EP2984155A1 - System and process for converting natural gas into saturated, cyclic hydrocarbons - Google Patents
System and process for converting natural gas into saturated, cyclic hydrocarbonsInfo
- Publication number
- EP2984155A1 EP2984155A1 EP14782942.8A EP14782942A EP2984155A1 EP 2984155 A1 EP2984155 A1 EP 2984155A1 EP 14782942 A EP14782942 A EP 14782942A EP 2984155 A1 EP2984155 A1 EP 2984155A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrogen
- reaction zone
- separation membrane
- dehydroaromatization
- reaction
- 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- Withdrawn
Links
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
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
- C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
-
- 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
Definitions
- the present invention relates to method for the production of saturated, cyclic hydrocarbons from methane. More particularly, the present invention produces aromatic intermediates via dehydroaromatization (DFLA) of methane followed by hydrogenation of the intermediates to form saturated, cyclic hydrocarbons such as cyclohexane and decalin.
- DFLA dehydroaromatization
- Benzene which is currently produced from crude oil, is a chemical of great industrial importance with current global consumption in excess of 30 million metric tons per annum and net growth of 4% annually, leading to a total market size of more than $50,000,000,000. It is a starting material for nylons, polycarbonates, polystyrene and epoxy resins. Also, benzene can be directly converted to aniline, chlorobenzene, maleic anhydride, succinic acid, and countless other useful industrial chemicals. Benzene is a gasoline component and can be converted to cyclohexane, another gasoline component via a commercial process.
- Benzene can be synthesized from natural gas (methane) using a catalyst in a single step via dehydroaromatization (DHA) route in the absence of oxygen as follows:
- Cyclohexane and decalin are cyclic hydrocarbons of great industrial importance.
- Cyclohexane is the raw material for production of adipic acid and caprolactum at industrial scales, which are further used to produce Nylon 6 and Nylon 66 respectively.
- Cyclohexane is also used as a solvent for a variety of applications and is a gasoline component.
- Decalin is used as a solvent for a number of industrial applications.
- Cyclohexane is produced industrially via hydrogenation of benzene, wherein the benzene is produced in turn via catalytic reforming of light naphtha, toluene hydrodealkylation, or steam cracking of heavy naphtha.
- the primary raw material for all of these processes is petroleum crude.
- Decalin is produced from hydrogenation of naphthalene, which is in turn produced from coal tar or petroleum.
- an apparatus to produce one or more cyclic, saturated hydrocarbons includes: a first reaction zone comprising a dehydroaromatization catalyst; a second reaction zone comprising a hydrogenation catalyst; a first inlet that provides a reactant hydrocarbon to the first reaction zone; a heater for heating the first reaction zone; a hydrocarbon transfer conduit located between the first and second reaction zones; a hydrogen transfer conduit located between the first and second reaction zones; and a hydrogen separation membrane disposed between the first reaction zone and the hydrogen transfer conduit.
- hydrocarbons includes: contacting a reactant hydrocarbon with a dehydroaromatization catalyst in a first reaction zone to produce one or more aromatic intermediates; heating the first reaction zone; removing hydrogen from the first reaction zone through a hydrogen separation membrane; transferring the aromatic intermediate from the first reaction zone to the second reaction zone; providing the separated hydrogen to the second reaction zone; and contacting the aromatic intermediate with a hydrogenation catalyst in a second reaction zone resulting in one or more cyclic, saturated hydrocarbons.
- the first and second reaction zones are located in a single reactor. In some embodiments, the first and second reaction zones are located in separate reactors.
- the hydrogenation catalyst is nickel or cobalt.
- the hydrogen separation membrane selectively transports H + ions under a hydrogen partial pressure gradient, a concentration gradient, or an applied voltage.
- the hydrogen separation membrane comprises a perovskite, a doped cerate, a doped zirconate, or an acidic phosphate.
- the hydrogen separation membrane comprises a Ba-cerate ceramic composite.
- the apparatus includes a hydrocarbon separator capable of separating reactant hydrocarbon from the first reaction zone.
- the apparatus includes a vacuum means operably connected to the hydrogen separation membrane and hydrogen transfer conduit.
- the reactant hydrocarbon is methane.
- the method includes periodically regenerating the dehydroaromatization catalyst by contacting the dehydroaromatization catalyst with hydrogen.
- the one or more cyclic, hydrocarbons includes decalin. In some embodiments, the one or more cyclic, hydrocarbons includes cyclohexane.
- Figure 1 depicts the combination of a hydrogen separation membrane and a dehydroaromatization catalyst usable in the disclosed system and process.
- Figure 2 depicts a system for efficient dehydroaromatization of a reactant composition to produce an aromatic hydrocarbon using a combination of a hydrogen separation membrane and a dehydroaromatization catalyst.
- Figure 3 depicts another system for efficient dehydroaromatization of a reactant composition to produce an aromatic hydrocarbon using a combination of a hydrogen separation membrane and a dehydroaromatization catalyst.
- Figure 4 is a schematic representation of a system for dehydroaromatization of a reactant composition to produce an aromatic hydrocarbon.
- Figure 5 is schematic representation of a CHEMKIN® chemical model and simulation methodology for the disclosed system and process.
- Figure 6 is a graph of experimental results compared with chemical model simulated product selectivities as a function of methane conversion.
- Figure 7 is a conceptual model of six equilibrium reactors used by chemical process simulation software to evaluate methane conversion as a function of percentage hydrogen removal.
- Figure 8 is a graph showing the results of the chemical process simulation evaluating methane conversion as a function of percentage hydrogen removal.
- Figure 9 depicts a system for producing saturated, cyclic hydrocarbons using an embodiment of the invention.
- Figure 10 is a graph showing the results of a chemical process simulation for conversion of methane to aromatic hydrocarbon intermediates with benzene selectivity and yield as a function of hydrogen removal in an embodiment of the invention.
- Fig. 1 depicts some features of the system and process schematically.
- the system 100 includes a first reaction zone 110 containing a dehydroaromatization catalyst 112.
- a reactant composition is supplied to the first reaction zone 110.
- the reactant composition may comprise one or more C C 4 alkanes, including by not limited to methane, ethane, propane, and butane.
- the reactant comprises natural gas.
- Fig. 1 depicts a reactant composition comprising methane.
- Methane undergoes dehydroaromatization in the presence of catalyst 112 to produce one or more aromatic hydrocarbons.
- Intermediate compounds are typically produced, such as methane radical ( # CH 3 ) and ethylene (C 2 H ).
- Fig. 1 depicts the formation of the aromatic hydrocarbons benzene 114 and naphthalene 116.
- the dehydroaromatization reaction releases hydrogen.
- a hydrogen separation membrane 118 is disposed between the reaction zone 110 and a hydrogen stream exit 120.
- the reaction zone 110 is on the retentate side of the membrane 118 and the hydrogen stream exit 120 is on the permeate side of the membrane.
- the hydrogen separation membrane 118 selectively removes hydrogen produced in the reaction zone 110.
- Fig. 1 depicts the hydrogen separation membrane 118 disposed on a porous substrate 122.
- a porous substrate may be advantageous depending upon the strength and thickness of the membrane 118.
- Dehydroaromatization catalysts 112 are known. Some suitable catalysts are metal/zeolite catalysts based on HZSM-5 zeolites. Several different metals have been proposed, including molybdenum, tungsten, rhenium, vanadium, and zinc, with the HZSM-5 zeolites.
- the rhenium exchanged zeolite (Re/ZSM-5) catalyst is a presently preferred dehydroaromatization catalyst because Re-based H-ZSM5 systems are superior in reactivity, selectivity and stability than the Mo-based systems.
- the hydrogen separation membrane 118 is a ceramic membrane that selectively transports H + ions at dehydroaromatization operating temperatures.
- a variety of metallic, ceramic and polymer membranes have been used for H 2 separation from gas streams. The most common metallic membrane materials are palladium (Pd) and palladium alloys. However, these materials are expensive, strategic and less suitable for H 2 separation from dehydroaromatization reaction since Pd promotes coking.
- a number of organic membranes e.g. Nafion® a registered mark of the Dupont Corporation
- the invention preferably uses a ceramic hydrogen separation membrane 118 that can withstand operation temperatures under a wide range of high-temperatures and that are suitable for promoting the DHA reaction.
- the hydrogen separation membrane 118 is thermally stable and effective at a temperature above 800°C.
- the hydrogen separation membrane 118 selectively transports H + ions under a hydrogen partial pressure gradient, a concentration gradient, or an applied voltage.
- Non-limiting examples of materials from which the hydrogen separation membrane 118 is fabricated include a perovskite, a doped cerate, a doped zirconate, or an acidic phosphate.
- the hydrogen separation membrane 118 comprises barium.
- the membrane 118 comprises cerate.
- the membrane 118 is a composite comprising BaCe0 3 and an electronic conducting phase. The membrane may comprise a 10-30 ⁇ pinhole-free dense membrane.
- Fig. 2 illustrates one non-limiting system to produce an aromatic hydrocarbon via catalyzed nonoxidative dehydroaromatization.
- the system 200 includes a first reaction zone 210 containing a dehydroaromatization catalyst 212.
- a reactant composition 213 is supplied to the first reaction zone 210.
- the reactant composition 213 may comprise one or more C C 4 alkanes, including but not limited to methane, ethane, propane, and butane.
- the reactant composition comprises natural gas.
- Fig. 2 depicts a reactant composition 213 comprising methane. Methane undergoes dehydroaromatization in the presence of catalyst 212 to produce one or more aromatic hydrocarbons 214.
- Fig. 2 depicts the formation of benzene (C 6 H 6 ) as the aromatic hydrocarbon 214.
- Other aromatic hydrocarbons may be produced, including but not limited to, toluene, ethylbenzene, styrene, xylene or naphthalene.
- the dehydroaromatization reaction may also produce a benzene precursor, such as ethylene.
- the dehydroaromatization reaction of methane releases hydrogen according to the reaction, 6CH ⁇ C 6 H 6 + 9H 2 .
- a hydrogen separation membrane 218 is disposed between the reaction zone 210 and a hydrogen stream exit 220.
- a vacuum or negative pressure may be applied to the hydrogen stream exit 220 to facilitate hydrogen removal.
- the pressure differential may also facilitate hydrogen transporting across the hydrogen separation membrane 218 from the first reaction zone 210 to the hydrogen stream exit 220.
- a heater 224 may be provided to control and maintain the reaction zone 210 at a suitable dehydroaromatization temperature.
- the dehydroaromatization reaction typically occurs at a temperature in the range from about 500°C to 1000°C. In some embodiments, the dehydroaromatization reaction occurs at a temperature in the range from about 700°C to 900°C.
- the system 200 depicted in Fig. 2 shows a center hydrogen stream exit 220 surrounded by the reaction zone 210.
- This configuration may be constructed using concentric tubes, with the center tube being fabricated of a ceramic hydrogen separation membrane material and the outer tube being fabricated of a suitable temperature resistant and inert material.
- the configuration shown in Fig. 2 may be constructed of parallel plates with suitable sidewalls and seals to form the first reaction zone 210 and hydrogen stream exit 220.
- Fig. 2 depicts the dehydroaromatization catalyst 212 disposed in close proximity to the hydrogen separation membrane 218, it is to be understood that the relative sizes and distances shown in Fig. 2 are for illustration only.
- the catalyst may substantially fill the reaction zone 210.
- the outer walls 226 may be disposed close to the catalyst.
- Fig. 3 depicts another non-limiting system to produce an aromatic hydrocarbon via catalyzed nonoxidative dehydroaromatization.
- the system 300 of Fig. 3 is a variation of the system 200 of Fig. 2 and not all common features are illustrated and discussed below.
- the system 300 includes a first reaction zone 310 containing a dehydroaromatization catalyst 312.
- a reactant composition 313 is supplied to the reaction zone 310.
- Fig. 3 depicts a reactant composition 313 comprising methane. Methane undergoes dehydroaromatization in the presence of catalyst 312 to produce one or more aromatic hydrocarbons 314.
- a hydrogen separation membrane 318 is disposed between the reaction zone 310 and a hydrogen stream exit 320. As mentioned above, the reaction zone 310 is on the retentate side of the membrane 318 and the hydrogen stream exit 320 is on the permeate side of the membrane.
- the system 300 depicted in Fig. 3 shows multiple first reaction zones 310, multiple hydrogen separation membranes 318, and multiple hydrogen stream exits 320. It will be appreciated that even more first reaction zones 310, combined with hydrogen separation membranes 318 and hydrogen stream exits 320, may be included in alternative systems. Such configurations may be constructed of stacked parallel plates with suitable sidewalls and seals to form the disclosed reaction zones 310 and hydrogen stream exits 320.
- Fig. 4 shows a schematic representation of a non-limiting system 400 to produce an aromatic hydrocarbon (AHC) via catalyzed nonoxidative dehydroaromatization.
- a reactant feed stream 430 supplies a reactant composition (R) to a reactor 440.
- the reactor 440 includes one or more reaction zones dehydroaromatization catalyst as disclosed above.
- the reactor 440 also includes one or more hydrogen separation membranes which enable continuous removal of hydrogen from the reaction zone(s).
- a hydrogen stream exit 450 which may provide collection of hydrogen from multiple reaction zones, allows for removal and recovery of hydrogen produced during the dehydroaromatization reaction.
- a product stream exit 460 removes the aromatic hydrocarbon (AHC) produced by the nonoxidative dehydroaromatization of the reactant composition (R) from the reactor 440.
- a hydrogen recycle stream 480 diverts a portion of hydrogen from the hydrogen stream exit 450 and adds the portion of hydrogen to the reactant composition (R) supplied to the reactor 440.
- the hydrogen may also be used to regenerate the dehydroaromatization catalyst. As hydrogen is removed from reactant composition, the resulting hydrocarbon becomes more carbon-rich until coke is formed on the catalyst. Coke deactivates the catalyst.
- the catalyst may be regenerated by exposing the coke with hydrogen and forming methane according to the following reaction: C + 2H 2 ⁇ CH . Catalyst regeneration may be achieved by closing the supply of reactant composition to the reactor with valve 490 and instead supplying hydrogen via the recycle stream 480. To enable continuous operation multiple systems 400 may be used in parallel or series such that while one system is stopped to regenerate the catalyst, other systems may continue operation uninterrupted.
- benzene can be produced from natural gas in a single step conversion processes via the dehydroaromatization (DHA) route in the absence of oxygen as follows:
- the reaction also produces naphthalene and to a limited extent ethylene.
- the process suffers from limited equilibrium conversion at high temperature (12% conversion at 700°C). Overcoming the equilibrium limitation requires continuous separation of hydrogen at the reaction temperature. Nearly 100% single pass conversion can be enabled with complete removal of hydrogen. Further, the separated hydrogen can be utilized as a feedstock for subsequent hydrogenation reactions.
- benzene conversion to cyclohexane is carried out via hydrogenation over a nickel (Ni), cobalt (Co) or precious metal catalyst supported on Alumina or similar support.
- Ni nickel
- Co cobalt
- the reaction proceeds as follows:
- Suitable precious metal catalysts include palladium and platinum.
- the catalyst may be in the form of oxidized forms such as Pt0 2 .
- the hydrogenation reaction is simple. It requires a hydrogen source however. It is costly to produce hydrogen as it requires a steam reformer for conversion from methane. Methane is converted syngas (a mixture of CO and H 2 ). Thus, the production of hydrogen often leads to C0 2 emissions from the carbon content in methane. It would, therefore, be beneficial to have a supply of hydrogen that is not produced from a steam reformer. Hydrogen produced from the dehydroaromitization processes discussed above can be used as a substitute for the reformer source of hydrogen.
- a method of producing one or more saturated, cyclic hydrocarbons includes conversion of natural gas to benzene and naphthalene in a catalyst-membrane reactor; separating hydrogen from the reaction mixture at the temperature of the reaction (700 - 900°C) to significantly increase the single pass conversion; adding separated hydrogen in a separate reactor wherein benzene from the first reactor is fed over a catalyst; or adding the separated hydrogen in a separate reactor wherein naphthalene from the first reactor is fed over a catalyst.
- the two reactors are in series.
- the two reactions can occur simply in a single reactor with two reaction zones wherein the first reaction zone converts natural gas to benzene and naphthalene and comprises a membrane to separate hydrogen.
- the second reaction zone contains a hydrogenation catalyst to convert benzene to cyclohexane and naphthalene to decalin.
- the second reactor (or reaction zone) converts benzene to cyclohexane and naphthalene to decalin over a hydrogenation catalyst such as nickel, cobalt or a precious metal.
- a hydrogenation catalyst such as nickel, cobalt or a precious metal.
- the conversion of benzene to cyclohexane and conversion of naphthalene to decalin can be carried out in the same reactor or two different reactors.
- the unreacted natural gas (methane) is separated and recycled back to the first reaction zone.
- Fig. 9 depicts some features of the system and process schematically.
- the system 600 includes a first reaction zone 610 containing a dehydroaromatization catalyst 612.
- a reactant composition is supplied to the first reaction zone 610 via an inlet 630.
- the reactant composition may comprise one or more C C 4 alkanes, including by not limited to methane, ethane, propane, and butane.
- the reactant comprises natural gas.
- Methane undergoes dehydroaromatization in the presence of catalyst 612 to produce one or more aromatic hydrocarbons.
- Intermediate compounds are typically produced, such as methane radical ( # CH 3 ) and ethylene (C 2 H ).
- the dehydroaromatization reaction releases hydrogen.
- a hydrogen separation membrane 618 is disposed between the reaction zone 610 and a hydrogen stream exit 620.
- the reaction zone 610 is on the retentate side of the membrane 618 and the hydrogen stream exit 620 is on the permeate side of the membrane.
- the hydrogen separation membrane 618 selectively removes hydrogen produced in the reaction zone 610.
- a separator may be used to separate the different aromatic intermediates present in the effluent of the first reaction zone. For example, benzene may be separated from naphthalene using a flash drum or other flash evaporation.
- a separator may be used to separate the unreacted hydrocarbon (e.g. methane) from reacted hydrocarbon (e.g. benzene). The separator may, therefore, serve the purpose of enabling recycling of unreacted feed stream
- a separator may be used to separate the different saturated, cyclic hydrocarbons present in the effluent of the second reaction zone.
- cyclohexane may be separated from decalin using a distillation column.
- the CHEMKIN® chemistry simulation results suggest that bi-functional catalysts, such as Metal/H-ZSM5, with continuous H 2 removal provide almost complete CH conversion at practical residence time (100 s) and intermediate values of dimensionless transport rates (ratio of permeation to reaction of 1-10. For currently available hydrogen separation membrane materials, such values suggest a membrane thickness less than 100 ⁇ of dense ceramic material.
- the model results also mapped appropriately with experimental data as shown in Fig. 6 which graphically presents experimental results verses chemical model simulated product selectivities as a function of methane conversion, which was varied by changing the reactor residence time at constant temperature (950 K) and inlet methane partial pressure (0:5 bar) and by allowing the number of sites within the reactor to decrease as deactivation occurs.
- Fig. 10 is a graph showing the results of a chemical process simulation for conversion of methane to aromatic hydrocarbon intermediates with benzene selectivity and yield as a function of hydrogen removal. Reactor and process modeling was performed using Matlab (version R2013b) and Aspen Plus (version 8.0), respectively.
- the reactor scheme in Matlab consists of isothermal differential plug flow reactor equations describing a set of three equilibrium reactions.
- the reactor simulations are carried out at 973 K and 1.01 bar with reactor dimensions of 1.47 cm radius and 1.8 cm length. Inputs to the simulation are the feed composition (85% methane, 15% argon) and flow (27.3 seem), hydrogen removal, equilibrium constants, and reaction rate constants.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361809914P | 2013-04-09 | 2013-04-09 | |
PCT/US2014/033516 WO2014169047A1 (en) | 2013-04-09 | 2014-04-09 | System and process for converting natural gas into saturated, cyclic hydrocarbons |
Publications (2)
Publication Number | Publication Date |
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EP2984155A1 true EP2984155A1 (en) | 2016-02-17 |
EP2984155A4 EP2984155A4 (en) | 2017-01-04 |
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EP14782942.8A Withdrawn EP2984155A4 (en) | 2013-04-09 | 2014-04-09 | System and process for converting natural gas into saturated, cyclic hydrocarbons |
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EP (1) | EP2984155A4 (en) |
WO (1) | WO2014169047A1 (en) |
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CN111320518B (en) * | 2018-12-14 | 2021-08-31 | 中国科学院大连化学物理研究所 | Method for preparing olefin and aromatic hydrocarbon by hydrogen-assisted methane activation |
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US6296687B2 (en) * | 1999-04-30 | 2001-10-02 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources | Hydrogen permeation through mixed protonic-electronic conducting materials |
IT1317757B1 (en) * | 2000-02-03 | 2003-07-15 | Enitecnologie Spa | METHOD FOR THE PREPARATION OF HYDROGENATED HYDROCARBONS. |
KR20030031916A (en) * | 2000-07-27 | 2003-04-23 | 코노코필립스 컴퍼니 | Catalyst and process for aromatic hydrocarbons production from methane |
RU2417974C2 (en) * | 2004-12-22 | 2011-05-10 | Эксонмобил Кемикэл Пейтентс Инк. | Synthesis of alkylated aromatic hydrocarbons from methane |
RU2405764C2 (en) * | 2004-12-22 | 2010-12-10 | Эксонмобил Кемикэл Пейтентс, Инк. | Production of liquid hydrocarbons from methane |
CN101316807B (en) * | 2005-10-28 | 2012-11-28 | 巴斯夫欧洲公司 | Method for the synthesis of aromatic hydrocarbons from C1-C4 alkanes, and utilization of a C1-C4 alkane-containing product flow |
WO2007123977A2 (en) * | 2006-04-21 | 2007-11-01 | Exxonmobil Chemical Patents Inc. | Production of aromatics from methane |
US7781636B2 (en) * | 2006-04-21 | 2010-08-24 | Exxonmobil Chemical Patents Inc. | Process for methane conversion |
US20100312029A1 (en) * | 2007-12-05 | 2010-12-09 | Dow Global Technologies Inc. | Continuous process for oxygen-free conversion of methane |
CN101945703B (en) * | 2008-02-21 | 2013-05-08 | 埃克森美孚化学专利公司 | Production of aromatics from methane |
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2014
- 2014-04-09 EP EP14782942.8A patent/EP2984155A4/en not_active Withdrawn
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WO2014169047A1 (en) | 2014-10-16 |
EP2984155A4 (en) | 2017-01-04 |
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