EP3160641A1 - Method for preparing shaped porous inorganic materials, by reactive extrusion - Google Patents
Method for preparing shaped porous inorganic materials, by reactive extrusionInfo
- Publication number
- EP3160641A1 EP3160641A1 EP15734117.3A EP15734117A EP3160641A1 EP 3160641 A1 EP3160641 A1 EP 3160641A1 EP 15734117 A EP15734117 A EP 15734117A EP 3160641 A1 EP3160641 A1 EP 3160641A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixture
- precursor
- extruder
- porous inorganic
- mixing
- 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- Withdrawn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
- 238000000034 method Methods 0.000 title claims abstract description 63
- 229910010272 inorganic material Inorganic materials 0.000 title claims abstract description 31
- 239000011147 inorganic material Substances 0.000 title claims abstract description 31
- 238000001125 extrusion Methods 0.000 title description 21
- 239000002243 precursor Substances 0.000 claims abstract description 63
- 239000000203 mixture Substances 0.000 claims abstract description 50
- 238000002156 mixing Methods 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- 238000007493 shaping process Methods 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 239000010955 niobium Substances 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010937 tungsten Substances 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 2
- 230000008569 process Effects 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 9
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 9
- 230000002776 aggregation Effects 0.000 claims description 8
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000009472 formulation Methods 0.000 claims description 6
- 230000012010 growth Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 6
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 230000006911 nucleation Effects 0.000 claims description 5
- 238000010899 nucleation Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 4
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005054 agglomeration Methods 0.000 claims description 4
- 238000004220 aggregation Methods 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000002441 X-ray diffraction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 238000004898 kneading Methods 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000002923 metal particle Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000000207 volumetry Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- -1 polypropylene Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000004438 BET method Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical class O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- FGLJARWAXPXMGZ-UHFFFAOYSA-N 2-methylbutan-1-ol;3-methylbutan-1-ol Chemical compound CCC(C)CO.CC(C)CCO FGLJARWAXPXMGZ-UHFFFAOYSA-N 0.000 description 1
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- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
Definitions
- the present invention relates to the field of shaped porous inorganic materials, particularly oxide-based materials having a porosity particularly suitable for catalytic applications, particularly in the field of refining and petrochemistry. It relates more specifically to the preparation of these materials which are obtained by the use of the technique of synthesis and shaping known as "reactive extrusion".
- an extrusion process allows the shaping of solids formulated in paste form by a suitable kneading of the powder at a given temperature (in the presence of possible additives and / or liquids), via a forced flow. material through a finite-size orifice (die).
- the extruder may also behave like a chemical reactor, the seat of reactions between molecular or macromolecular reagents leading to the formation at the die exit of a solid material or object. This characteristic is particularly used in the field of polymers.
- twin-screw extruder The tool well known to those skilled in the art most suitable for operating in reactive mode is the twin-screw extruder, the latter being constituted, as its name suggests, two screws that can be counter-rotating or co-rotating.
- rotary machines which rotate inside a cylindrical sheath regulated in temperature by heating and / or cooling means.
- Reactive extrusion is therefore a process that combines, in a continuous mode of operation, both the steps of "synthesis” and “shaping" of solids.
- a process is widely used in the food industry and in the polymer industry.
- the extruder in addition to shaping the polymer objects, can be considered as a polymerization reactor. More specifically, the steps involved are as follows: 1) introduction of monomer-type reagents, 2) realization of the polymerization reactions at the beginning of kneading and 3) shaping of the polymer thus formed at the extruder outlet.
- Such a process has thus made it possible to obtain different families of polymers (polyamides: B. Lee, J.
- nanocomposite materials have also been studied, the latter being derived from the assembly of at least two immiscible materials, of which at least one of the components is of nanometric size. More recently, by the combination of "sol-gel” chemistry (hydrolysis-condensation reactions of inorganic precursors) and a polymer matrix, polymeric nanocomposites / inorganic materials have also been obtained by reactive extrusion, such as for example polypropylene / titanium dioxide (W. Bahloul, O. Oddes, V. Bounor-Legaré, F. Melis, P. Cassagnau, B.
- Twin-screw extruders are also used as extrusion kneading tools for the manufacture of catalyst supports such as alumina-based substrates, which are not reactive extrusion but rather operations of implementation. classic form in a continuous tool.
- the main advantage of reactive extrusion is that it enables the synthesis and shaping of solids in a single step.
- the associated tool can operate at high temperature, with significant thermal gradients, as well as under high pressures. Highly viscous media, in total absence or almost solvent (s), can be extruded. Thus, this method is known to be more economical but also more environmentally friendly than some other methods of synthesis or formatting.
- the transport and mixing capacity of the tool can be limited or degraded when the reagents or products involved have too low viscosity.
- the transposition to the case of the synthesis and the shaping of porous inorganic materials is not easy because it requires working from at least one precursor in liquid form (viscosity close to that of water ), poorly adapted to the use of an extruder, the conveying and mixing being made delicate by the low viscosity.
- the Applicant has discovered a method of preparation and operating conditions which make it possible to drastically reduce the synthesis time of a porous inorganic material and to reduce the supply of external solvents by minimizing the variations in loss of ignition throughout the synthesis process. until obtaining the inorganic porous shaped material.
- the invention relates to a process for the preparation by reactive extrusion of a shaped porous inorganic material.
- the Applicant has discovered that it is possible to apply the reactive extrusion process to the synthesis and forming, in a single step and continuously, of porous inorganic materials.
- the idea of the present invention is to use the extruder as a chemical reactor to perform the hydrolysis and condensation reactions involved in the nucleation / growth steps during the synthesis of porous oxide-based inorganic materials. (s).
- the innovative use of this technology in this field has in particular made it possible to access materials presenting properties of interest (textural, mechanical, acid-base, etc.) in a single operation and continuously, contrary to the technologies used more conventionally.
- the invention relates to a process method for preparing a porous inorganic material comprising at least the following steps:
- the preparation process comprises a step a) of reacting a mixture comprising at least one precursor of the oxide of a metal X in solution in a solvent and an oxide precursor of a metal Y, at a temperature between 30 and 70 ° C.
- X and Y are independently selected from the group consisting of aluminum, cobalt, indium, molybdenum, nickel, silicon, titanium, zirconium, zinc, iron, copper, manganese , gallium, germanium, phosphorus, boron, vanadium, tin, lead, hafnium, niobium, yttrium, cerium, gadolinium, tantalum, tungsten, antimony, europium and neodymium.
- the element X is selected from the group consisting of aluminum, silicon, titanium and zirconium, and very preferably in the group consisting of aluminum and silicon.
- the element Y is chosen from the group consisting of aluminum, silicon, titanium, boron, phosphorus and zirconium, and very preferably from the group consisting of aluminum, phosphorus, and silicon.
- the precursor of the oxide of the metal X may be any compound comprising the element X and capable of releasing this element in solution, for example in aqueous, aquo-organic or organic solution, preferably in aqueous solution, in reactive form.
- Z is chlorine.
- the precursor of the element X under consideration may also be an oxide or hydroxide of the element X.
- the precursor of the element X considered employed can also be of the form XOZ 2 , Z being a monovalent anion such as a halogen or the group N0 3 .
- said element X is chosen from the group consisting of silicon, aluminum, titanium and zirconium.
- the precursor of the element X in its oxide or hydroxide form, can also be solid silica powder, silicic acid, colloidal silica, dissolved silica, etc.
- the aluminum precursor is advantageously an inorganic aluminum salt of formula AIZ 3 , Z being a halogen, a nitrate or a hydroxide.
- Z is chlorine.
- the aluminum precursor may also be an aluminum sulphate of formula AI 2 (SO 3 ).
- R is s-butyl.
- Aiuminique the precursor can also be sodium aluminate or potassium or ammonium or alumina itself in one of its crystalline phases known to the skilled person (alpha, delta, teta, gamma) preferably in hydrated form or which can be hydrated. It is also possible to use mixtures of the precursors mentioned above. In particular, some or all of the aluminic and silicic precursors may optionally be added in the form of a single compound comprising both aluminum atoms and silicon atoms, for example an amorphous alumina silica.
- Said solvent is advantageously water, ethanol, propan-1-ol, propan-2-ol, 2-methylpropan-1-ol, 2-methyl-propan-2-ol, 2.2 dimethylpropanol, butanol, 2-butanol, 2-methylbutan-2-ol, 3-methyibutan-2-ol, pentanol, 2-methylbutan-1-ol, 3-methylbutan-1-ol, pentan-2-ol, pentan-3-ol, taken alone or in admixture, very advantageously water or ethanol alone or in mixture.
- said solvent is water.
- the precursor of the metal oxide Y may advantageously be added to the mixture of step a) in solution in said solvent or in powder form.
- the mixture reacting in step a) contains no surfactant generating mesoporosity.
- mesoporosity generating surfactant is meant an ionic or nonionic surfactant or a mixture of both.
- the ionic surfactants generating mesoporosity can be cationic and anionic surfactants.
- the cationic surfactants may be phosphonium or ammonium ions and very preferably quaternary ammonium salts such as cetyltrimethylammonium bromide (CTAB).
- CTAB cetyltrimethylammonium bromide
- the anionic surfactants may be sulphates such as, for example, sodium dodecyl sulphate (SDS).
- the nonionic surfactants may be any copolymer having at least two parts of different polarities conferring properties of amphiphilic macromolecules.
- Any other amphiphilic copolymer known to those skilled in the art may be, for example poly (styrene-b-acrylamide) (S. Fôrster, M. Antionnetti, Adv Mater, 1998, 10, 195, S. Fôrster , T. Patantenberg, Angew Chem Int, Ed, 2002, 41, 688, H. Colfen, Macromol, Rapid Commun, 2001, 22, 219).
- nucleation, growth, agglomeration and aggregation reactions of said precursors take place.
- PH and temperature are regulated at target values.
- the pH is maintained by regulating the ratio of the flow rates of the different precursors.
- the mixture reacting in step a) comprises at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid.
- said precursors are mixed before step a), for example in a static mixer, at a temperature between 30 and 70X.
- This mixture prior to step a) makes it possible, by initiating the synthesis reaction, to control more finely the textural properties of the porous inorganic material obtained by the process according to the invention.
- the precursors are introduced into the extruder by a feed means which may be a feed hopper for the powders, and / or a pump, a syringe pump and possibly a mixing device (internal mixer type, T-shaped mixer). , or any type of premixer known to those skilled in the art such as, for example, the Y mixer, the Rotor Stator, the Roughton Hartridge) for the liquids, said means being arranged upstream of the extruder.
- This feeding means is called the main feeding means.
- the mixture obtained at the end of step a) is kneaded at a temperature of between 80 and 150 ° C., the mixing time being adjusted so as to obtain a dough having a loss on ignition at the result of step b) of between 20 and 90%, preferably between 20 and 75%, preferably between 20% and 65%, preferably between 40% and 65%.
- the loss on ignition is calculated by the mass difference of the sample before and after calcination at 1000 ° C for 3 h as the ratio of the difference between the initial mass and the final mass on the initial mass. The percentage is therefore a weight percentage.
- This step makes it possible to eliminate a part of the solvent present in the mixture obtained at the end of step a) so as to reduce the loss in the fire of the mixture.
- the operating temperature of said step b) makes it possible to evaporate the solvent. It is also possible to adapt the screw profile in the module or modules of the extruder in the (s) is (s) is carried out said step b) so as to press the mixture, and thereby extract a portion of the solvent. Depending on the mixture obtained at the end of said step a), those skilled in the art adjust the length and / or the profile of the screw of the modules in which said step b) is implemented to ensure a sufficient residence time. to achieve the desired loss on fire.
- a washing step b1) is carried out within the extruder in order to eliminate the undesirable species for the targeted catalytic support.
- a solvent is incorporated in the mixture obtained at the end of step b) by kneading.
- Said solvent is advantageously water, an aqueous solutions of ammonium nitrate, ethanol, propan-1-ol, propan-2-ol, 2-methylpropan-1-ol, 2-methylpropan -2-ol, 2,2-dimethylpropanol, butanol, 2-butanol, 2-methylbutan-2-ol, 3-methylbutan-2-ol, pentanol, 2-methylbutan-1-ol 3-methylbutan-1-ol, pentan-2-ol, pentan-3-ol.
- a kneading step is carried out in the extruder at a temperature of between 80 and 150 ° C., the kneading time being adjusted in such a way as to obtain a dough having a loss on ignition at the end of step b2) between 20 and 90%, preferably between 20 and 75%, preferably between 20% and 65%, most preferably between 40% and 65% .
- This step makes it possible to eliminate a part of the solvent present in the mixture obtained at the end of step b1) so as to reduce the loss on ignition of the mixture.
- the operating temperature of said step b2) makes it possible to evaporate the solvent.
- This step is similar in its operation and its operation in step b) of mixing. The setting of the operating parameters therefore applies mutatis mutandis.
- an additive stage in which are added to the mixture obtained at the end of step b), or obtained at the end of step b2) if one or more washes were necessary, one or more formulation additives which are incorporated into the mixture by kneading.
- Said formulation additives may be solid, liquid or gaseous and preferably solid or liquid.
- formulation additive means the products well known to those skilled in the art for improving the conduct of the system, such as adjuvants to facilitate extrusion or to optimize the rheology of the system, peptization agents allowing to obtain a better dispersion of the binder or fillers, agents making it possible to improve the mechanical characteristics of the material (fillers, binders, compatibilizing agents). to adjust the porous properties (such as foaming agents, dispersing agents, coagulants), to optimize the surface characteristics, the physicochemical properties, chemical composition or other.
- These additives may be of mineral or organic composition. In the case of organic compounds, they can be advantageously removed during step d).
- Said formulation additives may also comprise metal particles.
- metal particles means particles having a size of at most 300 nm, preferably at most 50 nm and even more preferably at most 3 nm.
- the size of said metal particles is advantageously measured by transmission electron microscopy (TEM), when this is greater than 1 nm.
- TEM transmission electron microscopy
- the absence of MET metal particle detection therefore means that said metal particles have a size less than 1 nm.
- Said metal particles comprise at least one metal belonging to the family of transition metals corresponding to columns 3 to 12 of the periodic table according to the IUPAC classification and / or to the family of rare earth metals, and preferably actinides, belonging to the group consisting of Au, Pd, Pt, Ni, Co, Cu, Ag, Rh, Ru, Ir, Fe, Ti, Zr, Nb, Ta, Mo, W, Fe, Y, La, Cr, Ce, Eu, Nd , Gd, Sn, in taken alone or in a mixture, very preferably belonging to the group Au, Pd, Pt, Ni, Co, Rh, Ti, Zr, Mo, W, Sn, In taken alone or as a mixture, in forms reduced, oxide (whose form polymetallic oxide), chalcogenide and polyoxometallate (isopolyanion and heteropolyanion (HPA)).
- actinides belonging to the group consisting of Au, Pd, Pt, Ni, Co, Cu, Ag, Rh, Ru, Ir, Fe
- HPA HPA of the Andersen type (Nature, 1937, 150, 850), Keggin (A. Griboval, P. Blanchard, E. Payen, Heteropoly and Isopoiy Oxometalaies, Pope, Ed Springer-Verlag, 1983. M. Fournier, J, L. Dubois, Chem Lett, 1997, 12, 1259, C. Dablemont et al., Chemistry, 2006, 12, 36, 9150, LGA van de Water et al., J. Phys Chem B, 2005, 109, 14513) and Strandberg (WC, Cheng et al., J. Gattai, 1988, 109, 163).
- Said metal particles may advantageously be added in said step b3) in their reduced form, oxide, chalcogenide or polyoxometallate.
- organic additives polyethylene glycols, aliphatic mono-carboxylic acids, alkylated aromatic compounds, suiphonic acid salts, fatty acids, polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose, cellulose, hydroxyethylcellulose derivatives, carboxymethylcellulose, polyacrylates, polymethacrylates, polyisobutene, polytetrahydrofuran, starch, polysaccharide-type polymers (such as xanthan gum), alginates, sclerogiucane, lignosulfonates and galactomannan derivatives, taken alone or as a mixture.
- the oxides or precursors of oxides well known to those skilled in the art boehmite, alumina, silica, titanium oxide, zirconia, lanthanum, cerium, magnesia, zincite, iron, copper, mixed oxides such as alumino-silicates, spinels. perovskites, aluminates, titanates, zirconates. It is also possible to use clays, in particular those of the families of kaolinites, smectites or illites. Zeolites or mixtures of zeolites may also allow the optimization of the properties of the material.
- organic or inorganic acids or bases such as acetic acid, hydrochloric acid, sulfuric acid, formic acid, citric acid and nitric acid, alone. or in a mixture, sodium hydroxide, potassium hydroxide, ammonia, or else an amine, a quaternary ammonium compound, chosen, for example, from alkyl-ethanol amines or ethoxylated alkylamines, tetraethylammonium hydroxide or tetramethylammonium hydroxide.
- the various additives may be used alone or in a mixture, introduced together or sequentially.
- the paste obtained at the end of the last kneading or additivation step carried out is shaped.
- the shaping is done by passing through a die.
- This die may be a flat die, allowing to obtain films, or a rod die, to obtain a ring whose section corresponds to the shape of said die. They can thus be, for example, of hollow cylindrical shape or not, multilobed (with 2, 3, 4 or 5 lobes for example), fluted, slotted, twisted. Shear at the outlet of the die makes it possible to produce extrudates of determined length. It is not excluded that said materials obtained are then, for example, introduced into a device for rounding their surface, such as a bezel or other equipment allowing their spheronization.
- the porous inorganic product is obtained in the form of powder or agglomerates in the case of extrusion without the use of a die.
- All of the steps a) to c), and b1), b2) b3) when they are implemented, are carried out within an extruder.
- Said extruder has at least one screw capable of rotating inside a fixed envelope called sheath, at the end of which is positioned a die which imposes its shape on the extruded product.
- sheath a fixed envelope
- the process according to the invention can be carried out in a single-screw extruder, it is preferred to conduct it in a co-rotating or counter-rotating twin-screw extruder because of the highly flexible character thereof.
- the entire process is thermostated from the main supply means to the extrusion die.
- the extruder consists of successive modules arranged coaxially and having independent and adjustable heating zones, which makes it possible to apply the exact desired temperature for the material being kneaded / extruded as a function of its positioning in the process.
- the temperature range used ranges from 15 to 600 ° C, preferably from 15 to 350 ° C, even more preferably from 20 to 300 ° C, and most preferably from 30 to 150 ° C.
- the screws and the sleeves are made by the assembly of modules in series whose arrangement and the sequence are modifiable. We will thus be able to associate transport elements with no more or less wide, mixing blocks, retro-mixing blocks, turbines, etc. (Reactive extrusion processes, F. BERZIN, G. -H.
- twin-screw extruder makes it possible to link together unit operations such as feeding, transport and evaporation of solvents, mixing the reagents, reaction, devolatilization, pumping and shaping.
- introduction of other elements, such as washing solvents for example can be carried out via secondary supply zones positioned downstream of the main feed hopper. Consequently, withdrawal zones are present for the evacuation of any excess liquids.
- such a tool can also operate in an inert atmosphere via the scanning of a suitable carrier gas (N 2 , Ar), thus allowing the use of precursors decomposing in the presence of water or air.
- adaptable kneading modules constituting each of the two rotary screws used make it possible to apply kneading conditions according to the location of the material in the sheath, as well as the length of the mixing zone before extrusion.
- the operating conditions of the extrusion such as the screw profile, the residence time of the material, the screw rotation speed will be set by the skilled person according to the desired final characteristics.
- the extruder used for carrying out the method according to the invention advantageously has an L / D (length to diameter) of between 1 and 200, preferably between 2 and 120. preferably between 20 and 100, and so very preferred between 30 and 100.
- the reactive extrusion can be carried out advantageously with the following conditions:
- an average residence time of the mixture in the extruder that is to say the average time to carry out all the steps of a) to c), and thus possibly including the steps b1), b2) and b3) between 0.1 minute and 120 minutes, preferably between 0.1 and 60 minutes, preferably less than 30 minutes, and very preferably less than 10 minutes,
- the modules will be chosen by those skilled in the art so as to allow the realization of the steps of the preparation process according to the invention.
- the shaped material obtained at the end of step c) may optionally be subjected to one or more thermal processing steps.
- the shaped material obtained at the end of step c) may optionally undergo a drying step, which may be performed by any technique known to those skilled in the art. In particular, it is carried out by passing in an oven at a temperature of between 50 and 150 ° C.
- said drying step will be performed in an inert atmosphere.
- an autoclaving step can be implemented in the case where it is desired to crystallize the shaped porous inorganic material obtained at the end of step c).
- This autoclaving step which is a specific hydrothermal treatment, consists in placing said shaped material in a closed chamber in the presence of a solvent at a given temperature so as to work with autogenous pressure inherent to the operating conditions chosen.
- the solvent used is advantageously a protic polar solvent.
- the solvent used is water.
- the volume of solvent introduced is defined relative to the volume of the autoclave selected, the mass introduced and the treatment temperature.
- the volume of solvent introduced is in a range of 0.01 to 20% relative to the volume of the autoclave chosen, preferably in a range of 0.05 to 5% and more preferably in a range of 0. , 05 to 1%.
- the autoclaving temperature is between 50 and 200 ° C, preferably between 60 and 170 ° C and still more preferably between 60 and 120 ° C.
- This treatment makes it possible, if necessary according to the final properties desired for the porous inorganic material, to carry out the growth of zeolite entities in the walls of the matrix based on oxide (s).
- the autoclaving is maintained over a period of 1 to 96 hours and preferably over a period of 10 to 72 hours. hours.
- the drying of the particles after autoclaving is advantageously carried out by placing in an oven at a temperature of between 50 and 130 ° C.
- the shaped material obtained at the end of step c) may also optionally undergo a calcination step in air in a temperature range of 130 to 1000 ° C. and more precisely in a range of 300 to 600 ° C. for duration of 1 to 24 hours and preferably for a period of 2 to 12 hours.
- the material shaped at the end of step c) may also optionally undergo a hydrothermal steaming type treatment in an oven in the presence of steam.
- the temperature during the steaming may be from 300 to 1100 ° C and preferably above 700 ° C for a period of time from 30 minutes to 12 hours, preferably from 30 minutes to 4 hours.
- the water vapor content is greater than 20 g of water per kg of dry air and preferably greater than 40 g of water per kg of dry air and preferably greater than 100 g of water per kg. dry air.
- Such treatment may, if necessary, completely or partially replace the calcination treatment.
- the material used according to the invention is characterized by several analysis techniques according to its final properties and in particular by: X-ray diffraction at low angles (X-ray at low angles), X-ray diffraction at large angles (XRD) by nitrogen volumetric (BET).
- X-ray at low angles X-ray at low angles
- XRD X-ray diffraction at large angles
- BET nitrogen volumetric
- metal particles as described in the present description can be demonstrated by various techniques, in particular by Raman, UV-visible or infrared spectroscopies. Techniques such as nuclear magnetic resonance (NMR) or electronic paramagnetic resonance (EPR) can also be used according to the precursors employed.
- NMR nuclear magnetic resonance
- EPR electronic paramagnetic resonance
- the low-angle X-ray diffraction technique makes it possible to characterize the periodicity at the nanoscale generated by the organized mesoporosity of the oxide-based matrix ( s) when it is said mesostructured.
- the X-ray analysis is carried out on powder with a diffractometer operating in reflection and equipped with a rear monochromator using copper radiation (wavelength of 1.5406 A).
- the X-ray diffraction technique at large angles makes it possible to characterize a crystallized solid defined by the repetition of a unitary unit or elementary cell at the molecular scale. It follows the same physical principle as that governing the low-angle X-ray diffraction technique.
- the wide-angle DRX technique is therefore used to analyze the materials used according to the invention because it is particularly suitable for the structural characterization of the crystallizable metal particles and nanocrystals of zeolites possibly trapped in the walls of the matrix based on oxide (s), as well as the structural characterization of the zeolite entities possibly constitutive of said walls.
- the nitrogen volumetry corresponding to the physical adsorption of nitrogen molecules in the porosity of the inorganic material obtained according to the invention via a progressive increase in pressure at constant temperature provides information on the textural characteristics (pore diameter, pore volume specific surface area) of the material used according to the invention. In particular, it provides access to the specific surface and the mesoporous distribution of the material.
- Specific surface area is defined as the BET specific surface area (S BET in m2 / g) determined by nitrogen adsorption in accordance with ASTM D 3663- 78 established from the Brunauer-Emmett-Teller method described in "The Journal of the American Society, 1938, 60, 309.
- the representative porous distribution of a mesopore population centered in a range of 2 to 50 nm is determined by the Barrett-Joyner-Halenda model (BJH).
- BJH Barrett-Joyner-Halenda model
- the nitrogen adsorption-desorption isotherm according to the BJH model thus obtained is described in the periodical 'The Journal of American Society', 1951, 73, 373, written by EP Barrett, LG Joyner and PP Halenda.
- the diameter of the mesopores f of the matrix to Oxide base (s) is the value of the maximum diameter read on the pore size distribution curve obtained from the adsorption branch of the nitrogen isotherm.
- the shape of the nitrogen adsorption isotherm and the hysteresis loop can provide information on the nature of the mesoporosity and the presence of the possible microporosity of the inorganic material obtained according to the invention.
- the quantitative analysis of the microporosity of the inorganic material obtained according to the invention is carried out using methods "t” (method Lippens-De Boer, 1965) or "as” (method proposed by Sing) that correspond to transformations of the starting adsorption isotherm as described in the book "Adsorption by powders and porous solids, Principles, methodology and applications” written by F. Rouquerol, J. Rouquerol and K. Sing, Academy Press, 1999. These methods allow to access in particular the value of the microporous volume characteristic of the microporosity of the inorganic material obtained according to the invention.
- the precursors a basic aluminum salt [AlOONa] and an acidic aluminum salt [Al 2 (SO 3) 3] are fed continuously for 30 minutes in a reactor of 5 I, at a temperature of 60 ° C. which precipitation takes place.
- the ratio of the acid / solid flow rates is adjusted so that the pH is equal to 9.
- a final concentration of alumina of 45 g / l is aimed at.
- the suspension obtained is then filtered by displacement of water on a sintered Buchner type tool and the alumina gel obtained is washed 3 times with 5 l of distilled water.
- the fire loss of the powder at the end of this step is about 90%.
- the alumina gel is dried at 120 ° C in an oven overnight.
- the fire loss of the powder at the end of this step is about 23%.
- the dried gel forms a powder which is introduced into a Brabender type mixer.
- An aqueous solution of nitric acid at a total acid content of 3%, expressed by weight relative to the mass of dried gel introduced into the kneader, is added in 10 minutes, during mixing at 20 rpm (Loss at 62% fire).
- the acid kneading is continued for 5 minutes.
- a neutralization step is then carried out by adding an ammoniacal solution in the mixer (61% loss on ignition). The kneading is continued for 3 minutes.
- the paste obtained is then extruded through a 2 mm trilobal die.
- the extrudates obtained are dried at 100 ° C. overnight, then calcined for 2 hours at 500 ° C. under a moist air stream in a tubular furnace.
- porous inorganic material therefore requires many manipulations. It also flows more than 24 hours between the introduction of the precursors and obtaining the extruded.
- Example 2 (in conformity) - Production of a porous inorganic material from a mixture of two liquid precursors without premixer
- Two aluminum precursors in solution in water, aluminum nitrate AI 2 (N0 3 ) 3 and sodium aluminate AI0 2 Na previously preheated to 60 ° C, are fed into the first module via the main hopper feeding the extruder, which is operated with a mixing speed of 50 rpm.
- This first module makes it possible to carry out the reaction step a), during which the nucleation, growth, aggregation and agglomeration reactions take place.
- the precursors in solution are introduced using two peristaltic pumps.
- the sum of the flows is equal to 3 l / h, and the ratio of amount of basic aluminum precursor to amount of aluminum acid precursor is adjusted so as to allow regulation of the pH to 9.
- the loss on ignition is more than 80%.
- the following modules are organized in a succession of conveying elements and kneading elements.
- the beginning of the extruder (modules 2 to 5) is used as a conveying zone and drying of the dough in which is implemented step b).
- the temperature of the modules 2 to 5 is regulated at 1 10 ° C.
- the loss on ignition of the pulp is 60%, the loss on ignition being calculated by the difference in mass before and after caicination at 1000X.
- the modules 6 to 10 are carried out the step b3) additivation. These modules are regulated at a temperature of 20 ° C.
- nitric acid 4% by weight of acid relative to Al 2 O 3
- methocel TM 1% by weight relative to the dry mass
- an ammoniacal solution is added (40% by weight relative to the amount of acid introduced).
- the paste obtained at the end of the module 10 is then extruded via a three-lobed die 3 rushes so as to obtain rods with a diameter of 3 mm. These are then dried for 12 hours in an oven at 80 ° C. and then calcined under air for 2 hours at 550 ° C.
- the solid is characterized by XRD and nitrogen volumetry.
- the mesoporous diameter obtained by the BJH method is 7.4 nm.
- XRD analysis makes it possible to identify the alumina gamma phase.
- Example 2 differs from Example 2 only in that a Y-premixer is placed upstream of the feed hopper to control the nucleation steps of co-precipitation growth. The aggregation and agglomeration steps then take place in module 1.
- the solid is characterized by XRD and nitrogen volumetry.
- the mesoporous diameter obtained by the BJH method is 7.8 nm.
- XRD analysis makes it possible to identify the alumina gamma phase.
- Example 3 differs from Example 3 only in that, moreover, at the inlet of the module 7, an injection is made of a solution containing phosphoric acid corresponding to 1% by weight of P 2 0 5 relative to Al 2 0 3 .
- the solid is characterized by XRD and nitrogen volumetry.
- the mesoporous diameter obtained by the BJH method is 5.1 nm.
- XRD analysis makes it possible to identify the alumina gamma phase.
- This example differs from Example 3 only in that the procedure is more, the input of the module 7, to an injection of a solution containing silicic acid corresponding to 1 wt% of Si0 2 with respect to Al 2 0 3 .
- the solid is characterized by XRD and nitrogen volumetry.
- the mesoporous diameter, obtained by the BJH method, is 6.1 nm.
- XRD analysis makes it possible to identify the alumina gamma phase.
- a viscous solution, or colloidal suspension, containing 10% by weight of a Pural TM boehmite and 3% by weight of nitric acid relative to Al 2 0 3 is fed into the main hopper at the inlet of the module 1.
- a soil is introduced.
- silica to obtain a final porous inorganic material containing 30% by weight of Si0 2 with respect to the sum Si0 2 + Al 2 0 3 .
- Module 1 is temperature controlled at 60 ° C.
- the extruder is operated with a screw rotation speed of 50 rpm.
- the reaction leading to the aluminosilicate takes place in module 1.
- the following modules are organized into a succession of conveying elements and mixing elements.
- the beginning of the extruder (modules 2 to 5) is used as a zone of conveying and drying the dough in which is implemented step b).
- the temperature of the modules 2 to 5 is regulated at 110.degree.
- the loss on ignition of the pulp is 70%, the loss on ignition being calculated by the difference in mass before and after calcination at 1000 ° C.
- Modules 6 to 10 are regulated at a temperature of 20 ° C.
- the paste obtained at the end of the module 10 is then extruded via a three-lobed die 3 rushes so as to obtain rods with a diameter of 3 mm.
- These are then dried for 12 hours in an oven at 80 ° C. and then calcined under air for 2 hours at 550 ° C.
- the solid is characterized by XRD and nitrogen volumetry.
- the mesoporous diameter obtained by the BJH method is 4.1 nm.
- the XRD detects gamma alumina lines and the presence of amorphous material (amorphous silica).
- porous inorganic material for Examples 2 to 6 according to the invention is carried out continuously in one and the same tool. It only takes a few minutes between the introduction of the precursors and the extrusion.
Abstract
Description
Claims
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FR1456144A FR3022800A1 (en) | 2014-06-30 | 2014-06-30 | PROCESS FOR THE REACTIVE EXTRUSION PREPARATION OF SHAPED POROUS INORGANIC MATERIALS |
PCT/EP2015/064884 WO2016001246A1 (en) | 2014-06-30 | 2015-06-30 | Method for preparing shaped porous inorganic materials, by reactive extrusion |
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US (1) | US20170151555A1 (en) |
EP (1) | EP3160641A1 (en) |
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WO (1) | WO2016001246A1 (en) |
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FR3083992B1 (en) * | 2018-07-23 | 2020-07-24 | Ifp Energies Now | COMALAXE CATALYST FROM SOLUTIONS BASED ON HETEROPOLYANIONS, ITS PREPARATION PROCESS AND ITS USE IN HYDROCONVERSION OF HEAVY HYDROCARBON LOADS |
CN115869989A (en) * | 2022-09-27 | 2023-03-31 | 中国船舶重工集团公司第七一八研究所 | Preparation method of low-temperature denitration catalyst for tail gas of marine diesel engine |
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US20050142060A1 (en) * | 2003-12-30 | 2005-06-30 | Johnson Ivy D. | High solids materials processing |
CN102309994A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for alumina carrier |
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GB1470292A (en) * | 1974-03-20 | 1977-04-14 | Ici Ltd | Production of fibres |
GB8925979D0 (en) * | 1989-11-16 | 1990-01-04 | Shell Int Research | Process for the preparation of extrudates,extrudates,and use of the extrudates |
US5633217A (en) * | 1994-09-12 | 1997-05-27 | Corning Incorporated | Method of making a high strength catalyst, catalyst support or adsorber |
ES2284246T3 (en) * | 1998-03-31 | 2007-11-01 | GRACE GMBH & CO. KG | ZEOLITAS OF COMPACT STRUCTURE, A PROCESS FOR ITS PRODUCTION AND USE. |
US6156822A (en) * | 1998-11-12 | 2000-12-05 | The Goodyear Tire & Rubber Company | Prepared reinforced elastomer, elastomer composite and tire having component thereof |
US6388157B1 (en) * | 2000-11-03 | 2002-05-14 | Uop Llc | Aromatic alkylation process using UZM-5 and UZM-6 aluminosilicates |
-
2014
- 2014-06-30 FR FR1456144A patent/FR3022800A1/en active Pending
-
2015
- 2015-06-30 EP EP15734117.3A patent/EP3160641A1/en not_active Withdrawn
- 2015-06-30 WO PCT/EP2015/064884 patent/WO2016001246A1/en active Application Filing
- 2015-06-30 US US15/321,574 patent/US20170151555A1/en not_active Abandoned
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US20050142060A1 (en) * | 2003-12-30 | 2005-06-30 | Johnson Ivy D. | High solids materials processing |
CN102309994A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for alumina carrier |
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See also references of WO2016001246A1 * |
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US20170151555A1 (en) | 2017-06-01 |
WO2016001246A1 (en) | 2016-01-07 |
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