WO2010069582A1 - Procédé de conversion de méthane, contenu dans des courants gazeux, en hydrocarbures hydrogénés liquides - Google Patents

Procédé de conversion de méthane, contenu dans des courants gazeux, en hydrocarbures hydrogénés liquides Download PDF

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WO2010069582A1
WO2010069582A1 PCT/EP2009/009108 EP2009009108W WO2010069582A1 WO 2010069582 A1 WO2010069582 A1 WO 2010069582A1 EP 2009009108 W EP2009009108 W EP 2009009108W WO 2010069582 A1 WO2010069582 A1 WO 2010069582A1
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process according
treatment
previous
gas
methane
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PCT/EP2009/009108
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English (en)
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Luigina Maria Flora Sabatino
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Eni S.P.A.
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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/16—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring
    • C07C13/18—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring with a cyclohexane ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/47—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing ten carbon atoms
    • C07C13/48—Completely or partially hydrogenated naphthalenes
    • C07C13/50—Decahydronaphthalenes
    • 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
    • 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
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • 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
    • 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
    • B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/90—Regeneration or reactivation
    • 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
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/14—All rings being cycloaliphatic
    • C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
    • C07C2602/28—Hydrogenated naphthalenes
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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

  • the present invention relates to a process for the conversion of methane, contained in gaseous streams, into hydrogenated liquid hydrocarbons.
  • the present invention relates to a process for the preparation of hydrogenated hydrocarbons, consisting in treating a gas containing methane, of both a fossil and biological origin, at a high temperature, with a suitable catalyst, in order to prepare a mixture of higher hydrocarbons essentially consisting of cyclic and/or aromatic hydrocarbons, and subjecting the mixture obtained to hydrogenation.
  • the process object of the present invention is particularly useful for the conversion of gas containing methane, present close to oil fields or deriving from biological processes, for the collection, sorting and transportation of the product.
  • the same process is par- ticularly advantageous for the recovery and use of so- called associated gas and gas of a biological origin.
  • the objectives of refinery and chemical plant activities comprise the transformation of hydrocarbons having a relatively low value into more valuable hydrocarbon streams, or into actual chemical products.
  • Methane for example, the simplest of saturated hydrocarbons, can often be found in large quantities as by-product in mixtures with other hydrocarbons having a higher molecular weight, or as gas component at the out- let of process units.
  • methane is effectively used in some chemical reactions (such as the production of methanol and formaldehyde) , it is not as useful as hydrocarbons with a higher molecular weight . For this reason, process streams containing methane are normally burnt as fuel.
  • European patent application 192,289 describes the direct conversion of natural gas into aromatic hydrocarbons, at high temperatures, on a catalyst based on alka- line silicate and also includes aluminium and/or gallium.
  • International patent application WO 92/01656 describes the same conversion in the presence of a transition metal supported on a refractory material, essentially consisting of a metal oxide, at temperatures of up to 300 0 C.
  • European patent application 858,987 relates to a process for the conversion of a light hydrocarbon blend, in gaseous phase under normal temperature and pressure conditions and containing methane, into higher hydrocarbons, liquid under normal temperature and pressure conditions.
  • This process includes an absorption step of the mixture in question on a supported metal catalyst comprising a metal or combination of metals, at least one of which belonging to Group VIII of the Periodic System of Elements, followed by a desorption phase.
  • the first step is ef- feeted at temperature values not lower than 300 0 C.
  • the catalyst consisting of molybdenum supported on H- ZSM- 5 zeolite is of interest for the conversion of methane to aromatic compounds, as described in "Journal of Catalysis 181, 175-188 (1999)".
  • the methods for the production of higher hydrocarbons which the above-mentioned state of the art refers to, i.e.
  • the process proposed allows certain streams of natural gas to be upgraded, which could otherwise not be used or which would be difficult to transport as gas, into liquid hydrocarbon products, compatible with the oil itself.
  • the possibility of transforming associated gas into liquid hydrocarbons also enables oil fields to be exploited which, for logistic reasons or environment regulations (restrictions on gas flaring) could not be put into production as they are not capable of treating the gas component .
  • An object of the present invention therefore relates to a process for the direct conversion of methane, con- tained in a blend with other gases, into liquid hydrogen- ated hydrocarbons, which can be obtained with a high selectivity, using a catalyst comprising Mo supported on a zeolite.
  • the process is described in the enclosed claims. All the catalysts mentioned in the state of the art are suitable for the preliminary conversion of methane (natural, associated, biological, etc.) into liquid products .
  • the use can therefore be envisaged of the supported catalyst described in the above-mentioned European patent application EP 858,987, consisting of one or more metals selected from those of Group VIII of the Periodic System of Elements, deposited on a carrier represented by an oxide.
  • the nickel/copper mixture is particularly preferred.
  • the catalytic composition described in International patent application WO 99/03949 can also be used, consist- ing of a mixture including a zeolite and zinc aluminate, previously treated with a reducing gas at a
  • compositions can be used in the process according to the present invention: a catalyst consisting of a zeolite and one or more of the following components: oxides of alkaline and alkaline-earth metals; oxides of Group IIIA; metals of Groups IVB, VB, VIB, VIIB, VIIIB, IB, HB, IHB and a binder consisting of refractory oxides, or a mixture thereof, selected from SiO 2 , Al 2 O 3 , ZrO 2 , TiO 2 , MgO.
  • the zeolite is selected from:
  • Zeolites selected from those mentioned above, wherein part or all of the Al is substituted by B, Fe, Ga, V, Cr;
  • a promoter such as Ru, Rh, Pd, Pt in quantities ranging from 0.001 to 5% preferably from 0.01 to 2% by weight.
  • the catalyst can be formed by one or more of the above-mentioned components, impregnated with an alkaline metal .
  • the metal (s) can be deposited on zeolite by ionic ex- change in solution, ion exchange in the solid state, im- pregnation, precipitation.
  • Various metals can be deposited in a single step or following a step procedure.
  • the intermediates can be simply dried or dried and calcined.
  • the final catalyst is dried and calcined in the presence of air.
  • the process according to the present invention includes a first conversion step of associated gas into liquid products through dehydro-aromatization with the formation of aromatic products (mainly benzene and naphthalene) followed by hy- drogenation, which allows naphthenic products to be obtained.
  • aromatic products mainly benzene and naphthalene
  • the gas conversion can be effected at a temperature value of 350 to 800 0 C, depending on the gas composition and catalyst selected, at a pressure ranging from 0.2 to 5 bar and GHSV ranging from 500 to 50,000 h '1 .
  • the aromatization reaction of methane can be carried out in a reaction area comprising one or more catalytic beds in one or more reactors .
  • the arrangement of reactors can include one or more fixed or mobile bed reactors into which the catalyst, suitably formed, is introduced. All the systems can consist of various beds in series.
  • the gas/solid mixing can be favoured by mechanical stirring or through forced recirculation of the reaction fluids.
  • the circulation of the reagent gas can be effected in countercurrent with respect to the feeding direction of the catalyst particles.
  • the reactor configuration can consist of a reaction area, in turn consisting of one or more catalytic beds, and a regeneration area: portions of exhausted catalyst are periodically extracted from the reaction area to be transferred to the regeneration area.
  • the regeneration is effected by means of a regeneration gas and has the purpose of totally or partially removing the carbonaceous deposits possibly present on the catalyst.
  • the regeneration can be effected in a fixed bed, fluid or ebullated bed.
  • the regeneration beds can be one or more.
  • the catalyst in relation to the regeneration gas used, can be subjected to carburization in an area different from the regeneration and reaction area.
  • the carburization can be effected in one or more beds.
  • the bed can be fixed, fluid or ebullated.
  • the aromatic compounds obtained from the dehydro- aromatization reaction can be separated and possibly hy- drogenated.
  • the hydrogenation can be effected on catalysts consisting of supported metals of Group VIII (Pt, Pd, Ru, Ni) . If noble metals supported on zeolites are used, the hydrogenation effected at 260 to 315°C, at a pressure of 4.2 MPa, an LHSV of 3 to 4 h "1 , proves to be equal to or higher than 95%.
  • catalysts consisting of supported metals of Group VIII (Pt, Pd, Ru, Ni) . If noble metals supported on zeolites are used, the hydrogenation effected at 260 to 315°C, at a pressure of 4.2 MPa, an LHSV of 3 to 4 h "1 , proves to be equal to or higher than 95%.
  • the hydrogenation can be effected by feeding hydrogen to the blend produced during the preliminary high- temperature treatment or, according to a preferred embodiment, the same blend is removed during its formation to be then subjected to hydrogenation on the part of the same hydrogen gas produced and accumulated during the same thermal treatment .
  • the most critical aspect of this process consists in the rapid deactivation of the catalyst. The conversion, in fact, drastically diminishes with the reaction time due to the formation of carbonaceous deposits on the same catalyst.
  • the deactivation can be slowed down by reducing the acidity of the H-ZSM-5 (de-alumination or silanation) or by introducing small quantities of CO, CO 2 , H 2 , H 2 O, in the feed.
  • the effects obtained are extremely limited and unsatisfactory from a technological point of view ⁇ Krzysztof Skutil, Marian Taniewski, Fuel Proc . Techn. , 87 (2006) 511-521) .
  • the promoter selected belongs to the group of lanthanides, in particu- lar, Cerium was selected.
  • the capacity of Cerium oxide of being transformed from CeO 2 (+4) to Ce 2 O 3 (+3) through a relatively low activation energy, at least compared to other oxides, is in fact known.
  • the Ce 2 O 3 ( +3) can be easily re-oxidized to CeO 2 (+4) in an oxidizing environment. Even the loss of a considerable quantity of oxygen and therefore the formation of a large quantity of oxygen vacancies, does not cause variations in the structure of the crystal.
  • the CeO 2 can be used as an oxygen container: 2
  • the Cerium oxide can also be used as a carrier, in the preparation of a mixed carrier, added during the catalyst formation phase.
  • the process for the preparation of the hydrogenated hydrocarbons according to the present invention can be illustrated by the block scheme of Figure 1. It consists of the following units:
  • the hydrogen thus separated in the two separation units is used for the hydrogena- tion of the aromatic compounds, whereas the light hydrocarbons are recycled and, together with methane or its blends, represent the dehydro-aromatization feedstock;
  • the process can additionally include the removal of at least part of the catalyst present in the reaction zone and its regeneration with a suitable regeneration reagent in a regeneration area which can consist of one or more reactors.
  • the regeneration can be effected in a fixed or mobile bed regime.
  • the regeneration can be followed by a re-carburization phase of the catalyst effected in the carburization area which can consist of one or more reactors with a regime of the fixed or mobile bed type.
  • the regenerated catalyst, possibly also re-carburized can be totally or partially recycled, and introduced into the reactor in which the dehydro-aromatization reaction of methane takes place.
  • the carburization can be effected with the use of various carburization agents consisting of a hydrocarbon (methane, ethane, propane, butane, isobutane) alone or in a mixture with hydrogen, or a mixture consisting of hydrogen and CO and/or CO 2 .
  • the carburization can be effected at 300 to 900 0 C, and at a pressure of 1-10 bar.
  • a fixed quantity of catalyst is charged into a conversion reactor.
  • the activation of the catalyst is then effected, which can be carried out at a temperature selected within the range of 350-800 0 C, through a gas flow (for a duration of 15-120 minutes) .
  • the activation can be carried out with an inert gas (He, N 2 , Ar), with a reducing or oxidizing agent. After treating the catalyst in an oxidizing or reducing environment, the flow is substituted by an inert gas (15-20 minutes) . Once the reaction temperature has been reached, the reagent mixture is sent onto the catalyst.
  • an inert gas He, N 2 , Ar
  • a sample was used, under non-oxidizing conditions, consisting of Mo-ZSM-5, with a SiO 2 /Al 2 O 3 molar ratio within the range of 20-100, Mo (w/w) of between 0.5- 15%.
  • the zeolite was prepared according to what is de- scribed in US patent 3,702,886, the Molybdenum was introduced by impregnation, using a solution of ammonium hep- tamolybdate, whereas the promotion with cerium (0.1-5% w/w) was effected by impregnation of Mo/ZSM-5 with a ce- rium salt.
  • the reactor is heated with a slope of 10°C/min to the operating temperature (650- 800 0 C) maintained for 30 minutes under an air flow (100 ml/min) , then for 10 minutes in Argon (100 ml/min) .
  • the reactor is fed with pure methane having a GHSV (Gas Hourly Space Velocity) within the range of 750-1,500 ml/ (g cat h) .
  • GHSV Gas Hourly Space Velocity
  • the characterization of the products in gas phase is effected with a Varian CP-3800 gas chromatograph, using two TCDs as detector.
  • the characterization of the liquids is effected with an HP 5890 gas chromatograph, using a FID as detector.
  • the reaction products initially consist of CO and CO 2 . After about 60 minutes from the beginning of the feeding, the presence of CO and CO 2 is no longer registered and the first products appear, contemporaneously.
  • the conversion is calculated by the ratio: (CH 4 I n - CH 4 OUt) /CH 4 I n .
  • the selectivity is calculated by considering the ratio of the number of carbon atoms contained in the single molecule of product, with respect to the total carbon converted.
  • the performances of the catalyst can be at least partially restored (oxidation of the carbonaceous residues and polycondensates) by using a regeneration process which includes a cooling phase to 100 0 C in argon and a heating phase (5°C/min, final temperature 580-600 0 C) in air.
  • Figure 2 shows the conversion of methane for the reference sample and for the optimized sample.
  • the optimization leads to a material having a higher activity and stability.
  • Regeneration processes also allow optimum per- formances to be obtained by the optimized material.
  • the conversion of methane with respect to the time obtained for the fresh optimized sample and after regeneration, is shown in Figure 3.
  • the stability of the catalyst can be increased by introducing CO 2 in the feed. Activity tests in the presence of CO 2 indicate, mainly after regeneration and for quite long reaction times, an increase in activity in terms of methane conversion, deactivation rate and also a higher stability in the distribution of the aromatic products.
  • the experimental conditions relating to the pre- treatment of the catalyst, space velocity and the analysis method are analogous to those relating to the conversion of pure methane.
  • the reaction temperature varied from 550 to 800 0 C.
  • the total conversion of hydrocarbons, for a feed consisting of natural gas, is higher with respect to that of pure methane. In the first 25 hours the conversion passes from 25 to 23%. After 25 hours of reaction, the deactivation becomes more pronounced and the total conversion of carbon tends towards the value observed for the CH 4 /CO 2 mixture .
  • a variation in the product distribution can also be observed, mainly passing from pure methane to the methane/carbon dioxide mixture.
  • There is an increase in the selectivity to naphthalene a decrease in the selectivity to benzene, whereas the selectivity to toluene remains unchanged.
  • the presence of ethane causes a further slight increase in the selectivity to naphthalene. Conversion of methane in the presence of the promoted catalyst
  • the experimental conditions relating to the pre- treatment of the catalyst, space velocity and analysis method are described in the paragraph relating to the methane conversion.
  • the reaction temperature varied from 550 to 800 0 C.
  • the aromatic compounds can be easily separated from the methane and other light gases, due to the consistent difference in relative volatility. It is possible to ef- feet the separation through compression, at room temperature. As an alternative to compression, resort can be made to a washing/extraction with a heavy hydrocarbon compound followed by fractionation. Using C 30 as absorbing liquid and simulating an absorption column of 10 theoretical steps, a recovery of 95% of benzene is obtained. Hydrogenation of the aromatic compounds
  • the aromatic compounds essentially consisting of benzene, toluene, naphthalene and methyl -naphthalenes, are hydrogenated to naphthenic products, after separation from the lower hydrocarbons .
  • the hydrogenation is carried out in a fixed bed reactor under the following conditions:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne la conversion de méthane, seul ou en mélange avec d'autres gaz, en hydrocarbures liquides, essentiellement en hydrocarbures aromatiques, en présence d'un système catalytique qui comprend une zéolithe H-ZSM-5 qui présente un rapport molaire SiO2/Al2O3 allant de 20 à 100, de 0,5 à 15 % en poids de molybdène et de 0,1 à 5 % en poids de cérium (IV), à une température de 500 à 900 °C, avec la production d'hydrogène en tant que produit secondaire de la réaction.
PCT/EP2009/009108 2008-12-19 2009-12-16 Procédé de conversion de méthane, contenu dans des courants gazeux, en hydrocarbures hydrogénés liquides WO2010069582A1 (fr)

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ITMI2008A002277 2008-12-19
ITMI2008A002277A IT1392390B1 (it) 2008-12-19 2008-12-19 Procedimento per la conversione di metano, contenuto in correnti gassose, in idrocarburi liquidi idrogenati

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WO2010069582A1 true WO2010069582A1 (fr) 2010-06-24

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US9493709B2 (en) 2011-03-29 2016-11-15 Fuelina Technologies, Llc Hybrid fuel and method of making the same
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WO2019164610A1 (fr) 2018-02-21 2019-08-29 Exxonmobil Chemical Patents Inc. Conversion d'hydrocarbures en c2 en présence de méthane
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Publication number Priority date Publication date Assignee Title
US9493709B2 (en) 2011-03-29 2016-11-15 Fuelina Technologies, Llc Hybrid fuel and method of making the same
WO2012150043A1 (fr) 2011-05-04 2012-11-08 Ggp. Gozdno Gospodarstvo Postojna, D.O.O. Traitement de la cellulose à l'aide d'un mélange contenant du glycol, du glycérol et de l'acide p-toluène sulfonique
US10195595B2 (en) 2012-08-16 2019-02-05 Mitsui Chemicals, Inc. Catalyst composition and process for producing aromatic hydrocarbon using the catalyst composition
US10308885B2 (en) 2014-12-03 2019-06-04 Drexel University Direct incorporation of natural gas into hydrocarbon liquid fuels
WO2018182948A1 (fr) * 2017-03-27 2018-10-04 Exxonmobil Chemical Patents Inc. Conversion de méthane
WO2019164610A1 (fr) 2018-02-21 2019-08-29 Exxonmobil Chemical Patents Inc. Conversion d'hydrocarbures en c2 en présence de méthane
US11254882B2 (en) 2018-02-21 2022-02-22 Exxonmobil Chemical Patents Inc. Conversion of C2 hydrocarbons in the presence of methane
CN115260483A (zh) * 2022-08-31 2022-11-01 江苏钟山新材料有限公司 一种制备聚醚多元醇的方法

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