EP1250191A2 - Catalyseurs en gel et procedes d'utilisation dans des processus de deshydrogenation catalytique - Google Patents

Catalyseurs en gel et procedes d'utilisation dans des processus de deshydrogenation catalytique

Info

Publication number
EP1250191A2
EP1250191A2 EP01942581A EP01942581A EP1250191A2 EP 1250191 A2 EP1250191 A2 EP 1250191A2 EP 01942581 A EP01942581 A EP 01942581A EP 01942581 A EP01942581 A EP 01942581A EP 1250191 A2 EP1250191 A2 EP 1250191A2
Authority
EP
European Patent Office
Prior art keywords
gel
composition
pores
solid material
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01942581A
Other languages
German (de)
English (en)
Inventor
Kostantinos Dino Kourtakis
Leo E. Manzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1250191A2 publication Critical patent/EP1250191A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/324—Catalytic processes with metals
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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
    • B01J37/0215—Coating
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/324—Catalytic processes with metals
    • C07C5/325—Catalytic processes with metals of the platinum group
    • 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
    • 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
    • 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
    • C07C2523/48—Silver or gold
    • C07C2523/52—Gold

Definitions

  • the present invention relates to a novel composition comprising a gel that has utility as a catalyst or as a catalyst support. Also disclosed are methods of preparing the compositions and processes for using the compositions for the dehydrogenation of C 2 _ ⁇ o hydrocarbons.
  • the present invention discloses a composition of matter, comprising: (i) a solid material having pores; (ii) a gel, said gel being substantially contained within the pores of said solid material and comprising at least one catalytically active element, and optionally when said catalytically active element is other than Cr, comprising chromium in addition to said element.
  • Another disclosure of the present invention is a process for preparing a composition of matter comprising: a solid material having pores; a gel, said gel being substantially contained within the pores of said solid material and comprising at least one catalytically active element, and optionally when said catalytically active element is other than Cr, comprising Cr in addition to said element, said process comprising: contacting in the presence of a solid material having pores, in any order a protic solution with a non-aqueous solution wherein said non-aqueous solution comprises a gel-forming precursor and wherein one of either the protic solution or the non-aqueous solution comprises at least one soluble compound comprising an inorganic element selected from the group consisting of Group 1 through Group 16 and the lanthanides of the Periodic Table, under conditions such that the solution added first is at incipient wetness, whereby gel formation occurs substantially within the pores of said solid material.
  • a further disclosure of the present invention is a composition of matter prepared by the process described immediately above.
  • the present invention also discloses an improved gel composition, wherein said improvement comprises: said gel is substantially contained within the pores of a solid material.
  • Yet another disclosure of the present invention is a method of using the composition disclosed wherein said method comprises contacting in a reactor said composition with a hydrocarbon feed in a dehydrogenation or dehydrocyclization process, said hydrocarbon being from C 2 to CJ Q .
  • the solid material having pores is selected from the group consisting of alumina, silica, titania, zirconia, carbon, molecular sieves (for example, zeolites). porous minerals (such as bentonite), microporous, mesoporous and macroporous materials, montmorillonites, aluminosilicate clays (for example, bentonite), binary ternary, quaternary and higher order oxides such as e.g., Fe 2 O3, NiO, CaO and CeO 2 (binary oxides), FeNbO 4 , Ni WO4 and Sr 2 TiO 4 (ternary oxides) and Ca 2 MgSi 2 O 7 (quaternary oxide), carbides, nitrides, phosphates, and sulfides. These materials are used as supports for the gels.
  • Higher order oxides are oxides beyond quaternary that contain more than four elements, including oxygen.
  • Some examples of higher order oxides include ganomalite (Pb9Ca 5 MnSi 9 O33), a lead calcium magnesium silicate, sodium calcium nickel arsenate (NaCa 2 Ni 2 As3 ⁇ 12 ) and barium copper europium lanthanum thorium oxide (Baj 3 3 Lao_67Eu ⁇ Th ⁇ 5 Q13O8 39).
  • Catalytically active elements which can be present as oxides, reduced metals, and in some cases phosphates of Group 1 (Li, Na, K, Rb, Cs), Group 2 (Be, Mg, Ca, Sr and Ba), Group 3 (Y, La) and the lanthanides (Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm Yb and Lu) of the Periodic Table can be used in C-H activation catalytic chemistries. Examples include methane coupling reactions to produce ethane and ethylene. In combination with other oxides of Groups 5, 6, 7, 8, 9, 10 of the Periodic Table, Groups 1, 2, 3 and the lanthanides can also be used for other oxidation chemistries.
  • Alkane and olefin oxidation are two examples.
  • Group 5 V, Nb, Ta
  • Group 6 Cr, Mo, W
  • Group 7 Mo, and Re
  • Group 9 Fe, Ru, Os
  • Two examples are the oxidation of butane to maleic anhydride and propylene oxidation to form acrolein.
  • Elements of Group 10 (Ni, Pd, Pt) and Group (11, Cu. Ag, and Au) can be used for alkane and olefin oxidation reactions, CO abatement, and for Pd, Pt, hydrogenation chemistries such as hydrogenation of ethylene to ethane.
  • Ag and its oxides can be used in epoxidation reactions, such as the epoxidation of ethylene to produce ethylene oxide.
  • Elements of Group 15, especially P, As, Sb Bi can be used for oxidation reaction chemistries, such as the ammoxidation of propylene to acrylonitrile, especially when combined with elements of Group 6 (Cr, Mo, and W) to form various oxide combinations.
  • Elements and their oxides of Group 16 (S, Se and Te) can be used for dehydrosulfurization chemistries, which are used to treat sulfur containing streams from petroleum distillates.
  • the gel is prepared from at least one soluble compound comprising an inorganic element precursor wherein at least one element is selected from the group consisting of Group 1 (i.e., Li, Na, K, Rb and Cs); Group 2 (i.e., Be, Mg, Ca, Sr and Ba); Group 3 (i.e., Y and La); Group 4 (i.e., Ti, Zr and Hf); Group 5 (i.e., V, Nb and Ta); Group 6 (i.e., Cr, Mo and W); Group 7, (i.e., Mn and Re); Group 8 (i.e., Fe, Ru and Os); Group 9 (i.e., Co, Rh and Ir); Group 10 (Ni, Pd and Pt); Group 11 (Cu, Ag and Au); Group 12 (i.e., Zn and Cd); Group 13 (i.e., B, Al and In); Group 14 (i.e.; Si, Ge, Sn and Pb); Group 15 (i.e.; P, As, S
  • one or more inorganic alkoxides or salts thereof is used as starting material, or precursors, for preparing the gels.
  • the gel-forming precursor comprises at least one soluble compound comprising an inorganic element wherein the element is selected from the group consisting of aluminum, silicon, titanium zirconium, niobium, tantalum, vanadium, molybdenum and chromium.
  • the alkoxides are the preferred compounds, and metal alkoxides are most preferred.
  • the inorganic metal alkoxides used in this invention may include any alkoxide which contains from 1 to 20 carbon atoms and preferably 1 to 5 carbon atoms in the alkoxide group, which preferably are soluble in the liquid reaction medium. Examples include, but are not limited to, tantalum n-butoxide, titanium isopropoxide, aluminum isopropoxide and zirconium isopropoxide. These alkoxides are preferred.
  • Inorganic materials have a range of pore sizes. Pore dimensions for some inorganic materials are relatively small.
  • the present invention discloses gel- forming precursors that fit within the pore structure of the solid materials that are used.
  • Commercially available alkoxides can be used.
  • inorganic alkoxides can be prepared by other routes.
  • Inorganic alkoxides can be prepared in various ways. One method of preparation includes direct reaction of zero valent metals with alcohols in the presence of a catalyst. Many alkoxides can be formed by reaction of metal halides with alcohols. Also, alkoxy derivatives can be synthesized by the reaction of the alkoxide with alcohol in a ligand interchange reaction. Direct reactions of metal dialkylamides with alcohol also form alkoxide derivatives. Additional methods for preparing alkoxides are disclosed in "Metal Alkoxides" by D. C. Bradley et al., Academic Press, (1978).
  • the gel formed in the composition of the present invention is made by preparing one or more non-aqueous alkoxide (or salt) solutions and a separate solution of a protic solvent, such as water. Promoters and other reagents may be added to the solution(s) of alkoxides. When the alkoxide solution is mixed with the protic solvent the alkoxide hydrolyzes and cross-links to form a gel.
  • a protic solvent such as water
  • the solvent media used in the process generally should be a solvent for the inorganic alkoxide or alkoxides which are utilized and the additional metal reagents and promoters which are added in synthesis. Solubility of all components in their respective media (aqueous and non-aqueous) is preferred to produce highly dispersed materials.
  • soluble reagents By using soluble reagents in this manner, mixing and dispersion of the active metals and promoter reagents can be near atomic, in fact mirroring their dispersion in their respective solutions.
  • the precursor gel thus produced by this process will contain highly dispersed active metals and promoters. High dispersion results in catalyst metal particles in the nanometer size range. These particles are substantially contained, or substantially localized, within the pores of the solid material.
  • the concentration of the amount of solvent used is linked to the alkoxide content.
  • a molar ratio of 26.5:1 ethanoktotal alkoxide can be used, although the molar ratio of ethanohtotal alkoxide can be from about 5: 1 to 53:1, or even greater. If a large excess of alcohol is used, gelation will not generally occur immediately; some solvent evaporation will be needed. At lower solvent concentrations, it is thought that a heavier gel will be formed having less pore volume and surface area.
  • the alkoxide solution with other reagents, water and additional aqueous solutions are contacted in the presence of a solid having pores. Due to the surface area provided by the porous character of the solid material, hydrolysis and condensation occurs substantially within the pores of the solid to form the gel.
  • the amount of water utilized in the reaction is the amount calculated to hydrolyze the inorganic alkoxide in the mixture.
  • a ratio lower than that needed to hydrolyze the alkoxide species will result in a partially hydrolyzed material which, in most cases, would reach a gel point at a much slower rate, depending on the aging procedure and the presence of atmospheric moisture.
  • a molar ratio of wate ⁇ alkoxide from about of 0.1:1 to 10:1 is used.
  • Reaction conditions and choice of gel-forming precursor i.e., a precursor which can react, hydrolyze and cross-link to form the gel
  • the molar ratio of the total water added to total catalytically active element added (for example, Ti, Zr, Ta, and Al), including water present in aqueous solutions, varies according to the specific inorganic alkoxide used. For tantalum(alkoxide) 5 ratios close to 5:1 can be used. Also, a ratio of 4:1 can be used for zirconium(alkoxide) 4 and titanium(alkoxides) 4 .
  • the addition of acidic or basic reagents to the inorganic alkoxide medium can have an effect on the kinetics of the hydrolysis and condensation reactions, and the microstructure of the oxyhydroxide matrices derived from the alkoxide precursor that comprises the soluble inorganic element.
  • a pH within the range of from 1 to 12 can be used, with a pH range of from 1 to 6 being preferred.
  • the first addition step is done under conditions of incipient wetness. The order of addition is not important, i.e., the either the protic solvent or the non-aqueous solvent can be added initially.
  • the second addition step can optionally be done under incipient wetness conditions.
  • the gelation process After gel formation occurs within the pores of the solid material, it may be necessary to complete the gelation process with some aging of the gel composition. This aging can range form one minute to several days. In general, the gel is aged in the pores of the solid material at room temperature in air for at least several hours.
  • Removal of solvent from the gel composition can be accomplished by several methods. Removal by vacuum drying or heating in air results in the formation of a xerogel.
  • a gel that is an aerogel of the material typically can be formed by charging in a pressurized system such as an autoclave. The gel composition can be placed in an autoclave where it can be contacted with a fluid above its critical temperature and pressure by allowing supercritical fluid to flow through the gel material until the solvent is no longer being extracted by the supercritical fluid. In performing this extraction to produce an aerogel material, various fluids can be utilized at their critical temperature and pressure.
  • fluorochlorocarbons typified by Freon ® fluorochloromethanes (e.g., Freon® 11 (CC1 3 F), 12 (CC1 2 F 2 ) or 114 (CC1F 2 CC1F 2 ), ammonia and carbon dioxide are all suitable for this process.
  • the extraction fluids are gases at atmospheric conditions.
  • the pores collapse due to the capillary forces at the liquid/solid interface are avoided during drying.
  • the gels formed within the pores of the solid material, whether they are xerogels or aerogels, can be described as precursor salts dispersed in an oxide or oxyhydroxide matrix.
  • the theoretical maximum for hydroxyl content corresponds to the valence of central metal atom.
  • x (OH) x ) 5 possesses a theoretical hydroxyl maximum when x is 2.
  • the molar H 2 O: alkoxide ratio can also impact the final xerogel stoichiometry; in this case, if H 2 O:Ta is less than 5, there will be residual -OR groups in the unaged gel. However, reaction with atmospheric moisture will convert these to the corresponding -OH, and -O groups upon continued polymerization and dehydration. Aging, even under inert conditions, can also effect the condensation of the -OH, eliminating H 2 O, through continuation of crosslinking and polymerization, i.e., gel formation.
  • the gel compositions of the present invention have utility as catalysts or as improved catalyst supports.
  • the solid material having pores provides mechanical integrity for the gel and generally does not inhibit the catalytic properties of the gel.
  • the mechanical integrity permits easier handling and transportation of the gel compositions since, without the solid material, these compositions are fluffy and powder-like, and not easily contained.
  • the gel compositions disclosed herein reduce waste and therefore, is more cost efficient.
  • compositions of the present invention are in the dehydrogenation of C 2 to CJ Q hydrocarbons.
  • the hydrocarbon feed that can be used in the present invention includes any C 2 to C 10 hydrocarbon with ethane, propane, isobutane and isooctane (2,2,4-trimethylpentane) being preferred.
  • the gel compositions contained within the pores of the solid materials disclosed in the present invention can be used as catalysts by contacting the gel composition with the hydrocarbon feed in a dehydrogenation process in a reactor. The contacting step may be done in various types of reactors, including a fixed bed, moving bed, fluidized bed, ebullating bed and entrained bed.
  • the less saturated hydrocarbon reaction products of this invention can be separated by conventional means such as distillation, membrane separation and absorption.
  • the gas hourly space velocity (GHSV) of the feed gas generally is in the range of from about 100 to about 3000 cc hydrocarbon feed/cc gel composition /hour, preferably from about 500 to about 1000 cc hydrocarbon feed/cc gel composition/hour.
  • the operating pressure is generally in the range of from about 7 kPa to about 700 kPa, preferably from about 7 kPa to about 400 kPa.
  • the dehydrogenation reaction temperature generally is in the range of from about 300°C to about 650°C, preferably from about 450°C to 600°C.
  • the gel-containing compositions of this invention can be regenerated periodically to remove coke.
  • the regeneration is done by conventional techniques of carbon removal such as heating with an oxygen-containing gas, preferably air.
  • compositions of the present invention are also useful as catalyst supports.
  • a chromium/aluminum gel supported in eta-alumina, prepared as described in Example 1 below, can be impregnated with a water soluble compound of platinum.
  • One such example would be impregnation with H 2 PtCl4-
  • the impregnated support is then dried and heated to 400°C in a 5% hydrogen/nitrogen stream for 4 hours and then cooled.
  • the reduced supported catalyst is then suspended in a solvent containing 1-hexene.
  • the suspension is then heated at about 100°C with stirring under a hydrogen atmosphere at about 3000 kPa for about two hours. Hexane can be separated from the reaction mixture.
  • compositions of the present invention also can be used as catalyst supports for oxidation (e.g., supported cobalt) and hydroformylation (e.g. supported rhodium) reactions.
  • the process for making the present invention may be implemented by using combinatorial methods for the rapid syntheses of catalysts. Such methods would permit the production of these catalysts using robotic tools, such as liquid delivery system, to a solid having pores, as described in the present invention, to create gel compositions substantially in the pores of the solid.
  • the catalyst charge was 2 mL for all the examples.
  • Catalyst tests were performed in a fixed bed continuous flow quartz reactor with 6.4 mm id.
  • the catalyst charge was 2.0 mL of-12/+20 mesh (-1.68/+0.84 mm) granules.
  • the reactor tube was heated in a tube furnace to 550°C in flowing nitrogen until the temperature was stable.
  • a thermocouple inside the catalyst bed was used to measure temperature. Once the desired temperature was achieved, a feed consisting of 50% isobutane/50% nitrogen (Examples 1 to 4) or a feed consisting of 50% propane/50% nitrogen (Examples 5 to 6) were passed over the catalyst bed. The contact times 3.2 seconds in all the examples.
  • An aqueous solution containing 0.1 M (with respect to chromium) (Cr3(OH) 2 )(ac) 7 was prepared by dissolving the chromium salt (4.022 g) in a sufficient quantity of commercially available ammonium hydroxide solution (28-30% NH4OH in water) to bring the solution volume to 200 mL.
  • chromium solution 5 mL was first added dropwise to the eta alumina support with agitation.
  • 0.05 M aluminum isopropoxide in isopropanol (20 mL) was slowly added to the wet support.
  • a second cycle additional chromium solution (2.5 mL) was added, and additional aluminum isopropoxide solution (20 mL) was added into the support.
  • additional chromium solution 2.5 mL
  • additional aluminum isopropoxide solution (20 mL) was added into the support.
  • 2.7 mL of the chromium solution was used, and 20 mL of the aluminum isopropoxide solution was employed.
  • 2.2 mL of the chromium solution was added along with 0.3 mL of NH 4 OH solution was added, followed by 20 mL of the aluminum isopropoxide solution.
  • the final cycle involved the addition of 2.5 mL of ammonium hydroxide solution (only) followed by 20 mL of the aluminum isopropoxide.
  • the final material was dried under vacuum for 5 hours at 120°C.
  • Cro.003432 A1 0.0137266 / C ⁇ .9828414 A 5 mL portion of the 0.1 M (with respect to chromium) chromium hydroxide acetate solution from Example 1 was added to carbon black (6.88 g) followed by 40 mL of the aluminum isopropoxide solution. In a second cycle, 5 mL of the chromium solution and 40 mL of the aluminum hydroxide solution were used. A third cycle used 5 and 40 mL, and a fourth cycle 4 and 40 mL were used. The final material was dried under vacuum for 5 hours at 120°C. The material was pelletized and granulated and sieved on -10, +20 mesh (-2.0, +0.84 mm) screens prior to reactor evaluations.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne une composition de gel presque entièrement contenue dans les pores d'une matière solide, à utiliser comme catalyseur ou comme support catalytique dans des processus de déshydrogénation et de déshydrocyclisation.
EP01942581A 2000-01-24 2001-01-23 Catalyseurs en gel et procedes d'utilisation dans des processus de deshydrogenation catalytique Withdrawn EP1250191A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US17779500P 2000-01-24 2000-01-24
US177795P 2000-01-24
PCT/US2001/002328 WO2001052985A2 (fr) 2000-01-24 2001-01-23 Catalyseurs en gel et procedes d'utilisation dans des processus de deshydrogenation catalytique

Publications (1)

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EP1250191A2 true EP1250191A2 (fr) 2002-10-23

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EP (1) EP1250191A2 (fr)
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US8592336B2 (en) 2006-04-11 2013-11-26 Agency For Science, Technology And Research Catalysts for ring-closing metathesis
CN102872869A (zh) * 2012-09-11 2013-01-16 常州大学 用于制备甲酸甲酯的甲醇脱氢催化剂及其制备和用途
CN106607022B (zh) * 2015-10-22 2020-08-07 中国石油化工股份有限公司 用于异丁烷脱氢的催化剂
JP2018061943A (ja) * 2016-10-14 2018-04-19 国立大学法人京都大学 排ガス浄化用鉄系複合酸化物触媒及びその製造方法
CN110496635B (zh) * 2018-05-17 2022-01-04 中国石油化工股份有限公司 异丁烷脱氢催化剂及其制备方法以及异丁烷脱氢制异丁烯的方法
CN110614108B (zh) * 2018-06-20 2022-07-12 中国石油化工股份有限公司 载体为具有三维立方笼状孔道分布结构的介孔分子筛的异丁烷脱氢催化剂及制法和应用
CN110614110A (zh) * 2018-06-20 2019-12-27 中国石油化工股份有限公司 载体为鸡蛋壳状介孔材料硅胶复合材料的异丁烷脱氢催化剂及制法和应用
CN110589763B (zh) * 2019-09-02 2023-02-10 四川普瑞思达科技服务有限公司 一种乙炔催化裂解制氢的方法
CN110721710B (zh) * 2019-10-21 2021-06-08 大连理工大学 一种有序大孔非金属催化剂及其制备方法
CN114405541B (zh) * 2021-12-29 2023-06-09 深圳华明环保科技有限公司 选择性氧化氨气的催化剂的制备方法

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WO2001052985A3 (fr) 2001-12-20
WO2001052985A2 (fr) 2001-07-26

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