon monoxide to carbon dioxide at a selected temperature, producing a gas stream depleted in carbon monoxide,
- step a) is carried out under appropriate conditions, especially with regard to the nature of the catalyst, the temperature and the possible presence of an inert gas as thermal ballast, according to the methods known to man. of the art, making it possible to manufacture the desired hydrocarbon derivative.
- the reaction carried out may be an oxidation reaction or an oxygen addition reaction on an unsaturated hydrocarbon.
- step a) is carried out in the presence of an inert thermal ballast under the conditions of the reaction implemented.
- Step b) consists of recovering the hydrocarbon derivative according to conventional methods using techniques such as absorption in a solvent and then extraction, distillation, crystallization, condensation.
- the gaseous stream largely freed from the hydrocarbon derivative generally comprising unconverted hydrocarbon, oxygen, water vapor, inert gases such as nitrogen and argon, carbon monoxide and carbon dioxide are contacted with a solid catalyst capable of oxidizing carbon monoxide to carbon dioxide at a selected temperature in a fluidized bed (step c) , leading to a depleted flow of carbon monoxide, which can be recycled, according to step d), to the reaction step a), optionally after having purged a portion of the carbon dioxide formed.
- a solid catalyst capable of oxidizing carbon monoxide to carbon dioxide at a selected temperature in a fluidized bed
- the process for producing a hydrocarbon derivative incorporating a step c) of selective oxidation of CO to C0 2 by means of a fluidized bed concerns the production of acrylic acid by catalytic oxidation of propylene using oxygen or a mixture containing oxygen and in the presence of propane as thermal ballast.
- the first step carries out the substantially quantitative oxidation of propylene to a mixture rich in acrolein, in which acrylic acid is a minor, and then, in the second step, the selective oxidation of acrolein to acrylic acid.
- the reaction conditions of these two stages, carried out in two reactors in series or in a single reactor containing the two reaction stages in series, are different and require catalysts adapted to the reaction; however, it is not necessary to isolate the first step acrolein during this two-step process.
- the reactor may be fed with a propylene feed of low purity, that is to say comprising propane such that the propane / propylene volume ratio is at least equal to 1.
- propane such that the propane / propylene volume ratio is at least equal to 1.
- the large propane gas ballast leading to better management of the exotherm of the reaction the reactor can be fed with a more concentrated load of propylene to increase the productivity of the process.
- the other components of the reactive stream may be inert compounds such as nitrogen or argon, water, and oxygen.
- the gaseous mixture resulting from the oxidation reaction of acrolein consists, apart from acrylic acid:
- incondensable light compounds under the conditions of temperature and pressure usually used: unconverted nitrogen, oxygen and propylene, propane present in propylene or added as thermal ballast, carbon monoxide and carbon dioxide formed in small quantities by ultimate oxidation or rotating in circles, by recycling, in the process,
- condensable light compounds in particular, water generated by the propylene oxidation reaction, unconverted acrolein, light aldehydes, such as formaldehyde and acetaldehyde, acids such as acetic acid, main impurity generated in the reaction section,
- the second stage of manufacture corresponding to step b) of the process according to the invention consists in recovering the acrylic acid contained in the gaseous effluent resulting from the oxidation reaction.
- This step can be performed by absorption against the current.
- the gas is introduced from the reactor at the bottom of an absorption column where it encounters a countercurrent solvent introduced at the top of the column.
- the light compounds under the conditions of temperature and pressure usually used (respectively more than 50 ° C. and less than 2.10 5 Pa) are eliminated at the head of this absorption column.
- the solvent used in this column is water.
- the water could be replaced by a hydrophobic solvent with a high boiling point, as described for example in the patents of BASF FR 2.146.386 or US 5.426.221, as well as in patent FR 96.14397.
- the gaseous reaction mixture is introduced at the bottom of the column at a temperature of between 130 ° C. and 250 ° C.
- the water is introduced at the top of the column at a temperature of between 10 ° C. and 60 ° C.
- the respective amounts of water and gaseous reaction mixture are such that the mass ratio water / acrylic acid is between 1 / let 1/4.
- the operation is conducted at atmospheric pressure.
- This crude acrylic acid is then subjected to a combination of stages which can differ by their sequence according to the process: dehydration eliminating water and formaldehyde (dehydrated acrylic acid), elimination of light (in particular acetic acid), elimination heavy, possibly elimination of certain impurities by chemical treatment.
- the gas stream leaving the previous step of extraction of acrylic acid by countercurrent absorption consisting mainly of unconverted propylene and oxygen, propane, CO and CO 2 , and other inert gases or minor minor impurities is contacted with a solid catalyst capable of oxidizing carbon monoxide to carbon dioxide at a selected temperature in a fluidized bed, resulting in a depleted flow of carbon monoxide, which can be recycled to the reaction stage , possibly after having purged some of the carbon dioxide formed.
- all or part of the gas stream exiting the carbon monoxide conversion unit to carbon dioxide is sent to a selective permeation unit to separate a first stream comprising mainly the inert compounds such as that CO, CO 2 , nitrogen and / or argon and a second stream comprising mainly propylene and propane.
- the permeation unit puts one or more semipermeable membranes having the ability to separate the inert from the hydrocarbons. This separation is generally carried out at a pressure of the order of 10 bars and at a temperature of about 50 ° C.
- membranes based on hollow fibers composed of a polymer chosen from: polyimides, cellulose-type polymers, polysulfones, polyamides, polyesters, polyethers, polyether ketones, polyetherimides, polyethylenes, polyacetylenes, polyethersulfones, polysiloxanes, polyvinylidene fluorides, polybenzimidazoles, polybenzoxazoles, polyacrylonitriles, polyazoaromatician and copolymers of these polymers.
- a polymer chosen from: polyimides, cellulose-type polymers, polysulfones, polyamides, polyesters, polyethers, polyether ketones, polyetherimides, polyethylenes, polyacetylenes, polyethersulfones, polysiloxanes, polyvinylidene fluorides, polybenzimidazoles, polybenzoxazoles, polyacrylonitriles, polyazoaromatician and copolymers of these polymers.
- Said second stream enriched with propylene and propane is advantageously recycled to the reaction stage without accumulation of CO 2 and other inert gas such as argon in the recycling loop.
- all or part of the gas stream entering the carbon monoxide conversion unit to carbon dioxide is previously sent to a selective permeation unit such as that described above, to separate at least a portion of CO 2 , the gas stream entering the CO converter is then depleted in CO 2 and unconverted oxygen.
- Oxidation tests of pure compounds were carried out using a catalyst from Johnson Matthey (2% Pt on CeO 2 ) in a molten salt bath reactor with an internal diameter of 25.4 mm and with a catalyst height of 30cm (ie 164g).
- the test consisted in following the conversion of the pure compound (conversion test where each constituent is tested individually) in a mixture of nitrogen and oxygen (3 mol%). For some tests, some of the nitrogen was replaced by water (20 mol%). The following concentrations (which represent the order of magnitude of the expected concentrations for each reagent in a real flow) were tested in conditions of SV 25,000 h -1 , determining the conversion of the compound as a function of temperature:
- Figures 1 and 2 reproduce the evolution of the oxidation of pure compounds as a function of temperature, respectively in the presence of water and in the absence of water.
- the conversion of CO is 100% for a temperature of 180 ° C. and the oxidation of propylene begins significantly at a temperature of 235 ° C.
- curve 1 corresponds to acrolein
- curve 2 to CO
- curve 3 to propylene.
- Example 2 (comparative) Example 1 is reproduced with the fixed bed of catalyst and a stream containing the mixture of compounds CO, CO 2 , propane, propylene, acrolein, water and oxygen with the following concentrations, in which it is desired to selectively oxidize CO to C0 2 :
- the temperature is not controlled: it is possible to measure a hot point where the temperature reached within the catalytic bed is at least 150 ° C higher than that of the oven. Consequently, this difference being much greater than that measured between the ignition temperatures of the pure substances, all the oxidation reactions are solicited at the same time, further increasing the overall exothermicity. Oxidation reactions are slowed down only when oxygen has been consumed.
- the test was repeated with a catalyst dilution of 90% by weight with inerts (silica-alumina beads from Saint-Gobain).
- the objective of the dilution of the catalyst is to reduce the catalytic activity of the reactor in order to better control its operating temperature.
- the reactor was filled with 10% by weight of the initial catalyst and 90% by weight of inert for an equivalent volume of catalyst + inert.
- the goal is also to distribute the calories of the oxidation reaction on a larger reaction volume. The calories of the reaction are removed by heat transfer through the wall, the inert solid provides a greater number of points of contact between the catalyst and the wall, and therefore should allow better control of the temperature in the catalyst bed.
- the difference in temperature between the hot spot of the catalytic bed and the temperature of the oven (or the temperature ignition of the oxidation reaction of CO) remains higher than the ignition temperature difference of CO and propylene.
- a catalyst is prepared by impregnating Puralox® SCCA 5-150 alumina from Sasol according to the following protocol:
- This alumina initially has grains whose median diameter is equal to about 85 ⁇ and has the surface characteristics and porosity indicated below:
- Example 2 is reproduced, but using a fluidized bed.
- Catalysts A and B are implemented in a fluidized bed, fed with a flow of composition described in Table 3 below, and preheated to 100 ° C. This flow ensures the fluidization of the catalyst.
- the total pressure in the reactor is 2.2 bar, with a linear gas velocity of 10 cm / sec.
- the products are collected at the outlet of the reactor and analyzed by chromatography after condensing the water.
- Example 5 The catalysts C, D and E defined below, are obtained in the form of granules, and were milled in a particle size less than 315 microns. 150 g of this powder are sieved to select the fraction between 80 and 160 microns.
- Catalyst C Catalyst ND-520 of NE Chemcat Pt / alumina, in the form of 3 mm beads, density 0.74 kg / l.
- Catalyst D NE Chemcat DASH 220 catalyst, 0.5% Pt / alumina, in the form of 3.2 mm granules, 100 m 2 / g specific surface area
- Catalyst E NE Chemcat ND103 catalyst, 0.5% Pd / alumina, in the form of beads 3 mm in diameter, 250 m 2 / g
- the fluidized bed consists of a stainless steel tube 41 mm in diameter and a total height of 790 mm.
- the fluidized bed is immersed in a fluidized sand bath, heated by electric elements installed inside the bath. Three thermocouples recorded the temperature gradient along the tube.
- a flow of molar composition described in Table 5 below was fed at a flow rate of 1760 ml / min (normal conditions), ie a linear gas velocity of about 2.2 cm / s, below a Porous metal plate that distributes gas through the reactor diameter.
- the total pressure in the fluidized bed is 1 bar and the temperature is maintained at about 100 ° C.
- the products are collected at the outlet of the fluidized bed and after having condensed ⁇ analyzed by liquid chromatography.
- Catalyst 0.5Pt (corresponding to 0.5% Pt and 0.5% Fe / on alumina Al 2 O 3 ) - bulk density 0.78 g / ml - average particle size 114 ⁇ .
- Catalyst 1.5Pt (corresponding to 1.5% Pt and 1.5% Fe / alumina Al 2 O 3 ) - bulk density 0.79 g / ml.
- Catalyst 2Pd (corresponding to 2% Pd / over zeolite D / UR from Engelhard / BASF) - well-known density 0.55 g / ml - average particle size 144 ⁇ .
- the first two catalysts were prepared according to the protocols below and the third catalyst is a catalyst marketed by BASF. The latter has been used as it is without any particular modification except prior drying.
- the catalysts for the selective oxidation of CO were prepared by impregnation of the precursors in solution (Pt and Fe salts) on Sasol Puralox SCCA 5-150 alumina. 1) In a first step, the catalysts for microfluidic bed tests were prepared by impregnation with incipient humidity.
- the platinum and iron salts as well as citric acid were weighed and dissolved in a beaker with water.
- the catalyst 0.5% Pt / 0.5% Fe / Alumina was prepared by mixing 0.049 g of citric acid, 0.0987 g of platinum (II) tetraamine hydrogen carbonate (at 50.6% Pt), 0.36 g of ferric nitrate hydrate, 8.10 g of water and 9.9 g of alumina.
- the total volume of the solution was calculated to be equal to the total pore volume of the support (0.87 ml / g).
- the solution was then gradually added to the support while stirring vigorously. This was completely integrated by the support and no liquid was detectable on the surface or between the particles.
- the resulting slurry was dried at 110-120 ° C for 24 h and then calcined in air for 2 hours at 485-520 ° C.
- the precursor solution and citric acid is fed dropwise over the support placed in a cylindrical quartz tube heated to 105-125 ° C and fluidized in air.
- the liquid flow rate was calculated and maintained at 0.5-1 ml / min.
- the injection nozzle was placed about 10 cm above the bed. Air was used as the fluidizing gas and the flow rate was adjusted to maintain a bubbling bed state as well as to prevent pneumatic transport of the particles.
- the solid thus obtained was dried for 24 hours at 120 ° C. and then calcined at 500 ° C.
- Example 7 Tests in a fluidized micro-reactor from the catalysts of Example 6
- a micro-reactor consisting of a quartz tube of 7 mm inner diameter in which 1 g of catalyst was placed on a sintered glass (20 ⁇ m) placed at middle of the tube acting as a dispenser.
- the entire assembly is computer controlled and it is possible to record all the relevant experimental parameters (temperatures, gas flow rates).
- the tests were carried out under 40 ml / min for 15 min. This corresponds to a space velocity SV of about 3000 h -1 .
- composition of the input gas fed to the micro-reactor is as follows:
- the temperature control was performed on the temperature of the furnace and not on that of the catalyst bed.
- the analysis of the gases at the outlet of the reactor was made by an in-line mass spectrometer.
- FIG. 3 is given by way of example and gives the composition of the exit gas after reaction as well as the evolution of the temperature of the catalytic bed. All realized experiments give the same type of profile with stationary levels. It is from these data that an average conversion has been calculated.
- Catalyst test reads at the beginning of the maximum furnace ° C X CO (%) X propylene (%) X propane (%) test (° C) of the bed (° C) (constant)
- Example 8 Tests in fluidized bed reactor.
- a larger fluidized bed allows tests on catalyst quantities of up to 300 g.
- the metal reactor is divided into two sections: a reactive section (diameter 3.5 cm, height 60 cm) and a zone of disengagement (diameter 4.5 cm, height 40 cm).
- the gases are fed and regulated via flow regulators. These allow to reach a maximum volumetric flow rate of 4L / min in this installation.
- the temperature is controlled by an external sand bath which ensures a good homogeneity of the temperature at the reactor.
- Four temperature measurement points were installed inside the reactor (two in the catalytic bed and two in the disengagement section).
- a valve was also installed on the exit line in order to be able to mount the reactor to the desired pressure.
- An HPLC type pump provides a constant flow of an aqueous solution of acrolein directly into the catalyst bed.
- An online mass spectrometer quantifies the products.
- a line heated to 110 ° C connects the mass spectrometer to the assembly and thus prevents any condensation of water. Filters installed on the line of exit prevent the particles from leaving the reactor and avoid the blocking of the lines.
- the tests were carried out on 150 g of 0.5Pt catalyst prepared according to Example 6.
- the volume flow rate of the gases was maintained at about 600 ml / min for 15 to 40 minutes (depending on the test and the stabilization time of the output concentrations) for the tests and for the argon purges to ensure good fluidification of the particles.
- Tables 9 and 10 summarize the results respectively for test 1 conducted under a pressure of 2.2 bar and test 2 conducted under a pressure of 1 bar.
- the duration of the reaction was adjusted to reach a steady state of the output concentrations.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Water Supply & Treatment (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
- Industrial Gases (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SG2012072641A SG184364A1 (en) | 2010-03-30 | 2011-03-29 | Process for the selective oxidation of carbon monoxide |
BR112012024627A BR112012024627A2 (pt) | 2010-03-30 | 2011-03-29 | processo de oxidação seletiva de monóxido de carbono |
US13/638,682 US20130131380A1 (en) | 2010-03-30 | 2011-03-29 | Process for the selective oxidation of carbon monoxide |
KR1020127028320A KR20130080434A (ko) | 2010-03-30 | 2011-03-29 | 일산화 탄소의 선택적 산화 방법 |
EP11720137A EP2553056A1 (fr) | 2010-03-30 | 2011-03-29 | Procede d'oxydation selective de monoxyde de carbone |
JP2013501910A JP5884128B2 (ja) | 2010-03-30 | 2011-03-29 | 一酸化炭素の選択酸化方法 |
CN2011800267977A CN102906233A (zh) | 2010-03-30 | 2011-03-29 | 一氧化碳的选择性氧化方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1052306 | 2010-03-30 | ||
FR1052306A FR2958185B1 (fr) | 2010-03-30 | 2010-03-30 | Procede d'oxydation selective de monoxyde de carbone |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011124824A1 true WO2011124824A1 (fr) | 2011-10-13 |
Family
ID=42941861
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2011/050692 WO2011124824A1 (fr) | 2010-03-30 | 2011-03-29 | Procede d'oxydation selective de monoxyde de carbone |
Country Status (9)
Country | Link |
---|---|
US (1) | US20130131380A1 (fr) |
EP (1) | EP2553056A1 (fr) |
JP (1) | JP5884128B2 (fr) |
KR (1) | KR20130080434A (fr) |
CN (1) | CN102906233A (fr) |
BR (1) | BR112012024627A2 (fr) |
FR (1) | FR2958185B1 (fr) |
SG (1) | SG184364A1 (fr) |
WO (1) | WO2011124824A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104043460A (zh) * | 2014-06-11 | 2014-09-17 | 华东理工大学 | 氧化镍负载钯催化剂的制备方法及在常温co催化氧化中的应用 |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104128192B (zh) * | 2014-07-14 | 2016-04-13 | 浙江工业大学 | 一种co低温催化氧化催化剂及其制备方法与应用 |
CN106715380B (zh) * | 2014-10-07 | 2020-12-15 | Lg化学株式会社 | 通过丙烷部分氧化反应连续制备丙烯酸的方法和设备 |
WO2016056851A1 (fr) * | 2014-10-07 | 2016-04-14 | 주식회사 엘지화학 | Procédé et appareil de fabrication d'acide acrylique en continu par l'intermédiaire d'une réaction d'oxydation partielle de propane |
CN106542993A (zh) * | 2015-09-17 | 2017-03-29 | 中国科学院大连化学物理研究所 | 丙烷一步氧化制备丙烯酸的系统及方法 |
CN107935836B (zh) * | 2016-10-13 | 2021-01-22 | 中国科学院大连化学物理研究所 | Co选择性氧化脱除方法、丙烷一步氧化制备丙烯酸的方法及系统 |
RU2724109C1 (ru) * | 2016-10-31 | 2020-06-22 | Публичное акционерное общество "СИБУР Холдинг" | Способ получения акриловой кислоты, способ селективного окисления монооксида углерода, катализатор селективного окисления монооксида углерода, способ его получения |
CN108212149A (zh) * | 2017-04-22 | 2018-06-29 | 天津大学 | 高分散型氧化钌催化剂及其制备方法和应用 |
JP6957020B2 (ja) * | 2017-12-21 | 2021-11-02 | 石福金属興業株式会社 | 白金粉末の製造方法および白金粉末を用いたペースト |
CN110292929A (zh) * | 2018-03-22 | 2019-10-01 | 中国科学院大连化学物理研究所 | 一种循环尾气中co选择性氧化脱除催化剂及其制备和应用 |
CN111974439B (zh) * | 2020-08-26 | 2023-03-28 | 国家能源集团宁夏煤业有限责任公司 | 负载型催化剂及其制备方法和应用 |
CN113318763B (zh) * | 2021-02-06 | 2022-05-17 | 南京工业大学 | 碳酸盐溶液制备负载型钯催化剂的方法 |
US11767276B2 (en) * | 2021-07-23 | 2023-09-26 | Ecocatalytic Inc. | Process for the removal of carbon monoxide from non-catalytic oxidative dehydrogenation product streams |
CN113617372B (zh) * | 2021-09-13 | 2023-10-27 | 中冶长天国际工程有限责任公司 | 一种高分散的co氧化催化剂及其制备方法和用途 |
US11685659B2 (en) | 2021-11-24 | 2023-06-27 | Uop Llc | Processes and apparatuses for reducing carbon monoxide levels in a gaseous stream |
CN115340067B (zh) * | 2022-08-29 | 2024-05-31 | 天津大学 | 利用金属氧化物进行co选择性氧化的系统和方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2146386A1 (fr) | 1971-07-21 | 1973-03-02 | Basf Ag | |
EP0293224A1 (fr) | 1987-05-27 | 1988-11-30 | Nippon Shokubai Co., Ltd. | Procédé pour la préparation de l'acide acrylique |
EP0484136A2 (fr) | 1990-10-31 | 1992-05-06 | The Boc Group, Inc. | Production de dérivés d'hydrocarbures |
EP0495504A2 (fr) | 1991-01-17 | 1992-07-22 | Sumitomo Chemical Company, Limited | Procédé pour la fabrication de l'acide méthacrylique par l'oxydation catalytique d'isobutane |
US5426221A (en) | 1993-03-13 | 1995-06-20 | Basf Aktiengesellschaft | Separation of acrylic acid from the reaction gases from the catalytic oxidation of propylene and/or acrolein |
EP1007499A1 (fr) | 1998-06-23 | 2000-06-14 | Pantochim S.A. | Procede a fort rendement de production d'anhydride maleique a partir de n-butane |
WO2003033625A2 (fr) * | 2001-10-13 | 2003-04-24 | Johnson Matthey Public Limited Company | Oxydation selective |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1041553A (fr) * | 1973-07-30 | 1978-10-31 | John P. Longwell | Production concurrente de methanol et de gaz natutel synthetique |
US5907076A (en) * | 1996-12-31 | 1999-05-25 | Exxon Chemical Patents Inc. | Process for selectively separating hydrogen, or both hydrogen and carbon monoxide from olefinic hydrocarbons |
US7524340B2 (en) * | 2001-07-11 | 2009-04-28 | May Walter R | Catalyst and method for improving combustion efficiency in engines, boilers, and other equipment operating on fuels |
CN1401429A (zh) * | 2001-08-13 | 2003-03-12 | 中国科学院兰州化学物理研究所 | 一种可燃气体完全氧化催化剂 |
CN1171677C (zh) * | 2001-12-25 | 2004-10-20 | 中国科学院大连化学物理研究所 | 一种用于甲醇重整气中微量一氧化碳选择氧化净化的贵金属催化剂 |
MXPA05011665A (es) * | 2003-05-09 | 2005-12-15 | Standard Oil Co | Reactor de lecho fluidizado con enfriador de gas. |
CN1579621A (zh) * | 2003-08-06 | 2005-02-16 | 中国科学院兰州化学物理研究所 | 消除一氧化碳催化剂及其制备方法 |
KR20080036960A (ko) * | 2005-06-01 | 2008-04-29 | 셀라니즈 인터내셔날 코포레이션 | 에테인의 에틸렌으로의 선택적 산화 방법 |
FR2897059B1 (fr) * | 2006-02-07 | 2008-04-18 | Arkema Sa | Procede de preparation d'acide acrylique |
CN101371985B (zh) * | 2007-08-23 | 2010-08-18 | 中国石油化工股份有限公司 | 一种脱除微量co的催化剂及其制备方法和应用 |
JP5204633B2 (ja) * | 2007-12-17 | 2013-06-05 | Jx日鉱日石エネルギー株式会社 | 一酸化炭素を選択的に酸化する触媒、一酸化炭素濃度を低減する方法および燃料電池システム |
-
2010
- 2010-03-30 FR FR1052306A patent/FR2958185B1/fr not_active Expired - Fee Related
-
2011
- 2011-03-29 JP JP2013501910A patent/JP5884128B2/ja not_active Expired - Fee Related
- 2011-03-29 KR KR1020127028320A patent/KR20130080434A/ko not_active Application Discontinuation
- 2011-03-29 BR BR112012024627A patent/BR112012024627A2/pt not_active IP Right Cessation
- 2011-03-29 SG SG2012072641A patent/SG184364A1/en unknown
- 2011-03-29 EP EP11720137A patent/EP2553056A1/fr not_active Withdrawn
- 2011-03-29 CN CN2011800267977A patent/CN102906233A/zh active Pending
- 2011-03-29 WO PCT/FR2011/050692 patent/WO2011124824A1/fr active Application Filing
- 2011-03-29 US US13/638,682 patent/US20130131380A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2146386A1 (fr) | 1971-07-21 | 1973-03-02 | Basf Ag | |
EP0293224A1 (fr) | 1987-05-27 | 1988-11-30 | Nippon Shokubai Co., Ltd. | Procédé pour la préparation de l'acide acrylique |
EP0484136A2 (fr) | 1990-10-31 | 1992-05-06 | The Boc Group, Inc. | Production de dérivés d'hydrocarbures |
EP0495504A2 (fr) | 1991-01-17 | 1992-07-22 | Sumitomo Chemical Company, Limited | Procédé pour la fabrication de l'acide méthacrylique par l'oxydation catalytique d'isobutane |
US5426221A (en) | 1993-03-13 | 1995-06-20 | Basf Aktiengesellschaft | Separation of acrylic acid from the reaction gases from the catalytic oxidation of propylene and/or acrolein |
EP1007499A1 (fr) | 1998-06-23 | 2000-06-14 | Pantochim S.A. | Procede a fort rendement de production d'anhydride maleique a partir de n-butane |
WO2003033625A2 (fr) * | 2001-10-13 | 2003-04-24 | Johnson Matthey Public Limited Company | Oxydation selective |
EP1434833A2 (fr) | 2001-10-13 | 2004-07-07 | Johnson Matthey Public Limited Company | Oxydation selective |
Non-Patent Citations (2)
Title |
---|
M.P. LOBERA ET AL., CATALYSIS TODAY, vol. 157, 2010, pages 404 - 409 |
UNKNOWN AUTHOR: "Fluidized bed reactor", 1 November 2007 (2007-11-01), XP002606266, Retrieved from the Internet <URL:http://en.wikipedia.org/wiki/Fluidized_bed_reactor> [retrieved on 20101021] * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104043460A (zh) * | 2014-06-11 | 2014-09-17 | 华东理工大学 | 氧化镍负载钯催化剂的制备方法及在常温co催化氧化中的应用 |
Also Published As
Publication number | Publication date |
---|---|
CN102906233A (zh) | 2013-01-30 |
FR2958185B1 (fr) | 2012-04-20 |
JP2013523432A (ja) | 2013-06-17 |
FR2958185A1 (fr) | 2011-10-07 |
JP5884128B2 (ja) | 2016-03-15 |
KR20130080434A (ko) | 2013-07-12 |
US20130131380A1 (en) | 2013-05-23 |
SG184364A1 (en) | 2012-11-29 |
EP2553056A1 (fr) | 2013-02-06 |
BR112012024627A2 (pt) | 2016-05-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2011124824A1 (fr) | Procede d'oxydation selective de monoxyde de carbone | |
EP3137417B1 (fr) | Procédé de réformage sec d'au moins un alcane. | |
EP1874720B1 (fr) | Procede de preparation d'acide acrylique a partir de glycerol | |
EP0820806A1 (fr) | Procédé et descriptif pour le fonctionnement d'une colonne à bulles triphasique avec application en synthese fischer-tropsch | |
EP2193114B1 (fr) | Procede de fabrication d'amines par hydrogenation de composes nitriles | |
FR2525212A1 (fr) | Procede de transformation catalytique d'alcanes en aldehydes insatures | |
FR2832649A1 (fr) | Composites a base de nanotubes ou nanofibres de carbone deposes sur un support active pour application en catalyse | |
CA2817684A1 (fr) | Procede de preparation d'un catalyseur mettant en oeuvre une etape de sechage rapide et son utilisation pour la synthese fischer-tropsch | |
EP2632883B1 (fr) | Procédé d'obtention d'acroléine par déshydratation catalytique de glycérol ou de glycérine | |
EP0377364B1 (fr) | Procédé et catalyseur d'oxychloration, leur application à la production du 1-2 dichloroéthane | |
WO2006040442A1 (fr) | Procede d'oxydation par l'oxygene d'hydrocarbures cycliques satures | |
FR2851246A1 (fr) | Procede de fabrication d'oxyde d'ethylene | |
JP4933047B2 (ja) | カルボン酸アルケニルの製造方法 | |
FR2880346A1 (fr) | Procede de preparation d'acide acrylique a partir du propane en absence de vapeur d'eau | |
EP0876210B1 (fr) | Procede de preparation de catalyseurs d'ammoxydation pour reacteur a lit fluidise ou a lit transporte | |
RU2356881C2 (ru) | Способ получения, по меньшей мере, одного продукта частичного окисления и/или аммокисления углеводорода, выбранного из группы, включающей акролеин, метакролеин, акриловую кислоту, метакриловую кислоту, акрилонитрил и метакрилонитрил | |
TW202415448A (zh) | 用於烯烴乙醯氧基化的催化劑 | |
EP0000460B1 (fr) | Catalyseurs à base d'argent et leur utilisation pour la production d'oxyde d'oléfines | |
WO2011051621A2 (fr) | Procédé et dispositif de production de dérivés d'alcènes | |
WO2008007014A1 (fr) | Procede de synthese d'aldehyde leger par oxydation catalytique de l'alcool correspondant en presence de methane | |
BE568481A (fr) | ||
FR2509722A1 (fr) | Procede d'oxydation catalytique, en phase vapeur, de la methacroleine en acide methacrylique par de l'oxygene moleculaire | |
FR2766835A1 (fr) | Procede de conversion d'hydrocarbures legers gazeux en hydrocarbures superieurs | |
EP1701791A1 (fr) | Procede de traitement des melanges methane/dioxyde de carbone | |
BE489637A (fr) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180026797.7 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11720137 Country of ref document: EP Kind code of ref document: A1 |
|
REEP | Request for entry into the european phase |
Ref document number: 2011720137 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011720137 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 8543/DELNP/2012 Country of ref document: IN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013501910 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13638682 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20127028320 Country of ref document: KR Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012024627 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112012024627 Country of ref document: BR Kind code of ref document: A2 Effective date: 20120927 |