GB2341853A - Process for the manufacture of an inorganic porous material - Google Patents
Process for the manufacture of an inorganic porous material Download PDFInfo
- Publication number
- GB2341853A GB2341853A GB9925446A GB9925446A GB2341853A GB 2341853 A GB2341853 A GB 2341853A GB 9925446 A GB9925446 A GB 9925446A GB 9925446 A GB9925446 A GB 9925446A GB 2341853 A GB2341853 A GB 2341853A
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- Prior art keywords
- inorganic
- process according
- solution
- organic molecules
- mixtures
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000011148 porous material Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 20
- 239000011800 void material Substances 0.000 claims abstract description 20
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 15
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 8
- 230000005494 condensation Effects 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims abstract description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000001939 inductive effect Effects 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 150000004679 hydroxides Chemical class 0.000 claims description 5
- 150000002823 nitrates Chemical class 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000008119 colloidal silica Substances 0.000 claims description 3
- 239000008131 herbal destillate Substances 0.000 claims description 3
- 239000008247 solid mixture Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 description 96
- 238000009826 distribution Methods 0.000 description 25
- 238000002524 electron diffraction data Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 23
- 238000001179 sorption measurement Methods 0.000 description 21
- 229920002994 synthetic fiber Polymers 0.000 description 13
- 125000001475 halogen functional group Chemical group 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 235000010215 titanium dioxide Nutrition 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000002003 electron diffraction Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 235000012245 magnesium oxide Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RTPQXHZLCUUIJP-UHFFFAOYSA-N 1,2-dimethyladamantane Chemical compound C1C(C2)CC3CC1C(C)C2(C)C3 RTPQXHZLCUUIJP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000000097 high energy electron diffraction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0296—Nitrates of compounds other than those provided for in B01J20/04
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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
- B01J20/02—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
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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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
- B01J20/28054—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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- 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
- B01J20/28078—Pore diameter
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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
- B01J20/28054—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
- B01J20/28088—Pore-size distribution
- B01J20/2809—Monomodal or narrow distribution, uniform pores
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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
- B01J20/3007—Moulding, shaping or extruding
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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
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A process for preparing an inorganic porous material comprising the steps of forming a solution of a hydrolysable inorganic compound with a non-ionic surfactant having organic molecules, inducing growth and condensation of a solid compensation comprising an inorganic composition in intimate contact with said organic molecules, and extracting said organic molecules from the inorganic composition so as to provide an inorganic porous material having mesopore void volume of at least 0.1 cc/g and having enhanced stability under thermal and hydrothermal conditions. The step of inducing growth and condensation can include adjustment of the solution of the pH to within Ò2 pH numbers of the isoelectric point mean value of the inorganic species. The extracting step can comprise calcination of the organic molecules at temperatures of about 400 to 800{C, for at least one hour. Also the process can include adding an organic water insoluble compound, e.g. p-xylene, trimethylbenzene to the solution, wherby the size and volume of the channels are enhanced.
Description
2341853 SYNTHETIC POROUS MTMERUL WrM MICROPORM WAUS DEFINING NARROW SIZE
DISTRIBUITON MOESOPMORES The invention relates to a synthetic material having a high void volume attributable to tortuous mesopore-sized channels having a mean diameter between about 15 1 and about 100 1 and a narrow size distribution of less than or equal to about 30 JL,, and a process for preparing same.
Processing of feedstocks having large organic molecules such as heavy hydrocarbons,, fine chemicals,, and/or pharmaceutical products involving catalysts or adsorbents is typically inefficient and/or expensive due to the lack of materials with appropriate qualities. one of the main constraints for these active agents is the lack of sufficient pores of appropriate size to carry out the desired processes.
U.S. Patent No. 5,098,684 discloses a family of materials containing an ordered array of uniformly sized mesoporesi, prepared with the aid of quaternary-amine surfactants (cationic surfactants). Although these materials contain large mesopore volumes distributed in narrow size distributions, they are constituted by, thin walls. This characteristic is inherent to the process used 2 in preparing the material. The 684 patent discloses the I use of cationic surfactants which give rise to strong electrostatic interactions with the inorganic species in solution, thereby leading to the formation of materials with thin amorphous walls (less than 151 thick). This material, however,, has limited practical value,, since the walls easily collapse under hydrothermal treatment conditions typical of many conventional hydrocarbon conversion processes. The use of quaternary amine surfactants as template agents is also undesirable because of the high cost and toxicity of these materials.
It is therefore evident that the need remains for a synthetic material having high void volume and appropriate pare sizes for use in treating feedstocks having large organic molecules.
It is therefore the primary aim of the present invention to provide a material having a high void volume associated to mesoporous channels with a narrow size distribution and having adequate hydrothermal stability.
It is a still further aim of the present invention to provide a process for preparing the synthetic material of the present invent.-I-on.
Other aim and advantages of the present invention will appear hereinbelow.
3 In accordance with the invention,, the foregoing aiw and advantages are readily attained.
According to the invention,, 'a synthetic material is provided which comprises an inorganic porous material having wall portions defining mesopore-sized channels having a mean diameter of between about 15 A to about 100 JL and a narrow diameter distribution of less than or equal to about 30 JL,, said material having a void volume from said mesopore-sized channels of at least about 0.1 cc/g.
Still further according to the invention, a process is provided for preparing the synthetic porous material according to the invention which process comprises the steps of forming a solution of a hydrolyzable inorganic compound with a non-ionic surfactant having organic molecules; inducing growth and condensation of a solid composition comprising an inorganic composition in intimate contact with said organic molecules; and extracting said organic molecules from said inorganic composition so as to provide said inorganic porous material having wall portions defining mesopore-sized. channels having a mean diameter of between about 15 A to about loo k and a narrow diameter distribution of less than or equal to about 30 A, said material having a void volume from said mesopore-sized channels of at least about 0.1 cc/g.
A detailed description of preferred and non-I'm'tng embodiments of the present invention follows, with reference to the attached drawings, wherein:
Figure 1 is the N2 adsorption isotherm for the product of Example 1.
Figure 2 is a derivative of the N2 adsorption volume as a function of pore diameter for the product of Example 1, showing its size distribution of mesopores.
Figure 3 is the N2 adsorption isotherm f or the product of Example 2.
Figure 4 is a derivative of the N2 adsorption volume as a function of pore diameter f or the product of Example 2, showing its size distribution of mesopores.
Figure 5 is an electron diffraction pattern of the product of Example 1.
Figure 6 is an electron diffraction pattern of the product of Example 2.
DETAILED DESCRIPTION
The invention relates to a synthetic material which advantageously possesses high void volume generated by mesoporous channels with a narrow size distribution and which further exhibits enhanced stability under thermal and hydrothermal treatment conditions.
According to the invention, a synthetic material is provided having a high void volume, prefer,:ibly at least 0.1 cc/g and more preferably at least about 0.2 cc/g,, wherein the void volume is attributable to or generated from tortuous channels defined in the material. The channels preferably have a mean diameter between about 15 A and about 100 1 and a narrow size distribution less than or equal to about 30 A. The material is preferably a short range order structure (as described below) which has enhanced hydrothermal stability. These advantageous characteristics allow the synthetic material of the present invention to be used in treating a feedstock having a fraction of largehydrocarbon molecules. During such treatment,, larger molecules are upgraded, converted or otherwise treated in sites within the mesoporous channels. In a different process, a component of the feedstock may also be separated by selective adsorption into the mesoporous channels of the synthetic material.
The synthetic material according to the invention also advantageously exhibits enhanced stability in the presence of steam and/or high temperatures, for example up to at least about 50oac, making the material excellently suited for use in processes involving thermal and hydrothermal steps. It is believed that the enhanced stability of material of the present invention results from relatively thick walls of the material that define the mesoporous tortuous channels.
- 6 The narrow size distribution of mesoporous channels in the synthetic material of the present invention is exhibited, f or example, by a nitrogen adsorption isotherm having sharp inflection points at P/Po values of between about 0. 05 to about 0. 8,, and a relatively f lat isotherm above P/Po of 0. 8,, indicating mesopore pore size distribution of between about 15 A to about 100 A. The short range order in the synthetic material of the present invention is exhibited, for example, by a high energy electron diffraction pattern (EDP) containing only diffuse halos at d spacing larger than 20 A. one or more halos may be exhibited. This short range order is indicative of material having structural features (believed to be the tortuous channels) that repeat themselves substantially throughout the material, but in correlations where the feature extends only a few times (up to about five times, while in the case of crystalline materials features can repeat them elves thousands, or at the very least hundreds of times). This material is referred to as a material having a repeat value of less than or equal to about 5.
In further accordance with the invention, a process for preparing the synthetic material of the present invention is provided. Advantageously, the process serves to provide a synthetic material having short range order and tortuous mesoporous channels formed therein wherein the channels are defined by walls believed to have a thickness sufficient to enhance resistance of the synthetic mater.ial to use in thermal and hydrothermal processes. This is advantageous in that conventionally prepared materials either possess very wide mesopore size distributions (between So I and 1000 A) or possess poor thermal and hydrothermal stability in same rendering the conventionally prepared materials undesirable for many processes, especially those involving treatment of feedstocks having large organic molecule fractions.
According to the invention, an inorganic porous material is prepared by forming a solution of a hydrolyzable inorganic compound with a non-ionic surfactant, having organic molecules. The solution is thoroughly mixed, and then treated so as to induce the formation of a solid material comprising an inorganic composition in intimate contact with the organic molecules of the non-ionic surfactant. Solids may be formed by gelation of the hydrolyzable inorganic compounds at pH values near the isoelectric point of the inorganic species in solution, and further condensation of the gel to form a solid material by aging of the gel at low temperatures, between about VC and 400C, and/or by thermal treatment at temperatures between about 400C and 1200C.
The solid material so obtained is then preferably separated from remaining liquid of the solution, for example by centrifugation, washed with water, and dried at room temperature, preferably under reduced pressure.
8 The washed and dried solid is then treated, preferably through calcination or solvent extraction, so as to extract the non-ionic surfactant f rom the inorganic composition so as to provide an inorganic material with a high void volume of at least about 0.1 cc/g generated by or attributable to the tortuous channels, and having a mean diameter between about 15 A to about 100 JL and a narrow size distribution of less than or equal to about 30 A. As set forth above,, the material formed in accordance with the process of the present invention is a short range order structure indicating a material which is an intermediate case between crystalline (long-range) and disordered materials.
In accordance with the invention, the conditions inducing the growth and condensation of the hydrolyzable compound are controlled so as to form chain-like polymeric inorganic species that favor attractive interactions (by hydrogen bonding and/or Van der Waals forces) with the polar groups of the non-ionic surfactant. This may suitably be carried out by providing and maintaining a pH of the solution which is equal to or within about 2 pH numbers-of the isoelectric point mean value of the inorganic species or combination of inorganic species in solution. At the isoelectric point the condensation step is relatively slow, and the hydrolyzable species tend to polymerize into linear molecules that are occasionally cross-linked. These molecular chains entangle and form additional branches.
9 These chain-like species are pervious to the non-ionic surfactant, facilitating the establishment of attractive interactions. At synthesis conditions far from the isoelectric point, the polymerization rate is fast, leading to the formation of more highly branched clusters that are not penetrable, and cannot easily interact with the nonionic surfactant. Furthermore, near the isoelectric point, the hydrolyzed groups of the inorganic species in solution contain for the most part hydroxyl groups, favoring attractive interactions with the electron donor groups of the non-ionic surfactant by H bonding.
The pH of the solution may be adjusted according to the invention by adding acid to the solution, preferably hydrochloric acid (HC1), although other acids may also be used.
In accordance with the invention, the hydrolyzable inorganic compound may suitably be selected from chlorides, alkoxides, nitrates, hydroxides,, sulphates, and mixtures thereof, among others, preferably nitrates, hydroxides and mixtures thereof. Also the inorganic species in solution can be prepared by dissolution of an oxide with an appropriate acid or base. Further, precursors to the oxides may be used, such as colloidal silica, alumina sols, suspensions of pseudo-bentonite, titania or zirconia and/or hydrosols of any oxide, among others.
The non-ionic surfactant of the prespnt invention may suitably be selected from ethoxylated alcohols, ethoxylated alkylphenols, amine oxides, ethoxylated amines and mixtures thereof. The nonionic surfactant may suitably be mixed in solution with the inorganic compound so as to provide a molar ratio of ionic surfactant to inorganic species of between about 0.05 to about 20.
Any metal oxide or mixture of oxides can be prepared with the method of the present invention, as long as the appropriate pH value is selected. An indication of this value is given by the isoelectric point of the respective solid oxides or hydroxides, some of which are stlimmarized in Table 1, and with an extensive compilation given by G.A. Parks, Chemistry Reviews, Vol. 65, pages 177 to 198, 1965.
TABLE I
MATERIAL ISOELECTRIC POINT Silica 1.8 to 2.2 Alumina 8.0 to 9.2 Titania 4.7 to 6.2 Magnesia 11 to 12 Iron Oxide 5.2 to 7.4 The isoelectric point mean value for the materials of TABLE 1, as used herein, are set forth in TABLE 2.
TABLE 2
ISOELECTRIC POINT MATERIAL MEAN VALUE Silica 2.00 Alumina 8.60 Titania 5.45 Magnesium 11.50 Iron Oxide 6.30 In accordance with the invention, the solid porous inorganic material obtained in accordance with the invention has a high void volume, at least about 0.1 cc/g, attributable to tortuous channels with a mean diameter between about 15 1 and about 100 A and a narrow size distribution of less than or equal to about 30 A. wherein the material is a short range order material having stability for use in thermal and hydrothermal treatments and processes.
As set forth above,, during solvent extraction or calcination, the nonionic surfactant is extracted and removed from intimate contact with the inorganic material, thereby vacating mesopore-sized tortuous channels having the desired mean diameter between about 15 k and about 100 L, and distributed in a narrow size distribution no more than 30 A wide. Calcining is preferably carried out in accordance with the invention at a temperature of between about 400C to about 8000C, for a period of at least about 1 hour. of course, different materials may require different calcination times and temperatures for a proper extraction.
- 12 It should be noted that the total volume of mesopore void volume formed in the final product depends upon the size and concentration of the non- ionic surfactant in the starting solution. Further, the actual size of mesoporesized channels depends upon the size or molecular weight of the organic molecules. Thus. the amount and size of organic molecule to be used in solution may be selected so as to provide the desired mesopore total void volume and mesoporous channel size.
The amount and size of the mesoporous-sized void volume can also be selectively controlled by adding organic water insoluble compounds to the mixture of the inorganic species and the non-ionic surfactant. These water-insoluble compounds combine with the hydrophobic tail of the surfactant, and increase the size of the micelle around which the inorganic species condense, thus increasing the size and volume of resulting mesopore-sized channels in the material of the present invention. Suitable organic water insoluble compounds according to the invention may be selected from p-xylene, trimethylbenzene, triethylbenzene, dimethyladamantane and mixtures thereof.
As is the case with many catalysts, it may be advantageous to combine the material of the present invention with a matrix material that has desirable thermal, mechanical or other properties. The material of the present - 13 invention may also be combined with other materials,, used as diluents to control the amount of conversion in a given process. Examples of such materials are aluminas, silicas, silica-aluminas, magnesias, titanias, zirconias, carbons and their precursors, clays and mixtures thereof. Also, , precursors to the above mentioned materials can be used, such as colloidal silica, alumina sols, suspensions of pseudo-bohemite, titania, or zirconia, and hydrosols of any above mentioned oxides, among others. These materials may be combined with the material of the present invention during preparation or in a post-synthesis process. Also, these materials may be provided in part in colloidal form so as to facilitate extrusion of the bound components.
The material of the present invention is useful as a catalyst for conversion of organic compounds, especially large hydrocarbons with molecular sizes of about 15A or more. It is particularly useful for catalyzing reactions that occur in the presence of acidic sites, in which the large hydrocarbon molecule is converted into products of lower molecular weight or into more valuable isomers. Examples of such reactions are involved in processes such as cracking, hydrocracking and isomerization. In such processes the material of the present invention presents various advantages over conventional catalysts. The large mesopore size and void volume allow large hydrocarbon molecules to easily access the catalytically active sites - 14 located on the material, thereby minimizi.g diffusional constraints. The improved diffusion through channels also allows the primary products from the transformation and or conversion of the large hydrocarbon molecule to exit the material before secondary reactions can take place. thereby retarding or even avoiding the formation of undesirable secondary products such as coke which could eventually plug the channels or deactivate catalytic sites on the material.
It may also be advantageous to incorporate into the material of the present invention minor amounts of metals as catalytic components, especially noble metals such as platinum, rhodium, rhenium, or iridium, or Group VIII metals such as nickel, iron or cobalt, or Group VI metals such as chromium, molybdenum or tungsten, or mixtures thereof. These metals may be present in their metallic state, or as oxides, sulfides or mixtures thereof. These metals could provide the material of the present invention with desired catalytic properties for processes such as hydrotreatment, hydroisomerization, hydrocracking, hydrogenation and/or reforming, to convert large hydrocarbon molecules into more valuable products.
The material of the present invention may also be advantageously used as a sorbent for the selective separation of one or more components in a feed. The narrow size distribution of mesopore-sized channels and the large void volume allow for separation of components in the feed by size exclusion of molecules. The walls of the material of the present invention provide f or sites that can be modif ied through incorporation of molecules that contain specific functional groups with affinity toward specific components in the mixture, allowing their separation from the feed. Examples include the incorporation of amines to preferentially adsorb acidic components in a feed, or chelating agents that separate metal contaminations off a stream. Also,, these sites on the walls of the material of the present invention can be used to incorporate compounds that can control the hydrophilicity of the environment within the pores or channels, advantageously allowing the separation of polar from non- polar components in a feed.
Although the material of the present invention is useful in the treatment of any hydrocarbon molecule, it is particularly advantageous when used for the treatment of large molecules that are too big to fit into the channels of more conventional catalysts and/or sorbents. The material of the present invention is especially suited for the treatment of high boiling point hydrocarbon fractions in crude oils such as atmospheric and vacuum gas oils, high boiling point products from processes such as catalytic cracking, thermal cracking, lube production and the like and non-distillable fractions from crude oil or from conversion processes such as residual feeds. The material of the present invention could also be utilized with f eeds of non- 16 petroleum origin.
71e following non-limiting examples further demonsu-ke the advantageous characteristics of the inorganic composition and process for preparation of same in accordance with the present invention.
pxle 1 In this example, a porous silicate composition is provided according to the invention.
An acid solution of non-ionic surf actant was formed by ing 17.7 g of water. 9.1 g of H= (37% vt) and 1.1 g para-nonyl phenol ethoxylated with fifteen moles of ethylene oxide per mole of alkylphenol (C9H19-Ph-O-(CH2CE2-0) 14CH2-CH2-OR, where Ph is phenyl group). The solution was mixed With 2.1 g of tetraethylorthosilicate (TEOS) (98.1 wt) for 2 minutes at room temperature, giving rise to a clear solution with the following molar composition:
1 Si02: 0. 10 C9R19 (E0) 15: 9. 00 HCl: 127.50 H20 This clear solution was placed in a sealed 60 =l teflon-wall reactor, where it was kept at 200C for 72 hours, and then heated to 600C for 72 wore hours. After this treatment a white solid was formed. This product was separated from the liquid by centrifuge, washed with water several times, and dried at room temperature under reduced pressure. Finally, the solid was calcined at 4000C for 18 hours, in a flow of air.
The mesopore size distribution of the calcined material was determined from its equilibrium N2 adsorption isotherm. according to ASTH Standard Practice D 4641. The N2 adsorption isotherm for the calcined material is shown in Figure 1. The isotherm has an inflection point at PJP, equal to 0.18. corresponding to the filling of pores 20 A in average diameter. Beyond PIP, values of 0.80, the N2 adsorption isotherm is essentially flat, indicating that the material does not contain pores larger than loo A in diameter. The well defined edge in the adsorption isotherm around its inflection point indicates that the material has a narrow size distribution of mesopores. This is better illustrated by plotting the derivative of the N2 adsorption volume as a function of pore diameter, which for the calcined material is shown in Figure 2. This figure indicates that the void volume associated to mesopores in the material can be allocated to a narrow size distribution with channels no larger than 25 A in diameter.
The volume associated to pores 15 A to 100 A in diameter is equal to 0.36 cclg, as determined from equilibrium N2 adsorption capacity at relative PIP, pressures between 0.05 and O.S.
The presence in the electron diffraction pattern (EDP) of a halo 0.0334 A' in radius, indicates that the product of - 18 this example contains short range order arxays with a d spacing (repeat distance) of 30 A (see Example 4), and it is indeed an embodiment of the material of the present invention.
To demonstrate the enhanced hydrothermal stability of the material of the present invention, the product of this example was treated in a flow of 100% steam for 3 hours at 823 K. After treatment, the material maintained its original properties; that is, a void volume of 0.3 cc/g, as determined from the equilibrium N2 adsorption capacity at relative P/Po pressures between 0.05 and 0.8, a narrow pore size distribution between 15 A and 25 A, centered around 20 A, as shown by a well defined inflection point at P/Po equal to 0. 18 in the N2 adsorption isotherm, and a halo in the EDP with a 0.0334 A" radius, indicative of short range order with a d spacing of 30 A.
Examiple 2 This example demonstrates the_ criticality of the us e of non-ionic surfactants according to the present invention.
An acid solution was formed by mixing 17.7 g of water and 9.1 g of HCI (37% wt). The solution was mixed with 2.1 g of tetraethylorthosilicate (TEOS) (98% wt) for 2 minutes at room temperature, giving rise to a clear solution with the following molar composition:
1 Si02: 9.00 HCI: 127.50 H20 - 19 This clear solution was placed in a sealed 60 mL Teflon-wall reactor, where it was kept at 200C for 72 hours, and then heated to 600C for 72 more hours. After this treatment a white solid was formed. This product was separated from the liquid by centrifuge. washed with water several times. and dried at room temperature under reduced pressure. Finally,, the solid was calcined at 4000C for 18 hours, in a flow of air.
The mesopore size distribution of the calcined material was determined from its equilibrium N2 adsorption isotherm, according to ASTH Standard Practice D 4641. The N2 adsorption isotherm for the calcined material is shown in Figure 1. The isotherm has an inflection point at P/p, equ al to 0.55, corresponding to the filling of pores 55 A in average diameter. Beyond PIP, values of 0.80, the N2 adsorption isotherm is essentially flat, indicating that the material does not contain pores larger than 100 A in diameter. The gradual raise in the adsorption isotherm around its inflection point indicates that the material has a broad size distribution of wesopores. This is better illustrated by plotting the derivative of the N2 adsorption volume as a function of pore diameter, which for the calcined material is shown in Figure 4. This figure indicates that the void volume associated to mesopores in the material can be allocated in a broad size distribution of pores between less than 20 A and 100 A in diameter.
- 20 The EDP for the product of this exalple only shows a well defined spot in the canter of the pattern due to transmitted non-scattered electrons. The absence of a halo in the EDP indicates that the product of the present example is disordered.
This example demonstratAs the criticality of the pE level during the gelification p according to the present invention.
Acid solutions of a non-ionic surfactant were prepared by mixintj 17.7 cj of water and 1. 1 g para-nonyl phenol ethoxylated with fiftu--en moles of ethylene oxide per mole of alkylphenol plus the sca: required to achieve pE levels of 1, 2 and 4.5. Each solution was mixed with 2.1 9 of tetraethylorthc>sil-,cate (TEOS) (98% wt) for 2 minutes at. room temperature, giving rise to clel, solutions with the following molar composition (excluding HCl):
1 SIC: 0.10 C9ph(E0)15: 127.50 E20 Each clear solution was placed in a sealed 60 =1 teflon-wall reactor, where they were kept at 200C for 72 hours, and then heaCed to GOOC faz 72 =are hours. After this treatment a white solid was formed in all cases. These products we-re separated frc= the liquid by centrifuge, washed with water several times,, and dried at room temperature under reduced I pressure. Finally, the solids were calcined at 4000C for 18 hours, in a flow of air.
kt pH equal to 1,, the material was prepared following the same procedure described in Example 1 which describes the properties of this material.
The textual properties of the calcined material prepared at pH equal to 2 were essentially the same as those of the one prepared at pH equal to 1. That is, the pH equal to 2 material exhibited an inflection point at P/Po equal to 0 - 18 in the N2 adsorption isotherm; a narrow size distribution of mesopores, between 15 A and 25 k in diameter; a flat region beyond P/Po values of 0.80,, indicating that no pores larger than 100 k in diameter are present; a volume associated to mesoporous channels equal to 0.30 cc/g; and a halo in the EDP with a 0.034 A" radius, indicative of a short range order with a d spacing of 30 The material prepared at pH equal to 4.5. however, presents undesirable properties. Its N2 adsorption isotherm shows a sharp raise at P/Po levels above 0.8, indicating the presence of a large fraction of pores larger than 100 1 in diameter; a broad mesopore size distribution, centered around 60 A in diameter and 50 A wide; and the absence of a halo in the EDP, demonstrating that the material is completely disordered.
22 ExamiDle 4 This example includes a more detailed description of the characterization by Electron Diffraction (ED) of the material of the present invention, prepared according to Example lo, compared to a material prepared according to U.S. Patent No. 5,098,684, which has long range order and the product of Example 2 which is completely disordered.
When a beam of high-energy electrons is directed toward a thin specimen, several phenomena can take place. One of them is the deflection of the incident electrons due to interactions with atoms in the specimen. Whenthe material has long range order (i.e. it is crystalline) electrons are deflected toward a discrete number of precise directions, generating well defined spots in an EDP. The position of these spots is related to the spatial symmetry of structural features in the material, according to Bragg's law, and those skilled in the art of electron diffraction are able to provide information about the structure of a crystalline material from analysis of its EDP. On the other hand, electrons impinging on disordered materials are deflected in all directions, and thus, no features stand out in an EDP. Short range order materials offer an intermediate case between crystalline (long-range) and disordered materials. In this latest class of materials, there are structural features (believed to be the tortuous channels) that repeat themselves substantially throughout the material, but in correlations where the feature extends only a few times (up to about five times, while in the case of crystalline materials features can repeat then elves thousands, or at the very least hundreds of times). As a consequence, the EDP from a short range order material does not contain well defined spots, as in the case of a crystalline one, but rather diffuse halos,, which radius is inversely proportional to the distance between the repeating features in the material. To illustrate these differences, EDP from three different materials are described: a long range order material (described in U.S. Patent No. 5,,098,684), a disordered material (the product of Example 2), and a short range order material (an embodiment of the material of the present invention, and the product of Example 1).
Samples from the products of Examples 1 and 2 to be analyzed by ED were prepared following essentially the same procedure described in Example 23 of U.S. Patent No. 5,098,684. Each material was embedded in a low viscosity acrylic resin,, which is then cured at BOOC overnight. Sections of the block, about 500 1-thick, were cut by ultramicrotomy using a diamond knife. The samples were loaded onto a porous carbon electron microscopy grid, and were ready for analysis.
The electron diffraction pattern (EDP) was obtained with a 120 kV transmission electron microscope in nanoprobe mode with a point-to-point resolution of 3.2 The incident beam used for the generation of the EDP shown in 24 Figures 5 and 6 was about So wide.
Figure 5 is an EDP obtained for an embodiment of the material of the present invention, prepared according to the method described in Example 1. As previously discussed, the presence of a halo 0.0334 1" in radius is indicative of short range order in this material, with a d spacing between the repeating features of about 30 This EDP is different from the one generated by a disordered material (Figure 6), where only a bright spot in the center of the pattern is observed, due to transmitted non-deflected electrons; and from the arrays of spots observed in Figure IS of U.S.
Patent 5,098,684, corresponding to a long-range order material.
Another indication that the halo is representative of short range order is the fact that its presence in the EDP is independent of sample orientation. A characteristic of short range order materials is that the repeating features are isotropically distributed throughout its bulk. Therefore, it is not necessary to orient the sample in a particular direction to observe the halo, since they are all equivalent. This is indeed the case for the EDP from the product of Example 1. On the contrary, for long range order materials, where the structural features repeat hundreds or even thousands of times but in specific directions, the corresponding EDP is only observable when the electron beam impinges the sample in certain orientations. This is the case in U.S. Patent No. 5,098,684, where the EDP of well defined spots indicative of a long range order with hexagonal symmetry is only observable when the electron beam bapinges the saiciple in the appropriate orientation.
Claims (13)
- I. A process for preparing an inorganic porous material, comprising the steps Offorming a solution of a hydrolyzable inorganic compound with a non-ionic surfactant having organic molecules; inducing growth and condensation of a solid composition comprising an inorganic composition in intimate contact with said organic molecules; and extracting said organic molecules from said inorganic composition so as to provide said inorganic porous material having mesopore void volume of at least about 0. 1 cc/g and having enhanced stability under thermai and hydrotre=ent conditions.
- 2. A process according to claim 1, wherein said hydrolyzable inorganic compound is selected from chlorides, alkoxides, nitrates, hydroxides, sulphates and mixtures thereof
- 3. A process according to claim 2, wherein said hydrolyzable inorganic compound is selected from nitrates, hydroxides and mixtures thereof
- 4. A process according to any of claims 1 to 3, wherein the step of inducing growth and condensation comprises the step of adjusting said solution to a pH equal to or within about 2 pH numbers of an isoelectric point mean value of inorganic species of said inorganic compound.
- A process according to claim 4, further comprising the step of adding an acid to said solution to adjust said pH.
- 6. A process according to claim 5, wherein said acid is HCL
- 7 A process according to any of claims I to 6, wherein said non ionic surfactant is selected from ethoxylated alcohols, ethoxylated alkylphenols, amine oxides, ethoxylated amines and mixtures thereof.
- 8. A process according to claim 7, wherein said non-ionic surfactant is present in a molar ratio of surfactant to inorganic species of said inorganic compound in the range of about 0.05 to about 20.
- 9. - A process according to any of claims I to 8, wherein said extracting step comprises calcining said solid composition so as to extract said organic molecules and thereby form said channels.
- 10. A process according to claim 9, wherein said calcining step is carried out at a temperature in the range of about 400"C to about 800"C, for a period of at least about I hour.
- 11. A process according to any of claims I to 10,. further comprising the step of adding an organic water insoluble compound to said solution, whereby size and volume of said channels are enhanced.
- 12. A process according to claim 111, wherein said organic water insoluble compound is selected from p-xylene, trimethylbenzene, triethylbenzene, dimethyladarnantane and mixtures thereof.
- 13. A process according to any of claims 1 to 12, wherein said solution is prepared using a precursor of said hydrolyzable inorganic compound, selected from colloidal silica, alumina sols, suspensions of pseudobentonite, titania, zirconia, oxide hydrosols and mixtures thereof.
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| GB9702523A GB2309967B (en) | 1996-02-09 | 1997-02-07 | Synthetic porous material with microporous walls defining narrow size distribution mesopores |
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| WO1996031434A1 (en) * | 1995-04-03 | 1996-10-10 | Massachusetts Institute Of Technology | Composition and method for producing hexagonally-packed mesoporous metal oxide |
| EP0739856A2 (en) * | 1995-04-25 | 1996-10-30 | The Institute Of Physical & Chemical Research | A silica-surfactant nanocomposite and its production process |
| WO1996039357A1 (en) * | 1995-06-06 | 1996-12-12 | Michigan State University | Porous inorganic oxide materials prepared by non-ionic surfactant templating route |
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| WO1996031434A1 (en) * | 1995-04-03 | 1996-10-10 | Massachusetts Institute Of Technology | Composition and method for producing hexagonally-packed mesoporous metal oxide |
| EP0739856A2 (en) * | 1995-04-25 | 1996-10-30 | The Institute Of Physical & Chemical Research | A silica-surfactant nanocomposite and its production process |
| WO1996039357A1 (en) * | 1995-06-06 | 1996-12-12 | Michigan State University | Porous inorganic oxide materials prepared by non-ionic surfactant templating route |
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