WO2021105253A1 - Alumine présentant un profil poreux particulier - Google Patents
Alumine présentant un profil poreux particulier Download PDFInfo
- Publication number
- WO2021105253A1 WO2021105253A1 PCT/EP2020/083438 EP2020083438W WO2021105253A1 WO 2021105253 A1 WO2021105253 A1 WO 2021105253A1 EP 2020083438 W EP2020083438 W EP 2020083438W WO 2021105253 A1 WO2021105253 A1 WO 2021105253A1
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- WO
- WIPO (PCT)
- Prior art keywords
- alumina
- pore volume
- weight
- equal
- alumina according
- Prior art date
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000011148 porous material Substances 0.000 title claims abstract description 120
- 238000001354 calcination Methods 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims description 76
- 239000007864 aqueous solution Substances 0.000 claims description 54
- 239000002245 particle Substances 0.000 claims description 39
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 37
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 35
- 239000011541 reaction mixture Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 23
- 229910052746 lanthanum Inorganic materials 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 17
- 229910052753 mercury Inorganic materials 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 15
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 13
- 238000002459 porosimetry Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 150000003385 sodium Chemical class 0.000 claims 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 3
- 239000000725 suspension Substances 0.000 description 30
- 239000000843 powder Substances 0.000 description 27
- 238000005259 measurement Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012066 reaction slurry Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- -1 for example Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004452 microanalysis Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101150063042 NR0B1 gene Proteins 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000006722 reduction reaction Methods 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
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 229910001928 zirconium oxide 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J35/615—100-500 m2/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J37/02—Impregnation, coating or precipitation
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- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the present invention relates to an alumina exhibiting a particular porous profile and good thermal stability.
- This alumina is also characterized by the fact that it has a high bulk density.
- Alumina is used as a support for precious metals, in particular platinum, palladium and / or rhodium. It can also be associated with other components of the catalyst, components which will depend on the catalyst and the intended application (diesel or gasoline pollution control).
- oxides based on rare earths such as cerium oxides or mixed oxides of cerium and zirconium used as oxygen mobility materials for gasoline engine catalysts ( so-called three-way catalyst (TWC in English) or gasoline particulate filters (GPF)).
- the alumina can also be combined with a zeolite used for example as a hydrocarbon trap for diesel catalysts or else with a zeolite exchanged with copper and / or iron for catalysts for the catalytic reduction of nitrogen oxides with ammonia ( SCR) for the reduction of NO x emitted by diesel engines.
- a zeolite used for example as a hydrocarbon trap for diesel catalysts or else with a zeolite exchanged with copper and / or iron for catalysts for the catalytic reduction of nitrogen oxides with ammonia ( SCR) for the reduction of NO x emitted by diesel engines.
- thermal stability of the alumina is required to be high because this makes it possible to maintain the efficiency of the catalyst over time, that is to say to maintain a good conversion of gaseous pollutants.
- thermal stability is understood to mean the fact of maintaining a high specific surface area after heat treatments at high temperature.
- a simple and common way to characterize the thermal stability of an alumina is to measure its specific surface area after heat treatment at high temperature, for example at 1200 ° C for 5 hours in air.
- the preparation of an automotive pollution control catalyst generally involves the deposition or coating of an alumina-based suspension on a substrate or on a monolith.
- the alumina of the invention is suitable for the preparation of a suspension having a low viscosity, which makes it possible to prepare a suspension having a high proportion of alumina. Furthermore, the high density of the alumina of the invention facilitates the handling of the alumina powder.
- thermal stability of aluminas is generally partly linked to the pore volume of the alumina. By increasing this pore volume, thermal stability is generally increased. This increase in pore volume, however, leads to a lowering significant in the density of the alumina and an increase in the viscosity of the alumina slurry during the catalyst preparation process.
- the specific porosity of the alumina of the invention makes it possible to obtain both high thermal stability as well as high bulk density.
- Fig. 1/1 represents a diffractogram of the alumina of the invention (example 1). It can be seen that this alumina exhibits the peaks characteristic of a crystallized alumina.
- the invention relates to an alumina as defined in one of claims 1 to 42.
- alumina comprises the elements Al and O and also an additional element (E) which is La, Pr or a combination of La + Pr, the proportion of the element (E) possibly being between 0.1% and 6 , 0% by weight, or even between 0.5% and 6.0% by weight, or even between 1.0% and 6.0% by weight, or even between 2.0% and 6.0% by weight, this proportion being expressed by weight of element (E) expressed in oxide form relative to the total weight of alumina, and it is characterized by at least one of the following two porosity profiles:
- ⁇ 1 st profile a pore volume in the area of the pores, the size of which is between 5 nm and 100 nm which is between 0.60 and 0.85 mL / g, more particularly between 0.60 and 0.80 mL / g; and a pore volume in the area of the pores, the size of which is between 100 nm and 1000 nm which is less than or equal to 0.20 ml / g, more particularly less than or equal to 0.15 ml / g, or even less than or equal at 0.10 ml / g, or even less than or equal to 0.05 ml / g; and or
- a pore volume in the area of pores having a size between 5 nm and 100 nm is between 0.50 and 0.75 mL / g , more particularly between 0.50 and 0.70 mL / g; and a pore volume in the area of the pores, the size of which is between 100 nm and 1000 nm which is less than or equal to 0.20 ml / g, more particularly less than or equal to 0.15 ml / g, or even less than or equal at 0.10 ml / g, or even less than or equal to 0.05 ml / g; these pore volumes being determined using the mercury porosimetry technique.
- This alumina can include sodium and sulfate as well as impurities.
- the invention also relates to a catalytic composition as defined in claim 43, as well as to the use of alumina as defined in claim 44.
- the invention also relates to a process for preparing an alumina as defined in one of claims 45 to 52.
- concentrations of the solutions or the proportions in alumina of the elements Al and element (E) are given in% by weight in oxide equivalents.
- oxides are thus used for the calculations of these concentrations or proportions: Al2O3 for the element Al, La2O3 for the element La and RGbOii for the element Pr.
- an aqueous solution of aluminum sulphate exhibiting a aluminum concentration of 2.0% by weight corresponds to a solution containing 2.0% by weight in AI2O3 equivalent.
- an alumina comprising 4.0% of lanthanum corresponds to 4.0% of La 2 C> 3.
- Particle is understood to mean an agglomerate formed from primary particles.
- Particle size is determined from a volume distribution of particle sizes obtained using a laser particle sizer.
- the particle size distribution is characterized using parameters D10, D50 and D90. These parameters have the usual meaning in the field of measurements by laser diffraction.
- Dx is denoted the value which is determined on the volume distribution of the sizes of the particles for which x% of the particles have a size less than or equal to this value Dx.
- D50 therefore corresponds to the median value of the distribution.
- D90 corresponds to the size for which 90% of the particles have a size which is less than D90.
- D10 corresponds to the size for which 10% of the particles have a size which is less than D10.
- the measurement is generally made on a dispersion of the particles in water.
- the porosity data are obtained by the mercury porosimetry technique. This technique makes it possible to define the pore volume (V) as a function of the pore diameter (D).
- a Micromeritics Autopore 9520 device fitted with a powder penetrometer can be used, complying with the instructions recommended by the manufacturer.
- the ASTM D 4284-07 procedure can be followed. With the help of these data, it is possible to determine the pore volume in the region of pores whose size is between 5 nm and 100 nm (VP5-100 nm ), the pore volume in the region of pores whose size is between 100 nm and 1000 nm (VPioo-iooo nm) and the total pore volume (TPV).
- the term “specific surface area” means the BET specific surface area determined by nitrogen adsorption determined using the Brunauer-Emmett-Teller method. This method has been described in the periodical "The Journal of the American Chemical Society, 60, 309 (1938)". The recommendations of the standard ASTM D3663 - 03 can be complied with.
- the calcinations for a given temperature and time correspond, unless otherwise indicated, to calcinations in air at a temperature plateau over the indicated time.
- the alumina of the invention is an alumina comprising an additional element (E) which is La, Pr or a combination of La + Pr.
- Element (E) can in particular and advantageously be element La.
- This type of alumina comprising such an element is generally described as a so-called doped alumina.
- the proportion of element (E) is between 0.1% and 6.0% by weight, or even between 0.5% and 6.0% by weight, this proportion being expressed by weight of element (E ) expressed in the form of oxide relative to the total weight of the alumina. This proportion may be between 1.0% and 6.0% by weight, or even between 2.0% and 6.0% by weight.
- Element (E) is generally present in alumina as an oxide.
- the alumina of the invention is characterized by a particular porosity.
- this alumina has at least one of the following two porosity profiles:
- 1 st profile a pore volume in the area of the pores, the size of which is between 5 nm and 100 nm which is between 0.60 and 0.85 mL / g, more particularly between 0.60 and 0.80 mL / g; and a pore volume in the area of the pores, the size of which is between 100 nm and 1000 nm which is less than or equal to 0.20 mL / g, more particularly less than or equal to 0.15 mL / g, or even less than or equal at 0.10 mL / g, or even less than or equal to 0.05 mL / g.
- 2 nd profile after calcination in air at 1100 ° C for 5 hours: a pore volume in the area of the pores the size of which is between 5 nm and 100 nm which is between 0.50 and 0.75 mL / g, more particularly between 0.50 and 0.70 mL / g; and a pore volume in the area of the pores, the size of which is between 100 nm and 1000 nm which is less than or equal to 0.20 mL / g, more particularly less than or equal to 0.15 mL / g, or even less than or equal at 0.10 mL / g, or even less than or equal to 0.05 mL / g.
- Alumina can also be defined by at least one of the following two porosity profiles:
- ⁇ 1 st profile a pore volume in the region of the pores, the size of which is between 5 nm and 100 nm which is between 0.60 and 0.85 mL / g; and a pore volume in the area of the pores the size of which is between 100 nm and 1000 nm which is less than or equal to 0.20 mL / g; and or
- ⁇ 2 nd profile after calcination in air at 1100 ° C for 5 hours: a pore volume in the area of pores having a size between 5 nm and 100 nm is between 0.50 and 0.75 mL / g ; and a pore volume in the area of the pores the size of which is between 100 nm and 1000 nm which is less than or equal to 0.20 mL / g.
- the alumina which is described in the present application can have at least one of the two aforementioned profiles, it being understood that it can have both profiles at the same time.
- the alumina can have a high specific surface. It may have a BET specific surface area of between 100 and 200 m 2 / g, more particularly between 150 and 200 m 2 / g. This specific surface can be greater than or equal to 120 m 2 / g, preferably greater than or equal to 140 m 2 / g. This specific surface can also be between 100 and 140 m 2 / g, or even between 100 and 120 m 2 / g.
- the alumina also has high thermal stability. It can have a BET specific surface after calcination in air at 1200 ° C. for 5 hours of between 45 and 60 m 2 / g.
- the alumina generally has a total pore volume which is generally strictly greater than 1.05 mL / g.
- This total pore volume can advantageously be at least 1.10 mL / g, or even at least 1. 20 mL / g, or even at least 1.30 mL / g or at least 1.40 mL / g or at least 1.50 mL / g.
- This total pore volume is generally at most 2.40 mL / g.
- the alumina retains a large total pore volume even after calcination at 1100 ° C. for 5 hours.
- the alumina after calcination at 1100 ° C. for 5 hours, the alumina generally exhibits a total pore volume which is at least 0.90 mL / g.
- This total pore volume is preferably at least 1.00 ml / g, or even at least 1.10 ml / g, or even more advantageously at least 1.20 ml / g.
- This total pore volume is generally at most 1.80 mL / g.
- the alumina can have an apparent density of between 0.25 g / cm 3 and 0.55 g / cm 3 , more particularly between 0.40 g / cm 3 and 0.55 g / cm 3 .
- This bulk density can be determined by the method described below. First, the volume of a cylindrical-shaped test tube of approximately 25 mL is precisely determined. To do this, the empty specimen is weighed (tare T). Distilled water is then poured into the test tube to the edge but without going over the edge (no meniscus). Weigh the test tube filled with distilled water (M). The mass of water contained in the test tube is therefore:
- the density of the water is for example equal to 0.99983 g / mL for a measurement temperature of 20 ° C.
- the alumina can have an D50 of between 2.0 ⁇ m and 80.0 ⁇ m. It may have a D90 less than or equal to 150.0 ⁇ m, more particularly less than or equal to 100.0 ⁇ m. It may have a D10 greater than or equal to 1.0 ⁇ m.
- the alumina has a D50 of between 2.0 and 15.0 ⁇ m, or even between 4.0 and 12.0 ⁇ m.
- the D90 can be between 20.0 pm and 60.0 pm, or even between 25.0 pm and 50.0 pm.
- the apparent density is between 0.25 and 0.40 g / cm 3 ;
- the total pore volume is between 1.40 and 2.40 mL / g.
- This total pore volume can be more advantageously between 1.50 and 2.40 mL / g.
- the alumina has a D50 of between 15.0 and 80.0 ⁇ m, or even between 20.0 and 60.0 ⁇ m.
- the D90 can be between 40.0 pm and 150.0 pm, or even between 50.0 pm and 100.0 pm.
- the apparent density may be between 0.40 and 0.55 g / cm 3 ;
- the total pore volume is between 1.05 (excluded value) and 1.80 mL / g.
- This total pore volume can be more advantageously between 1, 20 and 1, 80 ml / g.
- the alumina can include residual sodium.
- the residual sodium level may be less than or equal to 0.50% by weight, or even less than or equal to 0.15% by weight.
- the sodium level can be greater than or equal to 50 ppm. This rate can be between 50 and 900 ppm, or even between 100 and 800 ppm. This level is expressed by weight of Na 2 0 relative to the total weight of alumina. Thus, for an alumina having a residual sodium level of 0.15%, it is considered that there is per 100 g of alumina, 0.15 g of Na 2 0.
- the method for determining the sodium level in this range of concentrations is known to those skilled in the art. For example, the technique of inductively coupled plasma spectroscopy can be used.
- the alumina can include residual sulfate.
- the level of residual sulphate may be less than or equal to 1.00% by weight, or even less than or equal to 0.20% by weight, or even less than or equal to 0.10% by weight.
- the sulphate level can be greater than or equal to 50 ppm. This rate can be between 100 and 1500 ppm, or even between 400 and 1000 ppm. This rate is expressed in weight of sulphate relative to the total weight of alumina. Thus, for an alumina having a residual sulphate level of 0.50%, it is considered that there is per 100 g of alumina, 0.50 g of SO 4 .
- the method for determining the level of sulphate in this range of concentrations is known to those skilled in the art such as, for example, the technique of inductively coupled plasma spectroscopy. You can also use microanalysis techniques. A Horiba EMIA 320-V2 type microanalysis device could be suitable.
- Alumina can also contain impurities other than sodium and sulphate, for example impurities based on silicon, titanium or iron.
- the proportion of each impurity is generally less than 0.10% by weight, or even less than 0.05% by weight.
- the alumina is crystallized. This can be demonstrated using an X-ray diffractogram.
- the alumina can comprise a delta phase, a theta phase, a gamma phase or a mixture of at least two of these phases.
- the alumina of the invention may more particularly exhibit at least one of the following two porosity profiles:
- a pore volume in the area of the pores the size of which is between 5 nm and 100 nm which is between 0.60 and 0.85 mL / g, more particularly between 0.60 and 0.80 mL / g; and a pore volume in the area of the pores the size of which is between 100 nm and 1000 nm which is less than or equal to 0.05 mL / g; and or
- 2 nd profile after calcination in air at 1100 ° C for 5 hours: a pore volume in the area of the pores the size of which is between 5 nm and 100 nm which is between 0.50 and 0.75 mL / g, more particularly between 0.50 and 0.70 mL / g; and a pore volume in the area of the pores the size of which is between 100 nm and 1000 nm which is less than or equal to 0.05 mL / g.
- this particular alumina can have at least one of the two aforementioned profiles, it being understood that it can have both profiles at the same time.
- the sodium and sulfate levels are for that particular alumina as previously described.
- this particular alumina can also exhibit the characteristics of total pore volume as described above.
- it generally has a total pore volume which is generally strictly greater than 1.05 mL / g.
- This total pore volume can advantageously be at least 1.10 mL / g, or even at least 1. 20 mL / g, or even at least 1.30 mL / g or at least 1.40 mL / g or at least 1.50 mL / g.
- This total pore volume is generally at most 2.40 mL / g.
- This particular alumina retains a large total pore volume even after calcination at 1100 ° C. for 5 hours. Thus, after calcination at 1100 ° C.
- the alumina generally exhibits a total pore volume which is at least 0.90 mL / g.
- This total pore volume is preferably at least 1.00 mL / g, or even at least 1.10 mL / g, or even more advantageously at least 1.20 mL / g.
- This total pore volume is generally at most 1.80 mL / g.
- the alumina of the invention can be used in the field of catalysis for the depollution of the exhaust gases of gasoline or diesel heat engines.
- a catalytic composition comprising the alumina of the invention and at least one oxide based on cerium and optionally at least one rare earth other than cerium is used in this field.
- This oxide can be, for example, cerium oxide (generally represented by the formula CeC> 2), a mixed oxide based on cerium, on zirconium and optionally on at least one rare earth other than cerium.
- the rare earth other than cerium can be chosen from the group formed by yttrium, praseodymium or neodymium.
- the invention also relates to a process for preparing an alumina optionally containing an additional element (E) chosen from lanthanum, praseodymium or a combination of these two elements, in particular alumina as described above or as described. to one of claims 1 to 41, comprising the following steps:
- step (a2) either simultaneously (i) an aqueous solution of aluminum sulphate and (ii) an aqueous solution of sodium aluminate until a pH of the reaction mixture is obtained between 6.5 and 10.0, or even between 7.0 and 8.0 or between 8.5 and 9.5 so that at the end of step (a), the aluminum concentration in the reaction mixture is between 0.50% and 3, 0% by weight;
- the pH of the reaction mixture is optionally adjusted to a value between 7.5 and 10.5, or even between 8.0 and 9.0 or between 9.0 and 10.0;
- step (e) a dispersion in water of the solid recovered at the end of step (d) undergoes mechanical or ultrasonic treatment so as to reduce the size of the particles of the dispersion;
- step (g) the dispersion obtained at the end of step (f) is dried;
- step (h) the solid resulting from step (g) is then calcined in air. step (a)
- step (a) the following are introduced with stirring into a tank initially containing an acidic aqueous solution, the pH of which is between 0.5 and 4.0, or even between 0.5 and 3.5:
- step (a2) either simultaneously (i) an aqueous solution of aluminum sulphate and (ii) an aqueous solution of sodium aluminate until a pH of the reaction mixture is obtained between 6.5 and 10.0, or even between 7.0 and 8.0 or between 8.5 and 9.5; so that at the end of step (a), the aluminum concentration of the reaction mixture is between 0.50% and 3.0% by weight.
- the acidic aqueous solution initially contained in the tank has a pH of between 0.5 and 4.0, or even between 0.5 and 3.5.
- This solution may consist of a dilute aqueous solution of a mineral acid such as, for example, sulfuric acid, hydrochloric acid or nitric acid.
- the aqueous acidic solution can also consist of an aqueous solution of an acidic aluminum salt such as aluminum nitrate, chloride or sulfate.
- an acidic aluminum salt such as aluminum nitrate, chloride or sulfate.
- the aluminum concentration of this solution is between 0.01% and 2.0% by weight, or even between 0.01% and 1.0% by weight, or even between 0.10% and 1.0% by weight.
- the acidic aqueous solution is an aqueous solution of aluminum sulfate. This solution is prepared by dissolving aluminum sulfate in water or by diluting preformed aqueous solution (s) in water.
- the pH of the aqueous solution developed by the presence of aluminum sulfate is generally between 0.5 and 4.0, or even between 0.5 and 3.5.
- Step (a) is implemented according to two embodiments (a1) or (a2).
- an aqueous solution of sodium aluminate is introduced with stirring.
- an aqueous solution of aluminum sulphate and (ii) an aqueous solution of sodium aluminate are simultaneously introduced with stirring.
- the aqueous solution of sodium aluminate does not have precipitated alumina.
- the sodium aluminate preferably has an Na 2 0 / Al 2 C> 3 ratio greater than or equal to 1. 20, for example between 1. 20 and 1. 40.
- the aqueous solution of sodium aluminate may have an aluminum concentration of between 15.0% and 35.0% by weight, more particularly between 15.0% and 30.0% by weight, or even between 20.0% and 30.0% by weight. , 0%.
- the aqueous solution of aluminum sulphate can have an aluminum concentration of between 1.0% and 15.0% by weight, more particularly between 5.0% and 10.0% by weight.
- the aluminum concentration of the reaction mixture is between 0.50% and 3.0% by weight.
- step (a) the duration of introduction of the solution (s) is generally between 2 min and 30 min.
- step (a) the introduction of the aqueous solution of sodium aluminate has the effect of increasing the pH of the reaction mixture.
- the aqueous solution of sodium aluminate can be introduced directly into the reaction medium, for example by means of at least one introduction rod.
- the two solutions can be introduced directly into the reaction medium, for example by means of at least two introduction pipes.
- the solution (s) is / are preferably introduced into a well-stirred zone of the reactor, for example in a zone close to the stirring wheel, so as to obtain an effective mixture of the solution (s) introduced into the reaction mixture.
- the solutions are introduced via at least two introduction pipes, the injection points through which the two solutions are introduced into the reaction mixture are distributed so as to that the solutions dilute effectively in said mixture.
- two canes can be placed in the tank so that the points of injection of the solutions into the reaction mixture are diametrically opposed.
- step (b) an aqueous solution of aluminum sulphate and an aqueous solution of sodium aluminate are introduced simultaneously, the introduction rates of which are regulated so as to maintain the average pH of the reaction mixture in the range of pH referred to in step (a).
- the target value of the mean pH is between: between 8.0 and 10.0, or even between 8.5 and 9.5, for the case where the embodiment (a1) has been followed in step (a ); or else between 6.5 and 10.0, or even between 7.0 and 8.0 or between 8.5 and 9.5, for the case where the embodiment (a2) has been followed in step (a )
- the aqueous solution of sodium aluminate is introduced at the same time as the aqueous solution of aluminum sulphate at a rate which is regulated so that the average pH of the reaction mixture is equal to the target value.
- the flow rate of the aqueous sodium aluminate solution used to regulate the pH may fluctuate during step (b).
- the duration of introduction of the two solutions may be between 10 minutes and 2 hours, or even between 30 minutes and 90 minutes.
- the rate of introduction of the or both solutions can be constant.
- the temperature of the reaction mixture for steps (a) and (b) is at least 60 ° C. This temperature can be between 60 ° C and 95 ° C.
- the solution initially contained in the tank in step (a) may have been preheated before the start of the introduction of the solution (s). It is also possible to preheat the solutions which are introduced into the tank in steps (a) and (b) beforehand. step (cl
- step (c) the pH of the reaction mixture is optionally adjusted to a value between 7.5 and 10.5, or even between 8.0 and 9.0 or between 9.0 and 10.0, by l addition of a basic or acidic aqueous solution.
- the acidic aqueous solution which can be used to adjust the pH may consist of an aqueous solution of a mineral acid such as, for example, sulfuric acid, hydrochloric acid or nitric acid.
- the aqueous acidic solution can also consist of an aqueous solution of an acidic aluminum salt such as aluminum nitrate, chloride or sulfate.
- the basic aqueous solution which can be used to adjust the pH may consist of an aqueous solution of a mineral base such as, for example, soda, potassium hydroxide, ammonia.
- the basic aqueous solution can also consist of an aqueous solution of a basic aluminum salt such as sodium aluminate.
- aqueous solution of sodium aluminate is used.
- the pH is adjusted by stopping:
- the introduction of the aqueous solution of aluminum sulphate is stopped and the aqueous solution of sodium aluminate is continued to be introduced until a target pH of between 8.0 and 10.5 is reached. , preferably between 9.0 and 10.0.
- the duration of step (c) can be variable. This duration can be between 5 min and 30 min. step (d)
- step (d) the reaction mixture is filtered.
- the reaction mixture is generally in the form of a slurry.
- the solid collected on the filter can be washed with water. To do this, you can use hot water with a temperature of at least 50 ° C. step (e)
- step (e) a dispersion in water of the solid recovered at the end of step (d) undergoes mechanical or ultrasonic treatment so as to reduce the size of the particles of the dispersion.
- the pH of this dispersion before grinding can optionally be adjusted between 5.0 and 8.0. You can use a nitric acid solution, for example.
- the D50 of the particles of the dispersion before the mechanical or ultrasonic treatment is generally between 10.0 pm and 40.0 pm, or even between 10.0 pm and 30.0 pm.
- the D50 of the particles of the solid after the mechanical or ultrasonic treatment is preferably between 1.0 ⁇ m and 15.0 ⁇ m, or even between 2.0 ⁇ m and 10.0 ⁇ m.
- Mechanical treatment involves applying mechanical stress or shear forces to the dispersion so as to split the particles.
- the mechanical treatment can for example be carried out using a ball mill, a high pressure homogenizer or a grinding system comprising a rotor and a stator.
- Ultrasound treatment consists of applying a sound wave to the dispersion.
- the sound wave which propagates in the liquid medium induces a phenomenon of cavitation allowing the particles to be split.
- an ultrasound system with a Vibracell VC750 type sound generator equipped with a 13 mm probe. The duration and the power applied are adjusted so as to reach the target D50.
- step (fi) The mechanical or ultrasonic treatment can be carried out in batch mode or else continuously. step (fi).
- step (f) at least one salt of element (E) is added. It is also possible to consider adding an ammonia solution at this stage to raise the pH, preferably to a value between 5.0 and 8.0. step (qj)
- step (g) the dispersion from step (f) is dried, preferably by atomization.
- Spray drying has the advantage of resulting in particles with a controlled particle size distribution.
- This drying method also has good productivity. It involves spraying the dispersion into a cloud of droplets in a stream of hot gas (eg a stream of hot air) circulating in an enclosure.
- the quality of the spray controls the size distribution of the droplets and hence the size distribution of the dried particles.
- Spraying can be carried out using any sprayer known per se. There are two main types of spray devices: turbines and nozzles.
- turbines and nozzles There are two main types of spray devices.
- the flow rate and the temperature of the dispersion entering the sprayer are in particular the following: the flow rate and the temperature of the dispersion entering the sprayer; the flow rate, the pressure, the humidity and the temperature of the hot gas. of the gas is generally between 100 ° C. and 800 ° C.
- the gas outlet temperature is generally between 80 ° C. and 150 ° C.
- the D50 of the powder recovered at the end of step (g) is generally between 2.0 ⁇ m and 80.0 ⁇ m. This size is linked to the size distribution of the droplets at the outlet of the sprayer.
- the vaporizer capacity of the atomizer is generally related to the size of the enclosure. Thus, on a laboratory scale (Büchi B 290), the D50 can be between 2.0 and 15.0 ⁇ m. On a larger scale, the D50 can be between 15.0 and 80.0 ⁇ m. step (h)
- step (h) the solid from step (g) is calcined in air.
- the calcination temperature is generally between 500 ° C and 1000 ° C, more particularly between 800 ° C and 1000 ° C.
- the duration of the calcination is generally between 1 and 10 h. It is possible to use the calcination conditions given in the examples.
- step (g) it is conceivable to carry out the two steps (g) and (h) in the same equipment in which the dispersion resulting from step (f) undergoes a heat treatment allowing both drying and calcination to be carried out.
- the alumina which is recovered at the end of step (h) (that is to say at the end of the calcination) has a D50 generally between 2.0 ⁇ m and 80.0. pm. It generally has a D90 less than or equal to 150.0 ⁇ m, more particularly less than or equal to 100.0 ⁇ m.
- the D50 can be between 2.0 and 15.0 pm, or even between 4.0 and 12.0 pm.
- the D90 can be between 20.0 pm and 60.0 pm, or even between 25.0 pm and 50.0 pm.
- This embodiment can instead be implemented when step (f) is carried out on a laboratory scale using, for example, a Büchi B 290 atomizer.
- the D50 can be between 15.0 and 80.0 pm, or even between 20.0 and 60.0 pm.
- the D90 can be between 40.0 pm and 150.0 pm, or even between 50.0 pm and 100.0 pm. This embodiment can rather be implemented when step (f) is carried out on a larger scale.
- the process can also include a final step whereby the solid obtained in the previous step undergoes grinding in order to adjust the particle size of the solid.
- You can use a knife, air jet, hammer or ball mill.
- the ground product has an OD generally between 2.0 ⁇ m and 15.0 ⁇ m.
- the D90 can be between 20.0 pm and 60.0 pm, or even between 25.0 pm and 50.0 pm.
- the alumina of the invention is in the form of a powder.
- the term “specific surface area” is understood to mean the BET specific surface area determined by nitrogen adsorption in accordance with standard ASTM D 3663-03 established from the BRUNAUER-EMMETT-TELLER method described in the periodical "The Journal of the American Chemical Society, 60, 309 (1938) ".
- the specific surface is determined automatically using a device, for example of the T ristar II 3020 type of Micromeritics in accordance with the indications recommended by the manufacturer.
- the samples are pretreated at 250 ° C. for 90 min under vacuum (for example to reach a pressure of 50 mm of mercury). This treatment makes it possible to eliminate the volatile species physisorbed on the surface (such as for example H2O, ).
- the measurement is carried out using a mercury porosimetry measuring device.
- a Micromeritics Autopore IV 9520 device fitted with a powder penetrometer was used, complying with the instructions recommended by the manufacturer.
- the following parameters were used: penetrometer used: 3.2 ml (Micromeritics reference: type No. 8 penetrometer); capillary volume: 0.412 ml; max pressure ("head pressure")
- a MALVERN Mastersizer 2000 or 3000 laser diffraction particle size analyzer is used (more details on this device given here: https://www.malvernpanalvtical.com/fr/products/product-range/mastersizer - ranqe / mastersizer-3000).
- the laser diffraction technique used consists in measuring the intensity of the light scattered during the passage of a laser beam through a sample of dispersed particles. The laser beam passes through the sample and the intensity of the scattered light is measured as a function of the angle. The diffracted intensities are then analyzed to calculate the particle size using Mie scattering theory. The measurement makes it possible to obtain a volume size distribution from which the parameters D10, D50 and D90 are deduced.
- Example 1 preparation of an aluminum oxide according to the invention containing 4% lanthanum (96% Al2O3 - 4% LazOî) according to the embodiment (a1)
- step (b) the introduction of the aluminum sulphate solution is again started at a flow rate of 12 g of solution / min and the sodium aluminate solution is simultaneously introduced into the stirred reactor at a flow rate regulated so as to maintain the pH at a value of 9.0. This stage lasts 45 minutes,
- step (c) the introduction of the aluminum sulphate solution is stopped and the sodium aluminate solution is continued to be added with a flow rate of 5 g of solution / min until a pH of 9.5. The addition of the sodium aluminate solution is then stopped.
- step (d) the reaction slurry is poured onto a vacuum filter. After filtration, the cake is washed with deionized water at 60 ° C.
- step (e) the cake is redispersed in deionized water to obtain a dispersion with a concentration of around 11% by weight of oxide (Al2O3).
- a nitric acid solution with a concentration of 69% by weight is added to the suspension so as to obtain a pH close to 6.2.
- the suspension is passed through a Labstar Zêta brand bead mill from the manufacturer Netzsch. The operating conditions of the mill are adjusted so as to obtain a D50 of 4.2 microns.
- step (f) an aqueous solution of lanthanum acetate is prepared at a concentration close to 8% by weight of oxide (La2C> 3). This solution is added with stirring to the suspension resulting from step (e) so as to obtain a La 2 03 / (La 2 03 + Al 2 O 3) mass ratio of 4.0%.
- step (g) the suspension from step (f) is atomized to obtain a dry powder of aluminum hydrate doped with lanthanum.
- step (h) the atomized powder is calcined at 900 ° C for 2 hours (temperature rise rate of 4 ° C / min). The loss of mass observed during this calcination is 26.1%.
- Example 2 preparation of an aluminum oxide according to the invention containing 2% lanthanum (98% Al2O3 - 2% LazOî) according to the embodiment (a1)
- step (b) the introduction of the aluminum sulphate solution is again started at a flow rate of 570 g of solution / min and the sodium aluminate solution is simultaneously introduced into the stirred reactor at a flow rate regulated so as to maintain the pH at a value of 9.0. This stage lasts 45 minutes,
- step (c) the introduction of the aluminum sulphate solution is stopped and the sodium aluminate solution is continued to be added with a flow rate of 320 g of solution / min until a pH of 9.5. The addition of the sodium aluminate solution is stopped.
- step (d) the reaction slurry is poured onto a vacuum filter. After filtration, the cake is washed with deionized water at 65 ° C.
- step (e) the cake is redispersed in deionized water to obtain a suspension with a concentration of around 10% by weight of oxide (Al2O3).
- a nitric acid solution with a concentration of 69% by weight is added to the suspension so as to obtain a pH close to 6.
- the suspension is passed through a ball mill of the LME20 brand from the manufacturer Netzsch. The operating conditions of the mill are adjusted so as to obtain a D50 of 3.5 microns.
- step (f) a lanthanum acetate solution is prepared at a concentration close to 6.9% by weight of oxide (La 2 C> 3). This solution is added with stirring to the suspension resulting from step (e) so as to obtain a La203 / (La203 + Al2C> 3) mass ratio of 2%.
- step (g) the suspension from step (f) is atomized to obtain a dry powder of aluminum hydrate doped with lanthanum.
- step (h) the atomized powder is calcined at 940 ° C for 2 hours (temperature rise rate of 3 ° C / min). The mass loss observed during this calcination is 25.8%.
- Example 3 preparation of an aluminum oxide according to the invention containing 4% lanthanum (f96% AI2O3 - 4% La? Q3 ⁇ 4)
- Steps (a) to (e) of Example 2 are repeated.
- step (f) a lanthanum acetate solution is prepared at a concentration of 6.9% by weight of oxide (La 2 0s). This solution is added with stirring to the suspension resulting from step (e) so as to obtain a La 2 03 / (La 2 03 + Al 2 03) mass ratio of 4%. A 10.0% by weight ammonia solution is then added so as to obtain a pH of 8.7.
- step (g) the suspension from step (f) is atomized to obtain a dry powder of aluminum hydrate doped with lanthanum.
- step (h) the atomized powder is calcined at 940 ° C for 2 hours (temperature rise rate of 3 ° C / min). The mass loss observed during this calcination is 26.9%.
- Example 4 preparation of an aluminum oxide according to the invention containing 4% lanthanum (96% Al 2 O 3 - 4% La 2 C> 3) according to embodiment (a2) 120 kg of deionized water are introduced into the same stirred reactor, which are heated to 67 ° C. This temperature will be maintained throughout steps (a) to (c). Using an introduction rod close to the stirring unit, 1.85 kg of an aluminum sulphate solution with a concentration of 8.3% by weight of alumina (AI2O3) are introduced at a flow rate of 370 g of solution. / min. At the end of the introduction, the pH of the starter is close to 3.0 and the concentration expressed in oxide equivalent is 0.13% by weight.
- AI2O3 aluminum sulphate solution with a concentration of 8.3% by weight of alumina
- step (b) the introduction of the aluminum sulfate solution is maintained at a flow rate of 1020 g of solution / min and the sodium aluminate solution is simultaneously introduced into the stirred reactor at a regulated flow rate. so as to maintain the pH at a value of 7.3. This stage lasts 45 minutes,
- step (c) the introduction of the aluminum sulphate solution is stopped and the sodium aluminate solution is continued to be added with a flow rate of 1020 g of solution / min until a pH of 10.3. The addition of the sodium aluminate solution is stopped.
- step (d) the reaction slurry is poured onto a vacuum filter. After filtration, the cake is washed with deionized water at 65 ° C.
- step (e) the cake is redispersed in deionized water to obtain a suspension with a concentration of around 13% by weight of oxide (Al2O3).
- a nitric acid solution with a concentration of 69% by weight is added to the suspension so as to obtain a pH close to 6.2.
- the suspension is passed through an LME20 brand ball mill from the manufacturer Netzsch. The operating conditions of the mill are adjusted so as to obtain a D50 of 13.4 microns.
- step (f) a lanthanum acetate solution is prepared at a concentration of 6.9% by weight of oxide (La2C> 3). This solution is added with stirring to the suspension resulting from step (e) so as to obtain a La203 / (La203 + Al2C> 3) mass ratio of 4.0%.
- step (g) the suspension from step (f) is atomized to obtain a dry powder of aluminum hydrate doped with lanthanum.
- step (h) the atomized powder is calcined at 1035 ° C for 2 hours (temperature rise rate of 3 ° C / min). The loss of mass observed during this calcination is 33%.
- Example 5 preparation of an aluminum oxide according to the invention containing 4% lanthanum (96% Al 2 O 3 - 4% La 2 0 3 ) Steps (a) to (d) of Example 1 are reproduced.
- step (e) the cake from step (d) is redispersed in deionized water to obtain a dispersion with a concentration close to 11% by weight of oxide (Al2O 3 ).
- a nitric acid solution with a concentration of 69% by weight is added to the suspension so as to obtain a pH close to 6.2. 250 grams of this suspension are taken, which are treated with an ultrasound probe.
- the following equipment is used: ultrasound system with a 750 W generator of the Vibracell VC750 sound type equipped with a 13 mm probe (interchangeable tip) (converter: CV334 + 13 mm probe tip (Part No: 630-0220)
- the ultrasound treatment lasts 320 seconds
- the energy delivered as read on the generator is 33,000 Joules
- the final temperature of the suspension is 56 ° C.
- the suspension is allowed to cool. of this treatment, the D50 of the suspension is 6.2 microns.
- step (f) a lanthanum acetate solution is prepared at a concentration close to 8% by weight of oxide (La 2 Os). This solution is added with stirring to the suspension resulting from step (e) so as to obtain a La 2 0 3 / (La 2 0 3 + Al 2 0 s) mass ratio of 4.0%.
- step (g) the suspension from step (f) is atomized to obtain a dry powder of aluminum hydrate doped with lanthanum.
- step (h) the atomized powder is calcined at 900 ° C for 2 hours (temperature rise rate of 4 ° C / min). The mass loss observed during this calcination is 26.3%.
- Example 6 preparation of an aluminum oxide according to the invention containing 4% lanthanum (f96% AI2O 3 - 4% La? Q3 ⁇ 4)
- step (e) the cake is redispersed in deionized water to obtain a dispersion with a concentration of around 11% by weight of oxide (Al2O3).
- a nitric acid solution with a concentration of 69% by weight is added to the suspension so as to obtain a pH close to 6.2.
- 250 grams of this suspension are taken and passed through a Microcer brand ball mill from the manufacturer Netzsch. The operating conditions of the mill are adjusted so as to obtain a D50 of 3.3 microns.
- step (f) a lanthanum acetate solution is prepared at a concentration close to 8% by weight of oxide (La 2 0s). This solution is added with stirring to the suspension resulting from step (e) so as to obtain a La 2 0 3 / (La 2 0 3 + Al 2 0 s) mass ratio of 4.0%.
- step (g) the suspension from step (f) is atomized to obtain a dry powder of aluminum hydrate doped with lanthanum.
- step (h) the atomized powder is calcined at 900 ° C. for 2 hours (temperature rise rate of 4 ° C./min). The loss of mass observed during this calcination is 27.4%. Board
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Abstract
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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JP2022530252A JP2023503335A (ja) | 2019-11-29 | 2020-11-25 | 特定の細孔プロファイルを有するアルミナ |
EP20810989.2A EP4065270A1 (fr) | 2019-11-29 | 2020-11-25 | Alumine présentant un profil poreux particulier |
US17/781,310 US20220410128A1 (en) | 2019-11-29 | 2020-11-25 | Alumina with a particular pore profile |
CN202080083060.8A CN114761125A (zh) | 2019-11-29 | 2020-11-25 | 具有特定孔特性的氧化铝 |
CA3158808A CA3158808A1 (fr) | 2019-11-29 | 2020-11-25 | Alumine presentant un profil poreux particulier |
KR1020227021648A KR20220101721A (ko) | 2019-11-29 | 2020-11-25 | 특정 기공 프로파일을 갖는 알루미나 |
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EP19315154 | 2019-11-29 |
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US (1) | US20220410128A1 (fr) |
EP (1) | EP4065270A1 (fr) |
JP (1) | JP2023503335A (fr) |
KR (1) | KR20220101721A (fr) |
CN (1) | CN114761125A (fr) |
CA (1) | CA3158808A1 (fr) |
WO (1) | WO2021105253A1 (fr) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4154812A (en) | 1977-03-25 | 1979-05-15 | W. R. Grace & Co. | Process for preparing alumina |
US4301037A (en) * | 1980-04-01 | 1981-11-17 | W. R. Grace & Co. | Extruded alumina catalyst support having controlled distribution of pore sizes |
WO2004052534A1 (fr) * | 2002-12-06 | 2004-06-24 | Albemarle Netherlands B.V. | Procede d'hydrotraitement de charge lourde reposant sur l'utilisation d'un melange de catalyseurs |
US20070098611A1 (en) * | 2005-10-31 | 2007-05-03 | Yang Xiaolin D | Stabilized flash calcined gibbsite as a catalyst support |
US20170007987A1 (en) * | 2013-12-24 | 2017-01-12 | Heesung Catalysts Corporation | Exhaust gas oxidation catalyst for compressed natural gas combustion system |
US20170129781A1 (en) * | 2014-06-13 | 2017-05-11 | IFP Energies Nouvelles | Amorphous mesoporous and macroporous alumina with an optimized pore distribution, and process for its preparation |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2928364B1 (fr) * | 2008-03-05 | 2011-10-14 | Rhodia Operations | Composition a base d'un oxyde de zirconium,d'un oxyde de titane ou d'un oxyde mixte de zirconium et de titane sur un support en alumine,procedes de preparation et utilisation comme catalyseur |
US11583831B2 (en) * | 2016-12-23 | 2023-02-21 | Rhodia Operations | Mixed cerium- and zirconium-based oxide |
-
2020
- 2020-11-25 CN CN202080083060.8A patent/CN114761125A/zh active Pending
- 2020-11-25 KR KR1020227021648A patent/KR20220101721A/ko unknown
- 2020-11-25 US US17/781,310 patent/US20220410128A1/en active Pending
- 2020-11-25 WO PCT/EP2020/083438 patent/WO2021105253A1/fr unknown
- 2020-11-25 CA CA3158808A patent/CA3158808A1/fr active Pending
- 2020-11-25 JP JP2022530252A patent/JP2023503335A/ja active Pending
- 2020-11-25 EP EP20810989.2A patent/EP4065270A1/fr active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4154812A (en) | 1977-03-25 | 1979-05-15 | W. R. Grace & Co. | Process for preparing alumina |
US4301037A (en) * | 1980-04-01 | 1981-11-17 | W. R. Grace & Co. | Extruded alumina catalyst support having controlled distribution of pore sizes |
WO2004052534A1 (fr) * | 2002-12-06 | 2004-06-24 | Albemarle Netherlands B.V. | Procede d'hydrotraitement de charge lourde reposant sur l'utilisation d'un melange de catalyseurs |
US20070098611A1 (en) * | 2005-10-31 | 2007-05-03 | Yang Xiaolin D | Stabilized flash calcined gibbsite as a catalyst support |
US20170007987A1 (en) * | 2013-12-24 | 2017-01-12 | Heesung Catalysts Corporation | Exhaust gas oxidation catalyst for compressed natural gas combustion system |
US20170129781A1 (en) * | 2014-06-13 | 2017-05-11 | IFP Energies Nouvelles | Amorphous mesoporous and macroporous alumina with an optimized pore distribution, and process for its preparation |
Non-Patent Citations (3)
Title |
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BRUNAUER-EMMETT-TELLER, THE JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 60, 1938, pages 309 |
BRUNAUER-EMMETT-TELLER: "Cette méthode a été décrite dans le périodique", THE JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 60, 1938, pages 309 |
MASTERS: "SPRAY-DRYING", 1976, GEORGE GODWIN LONDON |
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JP2023503335A (ja) | 2023-01-27 |
EP4065270A1 (fr) | 2022-10-05 |
KR20220101721A (ko) | 2022-07-19 |
CA3158808A1 (fr) | 2021-06-03 |
CN114761125A (zh) | 2022-07-15 |
US20220410128A1 (en) | 2022-12-29 |
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