WO2017195817A1 - Procédé de reformage d'hydrocarbures, procédé de production de composés oxygénés organiques et système de production de composés oxygénés organiques - Google Patents

Procédé de reformage d'hydrocarbures, procédé de production de composés oxygénés organiques et système de production de composés oxygénés organiques Download PDF

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WO2017195817A1
WO2017195817A1 PCT/JP2017/017674 JP2017017674W WO2017195817A1 WO 2017195817 A1 WO2017195817 A1 WO 2017195817A1 JP 2017017674 W JP2017017674 W JP 2017017674W WO 2017195817 A1 WO2017195817 A1 WO 2017195817A1
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gas
organic
hydrogen
reforming
carbon monoxide
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PCT/JP2017/017674
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Japanese (ja)
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稔人 御山
真介 渡辺
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積水化学工業株式会社
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    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • 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

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  • the present invention relates to a hydrocarbon reforming method, an organic oxygenate production method, and an organic oxygenate production system.
  • This application claims priority on May 12, 2016 based on Japanese Patent Application No. 2016-096161 for which it applied to Japan, and uses the content here.
  • Patent Document 1 discloses a method in which a synthesis gas containing hydrogen and carbon monoxide is brought into contact with a metal catalyst such as rhodium and manganese to obtain organic oxygenates such as alcohol, acetaldehyde and acetic acid. Since the reaction efficiency by the metal catalyst is not 100%, unreacted hydrogen and carbon monoxide remain in the produced gas containing the produced organic oxygenate.
  • the product gas usually contains hydrocarbons having about 1 to 6 carbon atoms as a by-product. Not only recovering these unreacted hydrogen and carbon monoxide as raw materials, but also reforming by-product hydrocarbons to hydrogen and carbon monoxide by a reforming catalyst.
  • organic oxygenates such as alcohol contained in the product gas are recovered by gas-liquid separation in the cooler, and hydrocarbons remaining on the gas component side are introduced into the reforming unit together with water vapor to perform catalytic reaction.
  • a method for producing hydrogen and carbon monoxide is disclosed.
  • the conventional method is required to be improved because the efficiency and stability of reforming to obtain hydrogen and carbon monoxide from hydrocarbons is low.
  • the present invention relates to a method for producing an organic oxygenate capable of efficiently reforming a hydrocarbon produced as a by-product when producing an organic oxygenate from synthesis gas into hydrogen and carbon monoxide, and the method thereof
  • a production system and a hydrocarbon reforming method useful for the production method are provided.
  • a gas containing hydrocarbons and having an organic oxygenate content of less than 1000 ppm on a molar basis and water vapor are brought into contact with the reforming catalyst, and from the concentration of hydrogen and the concentration of carbon monoxide contained in the gas
  • a hydrocarbon reforming method comprising a reforming step of obtaining a reformed gas having a higher hydrogen concentration and carbon monoxide concentration.
  • Separation that reduces the content of the organic oxygenate contained in the gas to less than 1000 ppm on a molar basis by contacting the gas with activated carbon and separating at least a part of the organic oxygenate from the gas.
  • the hydrocarbon reforming method according to [1] comprising a step.
  • a production step of bringing a synthesis gas containing hydrogen and carbon monoxide into contact with a synthesis catalyst to obtain a product gas containing an organic oxygenate and a hydrocarbon, and separating at least a part of the organic oxygenate from the product gas A separation step of obtaining a separation gas containing hydrocarbons, bringing the separation gas and water vapor into contact with a reforming catalyst, and a concentration of hydrogen higher than a concentration of hydrogen and a concentration of carbon monoxide contained in the separation gas
  • a reforming step for obtaining a reformed gas having a concentration of carbon monoxide, and a method for producing an organic oxygenate having a content of the organic oxygenate in the separation gas used in the reforming step The manufacturing method of the organic oxygenate which is less than 1000 ppm on a molar basis.
  • [4] The method for producing an organic oxygenate according to [3], further including a recycling step of bringing the reformed gas into contact with the synthesis catalyst to obtain the product gas.
  • [5] The method for producing an organic oxygenate according to [3] or [4], wherein the organic oxygenate is at least one selected from the group consisting of ethanol and ethyl acetate.
  • [6] The method for producing an organic oxygenate according to any one of [3] to [5], wherein the separation step includes an adsorption treatment for adsorbing the organic oxygenate on activated carbon.
  • a synthesis catalyst that generates organic oxygenates and hydrocarbons from hydrogen and carbon monoxide is provided. When a synthesis gas containing hydrogen and carbon monoxide is introduced, the organic oxygenates and hydrocarbons are removed by the action of the synthesis catalyst.
  • the hydrocarbon produced as a by-product when an organic oxygenate is produced from synthesis gas is efficiently reformed to hydrogen and carbon monoxide. Can do.
  • the hydrocarbon can be efficiently reformed into hydrogen and carbon monoxide.
  • the production method of the organic oxygenate according to the first aspect of the present invention includes a production step of bringing a synthesis gas containing hydrogen and carbon monoxide into contact with a synthesis catalyst to obtain a production gas containing an organic oxygenate and a hydrocarbon, and the production gas A separation step of separating at least a part of the organic oxygenate from the mixture to obtain a separation gas containing the hydrocarbon, bringing the separation gas and water vapor into contact with a reforming catalyst, and a concentration of hydrogen contained in the separation gas And a reforming step of obtaining a reformed gas having a hydrogen concentration and a carbon monoxide concentration higher than the concentration of carbon monoxide.
  • the organic oxygenate can be recovered in the separation step.
  • a separation gas in which the total of the organic oxygenates is reduced to less than 1000 ppm on a molar basis is used in the reforming step.
  • the production process is a process in which a synthesis gas is brought into contact with a synthesis catalyst to obtain a production gas containing organic oxygenates and hydrocarbons.
  • a synthesis gas is brought into contact with a synthesis catalyst to obtain a production gas containing organic oxygenates and hydrocarbons.
  • a product gas containing the target organic oxygenate can be obtained.
  • it can be performed according to a known method such as Patent Document 1.
  • the synthesis gas is preferably composed mainly of hydrogen and carbon monoxide.
  • the lower limit of the total of hydrogen and carbon monoxide in the synthesis gas is preferably 50 to 70% by volume or more.
  • the upper limit of the total of hydrogen and carbon monoxide in the synthesis gas is not particularly limited, and may be 100% by volume.
  • the volume ratio represented by hydrogen / carbon monoxide (hereinafter sometimes referred to as H 2 / CO ratio) is preferably from 0.1 to 10, and more preferably from 0.5 to 3.
  • H 2 / CO ratio is within the above range, in the reaction for synthesizing the organic oxygenate from the synthesis gas, the stoichiometrically appropriate range is obtained, and the synthesis efficiency of the organic oxygenate can be improved.
  • the synthesis gas may contain an inert gas. If the synthesis gas contains an inert gas, the synthesis efficiency of the organic oxygenates may be improved. Examples of the inert gas include nitrogen and argon. The content of the inert gas is preferably 5 to 30% by volume with respect to 100% by volume of the synthesis gas. Although it is preferable that the synthesis gas does not contain impurities other than hydrogen, carbon monoxide, and inert gas, in practice, gases such as methane, ethane, ethylene, and water generated in the reaction system are impurities. May be included.
  • the temperature at which the synthesis gas and the synthesis catalyst are brought into contact is, for example, preferably 150 to 450 ° C., more preferably 250 to 300 ° C.
  • the pressure at which the synthesis gas and the synthesis catalyst are brought into contact is preferably, for example, 0.5 to 10 MPa, and more preferably 0.8 to 5 MPa.
  • the synthesis gas supply rate is, for example, a space velocity of the synthesis gas in the reaction bed (a value obtained by dividing the gas supply amount per unit time by the catalyst amount (volume conversion)) of 10 to 100,000 L / L-
  • the catalyst / h can be adjusted. More preferably, it is 2000 to 20000 L / L-catalyst / h.
  • the synthesis gas introduced into the reaction tube flows in contact with the synthesis catalyst in the reaction bed.
  • an oxygenate having 2 carbon atoms such as ethanol, acetic acid, or acetaldehyde, or an oxygenate having 4 carbon atoms such as ethyl acetate.
  • Organic oxygenates such as are produced.
  • hydrocarbons having about 1 to 6 carbon atoms are produced as by-products.
  • organic oxygenates examples include ethanol, acetic acid, acetaldehyde, ethyl acetate, methanol, 1-propanol, 1-butanol, 1-pentanol, methyl acetate, propyl acetate, butyl acetate, pentyl acetate, acetaldehyde diethyl acetal, and the like. It is done. When a plurality of types of organic oxygenates are included, the total of these is less than 1000 ppm.
  • the hydrocarbon examples include methane, ethane, ethylene, propane, propylene, butane, butene, pentane, hexane and the like.
  • the type and amount of the synthesis catalyst used in the production step is not particularly limited, and known metal catalysts used for obtaining organic oxygenates having 2 or more carbon atoms such as alcohol, acetaldehyde, acetic acid, and ester from synthesis gas are available.
  • a metal catalyst containing one or more platinum group elements selected from ruthenium, rhodium, palladium, osmium, iridium and platinum is preferable from the viewpoint of increasing the selectivity.
  • the synthetic catalyst may contain the following hydrogenation active metal and co-active metal as a metal (optional catalyst metal) other than the platinum group element.
  • Examples of the hydrogenation active metal include alkali metals such as lithium and sodium; chromium and molybdenum, elements belonging to Group 6 of the periodic table; manganese, rhenium and other elements belonging to Group 7 of the periodic table; iron, ruthenium Elements belonging to Group 8 of the periodic table; cobalt, elements belonging to Group 9 of the periodic table (excluding platinum group elements); elements such as nickel, belonging to Group 10 of the periodic table (however, platinum) Excluding group elements).
  • These hydrogenation active metals may be used individually by 1 type, and may be used in combination of 2 or more type. Further, some or all of these hydrogenation-activated metals may be oxidized or sulfided.
  • co-active metal examples include one or more selected from titanium, vanadium, chromium, boron, magnesium, lanthanoids, and elements belonging to Group 13 of the periodic table. Among these, titanium, magnesium, and vanadium are preferable. Titanium is more preferred.
  • the synthesis catalyst may have a carrier supporting a metal.
  • the type of the carrier is not particularly limited, and a carrier used in a conventional catalyst can be applied.
  • a porous carrier is preferable.
  • the material of the porous carrier is not particularly limited, and examples thereof include silica, zirconia, titania, magnesia, alumina, zeolite and the like, and among them, various products having different specific surface areas and pore diameters can be procured in the market. Silica is preferred.
  • the size of the porous carrier examples include a particle diameter of 0.5 to 5000 ⁇ m. The particle size is adjusted by sieving.
  • the porous carrier preferably has a narrowest particle size distribution.
  • the total pore volume of the porous carrier is preferably 0.01 to 1.0 mL / g, more preferably 0.1 to 0.8 mL / g, and further preferably 0.3 to 0.7 mL / g.
  • the total pore volume can be measured by a water titration method.
  • the water titration method is a method in which water molecules are adsorbed on the surface of a porous carrier and the pore distribution is measured from the condensation of the molecules.
  • the average pore diameter of the porous carrier is preferably 0.01 to 20 nm, more preferably 2 to 20 nm, further preferably more than 5 nm and less than 14 nm, particularly preferably more than 5 nm and not more than 10 nm.
  • the average pore diameter is a value measured by the following method. When the average pore diameter is 0.1 nm or more and less than 10 nm, it is calculated from the total pore volume and the BET specific surface area. When the average pore diameter is 10 nm or more, it is measured by a mercury porosimetry porosimeter.
  • the total pore volume is a value measured by a water titration method
  • the BET specific surface area is a value calculated from the amount of adsorption and the pressure at that time using nitrogen as an adsorption gas.
  • mercury intrusion method mercury is pressurized and pressed into the pores of the porous carrier, and the average pore diameter is calculated from the pressure and the amount of mercury inserted.
  • the specific surface area of the porous carrier is preferably 1 ⁇ 1000m 2 / g, more preferably from 300 ⁇ 800m 2 / g, more preferably 400 ⁇ 700m 2 / g.
  • the specific surface area is a BET specific surface area measured by a BET gas adsorption method using nitrogen as an adsorption gas.
  • Examples of the supported amount of the platinum group element with respect to 100 parts by mass of the carrier include 0.5 parts by mass or more and 10 parts by mass or less.
  • the supported amount of the hydrogenation active metal is, for example, 1 to 10 parts by mass with respect to 100 parts by mass of the porous carrier, with the total of the platinum group element and the hydrogenation active metal.
  • Examples of the loading amount of the co-active metal include 0.01 to 20 parts by mass with respect to 100 parts by mass of the carrier.
  • the separation step is a step of separating at least part of the organic oxygenate from the product gas obtained in the production step to obtain a separation gas containing the hydrocarbon.
  • the product gas derived from the reaction tube is introduced into a cooler and cooled to about 5 to 50 ° C., thereby condensing an organic oxygenate having a boiling point lower than the cooling temperature and moisture, thereby known gas-liquid A method of recovering organic oxygenates by a separation method is mentioned.
  • the boiling point of butane is ⁇ 1 ° C.
  • hydrocarbons having 1 to 4 carbon atoms do not condense only by cooling to about 5 to 50 ° C., and remain on the gas side by gas-liquid separation.
  • the separation gas obtained by gas-liquid separation by cooling usually contains mist (micro liquid phase particles) of about submicron to submillimeter.
  • mist micro liquid phase particles
  • the separated gas that has passed through the demister is dried by removing the mist, and contains hydrocarbons, unreacted hydrogen, carbon monoxide, and the like.
  • the present inventors passed the separation gas through an adsorber (activated carbon adsorber) filled with activated carbon in order to further separate the organic oxygenate remaining in the separated gas that passed through the demister.
  • the total amount of organic oxygenates contained in the separation gas is less than 1000 ppm (0.1 mol%), preferably less than 500 ppm (0.05 mol%), more preferably 100 ppm (0.01 mol%) on a molar basis. It has been found that the reforming efficiency in the latter stage can be significantly improved and the reforming reaction can be stabilized by lowering the ratio to below.
  • the organic oxygenated product adsorbed on the activated carbon is a desired product in the production process, it is preferably recovered.
  • a recovery process for recovering organic oxygenates from activated carbon for example, by heating the activated carbon, the organic oxygenates adsorbed on the activated carbon are vaporized and desorbed from the activated carbon, and the desorbed organic oxygenate is cooled in a cooler.
  • recovering by etc. is mentioned.
  • the method of reducing the total amount of organic oxygenates contained in the separation gas to less than 1000 ppm is not limited to the method of adsorbing to activated carbon.
  • adsorbents such as molecular sieve, silica gel, clay, activated alumina, and zeolite. You may apply the method of making it adsorb
  • the activated carbon adsorption method is preferable because it has a high ability to separate organic oxygenates.
  • the separation gas and water vapor are brought into contact with the reforming catalyst, and the reformed gas having a hydrogen concentration and a carbon monoxide concentration higher than the hydrogen concentration and the carbon monoxide concentration contained in the separation gas.
  • the total of the organic oxygenates in the separation gas used in the reforming step is less than 1000 ppm (0.1 mol%), preferably less than 500 ppm (0.05 mol%) on a molar basis. More preferably, it is less than 100 ppm (0.01 mol%). Ideally, it is 0 ppm.
  • hydrocarbons contained in the separation gas can be reformed by introducing the separation gas and water vapor into a reaction tube containing a reforming catalyst and controlling the temperature and pressure in the reaction tube.
  • the hydrocarbon is reformed by the action of water vapor and the reforming catalyst to generate hydrogen and carbon monoxide, and the concentration of hydrogen and the concentration of carbon monoxide in the separation gas are increased.
  • it can be performed according to a known method such as Patent Document 1.
  • the concentration of hydrogen (in terms of mol%) contained in the reformed gas is preferably 1.1 to 2.0 times the concentration of hydrogen contained in the separation gas.
  • the concentration (mole% conversion) of carbon monoxide contained in the reformed gas is preferably 1.1 to 2.0 times the concentration of carbon monoxide contained in the separation gas.
  • the temperature at which the separation gas and the reforming catalyst are brought into contact is preferably 600 to 1000 ° C., more preferably 700 to 900 ° C.
  • the pressure at which the separation gas and the reforming catalyst are brought into contact is preferably, for example, 0.5 to 10 MPa, and more preferably 0.6 to 2 MPa.
  • the space velocity of the separation gas in the reaction bed is 10 to 10,000 L / L- Catalyst / h, preferably 100 L / L-catalyst / h to 10000 L / L-catalyst / h can be adjusted.
  • the type and amount of the reforming catalyst used in the reforming step are not particularly limited, and known catalysts used for obtaining hydrogen and carbon monoxide from hydrocarbons and steam can be applied.
  • nickel, ruthenium From the viewpoint of improving the reforming efficiency, a metal catalyst containing at least one selected from platinum, rhodium is preferable.
  • an alumina-supported nickel-based catalyst main metal NiO
  • the reforming catalyst may have a carrier supporting a metal.
  • the type of the carrier is not particularly limited, and a carrier used in a conventional catalyst can be applied.
  • the porous carrier that can be used as the carrier of the synthetic catalyst described above is preferable.
  • the size of the reforming catalyst can be selected so as to obtain an appropriate packing density and a pressure loss during gas flow according to the reaction tube diameter and gas flow rate.
  • the particle diameter of the reforming catalyst is preferably 1 to 5 mm, more preferably 2 to 4 mm.
  • the particle diameter of the reforming catalyst can be adjusted by sieving.
  • the separated gas introduced into the reaction tube flows along with the water vapor while contacting the reforming catalyst in the reaction bed to generate hydrogen and carbon monoxide, and the reformed gas in which the concentration of hydrogen and carbon monoxide is increased. It becomes. Since this reformed gas is useful as a raw material for obtaining a product gas containing an organic oxygenate in the production process, the reformed gas can be supplied to the production process alone or mixed with a synthesis gas.
  • the method for producing an organic oxygenated product of the present embodiment may include a [reuse step] in which the reformed gas is brought into contact with the synthesis catalyst by the above supply to obtain the product gas.
  • the production system for an organic oxygenate includes a generation unit, a separation unit, and a reforming unit.
  • generation part is equipped with the synthetic catalyst which produces
  • a synthesis gas containing hydrogen and carbon monoxide is introduced into the production section, a production gas containing an organic oxygenate and a hydrocarbon is produced by the action of the synthesis catalyst.
  • the separation unit includes a cooler and an activated carbon adsorber or a scrubber. The cooler is preferably installed upstream of the activated carbon or scrubber.
  • the reforming unit includes a reforming catalyst that generates carbon monoxide and hydrogen from hydrocarbon and steam.
  • the concentration of hydrogen (in terms of mol%) contained in the reformed gas is preferably 1.1 to 2.0 times the concentration of hydrogen contained in the separation gas.
  • the concentration (mole% conversion) of carbon monoxide contained in the reformed gas is preferably 1.1 to 2.0 times the concentration of carbon monoxide contained in the separation gas.
  • the method for producing the organic oxygenate of the first aspect of the present invention described above is carried out, so that the reforming efficiency of the hydrocarbons contained in the separation gas is increased, and the target organic oxygen It is possible to increase the CO conversion rate to the chemical compound.
  • the total amount of organic oxygenates in the separation gas obtained in the separation part is preferably less than 1000 ppm, more preferably less than 500 ppm, and even more preferably less than 100 ppm on a molar basis.
  • concentration of the organic oxygenate in the separated gas the more the reforming catalyst can be prevented from being poisoned and the reforming efficiency can be increased.
  • the total of organic oxygenates in the separation gas used in the reforming section is preferably less than 1000 ppm, more preferably less than 500 ppm, and even more preferably less than 100 ppm on a molar basis.
  • concentration of the organic oxygenate in the separated gas the more the reforming catalyst can be prevented from being poisoned and the reforming efficiency can be increased.
  • FIG. 1 shows an example of a production system for organic oxygenates.
  • the production system 10 includes a reactor 1 and a reactor 2 connected in series to form a reaction bed filled with a synthesis catalyst, a cooler 3 having a demister 3a connected to an outlet of the reactor 2, and a cooler 3 and an activated carbon adsorption tower 4 having an activated carbon tank filled with activated carbon.
  • Activated carbon adsorption towers are installed in two or more in series, filled with different types of activated carbon, or installed in parallel in two or more towers so that they can be replaced when the adsorption capacity decreases. Good.
  • the downstream side of the activated carbon adsorption tower 4 is branched into a bypass line and a reforming line.
  • the bypass line connects the outlet of the activated carbon adsorption tower 4 to the inlet of the reactor 1 so that the separated gas derived from the activated carbon adsorption tower 4 can be supplied to the reactor 1.
  • the reforming line connects the outlet of the activated carbon adsorption tower 4 to the reformer 5 and is connected to the reforming line before the reformer 5 and the hydrocarbons contained in the separated gas derived from the activated carbon adsorption tower 4. It is possible to supply the steam from the steam supply pipe to the reformer 5.
  • a cooler 6 is installed on the downstream side of the reformer 5.
  • the reformed gas led out from the reformer 5 is cooled, and the water vapor is liquefied and recovered.
  • the reformed gas dried by the cooler 6 can be supplied to the reactor 1.
  • a gas booster (GB) and a mass flow controller (MFC) are installed at a desired position of a line (pipe) through which gas flows, and the gas pressure and gas flow rate can be adjusted. .
  • the reactors 1 and 2 may be filled with only the synthetic catalyst, or may be filled with the synthetic catalyst and the diluent.
  • the diluent is for preventing excessive heat generation of the synthesis catalyst during the production of the organic oxygenates, for example, the same as the carrier of the synthesis catalyst, quartz sand, alumina balls, aluminum balls, aluminum shots, etc. Is mentioned.
  • Two reactors 1 and 2 are not necessarily required in series, but only reactor 1 may be used, or two or more reactors may be installed in parallel.
  • the reactors 1 and 2 and the reformer 5 are preferably materials that are inert to the synthesis gas and the separation gas, and preferably tubular materials that can withstand heating of about 100 to 800 ° C. and pressurization of about 10 MPa, For example, a stainless steel cylindrical tube is used.
  • the coolers 3 and 6 known ones can be applied, and at least the cooler 3 is preferably provided with a known demister.
  • the kind of demister is not specifically limited, For example, a mesh demister is mentioned.
  • the activated carbon adsorption tower 4 is preferably a porous activated carbon having a large surface area and arranged so that gas can flow.
  • the activated carbon adsorption tower 4 includes a heating means capable of heating the activated carbon, and a line branched on the downstream side of the activated carbon adsorption tower 4 in order to recover the organic oxygenates desorbed from the activated carbon by heating. It may be.
  • a gas containing hydrocarbons and having a total content of organic oxygenates of less than 1000 ppm on a molar basis and water vapor are brought into contact with the reforming catalyst,
  • the hydrogen concentration (in terms of mol%) contained in the reformed gas is preferably 1.1 to 2.0 times the concentration of hydrogen contained in the gas.
  • the concentration of carbon monoxide contained in the reformed gas (in terms of mol%) is preferably 1.1 to 2.0 times the concentration of carbon monoxide contained in the gas.
  • the modification step of the third aspect can be applied as the modification step of the first aspect of the present invention described above.
  • the separation gas to be reformed in the third aspect is not necessarily limited to the separation gas derived from the product gas of the first aspect.
  • the modification step of the third aspect can be performed in the same manner as the modification step of the first aspect.
  • the organic oxygenate and the hydrocarbon-containing gas are brought into contact with activated carbon, and the organic oxygenate is separated from the gas to separate the organic oxygenate from the gas.
  • separation process which reduces the sum total of oxygenates to less than 1000 ppm on a molar basis.
  • the gas containing the organic oxygenate and the hydrocarbon in the separation step of the third aspect is not necessarily limited to the product gas of the first aspect.
  • the separation step of the third aspect can be performed in the same manner as the separation step of the first aspect.
  • Rhodium chloride trihydrate (RhCl 3 ⁇ 3H 2 O) 15.4 g, lithium chloride monohydrate (LiCl ⁇ H 2 O) 0.96 g, manganese chloride tetrahydrate (MnCl 2 ⁇ 4H 2 O) ) 122 mL of an aqueous solution containing 8.66 g was dropped onto the primary support, impregnated, dried at 110 ° C. for 3 hours, and further calcined at 400 ° C. for 3 hours to obtain catalyst particles ⁇ of the synthetic catalyst 1.
  • catalyst particles ⁇ of the synthesis catalyst 2 were subjected to the same reduction treatment as the catalyst particles ⁇ .
  • the reactor 1 and the reactor 2 connected in series were heated at 300 ° C. for 4 hours while flowing a reducing gas (hydrogen concentration 30 vol%, nitrogen concentration 70 vol%) at a pressure of 0.3 MPaG at 6 NL / min.
  • the synthesis catalyst was subjected to a reduction treatment again.
  • alumina-supported nickel-based catalyst for steam reforming hydrocarbons such as methane, made of stainless steel with an inner diameter of 29.9 mm and a length of 700 mm
  • Hydrogen was passed through the reforming reactor at a pressure of 0.3 MPaG at a rate of 3 NL / min and steam of 3.6 NL / min.
  • the temperature was increased from 150 ° C. to 760 ° C. at a rate of 2 ° C./min, and reduced to the reforming catalyst. Treated.
  • Procedure 1 The raw synthesis gas was introduced into the reactor 1 and then passed through the reactor 2 to perform a production step in which an organic oxygenate and a hydrocarbon having 1 to 6 carbon atoms were produced by the synthesis catalyst.
  • the product gas led out from the outlet of the reactor 2 was passed through a cooler to separate most of the organic oxygenates as liquefied components.
  • a gas component containing hydrocarbons was led out as a separation gas from the outlet of the cooler.
  • Step 2 Among the branched circulation lines, the separation gas is circulated through a bypass line not equipped with a reformer, and while increasing the gas flow rate of the entire system to an appropriate amount, the temperature of the reactor 1 and the reactor 2 is increased to a desired appropriate temperature. Raised.
  • Procedure 3 A part of the separated gas that circulates the bypass line is circulated together with steam to the reforming line equipped with the reformer, and the concentration of hydrogen and carbon monoxide is increased by the reforming reaction. A reforming step for obtaining a reformed gas was performed.
  • Procedure 1 After the reaction bed temperature was lowered to 240 ° C., a mixed gas having the composition shown in Table 1 was circulated at 6 NL / min, and the reaction pressure was increased to 2.4 MPa. The produced gas was cooled as a separated gas after being cooled by a cooler (refrigerant temperature 5 ° C.). The reaction temperature was raised to 280 to 290 ° C. at a rate of 1 ° C./minute, and when the temperature was stabilized, the reaction was started. Details of Procedure 2: The pressure was increased from 0.9 MPaG to 2.44 MPaG with a gas booster (GB) while introducing the separation gas into the bypass line.
  • GB gas booster
  • the bypass gas flow rate was increased by mass flow (MFC) to 36 NL / min.
  • MFC mass flow
  • the reaction temperature in reactors 1 and 2 was adjusted to 280 to 290 ° C.
  • the reforming step in the procedure 3 was performed when the concentration of hydrocarbons in the gas circulating in the system increased. Details of Procedure 3: Water vapor is passed through the reformer 5 at a flow rate of 3 NL / min, the outlet temperature is raised to 760 ° C., and the temperature stabilizes, and then the separated gas flowing through the bypass line is reformed.
  • the gas flow rate was increased to 16.5 NL / min. Thereafter, the reforming reaction bed outlet temperature was stabilized at 760 ° C., and then the reformer inlet gas composition was analyzed by gas chromatography. Table 3 shows the result of analyzing the reforming outlet gas. Further, Table 4 shows theoretical values obtained by calculating the equilibrium composition at 760 ° C. and 1.0 MPa (0.9 MPaG) in the case of the separation gas composition shown in Table 2.
  • the reformer inlet gas contained more than 1000 ppm (0.1 mol%) of ethanol and ethyl acetate produced in the reactors 1 and 2 on a molar basis.
  • the reforming catalyst was poisoned by these organic oxygenates and the reforming efficiency was lowered.
  • Example 1 As shown in FIG. 1, an activated carbon adsorption tower 4 filled with 860 g of activated carbon (manufactured by Nippon Enviro Chemicals Co., Ltd .: granular white rice cake G2c10 / 20-2) was installed before the reforming line.
  • the activated carbon adsorption tower 4 has an ability to reduce the total of organic oxygenates such as ethanol and ethyl acetate contained in the separation gas to 10 ppm or less on a molar basis.
  • Table 5 shows the composition of the separation gas derived from the outlet of the activated carbon adsorption tower 4.
  • the reforming catalyst stably exhibited excellent efficiency as theoretically by separating the organic oxygenates such as ethanol and ethyl acetate produced in the reactor 1 with the activated carbon adsorption tower 4. it is obvious. Furthermore, under this condition, CO 2 is reduced from 16.7 mol% to 11.8 mol%, and a part of CO 2 is also converted to CO, and it is clear that the carbon source can be used more effectively.
  • Example 2 The same system as in Example 1 was used, and the procedure was substantially the same, but the organic oxygenate was produced according to the following procedure, which was partially different. Details of Procedure 1: After the reaction bed temperature was lowered to 240 ° C., a mixed gas having the composition shown in Table 8 was passed at 3.5 NL / min, and the reaction pressure was increased to 2.05 MPa. The produced gas was cooled as a separated gas after being cooled by a cooler (refrigerant temperature 5 ° C.). The reaction temperature was raised to 280 to 290 ° C. at a rate of 1 ° C./minute, and when the temperature was stabilized, the reaction was started.
  • Procedure 1 After the reaction bed temperature was lowered to 240 ° C., a mixed gas having the composition shown in Table 8 was passed at 3.5 NL / min, and the reaction pressure was increased to 2.05 MPa. The produced gas was cooled as a separated gas after being cooled by a cooler (refrigerant temperature 5 ° C.). The reaction
  • the amount of the separation gas introduced into the reactor 1 from the bypass line was 21 NL / min together with the newly introduced synthesis gas.
  • the reaction temperature in reactors 1 and 2 was adjusted to 280 to 290 ° C.
  • the reforming step of procedure 3 was performed. Details of Procedure 3: Water vapor is passed through the reformer 5 at a flow rate of 3.7 NL / min, the outlet temperature is raised to 778 ° C., and after the temperature has stabilized, the separation gas flowing through the bypass line is The gas was passed through the reformer 5 and the gas flow rate was increased to 17.5 NL / min.
  • the reactor 1 inlet gas composition was changed to Table 9
  • the reactor 2 outlet gas composition was changed to Table 10
  • the cooler outlet gas composition was changed to Table 11
  • Table 12 shows the reformer inlet gas composition
  • Table 13 shows the reformer outlet gas composition.
  • Table 14 shows theoretical values obtained by calculating the equilibrium composition at 778 ° C. and 0.77 MPa (0.67 MPaG) in the case of the separation gas composition shown in Table 12.
  • the hydrocarbon produced as a by-product when an organic oxygenate is produced from synthesis gas is efficiently reformed to hydrogen and carbon monoxide. Can do.
  • the hydrocarbon can be efficiently reformed into hydrogen and carbon monoxide.

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Abstract

L'invention concerne un procédé de production de composés oxygénés organiques, le procédé comprenant : une étape de génération dans laquelle un gaz de synthèse contenant de l'hydrogène et du monoxyde de carbone est mis en contact avec un catalyseur synthétique pour obtenir un produit gazeux contenant des composés oxygénés organiques et des hydrocarbures ; une étape de séparation dans laquelle les composés oxygénés organiques sont séparés du gaz produit pour obtenir un gaz séparé contenant les hydrocarbures ; et une étape de reformage dans laquelle le gaz séparé et la vapeur sont mis en contact avec un catalyseur de reformage pour obtenir un gaz reformé qui a une concentration en hydrogène et une concentration en monoxyde de carbone élevées par rapport à la concentration en hydrogène et à la concentration en monoxyde de carbone contenues dans le gaz séparé. Le total des composés oxygénés organiques dans le gaz séparé utilisé dans l'étape de reformage est inférieur à 1 000 ppm sur une base molaire.
PCT/JP2017/017674 2016-05-12 2017-05-10 Procédé de reformage d'hydrocarbures, procédé de production de composés oxygénés organiques et système de production de composés oxygénés organiques WO2017195817A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012025655A (ja) * 2010-07-23 2012-02-09 IFP Energies Nouvelles 中間圧力でのパージによる水素製造方法
JP2012149089A (ja) * 2009-02-12 2012-08-09 Ichikawa Office Inc エタノールの製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012149089A (ja) * 2009-02-12 2012-08-09 Ichikawa Office Inc エタノールの製造方法
JP2012025655A (ja) * 2010-07-23 2012-02-09 IFP Energies Nouvelles 中間圧力でのパージによる水素製造方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Effect Of Shale Plays On U.S. Natural Gas Composition", PIPELINE & GAS JOURNAL, vol. 241, no. 7, July 2014 (2014-07-01), pages 38 - 41 *
"LNG Shokibo Kichi (Gijutsu Guideline", THE JAPAN GAS ASSOCIATION, December 2000 (2000-12-01), pages 1 *
KAGAKU BINRAN (OYOHEN, 25 October 1965 (1965-10-25), pages 1072 *

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