EP3801840A1 - <sup2/>? <sub2/>?x?catalyseur comprenant une zeolithe de type structural afx de tres haute purete et au moins un metal de transition pour la reduction selective de no - Google Patents
<sup2/>? <sub2/>?x?catalyseur comprenant une zeolithe de type structural afx de tres haute purete et au moins un metal de transition pour la reduction selective de noInfo
- Publication number
- EP3801840A1 EP3801840A1 EP19724197.9A EP19724197A EP3801840A1 EP 3801840 A1 EP3801840 A1 EP 3801840A1 EP 19724197 A EP19724197 A EP 19724197A EP 3801840 A1 EP3801840 A1 EP 3801840A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fau
- catalyst
- zeolite
- weight
- transition metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 163
- 239000010457 zeolite Substances 0.000 title claims abstract description 136
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 126
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 71
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 70
- 230000009467 reduction Effects 0.000 title claims abstract description 17
- 101100311330 Schizosaccharomyces pombe (strain 972 / ATCC 24843) uap56 gene Proteins 0.000 title 1
- 101150018444 sub2 gene Proteins 0.000 title 1
- 239000007787 solid Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 21
- 238000005342 ion exchange Methods 0.000 claims abstract description 21
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 18
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 18
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 18
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000012736 aqueous medium Substances 0.000 claims abstract description 7
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 76
- 239000010949 copper Substances 0.000 claims description 64
- 229910052802 copper Inorganic materials 0.000 claims description 50
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 41
- 239000011541 reaction mixture Substances 0.000 claims description 41
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 31
- 229910052742 iron Inorganic materials 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 21
- 239000011734 sodium Substances 0.000 claims description 20
- 229910052684 Cerium Inorganic materials 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 229910052758 niobium Inorganic materials 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims description 16
- 150000001340 alkali metals Chemical class 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- -1 nitrogenous organic compound Chemical class 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- CNCVKEUDSJBBSZ-UHFFFAOYSA-N hexane 1-methylpiperidine Chemical compound CCCCCC.CN1CCCCC1 CNCVKEUDSJBBSZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003344 environmental pollutant Substances 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 10
- 231100000719 pollutant Toxicity 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- VQNZPBUYTUEQBF-UHFFFAOYSA-N heptane 1-methylpiperidine Chemical compound CCCCCCC.CN1CCCCC1 VQNZPBUYTUEQBF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 239000010955 niobium Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- WIBNQMPNRVCVFL-UHFFFAOYSA-N 1-methylpiperidine pentane Chemical compound CCCCC.CN1CCCCC1 WIBNQMPNRVCVFL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 239000012071 phase Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 125000001477 organic nitrogen group Chemical group 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 135
- 238000006243 chemical reaction Methods 0.000 description 39
- 239000000243 solution Substances 0.000 description 35
- 239000000499 gel Substances 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 22
- 239000007789 gas Substances 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 241000894007 species Species 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 230000000977 initiatory effect Effects 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000010531 catalytic reduction reaction Methods 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 238000004876 x-ray fluorescence Methods 0.000 description 5
- FYIYCWCMIMXVTP-UHFFFAOYSA-N CCCCC.C[NH+]1CCCCC1.[OH-].[OH-].C[NH+]1CCCCC1 Chemical compound CCCCC.C[NH+]1CCCCC1.[OH-].[OH-].C[NH+]1CCCCC1 FYIYCWCMIMXVTP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000001272 nitrous oxide Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- RCBGBBAUJDMVAY-UHFFFAOYSA-M 1,3-bis(1-adamantyl)imidazol-1-ium hydroxide Chemical compound [OH-].C12(CC3CC(CC(C1)C3)C2)[N+]1=CN(C=C1)C12CC3CC(CC(C1)C3)C2 RCBGBBAUJDMVAY-UHFFFAOYSA-M 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000037452 priming Effects 0.000 description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- GVOQNVKDQMWHPF-UHFFFAOYSA-N CCCCCCC.C[NH+]1CCCCC1.[OH-].[OH-].C[NH+]1CCCCC1 Chemical compound CCCCCCC.C[NH+]1CCCCC1.[OH-].[OH-].C[NH+]1CCCCC1 GVOQNVKDQMWHPF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Definitions
- the invention relates to a process for the preparation of a catalyst based on a zeolite of structural type AFX and at least one transition metal, the catalyst prepared or capable of being prepared by the process, and its use. for the selective catalytic reduction of NOx in the presence of a reducing agent, in particular on internal combustion engines.
- the selective catalytic reduction is achieved by a reducing agent, generally ammonia, and can thus be designated NH 3 -SCR.
- a reducing agent generally ammonia
- the ammonia (NH 3 ) involved in the SCR process is usually generated via the decomposition of a aqueous solution of urea (AdBlue or DEF), and product N 2 and H 2 O during the reaction with NOx.
- Zeolites exchanged with transition metals are used in particular as catalysts for NH 3 -SCR applications in transport.
- Small-pore zeolites, particularly copper-exchanged chabazites, are particularly suitable. They exist commercially in the form of silico-aluminophosphate Cu-SAPO-34 and aluminosilicates Cu-SSZ-13 (or Cu-SSZ-62). Their hydrothermal behavior and their NOx conversion efficiency make them the current references. However, the standards being more and more constraining, the performance of the catalysts still needs to be improved.
- the application US 2016/0137518 describes a quasi-pure zeolite AFX, its synthesis from sources of silica and alumina in the presence of a structuring agent of type 1, 3-Bis (1-adamantyl) imidazolium hydroxide, the preparation a transition metal-exchanged zeolite AFX catalyst and its use for NFI3-SCR applications. No particular form of AFX zeolite is mentioned.
- application US 2018/0093259 discloses the synthesis of zeolites with small pores, such as the zeolite of the structural type AFX, from zeolite of FAU type in the presence of a structurant, such as 1,3-bis (1 - adamantyl) imidazolium hydroxide and an alkaline earth metal source. It also presents applications of the zeolite of AFX structural type obtained, in particular the use of this zeolite as a NOx reduction catalyst, after exchange with a metal such as iron.
- a structurant such as 1,3-bis (1 - adamantyl) imidazolium hydroxide and an alkaline earth metal source.
- the application US 2016/0096169A1 discloses the use in the NOx conversion of a catalyst based on a zeolite AFX structural type having a Si / Al ratio of 15 to 50 exchanged with a metal, the zeolite AFX being obtained from a structuring agent of type 1, 3-Bis (1-adamantyl) imidazolium hydroxide.
- the results obtained, in the conversion of NOx show in particular a selectivity of the catalysts prepared according to US 2018/0093259 and US 2016/0096169 to nitrous oxide not exceeding 20 ppm.
- JP 2014-148441 describes the synthesis of a solid related to an AFX zeolite, in particular an SAPO-56 comprising copper usable for the reduction of NO x .
- the solid is synthesized and then added to a mixture comprising an alcohol and a copper salt, the whole being calcined.
- the copper is therefore added after the formation of the SAPO solid which is related to the AFX structural type zeolite.
- This traded solid appears to have increased resistance to the presence of water.
- Ogura et al. show the very good activity of a copper-exchanged zeolite SSZ-16 relative to other zeolite structures, even after hydrothermal aging.
- WO 2017/080722 discloses a direct synthesis of a zeolite comprising copper. This synthesis requires starting from a zeolite of structural type FAU and using a complexing agent TEPA and an element M (OFI) x to result in different types of zeolites, mainly of the CFIA type. Zeolites of the ANA, ABW, PHI and GME type are also produced.
- TEPA complexing agent
- OFI element M
- a catalyst based on a zeolite of AFX structural type prepared according to a particular mode of synthesis and of at least one transition metal, in particular copper exhibited interesting performances of conversion of NO x and of selectivity towards N 2 0.
- the NOx conversion performances, in particular at low temperature (T ⁇ 250 ° C.) are in particular greater than those obtained with prior art catalysts, such as catalysts based on zeolite of the AFX structural type exchanged with copper, while maintaining a good selectivity towards nitrous oxide N 2 0.
- the invention relates to a method for preparing a zeolite catalyst of structural type AFX and of at least one transition metal comprising at least the following steps:
- a zeolite of structural type FAU having a molar ratio S102 (FAU Al2O3 (FAUJ between 6.00 and 200, inclusive limits, of a nitrogenous organic compound R, R being chosen from dihydroxide of 1,5-bis (methylpiperidinium) pentane, the dihydroxide of
- n 1.7-bis (methylpiperidinium) heptane, of at least one source of at least one alkali metal and / or alkaline earth metal M of valence n, n being an integer greater than or equal to 1, selected from lithium, potassium, sodium, magnesium and calcium and the mixture of at least two of these metals,
- S1O2 refers to the amount of S1O 2 provided by the FAU zeolite
- Al2O3 refers to the amount of AI 2 O 3 provided by the FAU zeolite, until a homogeneous precursor gel is obtained
- At least one ion exchange comprising contacting said solid obtained at the end of the preceding step with a solution comprising at least one species capable of releasing a transition metal, in particular copper, in solution in the form of reactive with stirring at room temperature for a period of between 1 hour and 2 days; iv) heat treatment by drying of the solid obtained at the end of the preceding step at a temperature of between 20 and 150 ° C. followed by at least calcining under an air stream at a temperature of between 400 and 700 ° C. .
- Steps iii) and iv) can be reversed, and possibly repeated.
- the reaction mixture of step i) may comprise at least one additional source of an oxide XO 2 , X being one or more tetravalent element (s) chosen from the group formed by the following elements: silicon , germanium, titanium, so that the molar ratio XO2 / S102 (FAU) is between 0.001 and 1, preferably between 0.001 and 0.9 and more preferably between 0.001 and 0.01, terminals inclusive, the content of Si0 2 (FAUJ in said ratio being the content provided by the zeolite of structural type FAU.
- X being one or more tetravalent element (s) chosen from the group formed by the following elements: silicon , germanium, titanium, so that the molar ratio XO2 / S102 (FAU) is between 0.001 and 1, preferably between 0.001 and 0.9 and more preferably between 0.001 and 0.01, terminals inclusive, the content of Si0 2 (FAUJ in said ratio being the content provided by the zeolite of structural type FAU.
- reaction mixture of stage i) advantageously has the following molar composition:
- X is silicon
- the reaction mixture of step i) may comprise at least one additional source of an oxide Y 2 O 3 , Y being one or more trivalent element (s) chosen from the group formed by the following elements. : aluminum, boron, gallium, so that the molar ratio Y 2 O 3 / Al 2 O 3 (FAU) is between 0.001 and 10, and preferably between 0.001 and 8, limits included, the content of Al 2 O 3 (FAU) in said ratio being the content provided by the zeolite of structural type FAU.
- Y being one or more trivalent element (s) chosen from the group formed by the following elements. : aluminum, boron, gallium, so that the molar ratio Y 2 O 3 / Al 2 O 3 (FAU) is between 0.001 and 10, and preferably between 0.001 and 8, limits included, the content of Al 2 O 3 (FAU) in said ratio being the content provided by the zeolite of structural type FAU.
- reaction mixture of stage i) then advantageously has the following molar composition:
- HI 2 0 / 5 ⁇ 0 2 (FAU) between 1 and 100, preferably between 5 and 60
- R / S1O2 (FAU) between 0.01 to 0.6, preferably between 0.05 and 0.5
- Si0 2 (FAU) being the amount of Si0 2 provided by the zeolite FAU
- Al 2 0 3 (FAU) being the amount of Al 2 O 3 provided by the zeolite FAU.
- Y is aluminum.
- the reaction mixture of stage i) may contain:
- the FAU zeolite representing between 5 and 95% by weight, preferably between 50 and 95% by weight, very preferably between 60 and 90% by weight, and even more preferably between 65 and 85% by weight relative to the total amount of trivalent and tetravalent elements SiO 2 (FAU), XO 2 , Al 2 O 3 (FAUJ and Y 2 O 3 of the reaction mixture, and the reaction mixture having the following molar composition:
- the precursor gel obtained at the end of stage i) advantageously has a molar ratio of the total amount expressed as tetravalent element oxides to the total amount expressed as trivalent element oxides of between 6.00 and 100. included.
- the zeolite of structural type FAU has a molar ratio Si0 2 / Al 2 O 3 of between 6.00 and 100 inclusive.
- Crystalline seeds of an AFX structural zeolite can be added to the reaction mixture of step i), preferably in an amount of between 0.01 and 10% by weight relative to the total mass of the sources of the tetravalent and trivalent elements. in anhydrous form present in said mixture, said seed crystals not being taken into account in the total mass of the sources of the tetravalent and trivalent elements.
- Step i) may comprise a step of maturing the reaction mixture at a temperature between 20 and 100 ° C, with or without stirring, for a period of between 30 minutes and 48 hours.
- the hydrothermal treatment of step ii) can be carried out under autogenous pressure at a temperature between 120 ° C and 220 ° C, preferably between 150 ° C and 195 ° C, for a period of between 12 hours and 12 days, preferably between 12 hours and 10 days.
- the ion exchange step iii) may be carried out by bringing the solid into contact with a solution comprising a single species capable of releasing a transition metal or by bringing the solid into contact successively with different solutions each comprising at least one of preferably a single species capable of releasing a transition metal, preferably the transition metals of the different solutions being different from each other.
- Said at least one transition metal released in the exchange solution of step iii) can be selected from the group consisting of the following elements: Ti, V, Mn, Mo, Fe, Co, Cu, Cr, Zn, Nb , Ce, Zr, Rh, Pd, Pt, Au, W, Ag, preferably in the group formed by the following elements: Fe, Cu, Nb, Ce or Mn, more preferably from Fe or Cu and even more preferred said transition metal is Cu.
- the transition metal content (aux) introduced by the ion exchange step iii) is advantageously between 0.5 and 6% by weight, preferably between 0.5 and 5% by weight, more preferably between 1 and 4% by weight, based on the total mass of the anhydrous final catalyst.
- the heat treatment step iv) comprises drying the solid at a temperature of between 20 and 150 ° C., preferably between 60 and 100 ° C., for a duration of between 2 and 24 hours, followed by at least a calcination in air, optionally dry, at a temperature of between 450 and 700 ° C., preferably between 500 and 600 ° C., for a duration of between 2 and 20 hours, preferably between 5 and 10 hours, more preferably between 6 and 9 hours, the optionally dry air flow being preferably between 0.5 and 1.5 L / h / g of solid to be treated, more preferably between 0.7 and
- the invention also relates to the catalyst based on an AFX zeolite and at least one transition metal obtainable or obtained directly by the preparation process.
- the metal or transition metals may or may be selected from the group consisting of: Ti, V, Mn, Mo, Fe, Co, Cu, Cr, Zn, Nb, Ce, Zr, Rh, Pd , Pt, Au, W, Ag, preferably in the group consisting of Fe, Cu, Nb, Ce or Mn, more preferably from Fe or Cu and even more preferably said transition metal is Cu.
- the total content of the transition metals is advantageously between 0.5 and 6 wt%, preferably between 0.5 and 5 wt%, more preferably between 1 and 4 wt%, relative to the total mass of the final catalyst. anhydrous.
- the catalyst comprises copper alone at a content of between 0.5 and 6%, preferably between 0.5 and 5%, more preferably between 1 and 4% by weight relative to total mass of the anhydrous final catalyst.
- the catalyst comprises copper in combination with at least one other transition metal selected from the group consisting of Fe, Nb, Ce, Mn, the copper content of the catalyst being between 0.05 and 2 % by weight, preferably 0.5 and 2% by weight, the content of said at least one other transition metal being between 1 and 4% by weight relative to the total weight of the anhydrous final catalyst.
- the catalyst comprises iron in combination with another metal selected from the group consisting of Cu, Nb, Ce, Mn, iron content being between 0.05 and 2% by weight, preferably between 0.5 and 2% by weight, the content of said other transition metal being between 1 and 4% by mass, relative to the total mass of the final catalyst; anhydrous.
- the invention also relates to the use of the above catalyst or of the catalyst obtainable or directly obtained by the preparation process, for the selective reduction of NO x by a reducing agent such as NH 3 or H 2 .
- the catalyst may be shaped by coating deposition, on a honeycomb structure or a plate structure.
- the honeycomb structure may be formed of parallel channels open at both ends or may comprise porous filtering walls for which the adjacent parallel channels are alternately plugged on either side of the channels.
- the amount of catalyst deposited on said structure is advantageously between 50 to 180 g / l for the filtering structures and between 80 and 200 g / l for structures with open channels.
- the catalyst may be combined with a binder such as ceria, zirconium oxide, alumina, non-zeolitic silica-alumina, titanium oxide, a mixed ceria-zirconia type oxide, a tungsten oxide and or spinel to be shaped by coating deposition.
- a binder such as ceria, zirconium oxide, alumina, non-zeolitic silica-alumina, titanium oxide, a mixed ceria-zirconia type oxide, a tungsten oxide and or spinel to be shaped by coating deposition.
- Said coating may be associated with another coating having pollutant adsorption capacities, in particular NOx, reduction of pollutants in particular NOx or promoting the oxidation of pollutants.
- Said catalyst may be in extruded form, containing up to 100% of said catalyst.
- the structure coated by said catalyst or obtained by extrusion of said catalyst can be integrated into an exhaust line of an internal combustion engine.
- FIG. 1 represents the chemical formulas of the nitrogenous organic compounds that may be chosen as structuring agent used in the synthesis process according to the invention.
- FIG. 2 represents the X-ray diffraction pattern of the AFX zeolite obtained according to Example 2.
- FIG. 3 represents the conversion C in% obtained during a catalytic test for the reduction of nitrogen oxides (NOx) by ammonia (NH 3 ) in the presence of oxygen (O 2) under Standard SCR conditions as a function of the temperature T in ° C for the catalysts synthesized according to Example 2 (CuAFX3, according to the invention, curve symbolized by squares), Example 3 (CuAFXI, according to the invention, curve symbolized by circles) and Example 4 (CuSSZ16, comparative, curve symbolized by triangles).
- FIG. 4 represents the conversion C in% obtained during a catalytic test for the reduction of nitrogen oxides (NOx) by ammonia (NH 3 ) in the presence of oxygen (O 2 ) under Fast SCR conditions in function of the temperature T in ° C for the catalysts synthesized according to Example 2 (CuAFX3, according to the invention, curve symbolized by squares)
- Example 3 (CuAFXI, according to the invention, curve symbolized by circles)
- Example 4 CuSSZ16, comparative, curve symbolized by triangles).
- FIG. 5 represents the conversion C in% obtained during a catalytic test for the reduction of oxides of nitrogen (NOx) by ammonia (NH 3 ) in the presence of oxygen (O 2 ) under Standard SCR conditions in function temperature T in ° C, after hydrothermal aging for the catalysts synthesized according to Examples 2 and 4, then aged according to the procedure described in Example 5 (CuAFX3 aged, according to the invention, curve symbolized by the triangles and aged CuSSZ16, comparative, curve symbolized by the circles)
- the present invention relates to a process for preparing a catalyst comprising an AFX structural zeolite and at least one transition metal, comprising at least the following steps:
- zeolite of FAU structural type having a molar ratio S102 FAU AI2O3 (FAUJ between 6 and 200, inclusive limits, of a nitrogenous organic compound R, also called specific structurant, chosen from 1,5-bis (methylpiperidinium) pentane dihydroxide, the dihydroxide of
- M 2 / n 0 / (SiO 2 (FAU)) between 0.005 to 0.45, preferably between 0.05 and 0.25 in which Si0 2 (FAU) is the amount of SiO 2 provided by the FAU zeolite, and Al 2 O 3 (FAU) being the amount of Al 2 O 3 provided by the FAU zeolite, HI the molar amount of water present in the reaction mixture, R the molar amount of said organic nitrogen compound, M 2 / n 0 the molar amount expressed as oxide form of M 2 / n O provided by the source of alkali metal and / or alkaline earth metal, and M is one or more alkali metal (s) and / or alkaline earth metal (s) selected from lithium, sodium, potassium, calcium, magnesium and a mixture of at least two of these metals very preferably M is sodium, step i) being conducted for a time to obtain a homogeneous mixture called precursor gel.
- Si0 2 (FAU) is the amount of SiO 2
- step ii) the hydrothermal treatment of said precursor gel obtained at the end of step i) at a temperature of between 120 ° C. and 220 ° C., for a duration of between 12 hours and 15 days to obtain a crystallized solid phase, so-called "Solid";
- iii) at least one ion exchange comprising contacting said solid obtained at the end of the preceding step with a solution comprising at least one species capable of releasing a transition metal, in particular copper, in solution in the form of reactive with stirring at room temperature for a period of between 1 hour and 2 days; iv) the heat treatment by drying of the solid obtained at the end of the preceding step at a temperature of between 20 and 150 ° C. followed by at least calcining under an air stream at a temperature of between 400 and 700 ° C. C; steps iii) and iv) can advantageously be inverted, and possibly repeated if necessary.
- the present invention also relates to the catalyst comprising a zeolite AFX structural type and at least one transition metal obtainable or obtained directly by the process described above.
- the invention finally relates to the use of a catalyst according to the invention for the selective catalytic reduction of NOx in the presence of a reducing agent.
- the catalyst according to the invention comprises at least one zeolite AFX type, and at least one additional transition metal, preferably copper.
- the metal or transition metals included in the catalyst is (are) selected from among the elements from the group formed by the elements of groups 3 to 12 of the periodic table of the elements including the lanthanides.
- the metal or transition metals included in the catalyst are (are) selected from the group consisting of the following elements: Ti, V, Mn, Mo, Fe, Co, Cu, Cr, Zn, Nb, Ce, Zr, Rh, Pd, Pt, Au, W, Ag.
- the catalyst according to the invention comprises copper, alone or in combination with at least one other transition metal, chosen from the group of elements listed above; in particular Fe, Nb, Ce, Mn.
- the total content of the transition metals is between 0.5 and 6 wt%, preferably between 0.5 and 5 wt%, and even more preferably between 1 and 4 wt%, relative to the total mass of the catalyst. final, in its anhydrous form.
- the content is between 0.5 and 6% by weight, preferably between 0.5 and 5% by weight, more preferably between 1 and 4% with respect to the total mass of the anhydrous final catalyst.
- the copper content of the catalyst is between 0.05 and 2% by weight, preferably 0.5 and 2% by weight, whereas that of the other transition metal is preferably between 1 and 4% by weight, the contents of transition metals being given as a percentage by weight relative to the total mass of the final dry catalyst.
- the content is between 0.5 and 4% and more preferably between 1.5 and 3.5% relative to the total weight of the anhydrous final catalyst.
- the iron content of the catalyst is between 0.05 and 2% by weight, preferably between 0.5 and 2% by weight, whereas that of the other transition metal is preferably between 1 and 4% by weight, the contents of transition metals being given as a percentage by weight relative to the total mass of the final dry catalyst.
- the catalyst according to the invention may also comprise other elements, such as, for example, alkali and / or alkaline earth metals, for example sodium, originating especially from synthesis, in particular from the compounds of the reaction medium of step i ) of the process for preparing said catalyst.
- other elements such as, for example, alkali and / or alkaline earth metals, for example sodium, originating especially from synthesis, in particular from the compounds of the reaction medium of step i ) of the process for preparing said catalyst.
- Step i) of mixing Step i) implements:
- a zeolite of FAU structural type having a molar ratio S102 FAU AI2O3 (FAUJ between 6 and 200, inclusive limits, of a nitrogenous organic compound R, also called specific structurant, chosen from 1,5-bis (methylpiperidinium) pentane dihydroxide, 1,6-bis (methylpiperidinium) hexane dihydroxide, or dihydroxide of
- M 2 / n 0 / (SiO 2 (FAU)) between 0.005 to 0.45, preferably between 0.05 and 0.25 in which S102 (FAU) is the amount of S102 provided by the FAU zeolite, and Al2O3 (FAU) being the amount of Al 2 O 3 provided by the FAU zeolite, H 2 0 the molar amount of water present in the reaction mixture, R the molar amount of said nitrogenous organic compound, M 2 / n 0 the molar amount expressed in oxide form M 2 / n 0 by the source of alkali metal and / or alkaline earth metal, and M is one or more alkali metal (s) and / or alkaline earth metal (s) selected from lithium, sodium, potassium, calcium, magnesium and a mixture of at least two of these metals very preferably M is sodium, step i) being conducted for a time to obtain a homogeneous mixture called precursor gel.
- S102 is the amount of S102 provided by the FAU
- the starting structural type zeolite FAU having a molar ratio S10 2 / Al 2 O 3 of between 6 and 200, inclusive limits can be obtained by any method known to those skilled in the art, for example by treatment with the Steaming and acid washings on a zeolite of structural type FAU of molar ratio S1O 2 / Al 2 O 3 of less than 6.00.
- the sources of FAU with a SiO 2 / Al 2 O 3 ratio greater than or equal to 6.00 the commercial zeolites CBV712, CBV720, CBV760 and CBV780 produced by Zeolyst, the commercial zeolites HSZ-350HUA, HSZ- 360HUA and HSZ-385HUA produced by TOSOH.
- the preparation process according to the invention therefore allows to adjust the ratio S1O 2 / Al 2 O 3 precursor gel containing a zeolite with structure type FAU depending on the zeolite chosen FAU structural type and the additional input or not within the reaction mixture of at least one source of at least one tetravalent element XO 2 and / or at least one source of at least one trivalent element Y 2 O 3 .
- Step i) comprises the mixing in an aqueous medium of a zeolite of FAU structural type having an SiO 2 molar ratio ( F AU AI 2 O 3 (FAUJ between 6 and 200, inclusive limits), of a nitrogenous organic compound R, R being the dihydroxide of
- reaction mixture having the following molar composition :
- Si0 2 (FAU J is the amount of SiO 2 provided by the FAU zeolite
- Al 2 0 3 (FAU) is the amount of Al 2 O 3 provided by the FAU zeolite
- M is one or more alkali metal (s) and / or alkaline earth metal (s
- the reaction mixture of step i) also comprises at least one additional source of an oxide X0 2 so that the molar ratio X0 2 / Si0 2 (FAU J is between 0.001 and 1, the mixture advantageously having the following molar composition:
- R / (X0 2 + Si0 2 (FAU)) between 0.01 to 0.6, preferably between 0.05 and 0.5 M 2 / n 0 / (X0 2 + Si0 2 (FAU) ) between 0.005 to 0.45, preferably between 0.05 and 0.25
- X is one or more tetravalent element (s) selected from the group consisting of silicon, germanium, titanium, preferably X is silicon, SiO 2 (FAU) being the amount of Si0 2 provided by the zeolite FAU, and Al 2 0 3 (FAU) being the amount of Al 2 O 3 provided by the zeolite FAU, R being the dihydroxide of 1,5-bis (methylpiperidinium) pentane, the dihydroxide of
- M is one or more alkali metal (s) and / or alkaline earth metal (s) selected from lithium, sodium, potassium, calcium, magnesium and the mixture at least two of these metals, very preferably M is sodium.
- the reaction mixture of step i) also comprises at least one additional source of an oxide Y 2 0 3 so that the molar ratio Y 2 O 3 / Al 2 O 3 (FAU) is between 0.001 and 10, the mixture advantageously having the following molar composition: Si0 2 (FAU (AI 2 0 3 (FAU) + Y 2 O 3 ) of between 6.00 and 200, preferably between 6.00 and 100
- R / SiO 2 (FAU) of from 0.01 to 0.6, preferably from 0.05 to 0.5
- M 2 / n 0 / SiO 2 (FAU) between 0.005 to 0.45, preferably between 0.05 and 0.25 in which Y is one or more trivalent element (s) chosen from group formed by the following elements: aluminum, boron, gallium, preferably Y is aluminum, Si0 2 (FAU) being the amount of SiO 2 provided by the zeolite FAU, and Al 2 0 3 (FAU) being the amount of Al 2 0 3 provided by the zeolite FAU, R being the dihydroxide of 1,5-bis (methylpiperidinium) pentane, the dihydroxide of
- M is one or more alkali metal (s) and / or alkaline earth metal (s) selected from lithium, sodium, potassium, calcium, magnesium and the mixture at least two of these metals, very preferably M is sodium.
- the reaction mixture of step i) contains a percentage between 5 and 95% by weight, preferably between 50 and 95% by weight, very preferably between 60 and 90% by weight and still more preferred between 65 and 85% by weight of a zeolite of structural type FAU with respect to the total amount of the sources of the trivalent and tetravalent elements of the mixture and also comprises at least one additional source of an oxide X0 2 and at least one source addition of an oxide Y 2 O 3 , the reaction mixture having the following molar composition:
- R / (X0 2 + Si0 2 (FAU)) between 0.01 to 0.6, preferably between 0.05 and 0.5 M 2 / n 0 / (X0 2 + Si0 2 (FAU) ) between 0.005 to 0.45, preferably between 0.05 and 0.25
- X is one or more tetravalent element (s) chosen from the group formed by the following elements: silicon, germanium, titanium, preferably X is silicon
- Y is one or more trivalent element (s) chosen from the group formed by the following elements: aluminum, boron, gallium, preferably aluminum
- S1O 2 FAUJ being the amount of S1O 2 provided by the zeolite FAU
- Al 2 O 3 FAU
- R being the dihydroxide of 1,5-bis (methylpiperidinium) pentane, the dihydroxide of
- M is one or more alkali metal (s) and / or alkaline earth metal (s) selected from lithium, sodium, potassium, calcium, magnesium and the mixture at least two of these metals, very preferably M is sodium.
- Step i) makes it possible to obtain a homogeneous precursor gel.
- a zeolite of structural type FAU having a molar ratio S102 (FAU Al2O3 (FAUJ between 6 and 200 inclusive, preferably between 6.00 and 100 inclusive) is incorporated into the reaction mixture.
- FAU Al2O3 FAUJ between 6 and 200 inclusive, preferably between 6.00 and 100 inclusive
- step (i) as a source of silicon and aluminum elements.
- R is a nitrogenous organic compound chosen from 1,5-bis (methylpiperidinium) pentane dihydroxide, the dihydroxide of
- 1.7-bis (methylpiperidinium) heptane said compound being incorporated in the reaction mixture for carrying out step (i), as organic structuring agent.
- the anion associated with the quaternary ammonium cations present in the structuring organic species for the synthesis of an AFX structural zeolite according to the invention is the hydroxide anion.
- At least one source of at least one alkali metal and / or alkaline earth metal M of valence n is used in the reaction mixture of step i), not being a higher integer or equal to 1, M being preferably selected from lithium, potassium, sodium, magnesium and calcium and the mixture of at least two of these metals. Most preferably, M is sodium.
- the source of at least one alkali metal and / or alkaline earth metal M is sodium hydroxide.
- At least one additional source of an oxide XO 2 X being one or more tetravalent element (s) chosen from the group formed by the following elements: silicon, germanium, titanium, and preferably X is silicon, so that the molar ratio X0 2 / Si0 2 (FAUJ is between 0.001 and 1, preferably between 0.001 and 0.9 and more preferably between 0.001 and 0.01, the content of Si0 2 (FAU) in said ratio being the content provided by the zeolite of structural type FAU, is advantageously implemented in the reaction mixture of step i).
- X being one or more tetravalent element (s) chosen from the group formed by the following elements: silicon, germanium, titanium, and preferably X is silicon, so that the molar ratio X0 2 / Si0 2 (FAUJ is between 0.001 and 1, preferably between 0.001 and 0.9 and more preferably between 0.001 and 0.01, the content of Si0 2 (FAU) in said ratio being the content provided by the zeo
- the source (s) of said tetravalent element (s) may be any compound comprising element X and capable of releasing this element in aqueous solution in reactive form.
- Ti (EtO) 4 is advantageously used as a source of titanium.
- the silicon source may be any of the sources commonly used for the synthesis of zeolites, for example powdered silica, silicic acid, colloidal silica, dissolved silica or tetraethoxysilane (TEOS).
- zeolites for example powdered silica, silicic acid, colloidal silica, dissolved silica or tetraethoxysilane (TEOS).
- TEOS tetraethoxysilane
- precipitated silicas especially those obtained by precipitation from an alkali metal silicate solution, pyrogenic silicas, for example "CAB-O-SIL" and silica gels.
- colloidal silicas having different particle sizes for example having a mean equivalent diameter of between 10 and 15 nm or between 40 and 50 nm, such as those sold under registered trademarks such as "LUDOX", may be used.
- the silicon source is CAB-O-SIL.
- Y is aluminum, so that the molar ratio Y 2 O 3 / Al 2 O 3 (FAUJ is between 0.001 and 10, and preferably between 0.001 and 8, the content of Al 2 O 3 (FAU) in said ratio being the content provided by the zeolite of structural type F AU.
- the source (s) of said trivalent element (s) Y may be any compound comprising element Y and capable of releasing this element in aqueous solution in reactive form.
- Element Y may be incorporated into the mixture in an oxidized form YO b with 1 ⁇ b ⁇ 3 (b being an integer or a rational number) or in any other form.
- the aluminum source is preferably aluminum hydroxide or an aluminum salt, for example chloride, nitrate, or sulphate, sodium aluminate, an aluminum alkoxide, or alumina proper, preferably in hydrated or hydratable form, such as for example colloidal alumina, pseudoboehmite, gamma alumina or alpha or beta trihydrate. It is also possible to use mixtures of the sources mentioned above.
- Step (i) of the process according to the invention consists in preparing an aqueous reaction mixture containing a zeolite of structural type FAU, optionally a source of an oxide X0 2 or a source of a oxide Y2O3, at least one nitrogen-containing organic compound R, R being chosen from 1,5-bis (methylpiperidinium) pentane dihydroxide, 1,6-bis (methylpiperidinium) hexane dihydroxide or 1,7-bis (methylpiperidinium) dihydroxide heptane in the presence of at least one source of one or more alkali metal (s) and / or alkaline earth metal, to obtain a precursor gel of an AFX structural type zeolite.
- the amounts of said reagents are adjusted as indicated previously so as to confer on this gel a composition allowing the crystallization of a zeolite of structural type AFX.
- seeds of an AFX structural zeolite may be added to the reaction mixture during said step i) of the process of the invention in order to reduce the time required for the formation of crystals of a zeolite of the type structural AFX and / or the total crystallization time.
- Said crystal seeds also promote the formation of said zeolite AFX structural type at the expense of impurities.
- Such seeds comprise crystalline solids, in particular crystals of an AFX structural zeolite.
- the crystalline seeds are generally added in a proportion of between 0.01 and 10% of the total anhydrous mass of the sources of said tetravalent (s) and trivalent (s) element (s) used in the reaction mixture, said crystalline seeds not being not taken into account in the total mass of the sources of the tetravalent and trivalent elements. Said seeds are also not taken into account to determine the composition of the reaction mixture and / or gel, defined further, that is to say in the determination of the different molar ratios of the composition of the reaction mixture.
- the mixing step i) is carried out until a homogeneous mixture is obtained, preferably for a period greater than or equal to 15 minutes, preferably with stirring by any system known to those skilled in the art at low or high shear rate.
- step i a homogeneous precursor gel is obtained.
- a ripening of the reaction mixture before the hydrothermal crystallization during said step i) of the process of the invention in order to control the crystal size of an AFX structural type zeolite. Said ripening also promotes the formation of said zeolite AFX structural type at the expense of impurities.
- the ripening of the reaction mixture during said step i) of the process of the invention can be carried out at room temperature. ambient temperature or at a temperature between 20 and 100 ° C with or without stirring, for a period advantageously between 30 min and 48 hours.
- step ii) of the process according to the invention the precursor gel obtained at the end of step i) is subjected to a hydrothermal treatment, preferably carried out at a temperature of between 120.degree. C. and 220.degree. a duration of between 12 hours and 15 days, until said zeolite of structural type AFX (or "crystallized solid") is formed.
- a hydrothermal treatment preferably carried out at a temperature of between 120.degree. C. and 220.degree. a duration of between 12 hours and 15 days, until said zeolite of structural type AFX (or "crystallized solid" is formed.
- the precursor gel is advantageously placed under hydrothermal conditions under an autogenous reaction pressure, optionally by adding gas, for example nitrogen, at a temperature of preferably between 120 ° C. and 220 ° C., preferably between 150 ° C. and 195 ° C, until the complete crystallization of a zeolite AFX structural type.
- gas for example nitrogen
- the time required to obtain the crystallization varies between 12 hours and 15 days, preferably between 12 hours and 12 days, and more preferably between 12 hours and 10 days.
- the reaction is generally carried out with stirring or without stirring, preferably with stirring.
- stirring system can be used any system known to those skilled in the art, for example, blades inclined with counterpanes, stirring turbines, screws Archimedes.
- the process of the invention leads to the formation of a zeolite of AFX structural type, free from any other crystallized or amorphous phase.
- the process for preparing the catalyst according to the invention comprises at least one ion exchange step comprising contacting the crystallized solid obtained with the result of the preceding step, that is to say of the AFX zeolite obtained at the end of step ii) or of the dried and calcined zeolite AFX obtained at the end of step iv) in the preferred case where the steps iii) and iv) are inverted, with at least one solution comprising at least one species capable of releasing a transition metal, preferably copper, in solution in reactive form, with stirring at room temperature for a period of between 1 hour and 2 days, advantageously for a period of between 0.5 days and 1.5 days, the concentration of said species able to release the transition metal in said solution being a function of the amount of transition metal that it is desired to incorporate in said crystallized solid.
- Said hydrogen form can be obtained by carrying out an ion exchange with an acid, in particular a strong mineral acid such as hydrochloric, sulfuric or nitric acid, or with a compound such as ammonium chloride, sulphate or nitrate before ion exchange with the transition metal (s).
- an acid in particular a strong mineral acid such as hydrochloric, sulfuric or nitric acid, or with a compound such as ammonium chloride, sulphate or nitrate before ion exchange with the transition metal (s).
- the transition metal released in the exchange solution is selected from the group consisting of: Ti, V, Mn, Mo, Fe, Co, Cu, Cr, Zn, Nb, Ce, Zr, Rh, Pd, Pt , Au, W, Ag.
- the transition metal is Fe, Cu, Nb, Ce or Mn, preferably Cu.
- the term "species capable of releasing a transition metal” means a species capable of dissociating in an aqueous medium, such as, for example, sulphates, nitrates, chlorides, oxalates or organometallic complexes of a transition metal or mixtures thereof.
- the species capable of releasing a transition metal is a sulphate or a nitrate of said transition metal.
- the solution with which the crystallized solid or crystallized solid dried and calcined is brought into contact comprises at least one species capable of releasing a transition metal, preferably a single species capable of releasing a transition metal, of preferably iron or copper, preferably copper.
- the process for preparing the catalyst according to the invention comprises a step iii) ion exchange by bringing the crystallized solid into contact with a solution comprising a species capable of releasing a transition metal or by bringing the solid into contact successively with several solutions each comprising a species capable of releasing a transition metal, the different solutions comprising species capable of releasing a different transition metal.
- the solid obtained is advantageously filtered, washed and then dried in order to obtain said catalyst in powder form.
- the total amount of transition metal, preferably copper, contained in said final catalyst is between 0.5 and 6% by weight relative to the total weight of the catalyst in its anhydrous form.
- the catalyst according to the invention is prepared by a process comprising an ion exchange step iii), the solid or the dried and calcined solid being brought into contact with a solution comprising a species capable of releasing copper. in solution in reactive form.
- the total amount of copper contained in said final catalyst is between 0.5 and 6%, preferably between 1 and 6% by weight, all percentages being percentages by weight relative to the total mass of the final catalyst according to the invention in its anhydrous form, obtained at the end of the preparation process.
- the preparation process according to the invention comprises a step iv) of heat treatment carried out at the end of the preceding step, that is to say at the end of the hydrothermal treatment step ii) or at the end of resulting from the ion exchange step iii), preferably at the end of the ion exchange step iii).
- Step iii) of the preparation process can advantageously be interchanged with step iv).
- Each of the two steps iii) and iv) can also optionally be repeated.
- Said heat treating step iv) comprises drying the solid at a temperature of between 20 and 150 ° C., preferably between 60 and 100 ° C., advantageously for a duration of between 2 and 24 hours, followed by at least one calcination in air, optionally dry, at a temperature advantageously between 450 and 700 ° C, preferably between 500 and 600 ° C for a period of between 2 and 20 hours, preferably between 5 and 10 hours, more preferably between 6 and 9 hours, the optionally dry air flow being preferably between 0.5 and 1.5 L / h / g of solid to be treated, more preferably between 0.7 and 1.2 L / h / g of solid to be treated.
- the calcination may be preceded by a gradual rise in temperature.
- the catalyst obtained at the end of step iv) of heat treatment is devoid of any organic species, in particular devoid of the organic template R.
- the catalyst obtained by a process comprising at least steps i), ii), iii), and iv) previously described has improved properties for the conversion of NO x .
- the catalyst comprises a zeolite AFX structure according to the classification of the International Zeolite Association (IZA), exchanged with at least one transition metal.
- This structure is characterized by X-ray diffraction (XRD).
- XRD X-ray diffraction
- the measurement error A (d hki ) on d hki is calculated using the Bragg relation as a function of the absolute error D (2Q) assigned to the measurement of 2Q.
- a zeolite of pure AFX structural type is used as a reference.
- the qualitative and quantitative analysis of the chemical species present in the materials obtained is made by X-ray fluorescence spectrometry (FX).
- FX X-ray fluorescence spectrometry
- This is a technique of chemical analysis using a physical property of matter, the fluorescence of X-rays.
- the spectrum of X-rays emitted by the material is characteristic of the composition of the sample, by analyzing this spectrum, one can deduce the elemental composition, that is to say the mass concentrations in elements.
- the loss on ignition (PAF) of the catalyst obtained after the drying step (and before calcination) or after the calcining step of step iv) of the process according to the invention is generally between 4 and 15% by weight.
- the loss on ignition of a sample corresponds to the mass difference of the sample before and after heat treatment at 1000 ° C for 2 hours. It is expressed in% corresponding to the percentage of loss of mass.
- the loss on ignition generally corresponds to the loss of solvent (such as water) contained in the solid but also to the elimination of organic compounds contained in the mineral solid constituents.
- the invention also relates to the use of the catalyst according to the invention, directly prepared or capable of being prepared by the process described above for the selective reduction of NO x by a reducing agent such as NH 3 or H 2 , advantageously shaped by deposition as a coating ("washcoat" according to the English terminology) on a honeycomb structure mainly for mobile applications or a plate structure that is found particularly for stationary applications.
- the honeycomb structure is formed of parallel channels open at both ends (flow-through in English) or has porous filtering walls and in this case the adjacent parallel channels are alternately plugged on either side of the channels in order to force the flow of gas through the wall (wall-flow monolith in English). Said honeycomb structure thus coated constitutes a catalytic bread.
- Said structure may be composed of cordierite, silicon carbide (SiC), aluminum titanate (AITi), alpha alumina, mullite or any other material whose porosity is between 30 and 70%.
- Said structure may be made of sheet metal, stainless steel containing chromium and aluminum, FeCrAI type steel.
- the quantity of catalyst according to the invention deposited on said structure is between 50 to 180 g / l for the filtering structures and between 80 and 200 g / l for structures with open channels.
- the coating itself (“washcoat”) comprises the catalyst according to the invention, advantageously associated with a binder such as ceria, zirconium oxide, alumina, non-zeolitic silica-alumina, titanium oxide, a mixed oxide of the cerine-zirconia type, a tungsten oxide, a spinel.
- Said coating is advantageously applied to said structure by a deposition method (washcoating in English) which consists of dipping the monolith in a suspension (slurry in English) of the catalyst powder according to the invention in a solvent, preferably water and potentially binders, metal oxides, stabilizers or other promoters. This quenching step can be repeated until the desired amount of coating is reached. In some cases the slurry can also be sprayed within the monolith.
- the coating once deposited, the monolith is calcined at a temperature of 300 to 600 ° C for 1 to 10 hours.
- Said structure may be coated with one or more coatings.
- the coating comprising the catalyst according to the invention is advantageously associated with, that is to say covers one or is covered by, another coating having pollutant adsorption capacity, in particular NOx, pollutant reduction in particular NOx or promoting the oxidation of pollutants, in particular that of ammonia.
- the structure obtained can contain up to 100% of catalyst according to the invention.
- Said structure coated with the catalyst according to the invention is advantageously integrated in an exhaust line of an internal combustion engine operating mainly in lean mixture, that is to say in excess of air relative to the stoichiometry of the combustion reaction as is the case for diesel engines for example.
- the exhaust gases contain in particular the following pollutants: soot, unburned hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NOx).
- Upstream of said structure coated with the catalyst according to the invention can be placed an oxidation catalyst whose function is to oxidize the HC and the CO and a filter for removing soot from the exhaust gases, the function of said coated structure being to remove NOx, its operating range being between 100 and 900 ° C and preferably between 200 ° C and 500 ° C.
- the catalyst according to the invention based on an AFX structural zeolite and at least one transition metal, in particular copper, has improved properties compared to the catalysts of the prior art.
- the use of the catalyst according to the invention makes it possible to obtain lower priming temperatures for the NOx conversion reaction and a better NO x conversion over the entire operating temperature range (150.degree. ° C - 600 ° C), while maintaining good selectivity in N 2 0. It also has a better resistance to hydrothermal aging, guaranteeing high performance even after aging.
- Example 1 Preparation of 1,6-bis (methylpiperidinium) hexane dihydroxide (structuring R).
- amorphous gel of aluminum hydroxide (Al (OH) 3 amorphous gel, 58.55% by weight of Al 2 O 3 , Merck), corresponding to a molar ratio (Al 2 0 3 (amorphous gel) / Al 2 O 3 ( FAU) of 6.49 are incorporated and the synthesis gel is stirred for 15 minutes
- the molar composition of the precursor gel is as follows: 1 SiO 2 : 0.05 Al 2 O 3 : 0.167 R: 0.093 Na 2 0: 36.7 H 2 O, ie a Si0 2 / Al 2 O 3 ratio of 20.
- the precursor gel is then transferred, after homogenization, into a 25-liter stainless steel reactor, the reactor is closed and then heated for 23 hours. at 170 ° C. under autogenous pressure and with stirring at 200 rpm with a system equipped with 4 inclined blades
- the crystalline solid product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C.
- the PAF of dried solid is 9.7%.
- the solid is then introduced into a muffle furnace where a calcination step is carried out: the calcining cycle comprises a rise of 1.5 ° C./min in temperature up to 200 ° C., a plateau at 200 ° C. maintained during 2 hours, a rise of 1 ° C / min in temperature up to 550 ° C followed by a bearing at 550 ° C maintained for 8 hours, then a return to room temperature.
- the calcined solid product was analyzed by X-ray diffraction and identified as consisting of a zeolite of AFX structural type, with a purity greater than 99%.
- the product has an SiO 2 / Al 2 O 3 molar ratio of 14.8 as determined by X-ray fluorescence.
- the calcined AFX zeolite is brought into contact with a solution of molar NH 4 NO 3 for 1 hour with stirring at 80 ° C. for ionic exchange with NH 4 + .
- the ratio of the volume of NH 4 NO 3 solution to the mass of solid is 10.
- the solid obtained is filtered and washed and the exchange procedure is repeated two more times under the same conditions.
- the final solid is separated, washed and dried for 12 hours at 100 ° C.
- a DRX analysis shows that the product obtained is a zeolite in ammoniacal form of pure AFX structural type.
- the AFX zeolite in ammoniacal form is then treated under an air stream at 550 ° C. for 8 hours with a temperature rise ramp of 1 ° C./min.
- the loss at fire (PAF) is 4% weight.
- the product obtained is an AFX zeolite in protonated form.
- the AFX zeolite calcined in protonated form is brought into contact with a solution of [Cu (NFl 3 ) 4 ] (NO 3 ) 2 for 1 day with stirring at room temperature. The final solid is separated, washed and dried for 12 hours at 100 ° C.
- the Cu-AFX exchanged solid obtained after being placed in contact with the [Cu (NFl 3 ) 4 ] (NO 3 ) 2 solution is calcined under a stream of air at 550 ° C. for 8 hours.
- the calcined solid product is analyzed by X-ray diffraction and identified as an AFX structural zeolite.
- the product has an SiO 2 / Al 2 O 3 molar ratio of 14.8 and a mass percentage of Cu of 3% as determined by X-ray fluorescence.
- the catalyst obtained is noted CuAFX3.
- amorphous gel of aluminum hydroxide (Al (OH) 3 amorphous gel, 58.55% by weight of Al 2 O 3 , Merck), corresponding to a molar ratio (Al 2 O 3 3 (amorphous gel) / Al 2 O 3 (FAU) of 6.49 are incorporated and the synthesis gel is stirred for 15 minutes
- the molar composition of the precursor gel is as follows: 1 Si0 2 : 0.05 AI 2 Ü 3 : 0.167 R: 0.093 Na 2 0: 36.7 Fl 2 0, a ratio Si0 2 / Al 2 0 3 of 20.
- the precursor gel is then transferred, after homogenization, into a 25 liter stainless steel reactor.
- the reactor is closed and then heated for 23 hours at 170 ° C. under autogenous pressure and with stirring at 200 rpm with a system provided with 4 inclined blades.
- the crystallized product obtained is filtered, washed with deionized water and then dried overnight at 100 ° C. PAF of the dried solid is 9.7%.
- the solid is then introduced into a muffle furnace where a calcination step is carried out: the calcining cycle comprises a rise of 1.5 ° C./min in temperature up to 200 ° C., a plateau at 200 ° C. maintained during 2 hours, a rise of 1 ° C / min in temperature up to 550 ° C followed by a bearing at 550 ° C maintained for 8 hours, then a return to room temperature.
- the calcined solid product was analyzed by X-ray diffraction and identified as consisting of an AFX structural zeolite, with a purity greater than 99%.
- the product has a molar ratio S102 / Al2O3 of 14.8 as determined by X-ray fluorescence.
- the calcined AFX zeolite is brought into contact with a solution of 3 molar NHI 4 NO 3 for 1 hour with stirring at 80 ° C. for ion exchange with NFI 4 + .
- the ratio between the volume of NFI 4 N0 3 solution and the mass of solid is 10.
- the solid obtained is filtered and washed and the exchange procedure is repeated two more times under the same conditions.
- the final solid is separated, washed and dried for 12 hours at 100 ° C.
- a DRX analysis shows that the product obtained is a zeolite in ammoniacal form of pure AFX structural type.
- the AFX zeolite in ammoniacal form is treated under a stream of air at 550 ° C. for 8 hours with a temperature rise ramp of 1 ° C./min.
- the loss on ignition (PAF) is 4% by weight.
- the product obtained is an AFX zeolite in protonated form.
- the burned zeolite AFX in protonated form is brought into contact with a solution of [CU (NH 3 ) 4 ] (NO 3 ) 2 for 1 day with stirring at room temperature.
- the final solid is separated, washed and dried for 12 hours at 100 ° C.
- the Cu-AFX exchanged solid obtained after being placed in contact with the solution of [CU (NH 3 ) 4 ] (NO 3 ) 2 is calcined under a stream of air at 550 ° C. for 8 hours.
- the calcined solid product is analyzed by X-ray diffraction and identified as an AFX structural zeolite.
- the product has an SiO 2 / Al 2 O 3 molar ratio of 14.8 and a mass percentage of Cu of 1% as determined by X-ray fluorescence.
- the catalyst obtained is noted CuAFXI.
- Example 4 In this example, a zeolite SSZ-16 exchanged with Cu is synthesized according to the prior art. In this example, the copper is introduced by ion exchange.
- the reaction mixture has the following molar composition: 100 SiO 2 : 1, 67 Al 2 O 3 : 50 Na 2 O: 10 DABCO-C 4: 4000 H 2 O
- the reaction mixture obtained in the mixing step is kept at room temperature with stirring for 24 hours.
- the gel obtained is left in an autoclave at a temperature of 150 ° C. for 6 days with stirring (200 rpm).
- the crystals obtained are separated and washed with water permutated until a wash water pH of less than 8 is obtained.
- the washed crystalline solid is dried for 12 hours at 100 ° C.
- a DRX analysis shows that the product obtained is a zeolite SSZ-16 synthetic and pure raw AFX structural type (ICDD sheet, PDF 04-03-1370).
- the synthetic SSZ-16 zeolite is treated under a flow of N 2 dry at 550 ° C for 8 h, and then calcined under a stream of dry air at 550 ° C for 8 hours.
- the loss on ignition (PAF) is 18% by weight.
- the calcined zeolite SSZ-16 is brought into contact with a solution of 3 molar NH 4 NO 3 for 5 hours with stirring at room temperature for ion exchange with NH 4 + .
- the ratio between the volume of NFI 4 N0 3 solution and the solid mass is 10.
- the solid obtained is filtered and washed and the exchange procedure is repeated again under the same conditions.
- the final solid is separated, washed and dried for 12 hours at 100 ° C.
- the zeolite SSZ-16 in ammoniacal form (NFI 4 -SSZ-16) is treated under a stream of dry air at 550 ° C. for 8 hours with a temperature rise ramp of 1 ° C./min.
- the loss on ignition (PAF) is 4% by weight.
- the product obtained is a zeolite SSZ-16 in protonated form (FI-SSZ-16).
- the FI-SSZ-16 zeolite is brought into contact with a solution of [Cu (NH 3 ) 4 ] (NO 3 ) 2 for 1 day with stirring at room temperature. The final solid is separated, washed and dried and calcined under a stream of dry air at 550 ° C. for 8 hours.
- a DRX analysis shows that the product obtained is a zeolite SSZ-16 of pure AFX structural type (ICDD file, PDF 04-03-1370).
- Example 2 200 mg of each of the samples synthesized according to Example 2 (CuAFX3), Example 3 (CuAFXI) and Example 4 (CuSSZ16) are placed in powder form in a quartz reactor. They are traversed by a flow rate of 150 L / h of a mixture of the following molar composition: 10% H 2 0, 20% 0 2 and N 2 in addition.
- the samples are subjected to these conditions for 4 hours at a temperature of 800 ° C.
- Example 2 The sample synthesized according to Example 2 and aged under the conditions of Example 5 is named CuAFX3vieilli.
- Example 5 The sample synthesized according to Example 3 and aged under the conditions of Example 5 is called CuAFXI aged.
- Example 5 The sample synthesized according to Example 4 and aged under the conditions of Example 5 is named CuSSZ16vieilli.
- a catalytic test for the reduction of oxides of nitrogen (NOx) by ammonia (NH 3 ) in the presence of oxygen (O 2 ) under Standard SCR conditions is carried out at different operating temperatures for the catalysts synthesized according to the example 2 (CuAFX3), Example 3 (CuAFXI) and Example 4 (CuSSZ16).
- An FTIR analyzer makes it possible to measure the concentration of NO, NO 2 , NH 3 , N 2 O, CO, CO 2 , H 2 O, O 2 species at the outlet of the reactor.
- the NOx conversions calculated as following:
- the CuAFXI catalyst synthesized according to the invention is particularly effective at high temperatures with 100% conversion of NOx from 350 ° C. and a maintained efficiency greater than 95% up to 550 ° C.
- the catalyst CuAFX3 synthesized according to the invention gives much higher performance to the catalyst synthesized according to the prior art in terms of NOx conversion over the entire temperature range tested. A maximum conversion of 100% is reached between 270 and 410 ° C for the CuAFX3 catalyst while the CuSSZ16 catalyst synthesized according to the prior art achieves only 89% conversion between 340 and 400 ° C.
- the initiation temperatures of the catalysts containing 3% copper are given below for Standard-SCR conditions:
- T50 is the temperature at which 50% of the NOx in the gas mixture is converted by the catalyst.
- T80 is the temperature at which 80% of the NOx in the gas mixture is converted by the catalyst.
- T90 is the temperature at which 90% of the NOx in the gas mixture is converted by the catalyst.
- T100 is the temperature at which 100% NOx of the gas mixture is converted by the catalyst.
- the catalyst CuAFX3 synthesized according to the invention gives much superior performance to the catalyst CuSSZ16 synthesized according to the prior art in terms of initiation temperatures and NOx conversion over the entire temperature range tested in Standard SCR condition. Indeed, at the same conversion rate (50% or 80%), the priming temperatures obtained with the catalyst according to the invention CuAFX3 are lower compared to those obtained with the catalyst CuSSZI 6.
- 200 mg of catalyst in powder form is placed in a quartz reactor. 218 L / h of a representative load of a mixture of exhaust gas of a diesel engine are fed into the reactor.
- This feed has the following molar composition: 200 ppm NO, 200 ppm NO 2, 400 ppm NH 3 , 8.5% O 2, 9% CO 2, 10% H 2 0, qpc N 2 for Fast SCR conditions.
- An FTIR analyzer makes it possible to measure the concentration of NO, NO 2, NH 3 , N 2 O, CO 2 , CO 2 , H 2 O, O 2 species at the outlet of the reactor.
- the NOx conversions calculated as following:
- Example 2 The NOx conversion results are shown in FIG. 4, the curves marked by squares, circles and triangles respectively corresponding to the tests carried out with the catalysts synthesized according to Example 2 (CuAFX3) Example 3 (CuAFXI) and Example 4 (CuSSZI 6).
- T50 is the temperature at which 50% of the NOx in the gas mixture is converted by the catalyst.
- T80 is the temperature at which 80% of NOx of the gaseous mixture are converted by the catalyst.
- T90 is the temperature at which 90% of the NOx in the gas mixture is converted by the catalyst.
- T100 is the temperature at which 100% NOx of the gas mixture is converted by the catalyst.
- the catalysts CuAFXI and CuAFX3 synthesized according to the invention give superior performance to the catalyst CuSSZ16 synthesized according to the prior art in terms of initiation temperatures and NOx conversion over the entire temperature range tested under Fast SCR conditions. Indeed, at the same conversion rate (50%, 80%, 90% or 100%), the initiation temperatures obtained with the catalysts according to the invention CuAFXI and CuAFX3 are lower compared with those obtained with the catalyst CuSSZ16 .
- nitrous oxide (N 2 0) emissions in the case of CuAFXI and CuAFX3 catalysts according to the invention, remain low over the entire temperature range tested ( ⁇ 15 ppm between 150 and 550 ° C.).
- a catalytic test for the reduction of nitrogen oxides (NOx) by ammonia (NH 3 ) in the presence of oxygen (O 2 ) under Standard SCR and Fast SCR conditions is carried out at different operating temperatures for the catalysts synthesized according to Examples 2 and 4 then aged according to the procedure described in Example 5, noted CuAFX3vieilli and CuSSZ16vieilli.
- 200 mg of catalyst in the form of a powder is placed in a quartz reactor. 145 l / h of a representative charge of an exhaust gas mixture are fed into the reactor.
- This feed has the following molar composition: 400 ppm NO, 400 ppm NH 3 , 8.5% 0 2 , 9% CO 2 , 10% H 2 0, qpc N 2 for Standard SCR conditions and the following molar composition: 200 ppm NO, 200 ppm N0 2 , 400 ppm NH 3 , 8.5% 0 2 , 9% C0 2 , 10% H 2 0, qpc N 2 for Fast SCR conditions.
- An FTIR analyzer makes it possible to measure the concentration of NO, NO 2 , NH 3 , N 2 O, CO, CO 2 , H 2 O, O 2 species at the outlet of the reactor.
- the NOx conversions calculated as following:
- Figure 5 shows the NOx conversion of aged CuAFX3 and aged CuSSZ16 catalysts as a function of temperature under Standard SCR conditions.
- T50 is the temperature at which 50% of the NOx in the gas mixture is converted by the catalyst.
- T80 is the temperature at which 80% of the NOx in the gas mixture is converted by the catalyst.
- T90 is the temperature at which 90% of the NOx in the gas mixture is converted by the catalyst.
- T100 is the temperature at which 100% NOx of the gas mixture is converted by the catalyst.
- the catalyst CuAFX3 synthesized according to the invention gives a much higher performance than the catalyst CuSSZ16 synthesized according to the prior art in terms of initiation temperatures and NOx conversion over the entire range of temperature tested under Standard SCR conditions after hydrothermal aging. Indeed, at the same conversion rate (50%), the initiation temperatures obtained with the catalyst according to the invention CuAFX 3 are lower compared with those obtained with the catalyst CuSSZ16. A conversion of 100% is reached between 275 and 330 ° C for the CuAFX3 catalyst while the CuSSZ16 catalyst achieves only 66% conversion at 330 ° C.
- the performance under Fast SCR conditions is also higher for the aged CuAFX3 catalyst synthesized according to the invention; the maximum conversion is 100% and is reached between 225 and 360 ° C while the aged CuSSZ16 catalyst reaches only 78% at most between 305 and 360 ° C.
- nitrous oxide (N 2 O) emissions are comparable for the two catalysts tested ( ⁇ 15 ppm between 150 and 550 ° C).
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1854387A FR3081348B1 (fr) | 2018-05-24 | 2018-05-24 | Catalyseur comprenant une zeolithe de type structural afx de tres haute purete et au moins un metal de transition pour la reduction selective de nox |
PCT/EP2019/062558 WO2019224086A1 (fr) | 2018-05-24 | 2019-05-16 | Catalyseur comprenant une zeolithe de type structural afx de tres haute purete et au moins un metal de transition pour la reduction selective de nox |
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EP3801840A1 true EP3801840A1 (fr) | 2021-04-14 |
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EP19724197.9A Withdrawn EP3801840A1 (fr) | 2018-05-24 | 2019-05-16 | <sup2/>? <sub2/>?x?catalyseur comprenant une zeolithe de type structural afx de tres haute purete et au moins un metal de transition pour la reduction selective de no |
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EP (1) | EP3801840A1 (fr) |
JP (1) | JP2021524373A (fr) |
FR (1) | FR3081348B1 (fr) |
WO (1) | WO2019224086A1 (fr) |
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FR3081347B1 (fr) | 2018-05-24 | 2023-07-28 | Ifp Energies Now | Procede de preparation d'une zeolithe de type structural afx de haute purete avec un structurant organique azote |
FR3095199B1 (fr) | 2019-04-19 | 2021-10-29 | Ifp Energies Now | Procédé de synthèse rapide d'une zeolithe de type structural AFX avec une source de faujasite |
FR3101259B1 (fr) * | 2019-09-30 | 2022-07-29 | Ifp Energies Now | Synthese a basse temperature de catalyseur a base de zeolithe afx et son application en nh3-scr |
FR3123006B1 (fr) * | 2021-05-21 | 2023-06-02 | Ifp Energies Now | Synthese d’un catalyseur a base de zeolithe afx contenant du palladium pour l’adsorption des nox |
CN114790406B (zh) * | 2022-05-20 | 2023-05-30 | 浙江桃花源环保科技有限公司 | 用于抑制生物质燃料燃烧中含氮污染物生成的燃料添加剂 |
FR3142917A1 (fr) * | 2022-12-09 | 2024-06-14 | IFP Energies Nouvelles | Catalyseur comprenant une zéolithe IZM-9 de type structural AFX de très haute pureté et au moins un métal de transition pour la réduction sélective de NOx |
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US5194235A (en) | 1992-08-27 | 1993-03-16 | Chevron Research And Technology Company | Synthesis of SSZ-16 zeolite catalyst |
JP6070230B2 (ja) | 2013-02-01 | 2017-02-01 | 東ソー株式会社 | Afx型シリコアルミノリン酸塩及びその製造方法、並びにこれを用いた窒素酸化物還元方法 |
KR102428707B1 (ko) * | 2014-10-07 | 2022-08-04 | 존슨 맛쎄이 퍼블릭 리미티드 컴파니 | 배기가스를 처리하기 위한 분자체 촉매 |
JP2018503578A (ja) | 2014-11-14 | 2018-02-08 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Publiclimited Company | Afxゼオライト |
US10486145B2 (en) | 2015-10-12 | 2019-11-26 | Umicore Ag & Co. Kg | One-pot synthesis of copper containing small-pore zeolites |
CA3005448A1 (fr) * | 2015-11-16 | 2017-05-26 | Exxonmobil Upstream Research Company | Materiaux adsorbants et procedes d'adsorption de dioxyde de carbone |
BR112018070992A2 (pt) * | 2016-05-24 | 2019-01-29 | Exxonmobil Chemical Patents Inc | zeólita sintética compreendendo um metal catalítico |
US10500573B2 (en) | 2016-09-30 | 2019-12-10 | Johnson Matthey Public Limited Company | Zeolite synthesis with alkaline earth metal |
-
2018
- 2018-05-24 FR FR1854387A patent/FR3081348B1/fr active Active
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2019
- 2019-05-16 WO PCT/EP2019/062558 patent/WO2019224086A1/fr unknown
- 2019-05-16 EP EP19724197.9A patent/EP3801840A1/fr not_active Withdrawn
- 2019-05-16 JP JP2020565881A patent/JP2021524373A/ja active Pending
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FR3081348B1 (fr) | 2023-11-10 |
FR3081348A1 (fr) | 2019-11-29 |
WO2019224086A1 (fr) | 2019-11-28 |
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