[go: up one dir, main page]

WO1992003225A1 - Catalyseur et procede d'oxydeshydrogenation du methane - Google Patents

Catalyseur et procede d'oxydeshydrogenation du methane Download PDF

Info

Publication number
WO1992003225A1
WO1992003225A1 PCT/US1991/005779 US9105779W WO9203225A1 WO 1992003225 A1 WO1992003225 A1 WO 1992003225A1 US 9105779 W US9105779 W US 9105779W WO 9203225 A1 WO9203225 A1 WO 9203225A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
oxygen
methane
hydrocarbons
alkali
Prior art date
Application number
PCT/US1991/005779
Other languages
English (en)
Inventor
Heinz Heinemann
Pedro R. Pereira
Gabor A. Somorjai
Original Assignee
The Regents Of The University Of California
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 The Regents Of The University Of California filed Critical The Regents Of The University Of California
Publication of WO1992003225A1 publication Critical patent/WO1992003225A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • 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
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/745—Iron
    • 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
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • 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
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel

Definitions

  • This invention relates to a method and catalyst compositions for oxidative coupling of hydrocarbons, particularlymethane, and more particularly to oxidative coupling processes over novel catalysts in the presence of steam for selectively converting Cj to C 2 and higher hydrocarbons, with selectivities approaching 100% and at least 8% conversion and yield.
  • the major considerations in oxidative Cj coupling are the parameters of selectivity, conversion, and yield.
  • the formation of CO and C0 2 is a major reaction which competes with the formation of C 2 hydrocarbons.
  • the selectivity term expresses the desirable C 2 , C 3 or C 4 product C +) formed as a percentage of the total Cj material converted. Lower selectivities thus implythat large quantities of CO x are generated in the process.
  • CO x represents a loss of both C, reactant and oxygen but equally important, CO x is an undesirable pollutant requiring removal from recycled unconverted methane by scrubbing with alkaline solution.
  • conversion is used to express the percentage of the C, feedstocks which has reacted in a single pass through the process reactor, i.e. conversion is the difference between the quantity of unreacted C j in the product stream and.the C, quantity present in the initial feed stream.
  • the reaction products in oxidative coupling processes are C 2 (and higher) hydrocarbons, water and CO-.
  • the magnitude of the conversion is normally a function of the characteristics of the catalyst and of the reactor as well as the process variables and thus varies somewhat with the flow rates, catalyst quantities, process temperature, and the like.
  • the conversion values for known processes and practical reactors are typically less than about 50%. Hence recirculation of product through the reactor is invariablyrequired in a practical plant. Since CO- build-up interferes with the reaction, a CO x removal step is thus required for all coupling processes having low selectivity parameters, which includes all oxidative coupling processes known thus far.
  • Yield is defined as the product of selectivity and conversion. This parameter expresses, as a percentage, the quantity of the desired C 2 or higher hydrocarbon product formed from a quantity of C_ starting material for a given reactor under given operating conditions.
  • Another object of the invention is to provide an oxidative coupling process in which the formation of CO x is eliminated to as large an extent as possible and to thus obviate the need of CO x removal entirely.
  • Yet another object of this invention is to provide catalysts which promote oxidative coupling with attendant high selectivities and which can be readily and reproducibly made.
  • Still another object of the invention is to provide a process of improved economics in regard to reagent requirements, minimizing the use of oxygen and employing steam, thus permitting the process to be carried out safely below the flammability limit.
  • This invention is a process for the oxidative coupling of hydrocarbons of lower chain length particularly methane, wherein methane is passed over a catalyst comprised of the oxides of an alkali, an alkaline earth and a transition metal together with steam and a small amount of oxygen at relatively low temperatures in the range of about 500 to about 650°C.
  • the optimal mole ratio of the feed gas mixture is about 3:1:6:5 of methane:oxygen:water.
  • the pressure may be between atmospheric and about 500 psig.
  • a significant aspect of the invention relates to the catalyst composition and its preparation.
  • the selectivity of the present catalysts has been generally superior to those of the prior art, i.e. 80% or higher, and essentially 100% for the preferred catalysts of this invention. However, within this range, establishing optimum activities and selectivities depends remarkably upon variations in chemical composition and preparation of the catalyst.
  • the preferred catalyst is a mixture of calcium, nickel, and potassium oxides in an atomic weight ratio of about 2:1:0.01.
  • the catalysts are prepared by drying, decomposing and oxidizing mixed aqueous solutions of calcium and nickel nitrates in air at elevated temperatures, and adding small amounts of potassium nitrate in the process.
  • Optimum catalysts have also been prepared in similar fashion from the corresponding hydroxides.
  • the catalyst formulations discovered in the course of the present invention are generally superior over those known heretofore, particularly in terms of their selectivities.
  • themost dramatic aspect of this invention relates to he discovery of catalyst formulations and preparation which allow achievement of selectivities of 599%+, since they permit oxidative coupling of methane to be carried out without evolution of CO x and hence without the need of separating CO x from the product stream prior to recirculation or recovery.
  • the permissible variation of the catalyst composition is as follows:
  • the Ca/Ni ratio may vary from about 2:1 to about 4:1, and the Ni/K ratio from about 1:0.05 to about 1:0.2.
  • the preparation of the catalyst may play an important role in obtaining catalysts of the desired characteristics.
  • the following processes have been found to routinely yield 599%+ selectivity catalysts.
  • the catalyst may be prepared from aqueous solutions of calcium nitrate, nickel nitrate, and potassium nitrate.
  • the catalyst may be prepared from the hydroxides or carbonates also. It appears to be important that the anions of the solutions are identical. It is preferred to produce the catalyst starting from aqueous nitrate solutions. Production of catalyst from hydroxide or carbonate would follow the same procedure.
  • aqueous solutions of the nitrates are prepared, in concentrations as high as their solubilities permit.
  • Appropriate quantities of the solutions are mixed to provide the desired Ca/Ni ratio.
  • An appropriate quantity of potassium nitrate may be mixed in at this point or later as discussed below.
  • the mixed solution is then dried and decomposed in air at about 700°C to form the corresponding oxides.
  • the potassium nitrate solution may alternatively be added to be dried and decomposed mixture of calcium and nickel oxides, followed by positive drying and decomposition in air at 700°C until a powdery mixture is formed.
  • the catalyst may be used in this form or may be pelletized by pressing or extruding.
  • Unsupported catalyst has been found satisfactory for loading into and use in the reactor.
  • an inert support such as a porous ceramic of AL ⁇ or Si0 2 to increase the surface area and permit transport of feedstock over the catalyst at higher space velocities or higher conversions.
  • the support material is added to the solution mixture prior to drying followed by processing as described.
  • the catalyst Prior to use, the catalyst must be activated. Activation may be accomplished prior to loading the catalyst into the reactor, or preferably by treatment in the reactor after loading, but prior to exposure to feedstock. To activate the catalyst, it is exposed to flowing oxygen or air, e.g. at a rate of about 2cc 0 2 per gram of catalyst, ⁇ t a mperatare ⁇ cit 680°C
  • the time period for which the catalyst is activated is important in that activation for longer periods increases conversion and also increases specific selectivity for hydrocarbons of greater chain length, and also affects the olefin/paraffin ratio, as shown in Table 1 below.
  • the present catalysts thus provide an important ability to convert methane to C 3 and C 4 hydrocarbons, and the activation step provides the means for optimizing production of the desired hydrocarbon species.
  • the preferred alkaline earth group of interest for the present catalyst comprises magnesium, calcium, and barium; the preferred transition metals are iron, cobalt and nickel; and the preferred alkalis are lithium, sodium, and potassium.
  • the preferred molar ranges of the alkaline earth/transition metal varies from about 2:1 to about 4:1, and the preferred molar ranges of transition metal/alkali is from about 1:0.05 to about 1:0.2.
  • reactor 10 which comprises flow through catalyst chamber 11, surrounded by heater means 12, whereby the temperature of the reactor may be regulated and maintained at the desired value.
  • the reactor is conventionally instrumented to permit measurement and control of the pressure, temperature and flow rate, using temperature control 13, temperature sensor 14, pressure gauges 15, and mass flow controller 16.
  • Reactor input port 17 receives the feedstream comprising methane, oxygen, and steam which pass over the catalyst in the catalyst chamber 11.
  • methane is supplied frommethane bottle 18, oxygen from oxygen reservoir 19, and water from syringe pump 20. Water is converted into steam in heated conduit 21.
  • methane, oxygen and steam would be supplied by suitable industrial sources. Also, since only a fraction of the initial hydrocarbon feed is converted tohigherhydrocarbons, recirculation of a corresponding fraction of the reactor output would be required as indicated by dashed line 22 leading from reactor output port 23 to the reactor input.
  • the product issuing from output port 23 is put through expander 24. Water is separated in water recipient 25.
  • the recirculation loop would also have to include a conventional scrubber for this purpose.
  • the product is analyzed" and monitored by attendant analytical instrumentation, shown here to comprise ad chromatography equipment 26 including reservoir 27 and valved lines 28 for supplying a known calibrating 29 mixture.
  • the catalyst is loaded into the reactor and activated as discussed above.
  • two catalyst chambers may be employed to permit continuous operation through alternating chambers, i.e. feedstock is processed in one chamber while catalyst is loaded and activated in the other chamber.
  • Catalyst may, of course, be activated prior to loading as discussed above. After catalyst activation, the reactor temperature is raised to between about 550 and 650°C, steam is generated by heating conduit 21 to about 140°C, and methane, oxygen and steam are introduced into the reactor.
  • the composition of the feedstream expressed in terms of the molar ratio of CH 4 /0 2 /H 2 0 may vary from 2/1/4 to 5/1/6, with che optimum ratio being about 3/1/6.5. It should be noted that the process is carried out below the explosive limit for methane and oxygen.
  • the use of steam as well as the reduced need for oxygen and operation at relatively low temperatures are considered major advantages of the present process generally and also facilitate safe operation.
  • the preferred flow rate of the feedstream is about 40 moles of methane per gram of catalyst per hour.
  • the material balance of carbon shows that carbon is absorbed by the catalyst for about 3 hours.
  • Figure 2 shows a graph of the material balance with time. Once a 100% carbon balance has been achieved, catalyst life is long and constanthydrocarbonyield prevails over at least two days of operation. Small but tolerable quantities of CO x may be generated in the course of preheating. Blank runs have shown that the C0 2 results from gas phase reactions int he preheat zone and are not attributable to lower catalyst selectivities. Comparison of blank runs over inert ceramic granules and catalyst show that gas phase conversion of methane to C0 2 is in fact reduced by the catalyst.
  • the selectivity dramatically deteriorates from early 100% to less than 10% and is restored to better than 90% upon return of the temperature to 600°C again.
  • a catalyst comprising oxides of calcium and nickel in an atomic ratio of 2:1 was prepared from a solution of the nitrates by drying in air decomposing the nitrates to oxides in air at 700 ⁇ C and activating the catalyst in flowing oxygen at 680°C for 20 hours.
  • the catalyst was charged to the reactor and a gaseous mixture of CH 4 , 0 2 and water in a 1 mole ratio of 3:1:6.5 was passed over the catalyst at 600C and atmospheric pressure at a rate of 40 moles of CH 4 per gram of catalyst per hour.
  • the selectivity to higher hydrocarbons in the product was about 80% at about 10% CH 4 conversion for a yield of 8% C 2 and C 3 .
  • Example 2 A catalyst comprising oxides of calcium, nickel and potassium oxides in an atomic ratio of 2:1:0.1 was prepared from a solution of the nitrates by drying the Ca and Ni nitrates in air decomposing them to the oxides in air at 700°C, adding a solution of potassium nitrate, drying and decomposing again at 700°C and activating the catalyst in flowing oxygen at 600°C for 20 hours.
  • Example 3 A catalyst comprising oxides of calcium, nickel and potassium in atomic ratio of 4:1:0.1 was prepared by the method described in example 2. This- catalyst gave the same conversion and selectivity as the catalyst of example 2.
  • a catalyst comprising oxides of Ca, Ni and K in an atomic ratio of 2:1:0.1 and prepared as in example 2 was activated in flowing oxygen at 700°C for 1 hour.
  • this catalyst for the oxidative coupling of CH 4 under the conditions described in example l, a selectivity of 100% to C 2+ hydrocarbons was obtained at a CH 4 conversion of only 2%.
  • Selectivity to C 2 hydrocarbons was 98% and to C 3 hydrocarbons was 2%.
  • the olefin/paraffin ratio of the C 2+ hydrocarbons was 0.2.
  • the catalyst prepared according to example 2 was activated for 40 hours in flowing 0 2 at 680°C. On testing this catalyst for the oxidative coupling of CH 4 under the conditions described in example 1, a selectivity of 100% to C 2+ hydrocarbons was obtained at 9.5% conversion of CH 4 . Selectivity to C 2 hydrocarbons was 86% to C 3 hydrocarbons 11% and to C 4 hydrocarbons 3%. The olefin/paraffin ratio was 0.8.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Catalyseur constitué d'oxydes métalliques mélangés (11) qui permet la conversion du méthane (18) en éthane, éthylène et hydrocarbures supérieurs à des températures inférieures à 600 °C en présence d'oxygène (19) et de vapeur (21) avec des sélectivités de 80 à 100 %, à des conversions de méthane dépassant 10 %. Ledit catalyseur comprend un oxyde alcalino-terreux, un oxyde d'un métal de transition des groupes VIB, VIIB et VIII du système périodique et une petite quantité d'un oxyde alcalin. Il est activé dans l'oxygène et la vapeur et reste actif seulement en présence de vapeur. En l'absence de vapeur et à des températures supérieures à 600 °C, ce type de catalyseur convertit du méthane avec de l'oxygène en hydrocarbures supérieurs et en dioxyde de carbone, avec des sélectivités aux hydrocarbures inférieures à 70 %. Une sélectivité élevée voisine de 100 % peut être obtenue avec un catalyseur préféré contenant un rapport atomique de Ca:Ni:K de 2-4:1:0.05-0.5 après prétraitement du catalyseur dans de l'oxygène.
PCT/US1991/005779 1990-08-21 1991-08-21 Catalyseur et procede d'oxydeshydrogenation du methane WO1992003225A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US57040890A 1990-08-21 1990-08-21
US570,408 1990-08-21

Publications (1)

Publication Number Publication Date
WO1992003225A1 true WO1992003225A1 (fr) 1992-03-05

Family

ID=24279533

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/005779 WO1992003225A1 (fr) 1990-08-21 1991-08-21 Catalyseur et procede d'oxydeshydrogenation du methane

Country Status (7)

Country Link
CN (1) CN1061164A (fr)
AU (1) AU8529091A (fr)
CS (1) CS258691A3 (fr)
MA (1) MA22262A1 (fr)
MX (1) MX9100757A (fr)
WO (1) WO1992003225A1 (fr)
ZA (1) ZA916611B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2224734C2 (ru) * 2001-08-08 2004-02-27 Институт химии нефти СО РАН Способ получения этилена
US7812201B2 (en) 2008-10-01 2010-10-12 Targa Resources, Inc. Process and catalyst for converting alkanes
WO2018073748A3 (fr) * 2016-10-21 2018-09-27 Sabic Global Technologies B.V. Catalyseurs stables pour le couplage oxydatif du méthane
CN114713282A (zh) * 2021-01-05 2022-07-08 中国石油化工股份有限公司 一种甲醇制烯烃催化剂的改性方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1049611C (zh) * 1993-03-22 2000-02-23 吉林大学 陶瓷纤维负载型高温反应催化剂的制备方法
CN1054114C (zh) * 1997-03-12 2000-07-05 天津大学 天然气电场增强等离子催化合成碳二烃

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3402022A (en) * 1965-01-04 1968-09-17 Universal Oil Prod Co Method for producing hydrogen and a catalyst therefor
US4009126A (en) * 1974-02-19 1977-02-22 Petro-Tex Chemical Corporation Catalyst for removing acetylenic impurities
US4450310A (en) * 1983-03-04 1984-05-22 The Standard Oil Company Conversion of methane to olefins and hydrogen
US4956327A (en) * 1989-05-31 1990-09-11 Institute Of Gas Technology Mixed basic metal oxide/sulfide catalyst
US4997802A (en) * 1987-12-11 1991-03-05 Ube Industries, Ltd. Catalyst for preparation of hydrocarbons

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3402022A (en) * 1965-01-04 1968-09-17 Universal Oil Prod Co Method for producing hydrogen and a catalyst therefor
US4009126A (en) * 1974-02-19 1977-02-22 Petro-Tex Chemical Corporation Catalyst for removing acetylenic impurities
US4450310A (en) * 1983-03-04 1984-05-22 The Standard Oil Company Conversion of methane to olefins and hydrogen
US4997802A (en) * 1987-12-11 1991-03-05 Ube Industries, Ltd. Catalyst for preparation of hydrocarbons
US4956327A (en) * 1989-05-31 1990-09-11 Institute Of Gas Technology Mixed basic metal oxide/sulfide catalyst

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2224734C2 (ru) * 2001-08-08 2004-02-27 Институт химии нефти СО РАН Способ получения этилена
US7812201B2 (en) 2008-10-01 2010-10-12 Targa Resources, Inc. Process and catalyst for converting alkanes
US7968755B2 (en) 2008-10-01 2011-06-28 Sajet Development Llc Process and catalyst for converting alkanes
WO2018073748A3 (fr) * 2016-10-21 2018-09-27 Sabic Global Technologies B.V. Catalyseurs stables pour le couplage oxydatif du méthane
CN114713282A (zh) * 2021-01-05 2022-07-08 中国石油化工股份有限公司 一种甲醇制烯烃催化剂的改性方法
CN114713282B (zh) * 2021-01-05 2023-08-04 中国石油化工股份有限公司 一种甲醇制烯烃催化剂的改性方法

Also Published As

Publication number Publication date
AU8529091A (en) 1992-03-17
CS258691A3 (en) 1992-04-15
CN1061164A (zh) 1992-05-20
ZA916611B (en) 1992-05-27
MX9100757A (es) 1992-04-01
MA22262A1 (fr) 1992-04-01

Similar Documents

Publication Publication Date Title
US5817904A (en) Method for the conversion of methane into longer chain hydrocarbons
US3186797A (en) Process for catalytically steam reforming hydrocarbons
Keller et al. Synthesis of ethylene via oxidative coupling of methane: I. Determination of active catalysts
US5012028A (en) Process for upgrading light hydrocarbons using oxidative coupling and pyrolysis
EP0206044B1 (fr) Procédé pour la conversion oxydante de composés organiques
Sofranko et al. Catalytic oxidative coupling of methane over sodium-promoted Mn/SiO2 and Mn/MgO
US4620057A (en) Methane conversion
Vrieland et al. Anaerobic oxidation of butane to butadiene over magnesium molybdate catalysts. I. Magnesia supported catalysts
WO1996033149A1 (fr) Procede de deshydrogenation oxydative
US4658076A (en) Composition of matter and method of oxidative conversion of organic compounds therewith
US5223471A (en) Fluorine-containing materials
EP0206043B1 (fr) Procédé de conversion de méthane
US2456072A (en) Conversion of hydrocarbons in the presence of a catalyst and calcium oxide together with steam and/or carbon dioxide
CA2283137A1 (fr) Emploi d'une phase d'un melange d'oxydes de ce et de zr pour la fabrication de styrene par deshydrogenation d'ethylbenzene
WO1992003225A1 (fr) Catalyseur et procede d'oxydeshydrogenation du methane
US4449006A (en) Preparation of methyl mercaptan from carbon oxides
EP0198251B1 (fr) Procédé pour la conversion de méthane
Kunimori et al. Partial oxidation of methane to synthesis gas over rhodium vanadate, RhVO4: redispersion of Rh metal during the reaction
US11724247B2 (en) Bifunctional catalysts and systems and methods for oxidative dehydrogenation of alkanes to olefins and high-valued products
EP0196541B1 (fr) Procédé pour la conversion de méthane
Iwamoto et al. Selective dehydrogenation of ethane by nitrous oxide over various metal oxide catalysts
EP0336622A2 (fr) Réaction pour la déshydrogénation d'hydrocarbures
US4775654A (en) Composition of matter
US4476344A (en) Oxidative dehydrogenation of paraffins
US4536492A (en) Catalyst for the preparation of methyl mercaptan from carbon oxides

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA FI HU JP KR LK NO PL SU

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA