WO1996033152A1 - Procede de deshydrogenation catalysee d'alcanes avec oxydation simultanee d'hydrogene - Google Patents

Procede de deshydrogenation catalysee d'alcanes avec oxydation simultanee d'hydrogene Download PDF

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WO1996033152A1
WO1996033152A1 PCT/US1995/007088 US9507088W WO9633152A1 WO 1996033152 A1 WO1996033152 A1 WO 1996033152A1 US 9507088 W US9507088 W US 9507088W WO 9633152 A1 WO9633152 A1 WO 9633152A1
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Prior art keywords
process according
dehydrogenation
alkane
catalyst comprises
oxidation catalyst
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PCT/US1995/007088
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English (en)
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Pradyot Adwaitanand Agaskar
Robert Karl Grasselli
James Nathaniel Michaels
Paul Thomas Reischman
David Lawrence Stern
John George Tsikoyiannis
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Mobil Oil Corporation
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Publication of WO1996033152A1 publication Critical patent/WO1996033152A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/18—Arsenic, antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/30—Tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof

Definitions

  • This invention relates to a process for the net catalytic oxidative dehydrogenation of alkanes to produce
  • the process involves simultaneous equilibrium dehydrogenation of alkanes to alkenes and combustion of the hydrogen formed to drive the equilibrium dehydrogenation reaction further to the product alkenes.
  • Catalytic dehydrogenation and aromatization of light paraffinic streams e.g., C--C. paraffins, commonly referred to as LPG
  • LPG light paraffinic streams
  • Catalytic dehydrogenation and aromatization of light paraffinic streams e.g., C--C. paraffins, commonly referred to as LPG
  • LPG is strongly endothermic and typically carried out at temperatures between 540° and 820°C (1000° 5 and 1500*F)
  • the problem of transferring sufficient heat to a catalytic reaction zone to carry out the paraffin upgrading reaction remains as an obstacle to commercialization of these processes.
  • Direct heat exchange techniques include circulation of inert or catalytically active particles from a high temperature heat source to the reaction zone, or the coupling of a secondary exothermic reaction with the primary endothermic reaction in a single catalytic reaction zone.
  • secondary exothermic reactions include (1) oxidative dehydrogenation of a portion of the feedstream, (2) sacrificial co-combustion of a part of the alkane/alkene mixture, and (3) combustion of carbonized species (e.g., coke) on the catalyst.
  • oxidative dehydrogenation are unfortunately not selective enough to achieve sufficiently high levels to allow for commercial practice and at least a part of the valuable product is over-oxidized, usually to the waste products, CO, C0_, and H 2 0.
  • Examples of such sacrificial co-combustion processes include those described in U.S. Patent No. 3,136,713 to Miale et al. which teaches a method for heating a reaction zone by selectively burning a portion of a combustible feedstream in a reaction zone. Heat is directly transferred from the exothermic oxidation reaction to supply the endothermic heat for the desired conversion reaction.
  • British Patent Application GB 2190397A describes a process for producing aromatic hydrocarbons by catalytic paraffin dehydrocyclodimerization.
  • the process upgrades C 2 -C 8 paraffins, i.e., ethane, propane, butane or a mixture thereof to a mixture of aromatic hydrocarbons and hydrogen by-product in a reactor provided with a membrane capable of selective, in-situ transfer of at least a portion of the hydrogen in the mixture across the membrane.
  • Catalysts useful in the paraffin upgrading process are said to include zeolites, and in particular gallium-containing zeolites.
  • the paraffin dehydrogenation reaction is equilibrium limited when carried out in a conventional reactor due to the thermodynamics of equilibrium dehydrogenation. For example, at 550*C the equilibrium propylene from propane dehydrogenation, irrespective of catalyst, is limited to 33%.
  • the state of the art of endothermic hydrogen-producing paraffin upgrading processes would clearly be advanced by a process and apparatus for increasing the extent of reaction while also providing a high temperature heat source to supply at least a portion of the endothermic heat of reaction.
  • n is the same for the alkane and the alkene and n is from 2 to 5, the process comprising contacting the alkane with a dehydrogenation catalyst and an oxidation catalyst and oxygen under conditions sufficient to selectively convert the alkane and oxygen to the alkene and water, wherein the dehydrogenation catalyst comprises at least one metal selected from Cr, Mo, Ga, Zn and a Group VIII metal, and wherein the oxidation catalyst comprises an oxide of at least one metal selected from Bi, In, Sb, Zn, Tl, Pb and
  • Figure 1 is a graph showing conversion of H 2 and propylene over Bi 2 0_/Si0_ during the course of 120 REDOX cycles.
  • Figure 2 is a graph showing conversions of hydrogen and propane as a function of residence time in a reactor.
  • Figure 3 is a graph showing conversions of hydrogen and propylene as a function of residence time in a reactor.
  • Alkanes are converted to olefins (and dienes) by an integrated process scheme which involves the direct equilibrium dehydrogenation of alkanes via known catalysts and the selective oxidation of the resulting hydrogen gas thus formed.
  • the light paraffins which may be utilized for such reactions include C 2 -C 5 , such as propane and isobutane.
  • the overall reaction scheme demonstrated for propane oxidative dehydrogenation, is thus: Scheme A: Cat. 1 ⁇ ' C 3 H 8 ⁇ > C 3 H 6 + H 2
  • Reaction 1 is documented in the literature and is known as propane equilibrium dehydrogenation. Butane and isobutane equilibrium dehydrogenation are also known and documented in the literature. Reaction 1 has been demonstrated to occur catalytically over Cr/Al 2 0_,
  • Reaction 2 can proceed in the absence (redox mode) , as opposed to the presence (cofed mode) of gaseous oxygen, over a number of reducible metal oxides.
  • Catalyst 1 and Catalyst 2 may be used together in the same reactor.
  • Typical operating temperatures are from 400 to ⁇ OO'C, 101 to 505 kPa (l ' to 5 atm.) pressure, either with or without a diluent.
  • the present invention differs from the system described above in that the reaction involves two separately functioning catalysts—an equilibrium dehydrogenation catalyst, and a hydrogen combustion catalyst. These components may be used in separate reactors, connected in series or in a recycle mode, so as to drive the equilibration reaction (equation 1 above) further to the product side than is normally possible with only an equilibration catalyst.
  • the hydrogen would be combusted to H-0 (or at least a portion of it) , thus driving the equilibrium represented by equation 1 to the side of the products.
  • the catalyst used in the dehydrogenation reaction may be an equilibrium dehydrogenation catalyst comprising a Group VIII metal (i.e., Fe, Co, Ni, Ru, Rh, Pd, Os, Ir or Pt) .
  • a Group VIII metal i.e., Fe, Co, Ni, Ru, Rh, Pd, Os, Ir or Pt
  • the noble metals i.e., Ru, Rh, Pd, Os, Ir and Pt
  • These Group VIII metals are preferably present in an at least partially reduced state with at least a portion thereof being in the free metal (i.e., zero valent) form.
  • Examples of such equilibrium dehydrogenation catalysts include Pt, Pd, or other Group VIII metals either in bulk phase or supported on oxide supports (alumina, silica, titania, zirconia, zinc aluminate, etc.).
  • a particular dehydrogenation catalyst, which may be used in the present dehydrogenation reaction is a Pt/Sn/ZSM-5 catalyst, especially as described in U.S. Patent Nos. 4,990,710 and 5,192,728.
  • Pt/Sn/ZSM-5 catalysts may comprise 0.1 to 20 weight percent platinum and 0.1 to 20 weight percent tin with the remainder being ZSM-5.
  • the ZSM-5 in this catalyst is essentially non- acidic and may comprise less than 0.1 weight percent of aluminum.
  • the oxides of bismuth are particularly selective for hydrogen combustion over hydrocarbon combustion, while the oxides of vanadium are not.
  • the metal oxides which are particularly selective for the present selective hydrogen combustion reaction, contain certain metals selected from a narrow quadrant of the periodic table, i.e., the upper right hand corner thereof. These metals include Bi, In, Sb, Zn, Tl, Pb, and Te. A review of the periodic table suggests that this group of elements is centered by the location of the particular elements, Bi, In, and Sb.
  • the oxidation catalyst may include other components such as supports for the catalytic metal oxide. Examples of such supports include nonreducible, essentially inert oxides, such as silica, alumina, zirconia, titania, hafnia, and mixtures of these oxides, such as silica/alumina.
  • oxides include one or more oxides of elements selected from the group consisting of Mo, , P and La. Although the question of whether such oxides of Mo, , P and La actually have a beneficial or promoting effect in the present selective hydrogen combustion reaction has been largely unexplored, it is at least believed that these particular oxides do not have a detrimental effect.
  • the oxidation catalyst may contain, for example, at least 1 wt.% of catalytically active metal oxide. Elemental analysis of the oxidation catalyst may reveal the presence of, for example, at least 0.5 wt.% of one or a combination of metals selected from the group consisting of Bi, In, Sb, Zn, Tl, Pb, and Te.
  • the oxidation catalyst described herein may be an oxide of a single metal, such as bismuth or antimony, or it may be a mixed metal oxide.
  • An example of a mixed metal oxide is a compound of the following empirical formula BiaSb.bTecAd,BeCf_0x V where
  • A P, La, Ce, Y, Ru, Co, Ni, Cu, Al, In, Ga, and/or
  • O oxygen
  • a,b,c 0 to 12 a+b+c > 0
  • Another example of a mixed metal oxide is a compound of the following empirical formula
  • B La, Ce, Y, Ru, Fe, Co, Ni, Cu, Al, In, Ga, and/or
  • the combined dehydrogenation catalyst and oxidation catalyst may be a homogeneous or heterogeneous material.
  • An example of such a homogeneous material is formed when a Group VIII metal and a reducible metal oxide are coimpregnated, in a simultaneous or step-wise fashion, onto a common support material.
  • the Group VIII metal and the reducible metal oxide may also be a heterogeneous material, wherein they are present as a mere physical mixture of separately formed materials, e.g., supported by different supports.
  • Such heterogeneous materials wherein discrete particles of dehydrogenation catalyst are physically mixed with discrete particles of oxidation catalyst, are contrasted with homogeneous oxidative dehydrogenation catalysts, wherein the active components thereof are coprecipitated into a homogeneous mass.
  • a gravimetric, Cahn balance apparatus was used to measure the reduction rates of several metal oxides with hydrogen and C 3 hydrocarbons at 500"C. These rates and the selectivity of the examined oxides for SHC are listed in Table 1.
  • MCC multicomponent catalyst
  • Table 1 shows that Bi 2 0 3 ; indium, bismuth, lanthanum, cerium, and aluminum molybdates; and MCC exhibit the highest selectivities for hydrogen combustion in the presence of propane, while V 2 0 5 exhibits the lowest.
  • EXAMPLE 2 An equimolar mixture of 15% hydrogen and 15% propylene in helium was passed over 1 g of 42% Bi_0 3 /58% SiO- at a total flowrate of 170 cc/min at 550"C for 140 seconds. The product gas was collected and analyzed with gas chromatography. H 2 conversion to H 2 0 was greater than 85%, while the conversion of propylene was less than 0.5%.
  • EXAMPLE 3 The same experiment was conducted as in Example 2, except that the feed was flowed over the sample for 600 seconds at a total flowrate of 40 cc/min.
  • the H_ conversion in the reactor effluent was 79%, while the conversion of propylene was approximately 1%.
  • EXAMPLE 5 The same experiment was conducted as in Example 4, except that the feed was flowed over the sample for 600 seconds at a total flowrate of 40 cc/min. The H 2 conversion in the reactor effluent was only 11%, while the conversion of propane to waste products was 24%. Examples 4 and 5 illustrate that, in sharp contrast to Bi 2 0 3 , V O does not exhibit SHC properties, since its lattice oxygen is particularly active for the conversion of hydrocarbons.
  • EXAMPLE 6 The same material as in Examples 2 and 3 was exposed to 120 consecutive redox cycles.
  • a redox cycle consists of an oxidation phase (flow of excess air for 5 minutes) followed by a reduction phase (flow of 15% H 2 , 15% C ⁇ at 170 cc/min for 140 seconds) .
  • the oxidation and reduction phases are separated by two helium purge phases.
  • the H 2 conversion as a function of cycle number is shown in Figure 1.
  • the conversion of propylene was negligibly small (less that 0.5%), mostly to C0 2 .
  • the conversion of H 2 is attributed to its oxidation to H 2 0 by the lattice oxygen of Bi 2 0 3 which did not oxidize virtually any of the hydrocarbon present.
  • the dashed line is the propylene conversion obtained with a 15% C ⁇ , 0% H 2 , 7.5% 0 2 feed.
  • the selectivity of Bi 2 0 3 for hydrogen combustion in the presence of propylene is still high, although not as high as in the presence of propane. Furthermore, the propylene conversion is less when hydrogen is present.
  • EXAMPLE 8 A series of metal oxides were examined with the experiment described in Examples 2 and 3 to evaluate their SHC properties. These results of these experiments are summarized in the following Table 2.
  • GaO ⁇ /Si0 2 170 ⁇ 10 6.0 40 ⁇ 10 8.4
  • Catalyst C 3 Conv. C 3 Yield CO ⁇ Yield £ 3 " Yield Pt-Sn-ZSM-5 24.2 22.1 0.6 1.5
  • EXAMPLE 10 The same experiment as in Example 9 was conducted over the mixed catalyst system, except that feed was passed over the catalyst for 332 sec. Propane conversion was 42.8%, and propylene, CO and cracked product yields were 38.8, 1.9, and 2.0%, respectively.
  • EXAMPLE 11 The same experiment as in Example 9 was conducted over the mixed catalyst system, except that feed was passed over the catalyst at a flowrate of 8.5 cc/ min for 332 sec. Propane conversion was 47.8% and propylene, CO , and cracked product yields were 39.7, 4.7, and 3.4%, respectively.
  • Example 9 The same experiment as in Example 9 was conducted over a mixture of 2 g Pt-Sn-ZSM-5 and 1 g Bi 2 0 /Si0 2 « Propane conversion in the collected product was 50.2% and propylene, CO , and cracked product yields were 40.7, 4.6, and 4.9%, respectively.
  • EXAMPLE 13 lg of Pt/Sn/ZSM-5 was mixed with lg of the metal oxide to be tested.
  • the catalyst mixture was first calcined in air at 550"C and the feed was 100% propane.
  • the reactor effluent was collected in an evacuated glass bulb and was analyzed.
  • the propylene and COx yields obtained with each metal oxide are shown in Table 3 below.
  • the base case experiment is with no metal oxide.
  • C ⁇ sel. stands for C ⁇ Yld divided by C 3 Conv.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract

L'invention concerne un procédé de deshydrogénation oxydative catalysée d'alcanes en alcènes. Le procédé consiste à effectuer simultanément une déshydrogénation des alcanes en alcènes jusqu'au point d'équilibre de la réaction et une combustion de l'hydrogène formé de manière à déplacer l'équilibre de la réaction de déshydrogénation en faveur des alcènes. Dans la présente réaction sont introduits avec l'oxygène dans un réacteur contenant en même temps un catalyseur de déshydrogénation des alcanes jusqu'au point d'équilibre et un catalyseur d'oxydation sélective à base d'oxydes métalliques. Dans ces conditions l'alcane est déshydrogéné et l'hydrogène produit est simultanément brûlé de manière sélective. Ce mode de fonctionnement particulier implique d'effectuer l'oxydation simultanément dans le même réacteur. Le catalyseur de déshydrogénation jusqu'au point d'équilibre peut contenir du platine et le catalyseur d'oxydation sélective à base d'oxydes métalliques peut contenir du bismuth, de l'antimoine ou du molybdène ou encore un de leurs mélanges.
PCT/US1995/007088 1995-04-17 1995-06-05 Procede de deshydrogenation catalysee d'alcanes avec oxydation simultanee d'hydrogene WO1996033152A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1050152C (zh) * 1997-03-18 2000-03-08 中国石油化工总公司 脱氢催化剂
WO2002055196A1 (fr) * 2001-01-12 2002-07-18 Universiteit Van Amsterdam Catalyseur capable d'oxyder de maniere selective l'hydrogene, utilisation de ce catalyseur et procede de preparation de ce dernier

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250346A (en) * 1980-04-14 1981-02-10 Union Carbide Corporation Low temperature oxydehydrogenation of ethane to ethylene
US4568790A (en) * 1984-06-28 1986-02-04 Union Carbide Corporation Process for oxydehydrogenation of ethane to ethylene
US4739124A (en) * 1985-09-16 1988-04-19 Uop Inc. Method for oxygen addition to oxidative reheat zone of ethane dehydrogenation process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250346A (en) * 1980-04-14 1981-02-10 Union Carbide Corporation Low temperature oxydehydrogenation of ethane to ethylene
US4568790A (en) * 1984-06-28 1986-02-04 Union Carbide Corporation Process for oxydehydrogenation of ethane to ethylene
US4739124A (en) * 1985-09-16 1988-04-19 Uop Inc. Method for oxygen addition to oxidative reheat zone of ethane dehydrogenation process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1050152C (zh) * 1997-03-18 2000-03-08 中国石油化工总公司 脱氢催化剂
WO2002055196A1 (fr) * 2001-01-12 2002-07-18 Universiteit Van Amsterdam Catalyseur capable d'oxyder de maniere selective l'hydrogene, utilisation de ce catalyseur et procede de preparation de ce dernier

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