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WO1999006502A2 - Procede de transformation du methane - Google Patents

Procede de transformation du methane Download PDF

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Publication number
WO1999006502A2
WO1999006502A2 PCT/RU1998/000242 RU9800242W WO9906502A2 WO 1999006502 A2 WO1999006502 A2 WO 1999006502A2 RU 9800242 W RU9800242 W RU 9800242W WO 9906502 A2 WO9906502 A2 WO 9906502A2
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Prior art keywords
methane
hydrocarbons
meτana
gas
conversion
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PCT/RU1998/000242
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English (en)
Russian (ru)
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WO1999006502A3 (fr
Inventor
Aleksandr Sergeevich Belyi
Sergei Petrovich Kildyashev
Valery Kuzmich Duplyakin
Valentin Nikolaevich Parmon
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Institut Kataliza Imeni G.K.Boreskova Sibirskogo
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Application filed by Institut Kataliza Imeni G.K.Boreskova Sibirskogo filed Critical Institut Kataliza Imeni G.K.Boreskova Sibirskogo
Priority to AU88926/98A priority Critical patent/AU8892698A/en
Publication of WO1999006502A2 publication Critical patent/WO1999006502A2/fr
Publication of WO1999006502A3 publication Critical patent/WO1999006502A3/fr

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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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane

Definitions

  • a beneficial effect of the known method is an increase in the stability of the work of the catalytic converter and, in part, an improvement in the temperature dependence of the value of the non-paid-for-profit number.
  • the disadvantageous method is the absence of methane conversions in carbohydrates with a higher molecular weight. This method does not ensure an increase in the yield of liquid hydrocarbons due to methane conversions.
  • the invention solves the problem of producing hydrocarbons with a number of carbon atoms larger than a unit of catalytic conversion of methane.
  • ⁇ a ⁇ aliza ⁇ is ⁇ lzuemy in ⁇ edlagaem ⁇ m s ⁇ s ⁇ be, ⁇ ichae ⁇ sya ⁇ ⁇ i ⁇ a ⁇ em, ch ⁇ ⁇ n s ⁇ de ⁇ zhi ⁇ elemen ⁇ y VIII g ⁇ u ⁇ y in i ⁇ nn ⁇ m s ⁇ s ⁇ yanii in s ⁇ e ⁇ eni ⁇ isleniya " ⁇ " greater than zero ( ⁇ > 0).
  • An essential offer of the proposed method is the addition of carbon raw materials to methane with the number of carbons not exceeding 5 months.% Is not used.
  • This process is carried out on the basis of catalytic conver- sion through a single transitional complex from methane molecules and more heavily loaded molecules.
  • a favorable configuration of the molecules on the surface of the catalyst is achieved, which ensures the conversion of methane to carbohydrates with a higher weight.
  • the conditions of the process include a temperature of at least 440 ° C, a rate of delivery of methane of at least 60 nm ⁇ per 1 meter of catalyst per hour, and a partial pressure of methane of at least 0.05 Pa.
  • the processed mixture with methane can be contained in the composition of hydrocarbons with the number of carbons from 2 to 4.
  • Hydrocarbon oxides that are processed in the process of hydrogenation are separated from hydrocarbons by gas separation and are discharged from the process in the process of processing.
  • the process is carried out in the system of processes, including from 1 to 5 of the successive process with a fixed or in- troduc- tive
  • the catalytic movement moves by the action of the actual weight in the downward direction.
  • the catalyst withdraws from the last raw material from the raw materials of the process for regeneration.
  • the retrieved catalytic converter is brought into the first stage of the process.
  • the reactive mixture between the processors is additionally heated in a multi-furnace. In the process, the reaction of the reaction is reversed.
  • PRODUCTS ARE A MIXTURE OF HYDROGEN, WITH 2- C-LIGHT CARBOHYDRATE GASES, WITH 5+ -Liquid ⁇ hydrocarbons and non-methane methane.
  • the reaction products cool and promote separation in the C-2.
  • the food is one of the basic products of the methane processing plant. .
  • the process conducts at a temperature of at least 440 ° C, the rate of delivery of methane is not less than 60 N ⁇ per 1 ⁇ catalyst per hour, the partial pressure of methane is not less than 0.05 ⁇ Pa.
  • the optimal range of methane partial pressures lies in the range of 0.5–4.0 Pa.
  • Reaction is ideal with a decrease in the number of moles. Particularly effective, with this point of view, is reaction (4).
  • One model of carbon dioxide is consumed by four mothals of hydrogen.
  • the products of the reaction are methane and water. They are condensed in the C-1 unit and withdrawn from the process as a by-product.
  • the methane is dried on the whole and mixed with hydrocarbons with a higher carbon content than the methane processing process (Fig. 2).
  • ⁇ b ⁇ azuyuschiysya in ⁇ tsesse gid ⁇ i ⁇ vaniya ⁇ sid ⁇ v ugle ⁇ da me ⁇ an na ⁇ avlyae ⁇ sya in ⁇ tsess in ⁇ aches ⁇ ve ⁇ sn ⁇ vn ⁇ g ⁇ is ⁇ chni ⁇ a sy ⁇ ya for ⁇ lucheniya vys ⁇ m ⁇ le ⁇ ulya ⁇ ny ⁇ uglev ⁇ d ⁇ d ⁇ v or d ⁇ bavlyae ⁇ sya ⁇ ⁇ sn ⁇ vn ⁇ mu ⁇ u me ⁇ ana, ⁇ davaem ⁇ g ⁇ on ⁇ e ⁇ e ⁇ ab ⁇ u.
  • Liquid methane inverters provide a mixture of aliphatic and aromatic carbohydrates. They condense in the C-2 unit and withdraw from the process. With 5+, liquid hydrocarbons are used as high-quality components of automobiles or as raw materials for non-chemical synthesis.
  • Carbon raw materials with the number of carbon atoms above the mixture are mixed with methane at the entrance to the first processing unit ⁇ -2 (Fig. 2) not less than 5% is supplied.
  • neobhodimosti hydrocarbon-like raw materials are added to the reactive mixture between the processes.
  • This reaction is from a whole complex of hydrocarbon reactions to catalysts containing metal of the VIII group, which is located in the most close proximity to the country (%).
  • the hydrocarbon mixture is mixed with methane and processed in the processing system ⁇ -2 - ⁇ - ⁇ .
  • Liquid methane inverters provide a mixture of aliphatic and aromatic carbohydrates. And ⁇ ⁇ ndensi ⁇ uyu ⁇ in se ⁇ a ⁇ a ⁇ e-2 and vyv ⁇ dya ⁇ of ⁇ tsessa. Methane and hydrogen reactors separate C 2 -C 4 hydrocarbon gases and mix with methane and carbohydrate feedstocks.
  • the proposed method of processing methane can be used for the production of high-speed components, automatic, or commercial 2- C 5 is an alternative.
  • the following chemical composition is used for catalysts, wt.%: Plate - 0.5, tin - 0.4, cool - 1.0, aluminum oxide - other.
  • the catalyst supports the platinum in the metal state. Molecules of water under conditions of hazardous substances do not interact with the platinum atoms, do not inhibit the adsorption of oxygen. ⁇ isl ⁇ d in e ⁇ i ⁇ usl ⁇ viya ⁇ ads ⁇ bi ⁇ ue ⁇ sya ⁇ i 20 ° C ⁇ liches ⁇ ve m ⁇ l 0.45 0 2 ⁇ asche ⁇ e all ⁇ liches ⁇ v ⁇ ⁇ la ⁇ iny in ⁇ a ⁇ aliza ⁇ e.
  • the quality of hydrocarbon feedstocks with a higher carbon content is higher than that of using a hydrotreated gasoline fraction with a sulfur content of about 1–50%.
  • the fraction contains hydrocarbons with the number of carbon atoms, wt.%: C 4 - 0.1, C 5 - 0.3, C 6 - 7.6, C 7 - 15.9, C 8 - 51.7, C 9th - 23.5.
  • n-paraffin (n-P) iso-paraffin ( ⁇ -P), intense ( ⁇ ) and aromatic ( ⁇ ) carbohydrates in the following ratio, wt.%: N-/ / ⁇ -P 31.7 / 16.8 / 36.0 / 15.5.
  • the methane is supplied to the reactor with a catalytic converter in the bulk of methane / gas ratio equal to 1/1.
  • Methane effluents, C 2 -C 4 are gaseous, C 5+ are liquid carbohydrates, 55.0, 5.0 and 39.0 wt.% Of the liquid catalyzed are 53.5 wt.% Of aromatic hydrocarbons.
  • the short-term number of capitalization is 81.3 p. ⁇ . ⁇ .
  • the process is not subject to these conditions under the condition of methane conversion in heavier hydrocarbons.
  • the methane yield increases by 5 wt.%, Obviously, as a result of the conversion of liquid hydrocarbons to the hydro genesis of hydrocarbons. For example, 2.
  • Example 1 The process is carried out by way of Example 1, with the exception that, in the sense of a catalytic converter, they use a catalytic converter that contains a fee to the extent of " ⁇ ".
  • the catalyst contains, wt.%:
  • the plate is 0.4 - (with an energy level of 4 25/2 valence electrons equal to 317.5 ⁇ 0.2 e ⁇ ), ⁇ ló ⁇ - 1.5, aluminum - 0.4, ores
  • the process is subject to the following conditions: pressure - 1. ⁇ Pa, temperature 5 - 500 ° ⁇ , speed of methane-containing gas supply - 2000nl / l catalyzed per hour. ⁇ es ⁇ v ⁇ e s ⁇ n ⁇ shenie S ⁇ 4 / petrol ⁇ avn ⁇ 1/1.
  • Methane effluents C 2 -C 4 - are gas, C 5+ - liquid hydrocarbons are 35.2, 15.5 and 48.2 wt.% Respectively.
  • the total yield of hydrocarbons with a higher molecular weight than methane was 64.7%.
  • C 2 -C 4 -gaseous hydrocarbons produce the following chemical mixture, wt.%: Ethane - 25, ⁇ pan - 35, butane - 40.
  • C 5+ liquid hydrocarbons provide a mixture of steam, 15 fuel and aromatic carbohydrates.
  • the chemical composition and the anti-national characteristics of the process are presented in Table 2.
  • Table 3 shows an active composition of 5+ liquid carbohydrates.
  • liquid hydrocarbons are contained in their composition as aromatic hydrocarbons.
  • Liquid catalyzes the processing of ethylene glycol.
  • the extract separates the product and then, by refining it from the ethylene glycol.
  • the yield of 0 amounts of aromatic hydrocarbons is 71.3, based on the delivered quantity of raw materials with 5+ liquid carbohydrates.
  • the product contains, wt.%: Benzene - 3.2, toluene - 13.4, aromatic hydrocarbons ⁇ 8 - 29.1, aromatic hydrocarbons ⁇ 9 - ⁇ 10 - 25.7.
  • aromatic hydrocarbons ⁇ 9 - ⁇ 10 - 25.7.
  • Example 2 The process is carried out in Example 2, with the exception that, in the case of a transaction with a catalytic effect that reduces the price to the extent that ⁇ > 0, it is ineffective. From the given material balance it follows that in 5 given conditions for the formation of hydrocarbons C > , are not observed.
  • Methane effluents C 2 -C 4 - are gas, C 5+ - liquid hydrocarbons are 91.3, 4.7 and 3.8 wt.% Respectively.
  • the total yield of C > , hydrocarbon content is 8.5%. Consequently, the implementation of a complex methane conversion under these conditions ensures an increase in C> of carbohydrates by
  • P ⁇ ime ⁇ 6 25 P ⁇ tsess ⁇ susches ⁇ vlyayu ⁇ ⁇ ⁇ ime ⁇ u 2 with ⁇ em ⁇ lichiem, ch ⁇ is ⁇ lzuyu ⁇ ⁇ a ⁇ aliza ⁇ s ⁇ de ⁇ zhaniem i ⁇ nn ⁇ y ⁇ la ⁇ iny with 1.0 wt.%, And in z ⁇ nu ⁇ ea ⁇ tsii ⁇ dayu ⁇ ⁇ liches ⁇ va me ⁇ ana gasoline and 5.0 and 95 wt.% S ⁇ ve ⁇ s ⁇ venn ⁇ ⁇ i ⁇ a ⁇ tsialn ⁇ m pressure me ⁇ ana 0.05 ⁇ Pa.
  • the methane delivery rate is 80 nm 3 per m 3 due to catalytic conversion.
  • Methane effluents, C 2 -C 4 are gas, C 5+ , liquid hydrocarbons, are 4.5, 11.3, and 82.1 wt.%, Respectively.
  • the total yield with m hydrocarbons is equal to 93%.
  • the methane inver- sion is 10 wt.% Of the quantity supplied to C ⁇ 4 .
  • the process is carried out for example 6, but methane and gasoline are fed and the following solutions: 3 and 97 (in wt.%).
  • the methane delivery rate in this case is 60 nm 3 per m 3 of catalyst per hour.
  • the methane partial pressure is 0.04 PSa.
  • Methane exhausts, C 2 -C 4 - are gaseous ⁇ , C 5+ - liquid hydrocarbons make up 5.3, 13.1 and 80.3 wt.%; into the reactive zone of liquid raw materials. Consequently, under these conditions methane conversion in heavier hydrocarbons does not occur.
  • the carrier emits a mixture of aluminum hydroxide and hydrochloric acid with the following acid, dry and fresh in the inlet of the inlet
  • the hostel contains, wt.%: ⁇ 2 0 3 - 90, ⁇ 2 - 9.4, ⁇ - 0.6.
  • the process is delivered to a device equipped with a processing unit with a moving catalyst bed.
  • the catalyst moves in the process by gravity downward in the same direction as the reactive mixture of hydrocarbons.
  • the catalyzed catalyst is removed from the lower part of the process and is directed to regeneration.
  • the retrofitted and recovered catalysts are supplied to the upper part of the process.
  • the download volume for the catalytic converter is 100cm 3 .
  • the catalyst moves at a speed of 5 cm 3 / hour
  • the process is carried out under the following ⁇ conditions ⁇ : pressure - 1.0 PSa, temperature - 490 ° ⁇ , speed of methane delivery - 1000nl / l catalyst per hour.
  • the average C ⁇ / gas ratio is equal to 1/1.
  • Methane effluents, C 2 -C - are gaseous ⁇ , C 5+ - liquid hydrocarbons, make up 34.3, 10.1 and 53.7 wt.%, Respectively.
  • the yield of hydrocarbons with the number of carbon atoms above the unit is 63.8%. Consequently, under these conditions, in comparison with the known method (Example 1), the biprocessing process ensures an increase in the yield of C> ⁇ carbohydrates by 24.8 wt.%.
  • the degree of methane conversion under these conditions is 31.4 wt.%
  • the process is carried out at Example 8, with the exception that the temperature of the process is 420 ° C.
  • Methane effluents, C 2 -C 4 gas and C 5+ liquids ⁇ hydrocarbons constitute 51.3, 2.3 and 45.5 wt.%, Respectively. Consequently, the application of the process at a temperature of 420 ° C does not affect the conversion of methane to high-molecular hydrocarbons.
  • the process is carried out by way of Example 8.
  • the process uses a catalytic converter, which contains, by weight, wt. 15
  • Natural gas contains, wt.%: Methane - 96, ethane - 2.5, C 3 -C-gas hydrocarbons - 1.5.
  • hydrocarbon raw materials with a higher carbon content they use a wide range of hydrocarbons that are wasteful to 85%.
  • the fraction contains hydrocarbons with a total of 0 carbons, wt.%: C 4 - 1.8, C 5 - 3.4, C 6 - 7.3, C 7 - 14.2, C 8 - 48.6, C 9 .Ju - 25.
  • Methane effluents C 2 -C 4 - are gas, C 5+ - liquid hydrocarbons 5 are 31.3, 8.4 and 57.6 wt.% Respectively. With 5+, liquid hydrocarbons contain, wt.%: Aromatic - 68, vapors - 22, ⁇ -paraffins - 8, paraffins - 2.0. Short number - 88 ⁇ . ⁇ . ⁇ ., the pressure of the smoking steams - 260 mm. ⁇ .st.
  • the process is of example 10, with the difference that the process delivers gasoline in the amount of 25 wt.% Of the supplied process pressure.
  • the methane conversion rate is 15.9 wt.%.
  • the main methane conversion products are C 2 -C 4 - hydrocarbon gases.
  • EXAMPLE 12 EXAMPLE 12, with the exception that the process is carried out at a temperature of 430 ° C.
  • Methane effluents, C 2 -C 4 - are gas, C 5+ - liquid hydrocarbons are 48.5, 2.2 and 49.0 wt.% Respectively.
  • the degree of methane conversion is 3.0 wt.%;
  • the economic constant value is 58 ⁇ . ⁇ . ⁇ . 0 Consequently, the application of the process and the temperature of less than 440 ° C do not affect the methane conversion to high-speed components.
  • Methane effluents, C 2 -C - are gaseous, C 5+ - liquid hydrocarbons are 0 30.8, 10.3 and 56.4 wt.%, Respectively.
  • the methane conversion rate is 38.4 wt.%.
  • the liquid catalyzed contains, wt.%: Benzene - 39.5, thorulol - 17, C ⁇ - aromatic hydrocarbons - 12.5.
  • the methane conversion rate makes up 30.6 wt.%.
  • the liquid catalysate contains 8- ⁇ -aromatic hydrocarbons - 78 wt.%.
  • EXAMPLE 15 is, for example, at a temperature of 450 ° C and a partial pressure of methane of 1.6 psi.
  • Methane effluents, C 2 -C - gas, C 5+ - liquid hydrocarbons are 44.3, 5.3 and 49.8 wt.% Respectively.
  • the methane conversion rate is 11.4% by weight.
  • the main methane conversion products are C 2 -C - aliphatic hydrocarbons. Consequently, the processing of methane and a narrow gasoline fraction (105-140 ° C) at temperatures less than 460 ° C with a partial pressure of more than 1.6 is not an absolute value for
  • EXAMPLE 17 Illustrated is the proposed method of processing methane in C 2 -C - aliphatic hydrocarbons.
  • the process is operating in a system consisting of five investigatively connected systems. ⁇ In the first stage, the following wt.%:
  • the agent emits a mixture of aluminum hydroxides (90 wt.%) And zinc (10 wt.%) With the following drying, drying and heating in the air.
  • the reactors of the catalyst systems are as follows, wt.%: 7.5 - nickel nickel, 0.15 - sulfur on the carrier.
  • the host emits a mixture of aluminum hydroxide (80 wt.%) And celite (20 wt.%) followsed by heating, drying, and heating in the air.
  • the following wt.% 3.5 - bulk, 3.5 - iron, 0.15 - sulfur on the carrier.
  • the host emits a mixture of aluminum hydroxide (60 wt.%) And celite (40 wt.%) followsed by heating, drying and heating at 550 ° ⁇ in the atmosphere.
  • the raw materials used are natural gas of the following composition, wt.%: Methane - 96, ethane - 2.5, hydrocarbons ⁇ 2 - ⁇ 4 - 1.5. 5 ⁇ a v ⁇ d in ⁇ e ⁇ vy ⁇ ea ⁇ for blending with ⁇ i ⁇ dnym gaz ⁇ m ⁇ dayu ⁇ ⁇ yam ⁇ g ⁇ nnuyu benzin ⁇ vuyu ⁇ a ⁇ tsiyu, vy ⁇ i ⁇ ayuschuyu in ⁇ edela ⁇ ⁇ em ⁇ e ⁇ a ⁇ u ⁇ 45-105 ° C.
  • the fraction contains hydrocarbons with the number of carbon atoms, wt.%: C - 4.3, C 5 - 37.6, C 6 - 42.9, C 7 - 15.2.
  • Methane effluents C 2 -C 4 - are gas, C 5+ -hydrocarbons are 30.2, 52.8 and 15.1 wt.% Respectively.
  • the degree of methane conversion is 15 39.6% by weight.
  • the basic direction of methane conversion under these conditions is the formation of C 2 -C-carbohydrates.
  • the process is operating in a system consisting of five investigatively connected systems.
  • the agent emits a mixture of aluminum hydroxides (90 wt.%) And zinc (10 wt.%) With the following drying, drying and heating in the air.
  • the reactors of the catalyst systems are as follows, wt.%: 7.5 - nickel nickel, 0.15 - sulfur on the carrier.
  • the host emits a mixture of 5 aluminum hydroxide (80 wt.%) And ⁇ celite (20 wt.%) followsed by heating, drying, and heating in the air.
  • the following wt.% 3.5 - bulk, 3.5 - iron, 0.15 - sulfur on the carrier.
  • the host emits a mixture of aluminum hydroxide (60 wt.%) And celite (40 wt.%) With 0 followed by heating, drying and heating at 550 ° ⁇ in the atmosphere.
  • the raw materials used are natural gas of the following composition, wt.%: Methane - 96, ethane - 2.5, hydrocarbons ⁇ 2 - ⁇ 4 - 1.5.
  • the Replacement sheet When entering the first reactor, it mixes with natural gas and supplies a direct gasoline fraction that is burnt out at temperatures of 45–105 ° ⁇ .
  • the fraction contains hydrocarbons with the number of carbon atoms, wt.%: C - 4.3, C 5 - 37.6, C 6 - 42.9, C 7 - 15.2.
  • 5 Process is subject to the following conditions: methane partial pressure -
  • the temperature is 480 ° ⁇
  • the methane delivery rate is 1000 nm 3 per 1 m 3 catalytic converter per hour
  • the quantity of gas supplied is 50% of the quantity supplied.
  • Methane effluents C 2 -C - are gas, C 5+ -hydrocarbons make up 41.1, 30.2 and 27.9 wt.% Respectively.
  • the methane conversion rate is 17.8% by weight.
  • the main methane conversion products are C 2 -C 4 - aliphatic hydrocarbons.
  • the process is of example 18, with the exception that the temperature in the reaction zone is maintained at 470 ° C, and the partial methane pressure is 2.0 ° C.
  • the degree of methane conversion is 8.4. 0
  • the main methane conversion products are C 5+ liquid hydrocarbons.
  • a decrease in the temperature of the process is less than 480 ° C and a decrease in the partial pressure of methane is less than 2.5 ⁇ Pa, which causes a change in the direction of methane conversion to the state of the C 5+ -fuel liquid.
  • ⁇ Reactor ⁇ -1 uses the following chemical composition, wt.%: Nickel nickel - 2.5, 1_a 2 0 3 - 2.5, aluminum oxide - other.
  • Replacement sheet ⁇ ⁇ ea ⁇ a ⁇ ⁇ -2, ⁇ -3 and ⁇ -4 is ⁇ lzuyu ⁇ ⁇ a ⁇ aliza ⁇ sleduyuscheg ⁇ ⁇ imiches ⁇ g ⁇ s ⁇ s ⁇ ava% wt./wt ⁇ la ⁇ ina i ⁇ nnaya - 0.35 ⁇ eny - 0.45 ⁇ l ⁇ v ⁇ - 0.2, ⁇ l ⁇ - 1.2 se ⁇ a - 0.1 ⁇ sid aluminum - ⁇ s ⁇ aln ⁇ e. .
  • the catalysts are loaded in the following quantities: in ⁇ -1 and ⁇ -3 at 20 g, in ⁇ -2 5 - 10 g, in ⁇ -4 - 40 g.
  • the process is subject to the following conditions: pressure - 1.0 PSa, temperature - 520 ° ⁇ , speed of carbon dioxide production - 11nm 3 / m 3 catalytic converter per hour
  • Carbon dioxide is mixed with a recycle-containing hydrogen gas and is hydrated in a reactor ⁇ -1 at a temperature of 350 ° ⁇ . Separate methane and water are separated in the S-1 unit. Come out of the process. ⁇ coming out of C-1 methane flow adds gasoline fraction that grows in the range of temperature 85-185 ° ⁇ and turns off in the ⁇ -2 - ieri reaction system. Hydrogen and C 2 -C 4 hydrocarbon gases are used to separate C 5+ - 15 liquid hydrocarbons and return them to mix with carbon dioxide.
  • Wastewater C 2 -C 4 gas, with 5+ liquid hydrocarbons and water are 11.3, 76.4 and 12.3 wt.% Respectively.
  • the proposed process due to the recirculation is achieved by the complete conversion of the methane produced, and the carbon dioxide is the main source of exhaustion.
  • EXAMPLE 21. 5 The process is of an example of 20, with the exception that the recycle water is mixed with gas and is free of gas and gas.
  • ⁇ b ⁇ azuyuschiesya ⁇ du ⁇ y ⁇ azdelyayu ⁇ se ⁇ a ⁇ a ⁇ e at C-2 and C 5+ -zhid ⁇ ie uglev ⁇ d ⁇ dy 15 withdrawn from installation as a finished product.
  • the supplying gas is directed to the separation in the S-3 separator.
  • C 2 -C 4 -gaseous products are discharged from the unit, and non-reacting methane and hydrogen are mixed with carbon dioxide.
  • the C 2 -C 4 gas fluids, the 5+ liquid hydrocarbons and water make up 0 51.7, 31.0 and 12.3 wt.%, Respectively.
  • the main direction of methane conversion under these conditions is C 2 -C 4 -gaseous hydrocarbons.
  • ⁇ react ⁇ -1 is loaded with 0 catalyst of the following composition, wt.%: 0.5 - metal plate, 0.3 - cold, aluminum oxide - other.
  • Replacement sheet P ⁇ tsess degid ⁇ genizatsii gasoline ⁇ v ⁇ dya ⁇ in ⁇ ea ⁇ e ⁇ -1 ( ⁇ is.2) in sleduyuschi ⁇ usl ⁇ viya ⁇ : pressure - ⁇ . ⁇ Pa, ⁇ b'emnaya s ⁇ s ⁇ ⁇ dachi sy ⁇ ya- 15h '1, ⁇ em ⁇ e ⁇ a ⁇ u ⁇ a - 460 ° C, s ⁇ n ⁇ shenie ⁇ 2 / gasoline 500 m 3 on m 3 gasoline.
  • the food is separated from the reaction and is partially mixed with the raw material, and the main part is withdrawn from the process.
  • C-2 hydrocarbons are added to the methane feed and supplied to the ⁇ -2, ⁇ -3 treatment system.
  • the following composition was loaded with catalysts, wt.%: Foreign plate - 0.25, germanium - 0.2, cool - 1.1, aluminum oxide - other.
  • Methane effluents, C 2 -C - are gas, C 5+ -hydrocarbons are 10.0, 15.1 and 72.9 wt.% Respectively.
  • the methane conversion rate is 66.7 wt.%
  • the basic methane conversion under these conditions is carbohydrate treatment 5+ .
  • the ⁇ 2 - ⁇ 4 fluids are gas-based, C 5+ are liquid hydrocarbons and water, wt.%: 14.3, 70.4 and 12.3 are respectively.
  • the cost of natural gas is much less than oil, and the stability of its production and effective reserves are much higher.

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Abstract

Cette invention concerne un procédé de transformation du méthane qui se déroule dans un système de réacteurs à l'aide d'un catalyseur contenant un métal du groupe VIII. Ce procédé permet de produire des hydrocarbures dont le nombre d'atomes de carbone est supérieur à un, ainsi que de l'hydrogène. Ce procédé consiste à ajouter au méthane des matières premières hydrocarbures ayant un nombre d'atomes de carbone supérieur à trois, ceci dans une quantité d'au moins 5,0 % en poids par rapport à la quantité totale de matières premières hydrocarbures que l'on introduit dans le système de réacteurs. Le processus se déroule sur un catalyseur contenant un métal du groupe platine selon un taux d'oxydation n supérieur à zéro (n > 0) ou, encore, sur un catalyseur contenant un métal du groupe VIII consistant en du cobalt, du fer ou du nickel, ainsi qu'un promoteur sur un support oxyde. Cette invention concerne également des variantes de ce procédé de transformation du méthane qui permettent d'obtenir des composants à indice d'octane élevé pour carburants automobiles, des hydrocarbures aromatiques ainsi que des hydrocarbures aliphatiques C2-C5 et de l'hydrogène.
PCT/RU1998/000242 1997-07-31 1998-07-28 Procede de transformation du methane WO1999006502A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU88926/98A AU8892698A (en) 1997-07-31 1998-07-28 Method for methane conversion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU97113155A RU2135441C1 (ru) 1997-07-31 1997-07-31 Способ переработки метана (варианты)
RU97113155 1997-07-31

Publications (2)

Publication Number Publication Date
WO1999006502A2 true WO1999006502A2 (fr) 1999-02-11
WO1999006502A3 WO1999006502A3 (fr) 1999-04-15

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/RU1998/000242 WO1999006502A2 (fr) 1997-07-31 1998-07-28 Procede de transformation du methane

Country Status (3)

Country Link
AU (1) AU8892698A (fr)
RU (1) RU2135441C1 (fr)
WO (1) WO1999006502A2 (fr)

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US10099972B2 (en) 2013-12-06 2018-10-16 Exxonmobil Upstream Research Company Methods and systems for producing liquid hydrocarbons

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RU2186755C1 (ru) * 2001-03-22 2002-08-10 Институт катализа им. Г.К.Борескова СО РАН Способ каталитической переработки метана
AU2005326677B2 (en) 2004-12-22 2009-03-12 Exxonmobil Chemical Patents, Inc. Production of liquid hydorocarbons from methane
AU2005319530B2 (en) * 2004-12-22 2009-04-23 Exxonmobil Chemical Patents, Inc. Production of aromatic hydrocarbons from methane
WO2006068800A2 (fr) 2004-12-22 2006-06-29 Exxonmobil Chemical Patents Inc. Production d'hydrocarbures aromatiques alkyles a base de methane
WO2007091912A1 (fr) * 2006-02-09 2007-08-16 Institut Problem Pererabotki Uglevodorodov Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk Procédé pour produire des carburants de moteur
RU2388794C2 (ru) * 2006-02-09 2010-05-10 Институт проблем переработки углеводородов Сибирского отделения Российской Академии Наук (ИППУ СО РАН) Способ получения компонентов моторных топлив
US7977519B2 (en) 2006-04-21 2011-07-12 Exxonmobil Chemical Patents Inc. Production of aromatic hydrocarbons from methane
JP5051924B2 (ja) * 2006-04-21 2012-10-17 エクソンモービル・ケミカル・パテンツ・インク メタン転換製造プロセス
US7754930B2 (en) 2006-05-31 2010-07-13 Exxonmobil Chemical Patents, Inc. Use of isotopic analysis for determination of aromatic hydrocarbons produced from methane
RU2568809C1 (ru) * 2014-12-11 2015-11-20 Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук (ИК СО РАН) Способ каталитической переработки легкого углеводородного сырья

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10099972B2 (en) 2013-12-06 2018-10-16 Exxonmobil Upstream Research Company Methods and systems for producing liquid hydrocarbons

Also Published As

Publication number Publication date
AU8892698A (en) 1999-02-22
WO1999006502A3 (fr) 1999-04-15
RU2135441C1 (ru) 1999-08-27

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