WO2002040402A1 - Solides inorganiques mesoporeux, leur procede de preparation et leurs utilisations notamment comme catalyseurs et adsorbants - Google Patents
Solides inorganiques mesoporeux, leur procede de preparation et leurs utilisations notamment comme catalyseurs et adsorbants Download PDFInfo
- Publication number
- WO2002040402A1 WO2002040402A1 PCT/FR2001/003496 FR0103496W WO0240402A1 WO 2002040402 A1 WO2002040402 A1 WO 2002040402A1 FR 0103496 W FR0103496 W FR 0103496W WO 0240402 A1 WO0240402 A1 WO 0240402A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dimethyl
- size
- particles
- pores
- mesoporous
- Prior art date
Links
- 229910003480 inorganic solid Inorganic materials 0.000 title claims abstract description 18
- 239000003463 adsorbent Substances 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 29
- 239000003054 catalyst Substances 0.000 title claims description 9
- 239000011148 porous material Substances 0.000 claims abstract description 69
- 239000007787 solid Substances 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 239000010954 inorganic particle Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 94
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 69
- 238000009826 distribution Methods 0.000 claims description 35
- 239000000377 silicon dioxide Substances 0.000 claims description 34
- 238000001179 sorption measurement Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 13
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- -1 phosphonium ions Chemical class 0.000 claims description 10
- 230000008961 swelling Effects 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000011164 primary particle Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000010419 fine particle Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000693 micelle Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- RKMJXTWHATWGNX-UHFFFAOYSA-N decyltrimethylammonium ion Chemical compound CCCCCCCCCC[N+](C)(C)C RKMJXTWHATWGNX-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000001483 mobilizing effect Effects 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000011163 secondary particle Substances 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 238000007323 disproportionation reaction Methods 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000003348 petrochemical agent Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 claims description 2
- IKANSXQHJXBNIN-UHFFFAOYSA-N trimethyl(octadecyl)phosphanium Chemical compound CCCCCCCCCCCCCCCCCC[P+](C)(C)C IKANSXQHJXBNIN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 14
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 238000012856 packing Methods 0.000 abstract description 3
- 239000000470 constituent Substances 0.000 abstract 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000003775 Density Functional Theory Methods 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- WECIKJKLCDCIMY-UHFFFAOYSA-N 2-chloro-n-(2-cyanoethyl)acetamide Chemical compound ClCC(=O)NCCC#N WECIKJKLCDCIMY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 210000004534 cecum Anatomy 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001033 granulometry Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- CTWJQOQFTNPBCX-UHFFFAOYSA-N 1-[2-(1h-inden-1-yl)ethyl]-1h-indene Chemical compound C1=CC2=CC=CC=C2C1CCC1C2=CC=CC=C2C=C1 CTWJQOQFTNPBCX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000019013 Viburnum opulus Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 description 1
- 229960004830 cetylpyridinium Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- QQJDHWMADUVRDL-UHFFFAOYSA-N didodecyl(dimethyl)azanium Chemical compound CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC QQJDHWMADUVRDL-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004237 preparative chromatography Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000004760 silicates Chemical class 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
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- APSPVJKFJYTCTN-UHFFFAOYSA-N tetramethylazanium;silicate Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.[O-][Si]([O-])([O-])[O-] APSPVJKFJYTCTN-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
- C01B33/185—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process of crystalline silica-polymorphs having molecular sieve properties, e.g. silicalites
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3491—Regenerating or reactivating by pressure treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
Definitions
- This invention relates to a process for the preparation of a new family of mesoporous inorganic particles; the process makes it possible to precisely control the particle size distribution and the morphology of the prepared particles which can advantageously be used as catalyst supports, as catalysts and / or for the separation of compounds in the gas phase having different boiling points as well as for the packing of chromatography columns.
- Prior art
- Mesoporous particles are very useful in the industrial field, both as catalysts, catalyst supports but also as adsorbents insofar as their high porosity expressed in terms of surface area to volume ratio allows the molecules with which they are brought into contact to easily access the core of the particles and react on a large surface thus enhancing the catalytic and / or adsorbent properties of these materials.
- MOBIL describes a method for preparing a composition of matter consisting of an inorganic, non-lamellar and crystalline phase having, after calcination, an arrangement of pores of uniform size equal to at least 1, 3 nm, with at least minus an X-ray diffraction peak corresponding to a reticular distance greater than 1.8 nm and having a benzene adsorption capacity greater than 15% by weight at 25 ° C. and 50 torr from a HiSil type silica mixed with a solution of tetramethylammonium silicate.
- syntheses of silicic mesoporous solids are carried out using tetraethylortho silicate (TEOS), a tetraalkylammonium or sodium silicate, precipitated silica.
- TEOS tetraethylortho silicate
- a tetraalkylammonium or sodium silicate precipitated silica.
- TEOS has the disadvantage, besides being an expensive reagent, of generating ethanol during hydrolysis. But, used in a non-basic medium, it is the only source of silica which makes it possible to prepare particles of mesoporous solids of a few ⁇ m.
- Another disadvantage of syntheses of mesoporous solids in neutral or acid medium relates to the yield of surfactant expressed as the ratio between the surfactant introduced at the start of synthesis and the surfactant retained in the solid formed which is clearly less than 100%.
- the granulation produces particles in the form of beads, therefore rather spherical, with a distribution of. large size, which, for certain applications, can constitute a handicap.
- the only way with this technique to obtain particles with a narrow particle size distribution is to make particle size selections subsequent to the actual granulation step to the detriment of yield and / or productivity.
- granulation is a technique rather suitable for particle sizes greater than one millimeter; - compaction is mainly used for the formulation of pharmaceutical products and concerns particles of even larger sizes: a few mm at least;
- the present invention relates to mesoporous inorganic solids in the form of primary and / or secondary inorganic particles of D10> 1 ⁇ m and D50> 3 ⁇ m, preferably of D10> 2 ⁇ m and D50> 10 ⁇ m whose size can go up to 10 mm, preferably up to 3 mm and advantageously up to 1.5 mm, of overall composition corresponding to the formula:
- M represents one or more ions, such as the ammonium ion, the ions of groups IA IIA and VIIB, and in particular the hydrogen and / or sodium ion , n and q represent respectively the equivalent fraction and the valence of the M ion (s) and n / q represents the number of moles or the molar fraction of the M ion (s),
- W represents one or more divalent elements, such as manganese, cobalt, iron and / or magnesium,
- X represents one or more trivalent elements, such as aluminum, boron, iron and / or gallium
- Y represents one or more tetravalent elements, such as silicon and / or germanium, and preferably silicon
- the pore volumes are measured by adsorption of N 2 to 77 K.
- the pore volumes corresponding to pores whose size is greater than or equal to 2 nm and less than or equal to 300 nm are measured by the DFT method (cylindrical pores) porous corresponding to pores whose size is less than or equal to 2 nm (microporous volume in the sense of TIUPAC) are measured by the t-plot method.
- D10, D50 and D90 represent the diameters of the particles below which are respectively 10%, 50% and 90% by weight of the particles, the D 50 giving a good approximation of the size of the particles.
- the invention also relates to a method for manufacturing the inorganic solids described above, comprising the following steps:
- a solid inorganic source in the form of primary and / or secondary particles of D10> 1 ⁇ m and D50> 3 ⁇ m, preferably of D10> 2 ⁇ m and D50> 10 ⁇ m whose size can range up to 10 mm, of composition global corresponding to the formula: where M, W, X, Y, Z, n, q, a, b, c, d and h have the same meaning as before,
- a solvent preferably water, optionally in the presence of a swelling agent which dissolves in the micelles, preferably trimethylbenzene,
- pore calibrators include: most particularly surfactants containing quaternary ammonium or phosphonium ions, substituted by aryl or alkyl groups having from 6 to 36 carbon atoms, identical or different, with which hydroxide, halide or silicate anions are associated and in particular those which contain cetyltrimethylammonium ions , cetyltrimethyiphosphonium, octadecyltrimethylammonium, octadecyltrimethylphosphonium, benzylt rimethylammonium, cetylpyridinium, decyltrimethylammonium, dimethyldidodecylammonium, trimethyldodecylammonium as well as amines such as dodecylamine and Thexadecylamine.
- the solvent can be organic but is preferably aqueous.
- oxide mobilizing agents mention may be made of mineral and organic bases, sodium hydroxide being particularly preferred.
- the pH of the reaction mixture is generally not critical and can vary between 1 and 14.
- the crystallization of the solid can be carried out with stirring or not, the latter having to be moderate enough not to cause attrition of the particles present and therefore the increase in the rate of fines.
- the crystallization temperature is generally between room temperature and 200 ° C and the duration of the crystallization reaction can generally range from a few minutes to a few days.
- the duration of the reaction step is controlled and optimized by SEM and laser granulometry, a reaction time that is too long risking increasing the level of fines.
- a solid is obtained in suspension in the solvent which is filtered, washed and dried; the product obtained is, after calcination intended in particular for removing the surfactant by combustion, in the form of inorganic solid particles having pores of regular size which can be of cubic or hexagonal symmetry depending on the synthesis conditions. In the case of hexagonal symmetry, the pores are all parallel.
- the method according to the invention is particularly advantageous when looking for narrow distributions of particle sizes; in this case, an oxide source should be used, the particle size distribution of which is narrow. 4.
- an oxide source should be used, the particle size distribution of which is narrow. 4.
- the pH allows the thickness of the walls to be varied: an interpretation commonly accepted by many authors is that in basic medium, silica is organized around the micelles of the surfactant by interaction between the cationic head of the surfactant and the ionized silanol groups which are found on the surface of the silica.
- the mesoporous volume corresponding to pores ranging from 4 to 15 nm is greater than or equal to 0.7 cm 3 / g, and preferably greater than or equal to 1 cm 3 / g,
- the concentration of swelling agent influences the size of the pores: the higher the concentration of swelling agent, the higher the size of the pores.
- the solids according to the invention are obtained, of which:
- the mesoporous volume corresponding to the pores ranging in size from 2 to 10 nm is greater than or equal to 0.18 crrrVg, and preferably greater than or equal to 0.3 cm 3 / g,
- A-2 the maximum peak diameter of the DFT distribution (Dmax) is such that 2 nm ⁇ Dmax ⁇ 10 nm, preferably 2nm ⁇ Dmax ⁇ 5 nm
- the pore volume corresponding to pores of size Dmax ⁇ 15% represents at least 70%, preferably at least 80% and advantageously 90% of the pore volume corresponding to pores of size between 2 and
- the particles according to the invention of D50> 10 ⁇ m can advantageously serve as supports for a catalytic component (as such, they can be called in the following "support particles") for the polymerization of various polymers, in particular polyamides, polyesters , olefins and styrenic compounds, together referred to below as olefins, etc. ;
- olefins is understood here to mean polymers derived from one or more monomers chosen from C2-C10 olefins, vinyl monomers such as vinyl acetate and vinyl aromatic monomers, such as styrene and its derivatives.
- a catalytic component for the polymerization of olefins can be obtained by association of a compound of a transition metal with the support particles.
- This transition metal can be titanium, zirconium, hafnium, chromium, vanadium or any other metal capable, under suitable conditions, of catalyzing the polymerization of olefins.
- a solid catalytic component can be obtained by association of the support, a titanium compound, chlorine, optionally an aluminum compound, optionally an electron acceptor or donor as well as any other compound usable in solid components of the Ziegler-Natta or metallocene type.
- Polymers in particular copolymers and prepolymers
- Polymers can be obtained by polymerization of monomer (s), in the presence of the catalytic component according to the invention by the processes in suspension, in solution, in gaseous phase or in mass.
- the particles according to the invention can also serve as catalysts in reactions in the field of refining and petrochemicals, typically alkylation, isomerization, disproportionation, cracking reactions, which are generally reactions of an acidic nature.
- the particles according to the invention can also be used as adsorbents to separate the components of a gaseous or liquid mixture made up of at least 2 different compounds in an adsorption process.
- the preferred adsorbents are those whose particle size is generally at least of the order of a millimeter.
- the particles according to the invention can be used, the particle size of which corresponds to that sought, or it may be necessary, if their particle size is insufficient, to agglomerate them before their application, for example according to one and / or the other of the agglomeration techniques described above (extrusion, agglomeration, compacting and atomization)
- adsorption process By way of example of adsorption processes, mention will be made very particularly of those operating in a cyclic manner which comprise the following stages operating alternately which are detailed below: a / passing said mixture through an adsorption zone containing the mesoporous particles and recover either the least adsorbed compound (s) or a gas mixture enriched in the least adsorbed compound (s) at the outlet of said adsorption zone, b / desorb the compound (s) (s) adsorbed in the adsorption zone and regenerate the adsorption zone so as to restore its adsorption capacity.
- the desorption / regeneration step b / is carried out by vacuum means
- suction by purging the adsorption zone with one or more inert gases and / or with part of the gas flow obtained at the exit from the adsorption zone, by temperature increase or by combination of regenerations by suction, by purging and / or temperature variation.
- the processes preferred by the applicant are of the PSA or VSA type, of the TSA type or of a combination of these different types of process (PTSA).
- This process is particularly well suited for the separation of VOCs present even at very low concentration in flows. gaseous preferably based on dry or humid air.
- the process of the present invention is also well suited for the purification of hydrocarbons, particularly oxygenated hydrocarbons and even more specifically of hydrocarbons belonging to the group of ketones, aldehydes, acids or alcohols, in admixture with compounds, preferably in the state of impurities or traces.
- particles according to the invention those with 1 ⁇ D10 ⁇ 3 ⁇ m and 3 ⁇ D50 ⁇ 15 ⁇ m, preferably those based on silica, can be advantageously used for the packing of chromatography columns.
- a particle of D50 close to 12 ⁇ m are used and in HPLC (high performance liquid chromatography) particles of D50 close to 5 ⁇ m are preferably used.
- HPLC high performance liquid chromatography
- the typical composition of the suspension is:
- reaction medium is brought to 100 ° C., the temperature at which it is maintained for 3 h.
- the solid is filtered then washed with 3 l of water and dried in a ventilated oven at 70 ° C and calcined at 550 ° C by rising in 5 h from 25 ° C to 550 ° C then holding at the plateau for 1 h.
- the solid is characterized by adsorption / desorption of N 2 at 77 K (ASAP 2010 from MICROMERITICS) and with the LASER granulometer (MALVERN)
- the pore size distribution is calculated according to the DFT method.
- Example 1 The synthesis of Example 1 is reproduced with the exception of the stirring mobile which is replaced by a magnetic stirring by means of a magnetic bar 3 cm in diameter rotating at 100 rpm.
- Example 1 The solid resulting from this synthesis has practically the same surface and porosity characteristics as that of Example 1 but reveals to the LASER granulometer the existence of fine particles estimated at 4-5% by weight of less than 2 ⁇ m; the use of a shear agitation system promotes abrasion of the particles.
- EXAMPLE 3 The synthesis of example 1 is reproduced by replacing LEVILITE® with a silica sold by GRACE under the name SYLOPOL® 2104; this silica has a narrow particle size distribution without fines (0% of particles smaller than 15 ⁇ m) and a large pore size distribution centered on approximately 20 to 40 nm. The characteristics of the starting silica and of the product resulting from the synthesis are indicated in Table 1.
- Example 1 The synthesis of Example 1 is reproduced, using as a source of silica ZEOSIL® 175 MP sold by RHODIA, the pore size distribution of which is wide and located in the macropores (> 50 nm)
- the particle size distribution of this silica shows a main peak around 150 ⁇ m with a wide drag towards particles of smaller particle size but no fines (0% of particles of size less than 4 ⁇ m)
- the characteristics of the starting silica and of the synthesized mesoporous solid are gathered in the table 1.
- Example 1 The synthesis of Example 1 is reproduced using SYLIPOL® 2104 as a source of silica and an Na 2 0 on silica ratio of 0.08 instead of 0.19.
- the mesoporous solid synthesized is of lower quality than those of the previous examples due to the lower basicity of the medium which only allowed a partial transformation of the solid.
- the characteristics of the starting silica-alumina and of the product resulting from the synthesis are indicated in Table 1 below.
- the product is then dried at 100 ° C for 2 h then activated in an oven by rising in 1 h to 550 ° C and maintained at this temperature for 2 h under N 2 sweep.
- the solid is then characterized by its adsorption / desorption isotherm from N 2 to 77 K which makes it possible to deduce the surface and porosity values.
- the adsorption / desorption isotherm of N 2 at 77 K shows that the solid is a mesoporous solid according to the invention well formed with a marked adsorption step and a relatively narrow pore size distribution.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nanotechnology (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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JP2002542736A JP2004525846A (ja) | 2000-11-14 | 2001-11-09 | メソ細孔無機固体と、その製造方法と、その触媒および吸着剤としての使用 |
KR10-2003-7006547A KR20030067685A (ko) | 2000-11-14 | 2001-11-09 | 메소다공성 무기 고형물, 이의 제조 방법 및 특히 촉매 및흡착제로서의 이의 용도 |
AU2002218356A AU2002218356A1 (en) | 2000-11-14 | 2001-11-09 | Mesoporous inorganic solids, method for preparing same and uses thereof in particular as catalysts and adsorbents |
CA002428734A CA2428734A1 (fr) | 2000-11-14 | 2001-11-09 | Solides inorganiques mesoporeux, leur procede de preparation et leurs utilisations notamment comme catalyseurs et adsorbants |
EP01996513A EP1334066A1 (fr) | 2000-11-14 | 2001-11-09 | Solides inorganiques mesoporeux, leur procede de preparation et leurs utilisations notamment comme catalyseurs et adsorbants |
US10/437,456 US20040035751A1 (en) | 2000-11-14 | 2003-05-14 | Inorganic mesoporous solids, a process for their preparation and their use, notably as catalysts and adsorbents |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR00/14595 | 2000-11-14 | ||
FR0014595A FR2816609B1 (fr) | 2000-11-14 | 2000-11-14 | Solides inorganiques mesoporeux, leur procede de preparation et leurs utilisations notamment comme catalyseurs et absorbants |
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US10/437,456 Continuation US20040035751A1 (en) | 2000-11-14 | 2003-05-14 | Inorganic mesoporous solids, a process for their preparation and their use, notably as catalysts and adsorbents |
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WO2002040402A1 true WO2002040402A1 (fr) | 2002-05-23 |
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PCT/FR2001/003496 WO2002040402A1 (fr) | 2000-11-14 | 2001-11-09 | Solides inorganiques mesoporeux, leur procede de preparation et leurs utilisations notamment comme catalyseurs et adsorbants |
Country Status (8)
Country | Link |
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US (1) | US20040035751A1 (fr) |
EP (1) | EP1334066A1 (fr) |
JP (1) | JP2004525846A (fr) |
KR (1) | KR20030067685A (fr) |
AU (1) | AU2002218356A1 (fr) |
CA (1) | CA2428734A1 (fr) |
FR (1) | FR2816609B1 (fr) |
WO (1) | WO2002040402A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004026473A1 (fr) * | 2002-09-18 | 2004-04-01 | Abb Lummus Global Inc. | Materiau mesoporeux et son utilisation pour l'oxydation selective de composes organiques |
WO2007036620A1 (fr) * | 2005-09-30 | 2007-04-05 | Rhodia Recherches Et Technologies | Silice de cohesion elevee, procede de preparation et utilisations |
US7608747B2 (en) | 1999-09-07 | 2009-10-27 | Lummus Technology Inc. | Aromatics hydrogenolysis using novel mesoporous catalyst system |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2404830C (fr) * | 2002-10-17 | 2011-03-22 | University Of Windsor | Tamis moleculaires mesaporeux metalliques pour oxyde metallique de transition utilises pour la production d'ammoniac par activation du diazote a la temperature ambiante |
JP4512060B2 (ja) * | 2006-04-18 | 2010-07-28 | 独立行政法人科学技術振興機構 | 3次元構造メソポーラスシリカとその製造方法 |
CN100529754C (zh) * | 2006-11-10 | 2009-08-19 | 中国科学院山西煤炭化学研究所 | 一种分离苯及其同系物的方法 |
US7824641B2 (en) * | 2007-05-25 | 2010-11-02 | Lehigh University | Periodic mesoporous phosphorus-nitrogen compounds |
US8088277B2 (en) * | 2008-06-11 | 2012-01-03 | General Electric Company | Methods and system for removing impurities from heavy fuel |
US8986836B2 (en) * | 2009-03-19 | 2015-03-24 | Ohio University | Microspheres and their methods of preparation |
WO2014188924A1 (fr) * | 2013-05-22 | 2014-11-27 | 三井化学株式会社 | Particules d'oxyde métallique poreuses, leur procédé de fabrication, et leur utilisation |
JP7320405B2 (ja) * | 2018-09-28 | 2023-08-03 | 住友化学株式会社 | 高分子化合物の製造方法 |
JP7484650B2 (ja) | 2020-10-15 | 2024-05-16 | トヨタ自動車株式会社 | 多孔質カーボン、触媒担体、及び多孔質カーボンの製造方法 |
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US5057296A (en) * | 1990-12-10 | 1991-10-15 | Mobil Oil Corp. | Method for synthesizing mesoporous crystalline material |
DE19530031A1 (de) * | 1995-08-16 | 1997-02-20 | Merck Patent Gmbh | Poröse monodisperse SiO¶2¶-Partikel |
US5795559A (en) * | 1995-06-06 | 1998-08-18 | Board Of Trustees Operating Michigan State University | Porous inorganic oxide materials prepared by non-ionic surfactant templating route |
JPH10328558A (ja) * | 1997-05-30 | 1998-12-15 | Toyota Central Res & Dev Lab Inc | 球状メソ多孔体及びその製造方法 |
EP0985636A1 (fr) * | 1998-09-09 | 2000-03-15 | Degussa-Hüls Aktiengesellschaft | Silices et métallosilicates à structure mésoporeuse régulière |
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US3556725A (en) * | 1969-02-26 | 1971-01-19 | Sylvania Electric Prod | Process for producing low-bulk density silica |
US5863515A (en) * | 1996-02-20 | 1999-01-26 | California Institute Of Technology | Mesoporous alumina and process for its preparation |
US5718878A (en) * | 1996-07-12 | 1998-02-17 | Akzo Nobel N.V. | Mesoporous titania and process for its preparation |
FR2764213B1 (fr) * | 1997-06-10 | 1999-07-16 | Inst Francais Du Petrole | Catalyseur d'hydrotraitement de charges hydrocarbonees dans un reacteur a lit fixe |
DE19730126A1 (de) * | 1997-07-14 | 1999-01-21 | Basf Ag | Aluminiumoxid enthaltender Feststoff mit großer Oberfläche |
DE19730125A1 (de) * | 1997-07-14 | 1999-01-21 | Basf Ag | Aluminiumoxid enthaltender Feststoff mit großer Oberfläche |
US6139814A (en) * | 1997-11-10 | 2000-10-31 | Ford Global Technologies, Inc. | Thermally stable, high-surface-area metal oxides made by organic templating |
US6027706A (en) * | 1998-05-05 | 2000-02-22 | Board Of Trustees Operating Michigan State University | Porous aluminum oxide materials prepared by non-ionic surfactant assembly route |
-
2000
- 2000-11-14 FR FR0014595A patent/FR2816609B1/fr not_active Expired - Fee Related
-
2001
- 2001-11-09 WO PCT/FR2001/003496 patent/WO2002040402A1/fr not_active Application Discontinuation
- 2001-11-09 AU AU2002218356A patent/AU2002218356A1/en not_active Abandoned
- 2001-11-09 EP EP01996513A patent/EP1334066A1/fr not_active Withdrawn
- 2001-11-09 KR KR10-2003-7006547A patent/KR20030067685A/ko not_active Application Discontinuation
- 2001-11-09 JP JP2002542736A patent/JP2004525846A/ja not_active Abandoned
- 2001-11-09 CA CA002428734A patent/CA2428734A1/fr not_active Abandoned
-
2003
- 2003-05-14 US US10/437,456 patent/US20040035751A1/en not_active Abandoned
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US5057296A (en) * | 1990-12-10 | 1991-10-15 | Mobil Oil Corp. | Method for synthesizing mesoporous crystalline material |
US5795559A (en) * | 1995-06-06 | 1998-08-18 | Board Of Trustees Operating Michigan State University | Porous inorganic oxide materials prepared by non-ionic surfactant templating route |
DE19530031A1 (de) * | 1995-08-16 | 1997-02-20 | Merck Patent Gmbh | Poröse monodisperse SiO¶2¶-Partikel |
JPH10328558A (ja) * | 1997-05-30 | 1998-12-15 | Toyota Central Res & Dev Lab Inc | 球状メソ多孔体及びその製造方法 |
EP0985636A1 (fr) * | 1998-09-09 | 2000-03-15 | Degussa-Hüls Aktiengesellschaft | Silices et métallosilicates à structure mésoporeuse régulière |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6906208B2 (en) | 1999-09-07 | 2005-06-14 | Abb Lummus Global Inc. | Mesoporous material and use thereof for the selective oxidation of organic compounds |
US7608747B2 (en) | 1999-09-07 | 2009-10-27 | Lummus Technology Inc. | Aromatics hydrogenolysis using novel mesoporous catalyst system |
WO2004026473A1 (fr) * | 2002-09-18 | 2004-04-01 | Abb Lummus Global Inc. | Materiau mesoporeux et son utilisation pour l'oxydation selective de composes organiques |
WO2007036620A1 (fr) * | 2005-09-30 | 2007-04-05 | Rhodia Recherches Et Technologies | Silice de cohesion elevee, procede de preparation et utilisations |
FR2891539A1 (fr) * | 2005-09-30 | 2007-04-06 | Rhodia Recherches & Tech | Silice de cohesion elevee, procede de preparation et utilisations |
Also Published As
Publication number | Publication date |
---|---|
KR20030067685A (ko) | 2003-08-14 |
AU2002218356A1 (en) | 2002-05-27 |
US20040035751A1 (en) | 2004-02-26 |
CA2428734A1 (fr) | 2002-05-23 |
FR2816609B1 (fr) | 2003-01-10 |
FR2816609A1 (fr) | 2002-05-17 |
EP1334066A1 (fr) | 2003-08-13 |
JP2004525846A (ja) | 2004-08-26 |
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