WO2007053283A1 - Stabilized flash calcined gibbsite as a catalyst support - Google Patents
Stabilized flash calcined gibbsite as a catalyst support Download PDFInfo
- Publication number
- WO2007053283A1 WO2007053283A1 PCT/US2006/040130 US2006040130W WO2007053283A1 WO 2007053283 A1 WO2007053283 A1 WO 2007053283A1 US 2006040130 W US2006040130 W US 2006040130W WO 2007053283 A1 WO2007053283 A1 WO 2007053283A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alumina
- rehydrated
- flash
- support
- calcined
- Prior art date
Links
- 229910001679 gibbsite Inorganic materials 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims description 85
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 198
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 35
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 26
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 24
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 239000010970 precious metal Substances 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 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 abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 239000003929 acidic solution Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000010953 base metal Substances 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
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- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 238000011068 loading method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 61
- 230000003197 catalytic effect Effects 0.000 description 31
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 25
- 239000000463 material Substances 0.000 description 23
- 230000008569 process Effects 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 12
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- 238000001354 calcination Methods 0.000 description 11
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 10
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- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 7
- 230000006641 stabilisation Effects 0.000 description 7
- 238000011105 stabilization Methods 0.000 description 7
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- 239000000126 substance Substances 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- -1 lanthanum aluminate Chemical class 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000003870 refractory metal Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 150000004684 trihydrates Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
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- 238000005245 sintering Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
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- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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Definitions
- the present invention relates generally to novel alumina based supports and uses of same in catalysts.
- Alumina is a well-known support for many catalyst systems. It is also well known that alumina has a number of crystalline phases such as alpha-alumina (often noted as ⁇ -alumina or ⁇ - AI 2 O 3 ), gamma-alumina (often noted as ⁇ -alumina or Y - AI 2 O 3 ) as well as a myriad of alumina polymorphs.
- Gamma- AI 2 O 3 is a particularly important inorganic oxide refractory of widespread technological importance in the field of catalysis, often serving as a catalyst support.
- Gamma- AI 2 O 3 is an exceptionally good choice for catalytic applications because of a defect spinel crystal lattice that imparts to it a structure that is both open and capable of high surface area. Moreover, the defect spinel structure has vacant cation sites giving the gamma-alumina some unique properties.
- Gamma-alumina constitutes a part of the series known as the activated, transition aluminas, so-called because it is one of a series of aluminas that can undergo transition to different polymorphs.
- Santos et al. (Materials Research, 2000; vol. 3 (4), pp. 104-114) disclosed the different standard transition aluminas using Electron Microscopy studies, whereas Zhou et al.
- Gamma-alumina is commonly employed as a catalytic support for automotive and industrial catalysts.
- Gamma alumina has a face-centered cubic close-packed oxygen sublattice structure having a high surface area typically of 150-300 m 2 /g, a large number of pores with diameters of 30 -120 angstroms and a pore volume of 0.5 to > 1 cm 3 /g. These characteristics are what make gamma alumina the specific type of alumina that is often utilized as a catalytic support.
- the oxides of aluminum and the corresponding hydrates can be classified according to the arrangement of the crystal lattice.
- Some transitions within a series are known; for example, low-temperature dehydration of an alumina trihydrate (gibbsite, AI(OH) 3 ) above 100 degree Celsius with the presence of steam provides an alumina monohydrate (boehmite, AIO(OH)).
- Boehmite AIO(OH)
- alpha-alumina has the lowest surface area, it is the most stable of the aluminas at high temperatures. Unfortunately, the structure of alpha-alumina is less well-suited to certain catalytic applications because of a closed crystal lattice, which imparts a relatively low surface area to the alpha- alumina particles.
- Alumina is ubiquitous as supports and/or catalysts for many heterogeneous catalytic processes. Some of these catalytic processes occur under conditions of high temperature, high pressure and/or high water vapor pressure. The prolonged exposure to high temperature typically such as 1000 degree Celsius combined with a significant amount of oxygen and sometimes steam can result in catalyst deactivation by support sintering.
- the sintering of alumina has been widely reported in the literature (see for example Thevenin et al, Applied Catalysis A: General, 2001 , vol. 212, pp. 189-197) and the phase transformation of alumina due to an increase in operating temperature is usually accompanied by a sharp decrease in surface area.
- U.S. 6,255,358 discloses a catalyst comprising a gamma-alumina support doped with an amount of lanthanum oxide, barium oxide, or a combination thereof effective for increasing the thermal stability of the catalyst.
- the patent discloses a catalyst comprising per 100 parts by weight of the support from about 10-70 parts by weight cobalt and optional components, including from about 0.5 to 8 parts by weight lanthana.
- U.S. 6,255,358 discloses a catalyst comprising per 100 parts by weight of the support from about 10-70 parts by weight cobalt and optional components, including from about 0.5 to 8 parts by weight lanthana.
- 5,837,634 discloses a process for preparing a stabilized alumina, e.g., gamma alumina, of enhanced resistance to high temperature surface area loss such as by the addition of lanthana to a precursor boehmite alumina.
- a stabilized alumina e.g., gamma alumina
- a mixture of boehmite alumina, nitric acid, and stabilizers such as lanthanum nitrate was dispersed and the mixture aged for 4 hours at 177 degree Celsius (350° F). Subsequently, the formed powder was calcined for 3 hours at 1200 degree Celsius.
- lanthana/alumina composite oxides were formed. It was found that as the lanthana weight loading increased, the surface area of the lanthana dispersed in the composite oxide also increased and reached a plateau at 8% La 2 ⁇ 3 loading.
- the composite oxides were prepared by the incipient wetness procedure in which the alumina was impregnated with lanthanum nitrate hexahydrate and the precursors dried and then calcined at 600 degree Celsius for 16 hours.
- the lanthanum is in the form of lanthanum oxide.
- alumina samples with different lanthanum concentrations were produced by impregnation with aqueous lanthanum nitrate, followed by calcination at various temperatures. It was found that up to a concentration of 8.5 ⁇ mol La/m 2 , the lanthana was in the form of a 2-dimensional overlayer, invisible by XRD.
- the excess lanthana formed crystalline oxides detectable by XRD.
- the crystalline phase was cubic lanthanum oxide.
- the lanthana reacted to form the lanthanum aluminate, LaAIO 3 .
- Automotive catalysts predominately utilize alumina supports having high thermal stability and high surface area. Having high surface area is important for supporting catalysts and providing the catalysts with sufficient effective area to work. For these reasons, gamma alumina is the most used type of alumina employed in automotive, chemical and high temperature catalytic applications.
- Rho-alumina also known as flash-calcined gibbsite, is one of the most important members of the alumina family. Two most striking characteristic features of rho-alumina are its high porosity and low cost. However, rho- alumina has several disadvantages that limit rho-alumina's greater usefulness. For instance, rho-alumina is unstable, highly reactive due to its high free energy, and because of the fast dehydration process used to form rho-alumina, is amorphous. Although rehydration helps to some degree in the formation of crystalline boehmite structure, still, the resulting material largely has an ill-defined structure in term of pores and surfaces that lead to its low thermal stability.
- TWC catalysts have utility in a number of fields including the abatement of nitrogen oxide (NOx), carbon monoxide (CO) and hydrocarbon (HC) pollutants from internal combustion engines, such as automobile and other gasoline-fueled engines.
- NOx nitrogen oxide
- CO carbon monoxide
- HC hydrocarbon
- Three-way conversion catalysts are polyfunctional because they have the ability to substantially and simultaneously catalyze the oxidation of hydrocarbons and carbon monoxide and the reduction of nitrogen oxides.
- Emissions standards for nitrogen oxides, carbon monoxide, and unburned hydrocarbon contaminants have been set by various government agencies and must be met by new automobiles. In order to meet such standards, catalytic converters containing a TWC catalyst are located in the exhaust gas line of internal combustion engines.
- TWC catalysts exhibiting good activity and long life comprise one or more platinum group metals, e.g., platinum, palladium, rhodium, ruthenium, and iridium. These catalysts are employed with a high surface area refractory oxide support.
- the refractory metal oxide can be derived from aluminum, titanium, silicon, zirconium and cerium compounds, preferably resulting in the oxides with the preferred refractory oxides including at least one of alumina, titania, silica, zirconia and ceria.
- the TWC catalysts are supported by gamma-alumina.
- the TWC catalytic support is carried on a suitable carrier or substrate such as a monolithic carrier comprising a refractory ceramic or metal honeycomb structure, or refractory particles such as spheres or short, extruded segments of a suitable refractory material.
- a suitable carrier or substrate such as a monolithic carrier comprising a refractory ceramic or metal honeycomb structure, or refractory particles such as spheres or short, extruded segments of a suitable refractory material.
- high surface refractory metal oxides are often employed as a support for many of the catalytic components.
- high surface area alumina materials also referred to as “gamma alumina” or “activated alumina” used with TWC catalysts typically exhibit a BET
- activated alumina is usually a mixture of the gamma and delta phases of alumina, but may also contain substantial amounts of eta, kappa and theta alumina phases.
- Refractory metal oxides other than activated alumina may be utilized as a support for at least some of the catalytic components in a given catalyst. For example, bulk ceria, zirconia, alpha alumina and other materials are known for such use. Although many of these materials have a lower BET surface area than activated alumina, that disadvantage tends to be offset by the greater durability of the resulting catalyst.
- Exhaust gas temperatures can reach 1000 degree Celsius in a moving vehicle and such elevated temperatures can cause activated alumina, or other support material, to undergo thermal degradation with accompanying volume shrinkage especially in the presence of steam. During this degradation, the catalytic metal becomes sintered on the shrunken support medium with a loss of exposed catalyst surface area and a corresponding decrease in catalytic activity.
- the unstable support is doped with a stabilizing material similar to the process described above.
- the stabilization of TWC catalysts are known in the art.
- U.S. Pat. No. 4,171 ,288 discloses a method to stabilize alumina supports against such thermal degradation by the use of materials such as zirconia, titania, alkaline earth metal oxides such as baria, calcia, or strontia, or rare earth metal oxides such as ceria, lanthana, and mixtures of two or more rare earth metal oxides.
- U.S. Pat. No. 4,438,219 discloses an alumina catalyst, stable at high temperatures, for use on a substrate.
- the stabilizing material is derived from barium, silicon, rare earth metals, alkali and alkaline earth metals, boron, thorium, hafnium, and zirconium. Barium oxide, silicon dioxide, and rare earth oxides including lanthanum, cerium, praseodymium, and neodymium are preferred.
- Contacting the stabilizing material with a calcined alumina film permits the calcined alumina film to retain a high surface area at higher temperatures.
- U.S. Pat. Nos. 4,476,246, 4,591.578 and 4,591 ,580 disclose three-way catalyst compositions comprising alumina, ceria, an alkali metal oxide promoter, and Noble metals.
- U.S. Pat. Nos. 3,993,572 and 4,157,316 describe attempts to improve the catalyst efficiency of Pt/Rh based TWC systems by incorporating a variety of metal oxides, e.g., rare earth metal oxides such as ceria and base metal oxides such as nickel oxides.
- 4,591 ,518 discloses a catalyst comprising an alumina support with catalytic components consisting essentially of a lanthana component, ceria, an alkali metal oxide, and a platinum group metal.
- U.S. Pat. No. 4,591 ,580 discloses an alumina supported platinum group metal catalyst modified to include support stabilization by lanthana or lanthana rich rare earth oxides, double promotion by ceria and alkali metal oxides and optionally nickel oxide.
- U.S. Pat. No. 4,294,726 discloses a TWC catalyst composition containing platinum and rhodium obtained by impregnating a gamma alumina carrier material with an aqueous solution of cerium, zirconium and iron salts or mixing the alumina with oxides of, respectively, cerium, zirconium and iron, and then calcining the material at 500 degree Celsius to 700 degree Celsius, in air after which the material is impregnated with an aqueous solution of a salt of platinum and a salt of rhodium dried and subsequently treated in a hydrogen-containing gas at a temperature of 250 degree Celsius - 650 degree Celsius.
- the alumina may be thermally stabilized with calcium, strontium, magnesium or barium compounds.
- the ceria-zirconia-iron oxide treatment is followed by impregnating the treated carrier material with aqueous salts of platinum and rhodium and then calcining the impregnated material.
- U.S. Pat. No. 4,504,598 discloses a process for producing a high temperature resistant TWC catalyst.
- the process includes forming an aqueous slurry of particles of gamma or activated alumina and impregnating > the alumina with soluble salts of selected metals including cerium, zirconium, at least one of iron and nickel and at least one of platinum, palladium and rhodium and, optionally, at least one of neodymium, lanthanum, and praseodymium.
- the impregnated alumina is calcined at 600 degree Celsius and then dispersed in water to prepare a slurry which is coated on a honeycomb carrier and dried to obtain a finished catalyst.
- a full discussion of TWC can be derived from U.S. Patent Number 6,777,370, which is incorporated by reference.
- rho alumina Due to the disadvantageous characteristics of rho-alumina, rho alumina has not been used with TWCs or other high temperature catalysts. TWCs have for the most part used the more expensive gamma alumina supports due to gamma alumina's high surface area, high purity and good stability. It has long been a desire in the catalytic art to provide a form of alumina that has excellent thermal and hydrothermal stability, can be provided with a low, but effective, precious metal content and is inexpensive. Such a catalyst support would have expanding uses.
- a novel catalyst support is made to replace gamma-alumina and other active aluminas for high temperature catalysis applications.
- the new catalyst support is made from a low cost flash-calcined gibbsite (or rho-alumina) by a simple chemical treatment and has excellent thermal stability, high sodium tolerance, high activity with low precious metal loading, and high pore volume and high surface area.
- rho-alumina flash-calcined gibbsite
- rho-alumina flash-calcined gibbsite
- rho-alumina flash-calcined gibbsite
- Additional improvements are obtained by doping the rehydrated rho alumina with a stabilizing metal followed by calcination. Once stabilized, the resulting catalyst support, can be effectively used in high temperature applications including as a catalyst support for TWC catalysts.
- the present invention is directed to stabilized, rehydrated flash- calcined gibbsite (or rho-alumina) catalyst support and method of making such support for use in chemical and automotive catalytic processes.
- the stabilized, rehydrated flash-calcined gibbsite (or rho-alumina) is processed into a stable catalyst support having characteristics similar to that of a gamma-alumina and other forms of activated aluminas.
- the stabilized, rehydrated flash-calcined gibbsite (or rho-alumina) not only provides a low cost catalyst support due to its simple manufacturing process, but also offers a novel route of making high-grade alumina for use as a catalyst support at high temperatures such as three way conversion (TvVC) catalysts.
- TvVC three way conversion
- High grade gamma-alumina is obtained mainly by the calcination of high purity boehmite or pseudo-boehmite.
- the dominant process of making boehmite or pseudo-boehmite is from the so-called Ziegler process owned by Sasol Corporation.
- Ziegler process aluminum sheets are first dissolved in alcohols and then hydrolyzed.
- Boehmite or pseudo-boehmite is produced as a by-product of the Ziegler process.
- Low grade pseudo- boehmite can be also obtained by the precipitation of aluminum-containing chemicals such as the reaction of sodium aluminate and aluminum sulfate.
- High-grade gamma-alumina is needed for TWC and other high temperature catalyst applications. It is highly desirable to have alternative production routes to produce catalyst substrates that can replace the high-grade alumina.
- Rho-alumina also known as flash-calcined gibbsite.
- Rho-alumina is a different raw material than the boehmite or pseudo-boehmite raw materials used to make gamma alumina.
- flash-calcined gibbsite is obtained mainly by a rapid, usually in about one second of contact time with heat, dehydration of alumina trihydrates, such as gibbsite and bayerite, though heating alumina trihydrates in vacuum for a longer period of time also forms rho alumina.
- Rho- alumina may be made using any alumina trihydrate or aluminum hydroxide.
- Rho-alumina is advantageous for being highly porous and inexpensive to produce and is utilized as adsorbents, catalysts, and catalytic support material in low temperature catalytic applications.
- gibbsite or bayerite is flash-calcined, an amorphous rho-alumina is produced which cannot be used as a catalytic support in high temperature applications.
- the amorphous nature of rho-alumina causes the activity level of rho-alumina to quickly decrease in high temperature applications.
- rho-alumina has not been utilized as a catalytic support in the same respect as gamma alumina since the crystalline structure of gamma alumina, and the attendant properties of high porosity and high surface area are favored for use in high temperature applications.
- These and other disadvantageous qualities of rho-alumina can be overcome with the novel preparations of this invention to allow rho-alumina to function effectively as a support in high temperature catalytic reactions. For instance, rehydrating rho-alumina can result in a N 2 BET surface area of up to about 400 m 2 /g. This makes rho-alumina a very useful and inexpensive adsorbent and catalyst for many large scale industrial applications.
- thermal stabilization of rho-alumina by the addition of a stabilizing metal such as lanthanum (La-doping) followed by calcination has demonstrated profound improvements in the thermal stability, surface properties, and Na-tolerance of the rehydrated rho-alumina.
- a stabilizing metal such as lanthanum (La-doping) followed by calcination
- rehydration of alumina involves adding a rho alumina slurry to water.
- the rho-alumina is rehydrated in an aqueous acidic environment having a pH generally of about 3.
- the acid included in the rehydrating solution can be organic such as formic, acetic, oxalic, glycolic, etc., or inorganic such as a nitric acid.
- the pH range of the aqueous solution used for acidic rehydration is preferably about 1 - 7. More preferably, the pH is about 1 - 5. Most preferably, the pH range of the solution used for acidic rehydration is 2 - 4. Adding an acidic aqueous solution to the rho-alumina not only rehydrates the rho-alumina, but also leaves the rho-alumina with low sodium impurity levels. Rho-alumina has not been used in many catalytic applications because it possesses high levels of sodium, generally about >2000ppm.
- the rho-alumina by rehydrating the rho-alumina with an aqueous acidic solution, sodium impurities are leached out or otherwise exchanged or removed from the alumina.
- the sodium impurity level in accordance with this invention will generally be ⁇ 400 ppm, and more preferably ⁇ 100 ppm.
- the rehydrated rho-alumina will have a higher pore volume than the pore volume of the flash-calcined gibbsite, which is approximately about 200 m 2 /g.
- the reaction time for rehydrating the rho-alumina can be from 0.5 to 24 hours, preferably 1-8 hours, most preferably 1-3 hours.
- the reaction temperature for rehydrating rho-alumina using an acidic solution can range from 50-120 degree Celsius.
- the rho-alumina can be rehydrated between a temperature of 70-120 degree Celsius.
- Most preferably the rho- alumina can be rehydrated between a temperature 80-120 degree Celsius.
- a reaction time of 2 hours and reaction temperature at about 95-100 degree Celsius is preferred for porosity optimization from a practical stand point, although other combinations of the reaction variables should lead to a similar product.
- alumina It is common practice to thermally stabilize alumina in order for the alumina to function as a high temperature catalyst support.
- metal- stabilized alumina has been well-studied and practiced in the catalytic arts, stabilization of rehydrated rho-alumina by metal doping has not been intensely evaluated nor considered for use in catalytic applications.
- the rehydrated rho-alumina is impregnated with known stabilizer precursors and then calcinced to form a stabilized metal oxide dispersed onto the alumina.
- the stabilizing metals include alkaline earth metals (Mg, Ca, Sr, Ba), boron, silicon, phosphorus, and rare-earth metals or combinations thereof with lanthanum as the most preferred.
- phosphorus precursor reacts with alumina to form surface aluminophosphate structure which stabilizes the alumina.
- the stabilizing metal the lanthanum will become uniformly distributed throughout the rho-alumina imparting advantageous qualities such as thermal stability and attrition resistant properties to the rehydrated rho-alumina.
- any lanthanide series metal compound may be used herein, lanthanum is the most common and most practical for use.
- the lanthanum will be present in the finally prepared support alone or the catalyst composition in the form of an oxide, preferably lanthanum oxide.
- the usual precursor material is a salt of lanthanum.
- the incorporation of the stabilizing metal can be accomplished either by impregnating rehydrated rho-alumina with a metal salt, such as lanthanum nitrate and acetate, by incipient wetness; through spray-drying a slurry of lanthanum nitrate and rehydrated rho-alumina; or by a solid-state reaction of the rehydrated rho-alumina with a lanthanum salt such as lanthanum carbonate at or above 800 degree Celsius.
- a metal salt such as lanthanum nitrate and acetate
- the rehydrated rho-alumina is doped with 0 - 24 wt% of the stabilizing metal. More preferably 0.1-12 wt% of the stabilizing metal is incorporated into the rehydrated rho-alumina. Even more preferred is the incorporation of 1-12 wt.% of the stabilizing metal into the rehydrated rho-alumina.
- the rehydrated rho-alumina may also be doped with either 3 wt.% or 4 wt.% the stabilizing metal. After the stabilizing metal has been incorporated into the rehydrated rho-alumina, the rehydrated rho-alumina is calcined.
- Calcination occurs at or above 550 degree Celsius to up to about 1100 degree Celsius, more preferably from 550 degree Celsius - 850 degree Celsius.
- the lower calcination temperature range is advantageous in that less energy is required to calcine the alumina while still being sufficient to burn off anionic components such as nitrates.
- porosity of the alumina is maintained. Calcination is necessary to make the rehydrated rho-alumina stable and inert so as not to interact with the catalyst.
- the stabilized, rehydrated rho-alumina has good stability, has a high surface area and pore volume and has the ability to hold a high amount of dispersed metals.
- the surface area of rehydrated rho-alumina can be over 80m 2 /g after being calcined at 815 degree Celsius (1500F).
- a BET surface area of 120 m 2 /g and higher have been found, which compares to gamma alumina and even lanthanum doped gamma alumina.
- the pore volume of stabilized rehydrated rho-alumina will be typically at least 0.20 cc/g, preferably at least 0.30 cc/g, more preferably at least 0.35 cc/g with pore volumes over 0.40 cc/g having been found, which is again comparable to gamma alumina.
- the stabilized rehydrated rho-alumina may be employed in many catalytic applications not previously considered such as in catalytic applications, including high temperature applications that had mainly used the costly gamma alumina.
- high temperature applications include chemical applications where the temperature ranges from 400 -700 degree Celsius, even 800 degree Celsius and in automotive applications wherein temperatures as high as or higher than about 1000 degree Celsius are found.
- the low cost stabilized rho-alumina may be used with any catalyst that utilizes alumina- based supports.
- the lanthanum-doped, rehydrated rho-alumina can serve as a support for catalysts employed in high temperature applications requiring high surface areas e.g., three way catalysts (TWC).
- the TWC catalyst comprises refractory oxide support(s) used to support precious metal(s). At least one precious metal component is utilized in the TWC with preferred precious metal components selected from gold, silver, platinum, palladium, rhodium, ruthenium and iridium, with more preferred precious metals components selected from at least one of platinum, palladium and rhodium.
- the La-doped, rehydrated rho-alumina serves as the refractory oxide support used to support the precious metal components. As shown in the examples below, the combination of the La-doped, rehydrated rho-alumina with the TWC catalysts exhibit good conversion rates of hydrocarbons, carbon monoxide and nitrogen oxides.
- the catalytic compositions made by the present invention can be employed to promote chemical reactions, such as hydrogenation, dehydrogenation, hydrorefining, desulfurization, dehydration, Fisher-Tropsch gas-to-liquid conversion, oxychlorition, alkylation, hydroformylation, Claus Reaction, water-gas-shift reaction, ammonium oxidation, methanation and especially the oxidation of carbonaceous materials, e.g., carbon monoxide, hydrocarbons, oxygen-containing organic compounds, and the like, to products having a higher weight percentage of oxygen per molecule such as intermediate oxidation products, carbon dioxide and water, the latter two materials being relatively innocuous materials from an air pollution standpoint.
- chemical reactions such as hydrogenation, dehydrogenation, hydrorefining, desulfurization, dehydration, Fisher-Tropsch gas-to-liquid conversion, oxychlorition, alkylation, hydroformylation, Claus Reaction, water-gas-shift reaction, ammonium oxidation, methanation and especially the oxidation
- the catalyst or catalyst promoter will contain at least one precious metal, an alkaline metal, an alkaline earth metal or a base metal.
- Suitable base metals include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, and tungsten.
- the metals will be supported by the stabilized rehydrated flash calcined gibbsite.
- the catalytic compositions can be used to provide removal from gaseous exhaust effluents of uncombusted or partially combusted carbonaceous fuel components such as carbon monoxide, hydrocarbons, and intermediate oxidation products composed primarily of carbon, hydrogen and oxygen, or nitrogen oxides.
- oxidation or reduction reactions may occur at relatively low temperatures, they are often conducted at elevated temperatures of, for instance, at least about 100 degree Celsius, typically about 150 degree Celsius to 900 degree Celsius, and generally with the feedstock in the vapor phase.
- the materials which are subject to oxidation generally contain carbon, and may, therefore, be termed carbonaceous, whether they are organic or inorganic in nature.
- the catalysts are thus useful in promoting the oxidation of hydrocarbons, oxygen-containing organic components, and carbon monoxide, and the reduction of nitrogen oxides.
- These types of materials may be present in exhaust gases from the combustion of carbonaceous fuels, and the catalysts are useful in promoting the oxidation or reduction of materials in such effluents.
- the exhaust from internal combustion engines operating on hydrocarbon fuels, as well as other waste gases, can be oxidized by contact with the catalyst and molecular oxygen which may be present in the gas stream as part of the effluent, or may be added as air or other desired form having a greater or lesser oxygen concentration.
- the products from the oxidation contain a greater weight ratio of oxygen to carbon than in the feed material subjected to oxidation. Many such reaction systems are known in the art.
- the method of the present invention for forming the catalyst support involves obtaining a commercially available flash calcined gibbsite and rehydrating the flash-calcined gibbsite under acidic conditions to form the rehydrated rho-alumina. Once the rehydrated rho-alumina is obtained, it is stabilized for high temperature applications by the incorporation of stabilization metals such as lanthanum and finally calcined.
- the low cost rehydrated rho-alumina catalyst support having excellent thermal and hydrothermal stability may be utilized in any catalytic application that normally uses gamma alumina.
- the present support may be utilized in automotive applications, high temperature applications or chemical processing applications including and not limited to oxidation, hydrogenation, dehydrogenation, hydrorefining, desulfurization, dehydration, Fisher-Tropsch gas-to-liquid conversion, oxychlorition, alkylation, hydroformylation, Claus Reaction, water-gas-shift reaction, methanation.
- a slurry was made of 3.5 Ib of rehydrated flash calcined gibbsite, as formed in Example 1 , 4.9 Ib of Dl-water, and 119 g of La(NO 3 ) 3 .6H2O (from Alfa Aesar). The slurry was spray-dried and the microspheres were calcined at 815 degree Celsius (1500° F) in air for two hours. The resulting lanthana doped, rehydrated flash calcined gibbsite had a surface area between 120- 150 m 2 /g.
- Tests were conducted on rehydrated flash calcined gibbsite and unhydrated flash calcined gibbsite to compare the sodium content, the surface area and the pore volume.
- the rehydration of the flash calcined gibbsite was accomplished using formic acid solution as cited above.
- the rehydrated flash calcined gibbsite had a drastically lower Na 2 O content than the unhydrated sample.
- the BET surface area increased about 40% from 296 to 408 m 2 /g and the pore volume almost doubled from 0.22 to 0.43 cc/g.
- the data shows that the doping of rehydrated flash-calcined gibbsite with 3% lanthanum leads to high pore volume and high surface area.
- the high porosity (high surface area) after 1093 degree Celsius makes the lanthana doped rehydrated flash calcined gibbsite a good support capable of holding a high amount of dispersed metal due to the high surface area.
- the data also indicates that by using a proper stabilization strategy, such as La- incorporation, a low grade of alumina precursor results in having more desired properties than a high grade ⁇ -alumina.
- TWC catalyst conversion data Comparison of lanthana doped rehydratred flash calcined gibbsite supported TWC catalysts and commercial un-doped gamma alumina supported TWC catalysts as automotive catalyst supports. All catalysts were aged and evaluated on vehicle using FTP method.
- the conversion rates of hydrocarbons, carbon monoxide and nitrogen oxides by the lanthana doped rehydratred flash calcined gibbsite supported TWC catalysts were better than the rates of the gamma alumina supported TWC catalysts.
- the lanthana doped rehydratred flash calcined gibbsite support used both less precious metals and less platinum than gamma alumina. The use of precious metals, especially the use of platinum by the alumina is known to inflate the cost of the support and thereby the overall cost of the TWC catalysts.
- the un-doped, gamma alumina used a total of 6 gcf
- the lanthana doped rehydratred flash calcined gibbsite used a total of 4 gcf.
- the lanthana doped rehydratred rho-alumina did not use any of the expensive platinum, but the gamma alumina used four grams of platinum.
- the lanthana doped rehydratred flash calcined gibbsite support costs less than the gamma alumina support.
- Example 6 thereby exhibits that the lanthanum-doped rehydrated flash calcined gibbsite supported TWC catalysts gives a higher conversion of HC, CO and NOx at a lower precious metal loading than when the gamma alumina supported TWC catalyst.
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Abstract
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JP2008538900A JP2009513345A (en) | 2005-10-31 | 2006-10-13 | Flash calcination and stabilized gibbsite as catalyst support |
CA002627878A CA2627878A1 (en) | 2005-10-31 | 2006-10-13 | Stabilized flash calcined gibbsite as a catalyst support |
EP06816887A EP1960100A1 (en) | 2005-10-31 | 2006-10-13 | Stabilized flash calcined gibbsite as a catalyst support |
BRPI0618153-8A BRPI0618153A2 (en) | 2005-10-31 | 2006-10-13 | alumina-based catalyst support, and methods for catalytically converting a gas stream from an internal combustion engine and for preparing the catalyst support |
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US11/263,242 US20070098611A1 (en) | 2005-10-31 | 2005-10-31 | Stabilized flash calcined gibbsite as a catalyst support |
US11/263,242 | 2005-10-31 |
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US (1) | US20070098611A1 (en) |
EP (1) | EP1960100A1 (en) |
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KR (1) | KR20080067688A (en) |
CN (1) | CN101321584A (en) |
BR (1) | BRPI0618153A2 (en) |
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Cited By (2)
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JP2015044193A (en) * | 2008-12-23 | 2015-03-12 | ビーエーエスエフ コーポレーション | Palladium catalyst product for small size engine and manufacturing method |
US9694347B2 (en) | 2012-04-04 | 2017-07-04 | Johnson Matthey Public Limited Company | High temperature combustion catalyst |
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JP2023503335A (en) * | 2019-11-29 | 2023-01-27 | ローディア オペレーションズ | Alumina with specific pore profile |
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CN114524444B (en) * | 2020-10-31 | 2024-02-09 | 中国石油化工股份有限公司 | Modification method of alumina |
CN112320833B (en) * | 2020-11-06 | 2022-08-02 | 湖南荣岚智能科技有限公司 | High temperature resistant SiO 2 -Gd 2 O 3 Composite aerogel and preparation method thereof |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3928239A (en) * | 1972-11-30 | 1975-12-23 | Nippon Catalytic Chem Ind | Method for the production of exhaust and waste gases purifying catalysts |
US20040138060A1 (en) * | 2002-11-11 | 2004-07-15 | Conocophillips Company | Stabilized alumina supports, catalysts made therefrom, and their use in partial oxidation |
US20060257305A1 (en) * | 2005-05-12 | 2006-11-16 | Yang Xiaolin D | Alumina-based perovskite catalysts and catalyst supports |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3867312A (en) * | 1972-02-07 | 1975-02-18 | Ethyl Corp | Exhaust gas catalyst support |
US3993572A (en) * | 1972-08-04 | 1976-11-23 | Engelhard Minerals & Chemicals Corporation | Rare earth containing catalyst composition |
MX4509E (en) * | 1975-08-27 | 1982-06-02 | Engelhard Min & Chem | IMPROVED CATALYTIC COMPOSITION FOR SIMULTANEOUS OXIDATION GASCOUS HYDROCARBONS AND CARBON MONOXIDE AND REDUCE NITROGEN OXIDES |
US4171288A (en) * | 1977-09-23 | 1979-10-16 | Engelhard Minerals & Chemicals Corporation | Catalyst compositions and the method of manufacturing them |
DE2907106C2 (en) * | 1979-02-23 | 1985-12-19 | Degussa Ag, 6000 Frankfurt | Catalytic converter and its use for cleaning exhaust gases from internal combustion engines |
US4438219A (en) * | 1981-10-28 | 1984-03-20 | Texaco Inc. | Alumina catalyst stable at high temperatures |
US4476246A (en) * | 1983-01-26 | 1984-10-09 | W. R. Grace & Co. | Doubly promoted platinum group metal catalysts for emission control |
US4591580A (en) * | 1983-01-26 | 1986-05-27 | W. R. Grace & Co. | Stabilized and doubly promoted platinum group metal catalysts for emission control and method of making same |
CA1213874A (en) * | 1983-05-12 | 1986-11-12 | Tomohisa Ohata | Process for producing honeycomb catalyst for exhaust gas conversion |
US4591518A (en) * | 1984-08-13 | 1986-05-27 | Ppg Industries, Inc. | Acrylic functional urethane alkyd resin coating compositions |
US4591578A (en) * | 1985-02-04 | 1986-05-27 | American Cyanamid Company | Catalyst of molybdenum on wide-pore carbon support |
US4780447A (en) * | 1987-07-10 | 1988-10-25 | W. R. Grace & Co.-Conn. | Catalysts for controlling auto exhaust emissions including hydrocarbon, carbon monoxide, nitrogen oxides and hydrogen sulfide and method of making the catalysts |
US5837634A (en) * | 1992-11-12 | 1998-11-17 | Condea Vista Company | Process for producing stabilized alumina having enhanced resistance to loss of surface area at high temperatures |
JPH09263440A (en) * | 1996-03-29 | 1997-10-07 | Ngk Insulators Ltd | Alumina sintered compact and its production |
US6087298A (en) * | 1996-05-14 | 2000-07-11 | Engelhard Corporation | Exhaust gas treatment system |
US6921738B2 (en) * | 1996-12-06 | 2005-07-26 | Engelhard Corporation | Catalytic metal plate |
US6255358B1 (en) * | 2000-03-17 | 2001-07-03 | Energy International Corporation | Highly active Fischer-Tropsch synthesis using doped, thermally stable catalyst support |
US6777370B2 (en) * | 2001-04-13 | 2004-08-17 | Engelhard Corporation | SOx tolerant NOx trap catalysts and methods of making and using the same |
US6962684B2 (en) * | 2001-05-31 | 2005-11-08 | Sumitomo Chemical Company, Limited | Activated alumina formed body and method for producing the same |
US6764665B2 (en) * | 2001-10-26 | 2004-07-20 | Engelhard Corporation | Layered catalyst composite |
-
2005
- 2005-10-31 US US11/263,242 patent/US20070098611A1/en not_active Abandoned
-
2006
- 2006-10-13 BR BRPI0618153-8A patent/BRPI0618153A2/en not_active IP Right Cessation
- 2006-10-13 JP JP2008538900A patent/JP2009513345A/en not_active Withdrawn
- 2006-10-13 KR KR1020087012914A patent/KR20080067688A/en not_active Application Discontinuation
- 2006-10-13 CN CNA2006800451387A patent/CN101321584A/en active Pending
- 2006-10-13 CA CA002627878A patent/CA2627878A1/en not_active Abandoned
- 2006-10-13 WO PCT/US2006/040130 patent/WO2007053283A1/en active Application Filing
- 2006-10-13 EP EP06816887A patent/EP1960100A1/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3928239A (en) * | 1972-11-30 | 1975-12-23 | Nippon Catalytic Chem Ind | Method for the production of exhaust and waste gases purifying catalysts |
US20040138060A1 (en) * | 2002-11-11 | 2004-07-15 | Conocophillips Company | Stabilized alumina supports, catalysts made therefrom, and their use in partial oxidation |
US20060257305A1 (en) * | 2005-05-12 | 2006-11-16 | Yang Xiaolin D | Alumina-based perovskite catalysts and catalyst supports |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015044193A (en) * | 2008-12-23 | 2015-03-12 | ビーエーエスエフ コーポレーション | Palladium catalyst product for small size engine and manufacturing method |
US9694347B2 (en) | 2012-04-04 | 2017-07-04 | Johnson Matthey Public Limited Company | High temperature combustion catalyst |
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JP2009513345A (en) | 2009-04-02 |
CA2627878A1 (en) | 2007-05-10 |
CN101321584A (en) | 2008-12-10 |
BRPI0618153A2 (en) | 2011-08-16 |
US20070098611A1 (en) | 2007-05-03 |
EP1960100A1 (en) | 2008-08-27 |
KR20080067688A (en) | 2008-07-21 |
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