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WO2018122758A1 - Procédé de déshydroaromatisation avec régénération du catalyseur - Google Patents

Procédé de déshydroaromatisation avec régénération du catalyseur Download PDF

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Publication number
WO2018122758A1
WO2018122758A1 PCT/IB2017/058456 IB2017058456W WO2018122758A1 WO 2018122758 A1 WO2018122758 A1 WO 2018122758A1 IB 2017058456 W IB2017058456 W IB 2017058456W WO 2018122758 A1 WO2018122758 A1 WO 2018122758A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
dehydroaromatization
regeneration
methane
gas stream
Prior art date
Application number
PCT/IB2017/058456
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English (en)
Inventor
Amit Kumar
Ziyad KOTTAVARITHOTTIL
Eswara Rao MUPPARAJU
Sreenivasarao GAJULA
Sivakumar SREERAMAGIRI
Original Assignee
Sabic Global Technologies B.V.
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.)
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Application filed by Sabic Global Technologies B.V. filed Critical Sabic Global Technologies B.V.
Publication of WO2018122758A1 publication Critical patent/WO2018122758A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • Aromatic hydrocarbons for example, benzene, toluene, ethylbenzene, xylenes, and polyaromatic hydrocarbons such as naphthalene, are important commodity chemicals in the petrochemical industry.
  • a method of preparing aromatic hydrocarbons is by the dehydroaromatization (DHA) of methane, as methane is one of the most abundant organic compounds on earth.
  • DHA dehydroaromatization
  • methane is the major constituent of natural gas; large amounts of methane are trapped in marine sediments as hydrates and in coal shale as coal bed methane; and it can also be derived from a biomass as a biogas.
  • Methane dehydroaromatization over catalysts is a promising process for the production of valuable aromatic compounds and hydrogen from natural gas.
  • Coke formation can decrease the life of the catalyst.
  • the equilibrium of the dehydroaromatization of methane is also low due to coke formation on the catalyst.
  • Coke formation is largely favored at high temperatures, particularly at 700°C and above.
  • Coke formation can be of two types, hard coke and soft coke.
  • Hard coke is mainly known as graphitic type coke.
  • Soft coke can be polyaromatic deposits.
  • This invention addresses the problem of reduced catalyst activity in a methane dehydroaromatization reaction due to coke formation.
  • dehydroaromatization of methane can comprise: contacting the deactivated
  • a method for dehydroaromatization of methane can comprise: passing a feedstock comprising methane gas to an aromatization reactor; converting a portion of the methane gas in the feedstock to aromatic hydrocarbons with a dehydroaromatization catalyst at a reaction temperature of 700°C to 850°C; and regenerating at least a portion of the
  • dehydroaromatization catalyst by contacting the dehydroaromatization catalyst with a first regeneration gas stream comprising hydrogen at a temperature of 700°C to 850°C, preferably 800°C to 850°C, contacting the dehydroaromatization catalyst with a second regeneration gas stream comprising 0.1 to 20 vol.% oxygen at a temperature of 400°C to 600°C.
  • FIG. 1 shows methane conversion on a Mo/ZSM-5 catalyst.
  • FIG. 2 shows Benzene selectivity in mol% on a Mo/ZSM-5 catalyst.
  • FIG. 3 shows methane conversion over time on Mo/HZSM-5 at 1,050 GHSV and 725°C using only oxygen regeneration at 550°C at 2500 GHSV under 5% 0 2 and 95% N 2.
  • FIG. 4 shows methane conversion over time on Mo/HZSM-5 at 1050 GHSV and 725°C using only hydrogen based regeneration at 800°C and 1,050 GHSV under 100% H 2.
  • FIG. 5 shows methane conversion over time on Mo/HZSM-5 at 1,050 GHSV and 725°C using both hydrogen based regeneration at 800°C and 1,050 GHSV under 100% H 2 for 30 minutes each followed by oxygen regeneration at 550°C at 2,500 GHSV under 5% 0 2 and 95% N 2 .
  • hard coke can only be removed under dilute oxygen at lower temperatures (400 to 550°C), while soft coke can be removed by pure hydrogen at higher temperatures (700 to 850°C).
  • the term "coke” is used to mean carbon containing solid materials, which are essentially non-volatile solids at the reaction conditions. Because cooling is required for regeneration of the catalyst using dilute oxygen, hydrogen is considered to be more effective for catalyst regeneration. However, hydrogen based regeneration alone does not give very long term catalyst stability. Therefore, periodic regeneration of the catalyst by decoking with dilute oxygen is described. This needs to be done at a lower temperature as regeneration with dilute oxygen at high temperatures can damage the catalyst.
  • the methane dehydroaromatization reaction disclosed herein converts methane to an aromatic compound by contacting the catalyst with a methane feed to produce an aromatic compound.
  • a methane gas feed used for converting to an aromatic compound can be supplied from, for example, at least one of a natural gas, methane hydrates, coal bed methane, synthetic gas, and biogas.
  • the aromatic compound can comprise at least one of benzene, toluene, naphthalene, and xylene.
  • the aromatic compound can comprise at least one of benzene and toluene.
  • the aromatic compound can further comprises traces of C 2 H 4 , C 2 H 6 , or C 3 H 6 , or a combination thereof. Further, the aromatic compound can be substantially benzene (e.g., greater than or equal to 80 vol.% of the aromatic compound can be benzene).
  • the aromatic compound can be produced under reaction conditions at a temperature range from 700°C to 850°C.
  • the temperature range for the production of the aromatic compound can be derived from any two exemplary temperatures.
  • the temperature can range from 710°C to 825°C, preferably 720°C to 800°C, or 720°C to 750°C.
  • the aromatic compound can be produced under reaction conditions at a gas hourly space velocity (GHSV) of 300 milliliters/grams/hour (ml/g/h) to 2,000 ml/g/h.
  • GHSV gas hourly space velocity
  • the GHSV can be in a range derived from any two exemplary values. 1000 to 3000 ml/g/hr.
  • a zeolite catalyst can be used in a methane dehydroaromatization reaction, for example a Mo/ZSM-5, Mo/ZSM-11 and Mo/MCM22 catalyst can be used.
  • a ZSM-5 catalyst can be used in a methane dehydroaromatization reaction, e.g., a molybdenum oxide ZSM-5 (Mo-oxide/ZSM-5) catalyst.
  • a Mo-oxide/ZSM-5 catalyst provides good catalytic performance, a high aromatic compound selectivity and productivity (for example greater than 85%, and even as high as 90% selectivity), a high hydrocarbon conversion (for example conversion greater than or equal to 6%).
  • Coke build up on the Mo-oxide/ZSM-5 catalyst can reduce catalyst performance and catalyst lifetime.
  • the method disclosed herein reduces coke build up on a Mo-oxide/ZSM-5 catalyst, thereby increasing the productivity of the methane dehydroaromatization reaction and the lifetime of the catalyst maintained a conversion of greater than 8% for at least 10 hours (hrs), for example, for 20 hrs.
  • the Mo-oxide/ZSM-5 catalyst can be reduced with hydrogen to form methane for several cycles and periodically cooled and exposed to oxygen (e.g., dilute oxygen) to form CO/C0 2 , as shown in Figures 3, 4, and 5.
  • the regeneration of the coked catalyst with hydrogen can be carried out at the temperature (700°C to 850°C or above).
  • the hydrogen regeneration can be at a temperature of 750°C to 850°C, e.g., 770°C to 825°C, or 800°C to 850°C.
  • the hydrogen stream can be pure hydrogen (for example 100 vol% hydrogen), or 90 vol% hydrogen or greater.
  • the hydrogen stream can be added directly to the methane dehydroaromatization reactor for the first regeneration of the Mo-oxide/ZSM-5 catalyst.
  • the hydrogen flow (GHSV) could be, for example, 1,000 to 3,000 ml/g/hr for 30 to 60 min for every 15 to 30 min reaction cycle. In other words, after each 15 to 30 min reaction cycle for the production of the aromatic compound, the catalyst can be regenerated with a hydrogen flow of 1,000 to 3,000 ml/g/hr for 30 to 60 min.
  • the hydrogen gas can be supplied from the product stream of the methane dehydroaromatization reaction.
  • the product stream of the methane dehydroaromatization reaction can be processed further to separate pure hydrogen from the remainder of the products.
  • the hydrogen separated from the product stream can be greater than 90 vol% hydrogen.
  • the hydrogen separated from the product stream with no more than 0.1 to 3% residual methane of the methane dehydroaromatization reaction can be used as the hydrogen stream for catalyst regeneration to save cost of supplying an additional hydrogen stream.
  • Coke removal by oxidation can be carried out with oxygen (e.g., dilute oxygen) at 400°C to 600°C, preferably at 500°C to 550°C.
  • oxygen e.g., dilute oxygen
  • the catalyst bed can be cooled to below 600°C (e.g., to 500 to 550°C) for regeneration with oxygen. Regeneration with oxygen at higher temperatures can damage the Mo-oxide/ZSM-5 catalyst.
  • the oxygen can be introduced, e.g., at a GHSV of 1,000 to 3,000 ml/g/hr for about 30 to 60 min to complete the regeneration.
  • the oxygen can be consumed by oxidizing the coke to C0 2 or CO.
  • the catalyst bed can be heated back to reaction temperature of 700°C to 850°C.
  • an inert gas is flowing (e.g., a gas that does not react with the catalyst, such as nitrogen gas) during the heating of the catalyst to sweep away any unreacted oxygen.
  • the oxygen regeneration can be based upon changes in the catalyst activity.
  • an initial catalyst activity AO can be determined (e.g., of the fresh catalyst).
  • the catalyst activity e.g., reaction catalyst activity (AO) can be monitored.
  • the reaction catalyst activity can be compared to the initial catalyst activity such that when the reaction catalyst activity is at least 30% (preferably at least 25%) less than the initial catalyst activity, the catalyst can be regenerated with oxygen.
  • the following equation can be used to determine when to regenerate the catalyst with oxygen:
  • the catalyst is regenerated with oxygen when the following equation is met:
  • the percent conversion using the catalyst with both hydrogen and oxygen based regeneration can be maintained at 6% and 12% for 1,000 minutes, and even for 1,440 minutes.
  • the conversion to the aromatic compound can be maintained at greater than or equal to 7% for 500 min., for example, for 800 min, and even for 1,000 min.
  • the conversion to the aromatic compound can be maintained at greater than or equal to 8% for 800 min., and even for 1,000 min.
  • the conversion to the aromatic compound can be maintained at greater than or equal to 9% for 800 min.
  • the selectivity and productivity of benzene, and an activity preservation ratio (APR) of the catalyst composition can be measured at time-on-stream (TOS) in the range from 1 hour to 40 hours.
  • TOS time-on-stream
  • the TOS can range from 3 hours to 38 hours, or from 5 hours to 30 hours, or from 8 hours to 25 hours.
  • the benzene yield of the disclosed catalyst composition including regeneration with both hydrogen and oxygen can be greater than or equal to 7%, even greater than or equal to 7.2%, when measured at a temperature between 670°C and 720°C.
  • the APR of the catalyst composition with regeneration with both pure hydrogen and dilute oxygen in the conversion of the methane to an aromatic compound, at 24 hours, can be 70% to 97%, for example 75% to 85%, or 75% to 80%.
  • the APR of the catalyst composition with regeneration with both pure hydrogen and dilute oxygen in the conversion of the methane to an aromatic compound can be at least 95.6 % or greater at 24 hours.
  • the APR of the catalyst composition with regeneration with both pure hydrogen and dilute oxygen in the conversion of the methane to an aromatic compound can be 97% or greater at 24 hours.
  • a methane to benzene reaction was carried out in a fixed bed reactor using a Mo zeolite catalyst, charged into a quartz tubular down-flow reactor.
  • the performance of the Mo zeolite catalyst was studied at a temperature 700 °C to 800 °C at a gas hourly space velocity of 525 to 3,000 ml/g/hr.
  • the catalyst was first pre-carburized and then the reaction was started. Reaction was carried out under 100% methane for 15 minutes followed by 30 minutes of hydrogen regeneration at a temperature 800 to 850°C.
  • the major products of the methane to benzene reaction are benzene, toluene, naphthalene and coke.
  • Coke formation on the surface of the catalyst blocks the pores which results in the deactivation of the catalyst.
  • the coke was removed from the surface of the catalyst using hydrogen regeneration and periodic oxygen regeneration. Oxygen regeneration was carried out at 450 to 600°C for 15 to 60 min. Temperatures were raised again to 700 °C to 800 °C in presence of methane after the dilute oxygen regeneration.
  • Oxygen regenerations were done at 450 to 600°C when the catalyst activity fell below 25% of the initial catalyst activity.
  • the benzene yields during these 72 cycles were stable which shows that the catalyst was active during all these cycles.
  • Benzene selectivity during all these 75 cycles was found to be between 85 to 100 mol% as shown in Figure 2.
  • Embodiment 1 A method for dehydroaromatization of methane, comprising: passing a feedstock comprising methane gas to an aromatization reactor; converting a portion of the methane gas in the feedstock to aromatic hydrocarbons with a dehydroaromatization catalyst at a reaction temperature of 700°C to 850°C; and regenerating at least a portion of the dehydroaromatization catalyst by contacting the dehydroaromatization catalyst with a first regeneration gas stream comprising hydrogen at a temperature of 700°C to 850°C, preferably 800°C to 850°C, contacting the dehydroaromatization catalyst with a second regeneration gas stream comprising 0.1 to 20 vol.% oxygen at a temperature of 400°C to 600°C.
  • Embodiment 2 A method of regenerating a dehydroaromatization catalyst used to convert methane to an aromatic compound, the method comprising: contacting the deactivated dehydroaromatization catalyst with a first regeneration gas stream comprising hydrogen at a temperature of 700°C to 850°C; and contacting the deactivated dehydroaromatization catalyst with a second regeneration gas stream comprising 0.1 to 10 vol.% oxygen at a temperature of 400°C to 600°C.
  • Embodiment 3 The method of any of the preceding Embodiments, wherein the second regeneration gas stream comprises 3 vol.% to 8 vol.% oxygen.
  • Embodiment 4 The method of any of Embodiments 1 - 2, wherein the second regeneration gas stream comprises 0.1 vol.% to 5 vol.% oxygen.
  • Embodiment 5 The method of any of any of Embodiments 1 - 2, wherein the second regeneration gas stream comprises air.
  • Embodiment 6 The method of any of the preceding Embodiments, wherein the deactivated dehydroaromatization catalyst is contacted with the first regeneration gas for at least 15 minutes, at a rate of at least 800 ml/g/h at STP conditions.
  • Embodiment 7 The method of any of the preceding Embodiments, wherein the deactivated dehydroaromatization catalyst is contacted with the second regeneration gas for at least 15 minutes, at a rate of at least 800 ml/g/h at STP conditions.
  • Embodiment 8 The method of any of the preceding Embodiments, wherein the first regeneration gas stream further comprises an inert gas.
  • Embodiment 9 The method of any of the preceding Embodiments, wherein the dehydroaromatization catalyst includes a zeolite-based catalyst.
  • Embodiment 10 The method of any of the preceding claims, further comprising determining an initial catalyst activity of the dehydroaromatization catalyst; monitoring a reaction catalyst activity of the dehydroaromatization catalyst; comparing the reaction catalyst activity to the initial catalyst activity; and when the reaction catalyst activity is at least 25% less than the initial catalyst activity, contacting the dehydroaromatization catalyst with the second regeneration gas stream.
  • Embodiment 11 The method of Embodiment 10, wherein the comparing is performed subsequent to contacting the dehydroaromatization catalyst with the first regeneration gas stream.
  • Embodiment 12 The method of any of the preceding embodiments, further comprising, subsequent to contacting the dehydroaromatization catalyst with the second regeneration gas stream, heating the dehydroaromatization catalyst back to the reaction temperature while flowing an inert gas over the dehydroaromatization catalyst.
  • Embodiment 13 The method of Embodiment 11, wherein the inert gas is nitrogen gas.
  • Embodiment 14 The method of any of the preceding embodiments, wherein the dehydroaromatization conditions include a time period of 1-30 mins, and a gas hourly space velocity of 1,000 -ml/g/h to 20,000 ml/g/h at STP conditions.
  • test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Cette invention concerne un procédé de déshydroaromatisation du méthane comprenant : le passage d'une charge comprenant du gaz méthane dans un réacteur d'aromatisation ; la conversion d'une partie du gaz méthane contenu dans la charge en hydrocarbures aromatiques à l'aide d'un catalyseur de déshydroaromatisation à une température de réaction de 700 à 850 °C ; et la régénération d'au moins une partie du catalyseur de déshydroaromatisation par mise en contact du catalyseur de déshydroaromatisation avec un premier flux de gaz de régénération contenant de l'hydrogène à une température de 700 à 850 °C, de préférence de 800 à 850 °C, et mise en contact du catalyseur de déshydroaromatisation avec un second flux de gaz de régénération contenant de 0,1 à 20 % en volume d'oxygène à une température de 400 à 600 °C.
PCT/IB2017/058456 2016-12-29 2017-12-28 Procédé de déshydroaromatisation avec régénération du catalyseur WO2018122758A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110980640A (zh) * 2019-12-31 2020-04-10 湘潭大学 一种催化甲烷直接转化制氢的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070249740A1 (en) * 2006-04-21 2007-10-25 Iaccino Larry L Production of aromatics from methane
US20090030253A1 (en) * 2007-07-24 2009-01-29 Teng Xu Production of Aromatics from Aliphatics
EP2140939A1 (fr) * 2007-06-07 2010-01-06 Meidensha Corporation Procédé de régénération d'un catalyseur d'aromatisation d'hydrocarbures inférieurs
US20100312029A1 (en) * 2007-12-05 2010-12-09 Dow Global Technologies Inc. Continuous process for oxygen-free conversion of methane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070249740A1 (en) * 2006-04-21 2007-10-25 Iaccino Larry L Production of aromatics from methane
EP2140939A1 (fr) * 2007-06-07 2010-01-06 Meidensha Corporation Procédé de régénération d'un catalyseur d'aromatisation d'hydrocarbures inférieurs
US20090030253A1 (en) * 2007-07-24 2009-01-29 Teng Xu Production of Aromatics from Aliphatics
US20100312029A1 (en) * 2007-12-05 2010-12-09 Dow Global Technologies Inc. Continuous process for oxygen-free conversion of methane

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110980640A (zh) * 2019-12-31 2020-04-10 湘潭大学 一种催化甲烷直接转化制氢的方法

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