WO2020175444A1 - Système de synthèse de méthanol et procédé destiné à ladite synthèse - Google Patents

Système de synthèse de méthanol et procédé destiné à ladite synthèse Download PDF

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WO2020175444A1
WO2020175444A1 PCT/JP2020/007378 JP2020007378W WO2020175444A1 WO 2020175444 A1 WO2020175444 A1 WO 2020175444A1 JP 2020007378 W JP2020007378 W JP 2020007378W WO 2020175444 A1 WO2020175444 A1 WO 2020175444A1
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Prior art keywords
oxygen carrier
reactor
reaction
hydrogen
rei
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PCT/JP2020/007378
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English (en)
Japanese (ja)
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阿尻　雅文
多紀郎 野口
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国立大学法人東北大学
株式会社スーパーナノデザイン
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Priority to JP2021502249A priority Critical patent/JP7451865B2/ja
Publication of WO2020175444A1 publication Critical patent/WO2020175444A1/fr

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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
    • C01B3/22—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/04—Methanol
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the present invention relates to a methanol synthesis system and a method thereof.
  • Methanol synthesis has a production amount comparable to that of ethylene, which is 1.21 million and propylene, which is 0.881:1. Reforming methane to synthesize hundred and! - 1 2, from the syngas, are methanol synthesis (2 7 0 ° ⁇ ⁇ 3 0 0 ° ⁇ ).
  • the methane reforming reaction is an endothermic reaction, which requires a reaction in a high temperature field, and methane combustion and hydrogen by-product combustion are performed to supply the heat. For this reason, it has become a accompanied process a large hundred 2 emissions.
  • a reforming reaction technique is known as a method for producing hydrogen from a hydrocarbon-based material.
  • the reforming reaction technique is steam reforming, dry reformate Min grayed using hundred 2, partial oxidation and the like with air-oxygen.
  • the ratio of ⁇ and hydrogen must be 1: 2 or more, Steam reforming is required.
  • Non-Patent Document 1 Low-temperature waste heat of less than 500 ° ⁇ is released to the outside of the chemical process system with almost no use, and by proposing a technology for utilizing low-temperature waste heat, energy conservation and 3_Rei there is ⁇ want room to reduce 2 emissions.
  • the total amount of low-temperature waste heat of less than 500 ° ⁇ in Japan is estimated to be 1,018 betajuules (") per year. This corresponds to about 10% of the total energy consumed in Japan (see Non-Patent Document 1). Loss of low-temperature waste heat is a common problem not only in Japan but around the world.
  • Non-Patent Document 1 The Energy conserveat i on Center, Japan, https ://www. as i ae ec-co L. eccj .or. j p/ (accessed 26 December 26, 2018)
  • the membrane reactor is not suitable for large-scale treatment of hydrocarbon materials, and it is desirable to solve the problem by another approach.
  • the present invention has been made in view of the above problems, and an object thereof is to perform steam reforming of a hydrocarbon-based material at low temperature by utilizing low-temperature waste heat of less than 700 ° C. To do.
  • the present inventors have found that a reaction that produces hydrogen and carbon oxides from a hydrocarbon-based material and a reaction that produces hydrogen from water. It was found that the above object can be achieved by individually executing the above, and the present invention has been completed. Specifically, the present invention provides the following. ⁇ 0 2020/175 444 4 (: 170? 2020 /007378
  • the invention according to the first feature comprises a hydrogen and synthesis gas production system, and a methanol synthesis system for synthesizing methanol using at least a part of the hydrogen and the synthesis gas as raw materials.
  • the gas production system includes a first reactor that reacts an oxygenated oxygen carrier with a hydrocarbon-based material to generate hydrogen and carbon oxides, and a reduced oxygen carrier and water with each other.
  • a hydrogen co-producing methanol synthesizer which has a second reactor for producing oxidized oxygen carrier and hydrogen, and the oxygen carrier circulates and flows between the first reactor and the second reactor. To do.
  • an oxidation reaction of a hydrocarbon-based material and a reduction reaction of an oxygen carrier occur in the first reactor.
  • the lattice oxygen of the oxygen carrier is used for the oxidation reaction of the hydrocarbon-based material, and the oxidation reaction produces hydrogen and carbon oxides. Since no water is used as a raw material in the first reactor, all substances that can be produced when a hydrocarbon material and water are reacted in a single reactor 1 to 1 2 ⁇ , ⁇ ⁇ , ⁇ ⁇ 2 , 1 to 1 2 ) do not exist in the same reaction field. Thus, all materials in the same reaction field constraints (0 ⁇ ⁇ 1-1 2 ⁇ , hundred, hundred 2, 1-1 2) caused by the presence reaction equilibrium can be avoided.
  • the oxygen component contained in water oxidizes the oxygen carrier, whereby hydrogen is produced.
  • the reaction in the second reactor depending on the type of oxygen carrier material (determined by the magnitude of the redox potential of the oxidation agent), for example in the case of using a Rei_6_rei 2,
  • the oxidized oxygen carrier which is an exothermic reaction and one of the reaction products in the second reactor, can recover the heat capacity generated by the exothermic reaction.
  • the oxygen carrier circulates and flows from the second reactor to the first reactor, and the oxygen carrier that has absorbed the waste heat in the first reactor is brought into contact with the hydrocarbon-based material so that the hydrocarbon-based material is The heat required for the endothermic reaction with is supplied. External waste heat from other processes can also be used. That is, in the invention according to the first feature, the oxygen carrier can function not only as a transport source of oxygen but also as a transport source of heat. ⁇ 0 2020/175 444 5 (: 170? 2020 /007378
  • the invention according to the second feature comprises: a hydrogen and synthesis gas production system; and a methanol synthesis system for synthesizing methanol using at least a part of the hydrogen and the synthesis gas as raw materials.
  • the gas production system includes a plurality of reactors filled with an oxygen carrier, the plurality of reactors are configured to be able to introduce a hydrocarbon-based material or water, and among the plurality of reactors, It is possible to introduce the hydrocarbon-based material into the reactor in which the oxygen carrier is in an oxidized state and oxidize the hydrocarbon-based material.
  • a methanol synthesizing apparatus capable of switching a material to be introduced between the hydrocarbon-based material and the water.
  • the invention according to the third feature provides an apparatus wherein the reaction temperature in the invention according to the first or the second feature is 600°C or less.
  • low temperature waste heat of 600°C or less is used as a hydrocarbon material. ⁇ 0 2020/175 444 6 ⁇ (: 170? 2020 /007378
  • cerium oxide (Rei_6_rei 2), chromium-doped cerium oxide ( ⁇ "one Rei_6 ⁇ 2 ), Iron oxide-zirconia-based composite oxide ( 6 ⁇ Father 2 “ ⁇ 2 ), Iron oxide (6 2 ⁇ 3 ), Indium oxide ( ⁇ n 2 ⁇ 3 ), Yttrium-stabilized zirconium oxide (3) ), scandium oxide-doped zirconium oxide (3 0 3 7), scandium oxide ( 3 0 2 0 3 ), lanthanum gallium oxide (!_
  • the oxygen carrier is a specific material
  • the low temperature waste heat generated by the known exothermic reaction such as methanol synthesis or ammonia synthesis can be used for the reforming reaction of hydrocarbon material to hydrogen. , ⁇ it wants to reduce energy saving and hundred 2 emissions.
  • the invention according to a fifth feature is the invention according to any one of the first to fourth features, wherein the oxygen carrier and the metal cocatalyst coexist inside the reactor. ⁇ 0 2020/175 444 7 ⁇ (: 170? 2020 /007378
  • the reforming reaction of the hydrocarbon-based material can be more efficiently advanced by the action of the metal promoter.
  • the invention according to a sixth feature provides a device in which the average primary particle diameter of the oxygen carrier in the invention according to any one of the first to third features is 1 or less.
  • the exposed surface area (contact possibility) with the hydrocarbon-based material that is the reactant in the first reactor and with the water that is the reactant in the second reactor is to become large, increasing efficiency for the oxygen carrier oxygen transfer, for advanced reforming reaction to hydrogen from hydrocarbon material even at low temperatures, as a result, energy saving - ⁇ wants to reduce and hundred 2 emissions.
  • the invention according to a seventh feature provides a system in which the oxygen carrier in the invention according to any one of the first to sixth features has a shape having the most active exposed surface.
  • the shape of the oxygen carrier is a substantially octahedral and / or substantially cubic body, oxygen carriers, a (1 1 1) plane and / or (1 0 0) plane It has as the main exposed surface.
  • the (100) plane of the oxygen carrier is unstable and has a greater oxygen mobility (oxygen storage/release capacity). Therefore, according to the engagement Ru invention ninth feature, since the advanced reforming reaction to hydrogen from hydrocarbon material even at low temperatures, as a result, ⁇ it wants to reduce energy saving and ⁇ 3_Rei 2 emissions.
  • the invention according to the eighth feature corresponds to a category difference from the invention according to the first feature.
  • the invention according to the ninth feature corresponds to a category difference from the invention according to the second feature. According to the inventions according to the eighth and ninth features, it is possible to process a large amount of reforming of a hydrocarbon material into hydrogen in a short time by utilizing a low temperature waste heat of 700 ° C. is there. ⁇ 0 2020/175444 8 ⁇ (: 170? 2020/007378 Effect of invention
  • Fig. 1 is a configuration example of a hydrogen and synthetic gas manufacturing system 1 in the methanol synthesizing apparatus according to the present embodiment.
  • FIG. 2 is a diagram showing the relationship between the oxygen storage/release capacity (0 30) of oxygen carriers and the oxygen release rate constant.
  • FIG trioctahedral is Kino ⁇ 3_Rei-hundred 2 emission map and was methane reforming reaction 9 0 0 ° ⁇ using system 1.
  • FIG 3 Snake is Kino ⁇ 3_Rei-hundred 2 emission map and was methane reforming reaction 6 0 0 ° ⁇ using the system 1.
  • FIG 3_Rei is Kino ⁇ 3_Rei-hundred 2 emission map and was methane reforming reaction 4 0 0 ° ⁇ using the system 1.
  • [30] 3 0 is Kino ⁇ 3_Rei-hundred 2 emission map and was methane reforming reaction 3 0 0 ° ⁇ using the system 1.
  • FIG. 4 eight shows a relationship between the Been methane reforming reaction Kino reaction temperature conversion and ⁇ 3_Rei 2 emissions using a system according to the prior art.
  • 4 Snake shows the relationship between the reaction temperature and the conversion and (3 0 2 emissions when subjected to methane reforming reaction using the hydrogen production system 1 according to this embodiment shaped condition.
  • FIG. 5 is a diameter of 1 0 and height 3 0_Rei the scale of the reactor at 1 5 0 0 1: - ⁇ 1-1 4 / day for feasible methane reforming This is the result of simulating the relationship between the oxygen carrier particle IV! (0) and the oxygen release rate constant.
  • Fig. 6 shows the flow of each compound and energy in each reactor in the hydrogen production system 1.
  • Fig. 7 shows the equivalence ratio in the reforming reaction from methane to methanol.
  • Fig. 8 is an example of a conventional methane reforming process.
  • FIG. 9 is in the synthesis of chromium-doped cerium oxide ( ⁇ "one Rei_6_rei 2) ⁇ 0 2020/175 444 9 ⁇ (: 170? 2020 /007378
  • FIG. 2 is a schematic diagram of a synthesizing apparatus 30 used.
  • FIG. 10 is a diagram showing the results of evaluation of oxygen storage/release capacity ( ⁇ ) in the low temperature range in Test Example 2-1.
  • Fig. 11 is a diagram showing the relationship between the atomic column of cerium element and the oxygen vacancy forming property in particles in Test Example 2-2.
  • Fig. 12 shows an image of the cerium element DET IV! in Test Example 2-2.
  • FIG. 13 is a diagram showing a rate of expansion of voids of cerium element in Test Example 2-2.
  • Fig. 14 shows the relationship between the ratio of lattice expansion in cerium nanoparticles and the energy required to form oxygen vacancies between cerium atoms in Test Example 2-2. Is.
  • Figure 1 5 is a test example 2 - In 3 is a diagram showing the results of the feeder and subjected to Metan oxygen carrier response experiments in a batch reactor when the oxygen carrier is a ⁇ 6_Rei 2 Nanokyu Bed ..
  • Figure 1 6 is Test Example 2 - In 3, the oxygen carrier is an iron oxide Jirukoni A-based composite oxide methane (6 ⁇ father one " ⁇ 2) batch reactor at a - oxygen carrier reaction It is a figure which shows the result at the time of experimenting.
  • Fig. 17 shows the result of simulating the industrial scale of the chemical loop manufacturing system 1 shown in Fig. 1.
  • the methanol synthesis apparatus includes a hydrogen and synthesis gas production system, and a methanol synthesis system that synthesizes methanol using at least a part of the hydrogen and the synthesis gas obtained from the production system as raw materials.
  • the hydrogen and synthesis gas production system in the present embodiment includes a first reactor and a second reactor.
  • the system may be a chemical loop type system in which an oxygen carrier circulates and flows between the first reactor and the second reactor, or a cyclic operation system in which gases are alternately switched to perform switching. Good.
  • the form of the system is not particularly limited, and may be a two-column circulation type fluidized bed or a form in which the stationary phase reactor is operated by switching. Among them, it is preferable that the system form is a two-column circulation type fluidized bed, since reforming of hydrocarbon material to hydrogen can be performed in a larger amount.
  • Figure 1 shows an example of the configuration of system 1 when system 1 is a two-column circulation type fluidized bed catalytic reactor.
  • the system 1 comprises a first reactor 10 and a second reactor 20.
  • the first reactor 10 has a first inlet 11 and a first outlet 12.
  • the hydrocarbon material is supplied from the first inlet 11. Then, as the hydrocarbon-based material moves from the first inlet 11 toward the first outlet 12, the hydrocarbon-based material and the oxidized oxygen carrier IV! inside the first reactor 10 ( ⁇ ) reacts with each other to generate reduced oxygen carrier IV! (), hydrogen and carbon oxide. Then, hydrogen and carbon oxides are discharged from the first outlet 12. On the other hand, the reduced oxygen carrier IV! () circulates and flows toward the second inlet 21 of the second reactor 20.
  • IV! ( ⁇ ) represents an oxidized oxygen carrier
  • IV! () represents a reduced oxygen carrier
  • an oxidation reaction of the hydrocarbon-based material and a reduction reaction of the oxygen carrier occur in the first reactor 10.
  • the lattice oxygen of the oxygen carrier is used for the oxidation reaction of the hydrocarbon-based material, and the oxidation reaction produces hydrogen and carbon oxides.
  • water is not used as a raw material in the first reactor 10, all substances (0 ⁇ 1 ⁇ 1 2 0) that can be produced when a hydrocarbon material and water are reacted in a single reactor. , hundred, hundred 2, 1-1 2) will not be present in the same reaction field.
  • all materials in the same reaction field (0 ⁇ 1-1 2 ⁇ , O O, 00 2, 1 and 1 2) can be avoided constraints caused by the reaction equilibrium that exists.
  • an oxygen carrier redox cycle is used.
  • the oxygen carrier is preferably a solid electrolyte so that the redox cycle can be realized at less than 700 ° .
  • the solid electrolyte is preferably a material finely divided into nanoparticles, and in the long-periodic periodic table, the boron of the group ⁇ ⁇ ⁇ ⁇ 1 ⁇ V ⁇ group silicon (3 I) — Arsenic of Group V (8 3) _ Tellurium of Group I
  • An example is an element on the line with the line as the boundary, and an element on the left side or below the boundary in the long period type periodic table.
  • the elements of the V group of V group are ⁇ , ⁇ , 1 ⁇ 1 [3 ⁇ 4 Rei_1, ⁇ 3, I ", 1: etc., the I Snake Group element in ⁇ Li, eight 9, Hachiri etc., Chapter II Snake group elements ⁇ , etc.
  • oxygen carrier cerium oxide (Rei_6_rei 2), chromium-doped oxidation of cerium ( ⁇ "one Rei_6_rei 2), iron oxide-zirconia based composite oxide (6 ⁇ Father Iron oxide (6 2 ⁇ 3), indium oxide ( ⁇ 2 ⁇ 3), said tri-um-stabilized zirconium oxide ( ⁇ 3), scandium oxide doped oxide Gilles Koniumu (3_Rei 3), scandium oxide (3_Rei 2 ⁇ 3 ), Lanthanum oxide ⁇ 0 2020/175 444 12 (: 170? 2020 /007378
  • the low temperature waste heat generated by known exothermic reactions such as methanol synthesis or ammonia synthesis can be used as a heat source from the outside to the first reactor 10. and ( ⁇ want to reduce 3_Rei 2 emissions.
  • the oxygen carrier cerium oxide (Rei_6_rei 2), chromium-doped oxide cell potassium ( ⁇ "one Rei_6_rei 2), iron oxide-zirconia based composite oxide (6 ⁇ father one" ⁇ 2), lanthanum It is preferable to contain at least one selected from the group consisting of strontium manganite (I-31 ⁇ / ⁇ ) and lanthanum threontium cobalt ferrate (!_30).
  • oxygen carriers may be used alone or in combination of two or more.
  • the oxygen carrier and the metal cocatalyst coexist inside the first reactor 10, or that the oxygen carrier carry the metal cocatalyst.
  • the reaction in the first reactor 1 0, as reforming reaction of hydrocarbon-based materials, in addition to the production of 1 to 1 2 is the reaction product, 1 1 to 1 2 is further oxidized to 1 2 A reaction that produces ⁇ also occurs.
  • the presence of metal promoter, from 1 to 1 2 can be released to the metal, to prevent oxidation from 1 to 1 2 to! - 1 2 ⁇ , as possible out to increase from 1 to 1 2 recovery amount.
  • the kind of the metal co-catalyst is not particularly limited, and transition metals, noble metals and alloys thereof can be exemplified. Specifically, 1 ⁇ 1 ⁇ ⁇ , [3 ⁇ 4, 9 ⁇ , 6 ⁇ 0,
  • the oxygen storage/release capacity of the oxygen carrier (030 means the number of moles of oxygen contained in the oxygen carrier of unit mass.
  • the value of ⁇ of the oxygen carrier is not particularly limited. In order to shorten the reaction time in the first reactor 10 and the second reactor 20 without increasing the size of the first reactor 10 and the second reactor 20, the oxygen storage/release capacity ( ⁇ 30 is preferably as large as possible.
  • the reaction temperature in the first reactor 10 is 0. 30. 0. 2 0 1 0 1 1/1 ⁇ 9 (200 1110 1/9) or higher. It is preferable that it is ⁇ 3 ⁇ 1 ⁇ ⁇ /1 ⁇ 9 (300 1110 1/9) or more, and it is ⁇ 4 ⁇ 1 ⁇ 1/1 ⁇ 9 (400 ⁇ 1/) or more. It is even more preferable, and it is particularly preferable that it is 0.51 ⁇ 10 1/1 ⁇ 9 (500° 1/) or more.
  • !_ 31 ⁇ / ⁇ is ⁇ 30 at 350° ⁇ ! .1 5 0 1 1/1 ⁇ 9 (1, 150 0 I/9).
  • the lanthanum strontium cono-noretoferrite (!_30) at 350°° is ⁇ 783 ⁇ 1 ⁇ 1/1 ⁇ 9 (783 ⁇ ! ⁇ ⁇ /9).
  • Oxygen carrier 03(3) is measured by the following method 1 or method 2.
  • the oxygen release rate constant corresponds to the time that the oxygen carrier stays inside the first reactor 10.
  • the lower limit of the oxygen release rate constant is not particularly limited, but in order to realize the shortening of the reaction time in the first reactor 10, the oxygen release rate constant is ⁇ 0.02 ⁇ n- l (reaction time : 50 minutes or less), ⁇ .03 ⁇ 1 ⁇ n- l or more (reaction time: 33 minutes or less), more preferably ⁇ .04 ⁇ 1 ⁇ n- l or more (reaction time: 25 minutes or less) is more preferable, and 0.05 min n- l or more (reaction time: 20 minutes or less) is more preferable, and 0.1 min. It is particularly preferable that it is I 1 -1 or more (reaction time: 10 minutes or less).
  • the oxygen release rate constant is not particularly limited, the oxygen release rate constant is not more than 0.25 25! I n - 1 (reaction time) in order to surely advance the reaction in the first reactor 10. : 4 minutes or more) is preferable, and ⁇ . It is more preferably n- l or less (reaction time: 5 minutes or more).
  • the product of 03 (3 and the oxygen release rate constant is an effective indicator of the reaction efficiency in the first reactor, and the unit is 111 ⁇ I It is 1 ⁇ 4.
  • the value of this product is not particularly limited, but when considering the above-mentioned large-scale synthesis of methanol as an example, the value of 0.04 1 0 1 0 1 If it is above, ⁇ ⁇ is ⁇ .
  • the size of the first reactor 10 is 700 ° in a normal size reactor having a diameter of 10 and a height of 30 .
  • Fig. 2 is a diagram showing the relationship between 03 (3 and the oxygen release rate constant, where the horizontal axis (X axis) is the oxygen release rate constant and the vertical axis (V axis) is 03 (3).
  • the release rate constant By setting the conditions so that it falls within the area surrounded by 25 (white area in Fig. 2), the low temperature waste heat of less than 700 ° C can be used without increasing the size of the first reactor. A large amount of methane reforming reaction can be realized in a shorter time.
  • the upper limit of the average primary particle size of the oxygen carrier is not particularly limited, but it should be 1 or less from the viewpoint of maximizing the exposed surface area (contactability) with the reactant and the ease of forming oxygen vacancies due to lattice strain. Is preferable, more preferably 100 nm or less, and 50 n It is more preferable that it is not more than 30 nm, and it is further preferable that it is not more than 30 nm. It is particularly preferable that
  • the lower limit of the average primary particle diameter of the oxygen carrier is also not particularly limited.
  • nano particles are made into secondary particles by compaction molding, and the secondary particles are used in a packed bed reactor for cyclic operation or as a circulating fluidized bed particle.
  • the average primary particle diameter of the oxygen carrier is determined by capturing an image of the oxygen carrier particles with a Ding 1 ⁇ /1 (transmission electron microscope), and analyzing the Ding 1 ⁇ /1 image by image analysis. ⁇ It is assumed that the value is obtained by analyzing with image measurement software.
  • the shape of the oxygen carrier has a greater oxygen mobility at low temperature (°30), it is necessary to expose the most active surface, which determines the particle shape. varies depending on the kind of the oxygen carrier material, it is the most unstable surface heat force histological its information can be easily obtained from your material data base over the scan, and the like.
  • 0-shaped oxygen carrier in the case of 6_Rei 2 is substantially cubic, (1 0 0) is preferably the surface and major exposed surfaces. for 6 3 ⁇ 4, preferably in the (1 1 0) plane of the major exposed surface.
  • 0 6_Rei second nanoparticle catalyst may be in the form of octahedral or cubic. Also, ⁇ 0 2020/175 444 17 ⁇ (: 170? 2020/007378
  • 0 6_Rei 2 nanoparticles catalysts have a (1 1 1) plane, 1 1 0 surface and / or (1 0 0) plane major exposed surface.
  • metal oxide nanoparticles having an active surface exposed at 30% or more of the particle surface are preferable.
  • the active surface is the most stable surface energetically, a Rei_6_rei in 2 (1 0 0) plane. This allows oxygen transfer at low temperatures.
  • ⁇ percentage is exposed (1 0 0) plane in the surface of the 6_Rei 2 nanoparticles, 3 0%, more preferably at least 50%, 7 0% or more is not more preferable .
  • the ratio that is exposed (1 0 0) plane in the surface of the ⁇ 6_Rei 2 nanoparticles are measured by Chomi IV!.
  • the Rei_6_rei 2 nanoparticles preferably a this transition element is doped.
  • ⁇ 60 2 Examples of transition elements doped into nanoparticles include ⁇ ”, ⁇ , “, etc. Among them, ⁇ ”, Is preferred.
  • the doping amount of the transition elements in ⁇ 6_Rei 2 nanoparticles is based on the total weight of Rei_6_rei 2, ⁇ . 1 ⁇ ⁇ % or more is preferable, ⁇ ⁇ % or more is more preferable, 100 ⁇ ⁇ % or more is still more preferable, 150 ⁇ 10 ⁇ % or more is still more preferable,
  • vacancies formed on the reduced ceria surface cause a reaction with water molecules and combine with oxygen to form the tetradecavalent state 0 6.
  • the released hydrogen molecules are transferred to a decomposition compound to cause a hydrogenation reaction.
  • the method for producing the oxygen carrier is not particularly limited, but when the oxygen carrier is metal oxide nanoparticles, for example, Patent No. 3 047 1 1 0 (one of the inventors of the patent is the present invention Can be manufactured by the method disclosed in (1).
  • metal salts (genus metal, genus genus, metal genus, genus genus metal, genus metal
  • Group I metal Group I metal, Group I metal, Group IV metal, Group IV metal, Group V metal,
  • a metal salt of V metal, VI metal, VII metal, transition metal, etc. at a temperature of 200°C or higher at a subcritical or supercritical condition of water, and a pressure of 160°C.
  • water is made into high-temperature and high-pressure water in a supercritical state or a subcritical state via a pressurizing means and a heating means, and before the fluid raw material is combined with this high-temperature and high-pressure water,
  • a method for producing fine particles using high-temperature high-pressure water in which the high-temperature high-pressure water is cooled to a temperature lower than the critical temperature, and then the high-temperature high-pressure water and the fluid raw material are combined and mixed in a mixing section and then guided to a reactor.
  • the metal oxide nanoparticles are produced by a method disclosed in, for example, Japanese Patent No. 39255936 (one of the inventors of the patent is the inventor of the present application). Can be collected afterwards.
  • the surface of the nanoparticles is organically modified by binding to the surface of the nanoparticles through
  • octahedra ⁇ 6_Rei 2 nanoparticles can be synthesized by a known method.
  • Nanoparticles cube 0 6_Rei 2 (1) Preparation child a raw material solution in toluene, (2) an organic modifier using a cube 0 6 ⁇ 2 in supercritical water conditions synthesizing the nanoparticles, and (3) is synthesized by a method comprising removing the organic modifier without changing the cube 0 6 0 2 forms.
  • the preparation of the nanoparticles of cubic ⁇ 6_Rei 2 can be performed as follows. This is a non-limiting example.
  • a nanoparticle precursor solution of cubic cerium oxide is prepared. After that, the precursor solution is mixed with continuous stirring to obtain a clear solution. The precursor solution is mixed with deionized water and heated rapidly to 600-700 by using a furnace. Then the mixture is cooled. Cubic cerium oxide nanoparticles are obtained as a dispersion in a mixture of water, toluene and unreacted raw materials. Add ethanol to the nanoparticles in the toluene phase and centrifuge and decant. ⁇ 0 2020/175 444 20 (: 170? 2020 /007378
  • the particles are dispersed in cyclohexan and then freeze dried under vacuum.
  • the collected nanoparticles are calcined in air at temperatures as high as 300 ° C for several hours in order to remove any organic ligands from the surface of the particles.
  • the calcined nanoparticle clarified by centrifugation and inclined ⁇ , then dried under reduced pressure, thereby obtaining nanoparticles cube 0 Yi_ ⁇ 2.
  • the hydrocarbon-based material refers to a compound containing carbon and hydrogen in the molecule or a mixture thereof, and may contain other elements such as oxygen in the molecule.
  • Examples of hydrocarbon-based materials include hydrocarbons, alcohols, ethers, biofuels and the like.
  • the hydrocarbons are materials containing an alicyclic hydrocarbon, a cyclic or acyclic aliphatic hydrocarbon as a single component or a mixed component.
  • Alicyclic hydrocarbons include, for example, cyclohexane, methylcyclohexane, dimethylcyclohexane, 1,3,5-trimethylcyclohexane and other monocyclic alicyclic compounds, decalin, methyldecalin, tetralin (tetrahydronaphthalene), methyltetralin. And the like, tricyclic alicyclic compounds such as tetradecahydroanthracene, and the like.
  • Acyclic aliphatic hydrocarbons include Alkanes consisting of (methane, ethane, propane, butane, etc.) are included. Also, as hydrocarbons, natural gas,! _ ⁇ (liquefied petroleum gas), city gas, gasoline, naphtha, kerosene, diesel oil, etc. are also included.
  • Examples of alcohols include methanol, ethanol, 2-propanol and the like.
  • Examples of ethers include dimethyl ether and the like.
  • Examples of biofuels include biogas, bioethanol, biodiesel, and biojet.
  • the upper limit of the reaction temperature is not particularly limited, however, since the low temperature waste heat is used, the upper limit is preferably 600°C or less, more preferably 55°C or less. ⁇ 0 2020/175444 21 ⁇ (: 170? 2020 /007378
  • the lower limit of the reaction temperature should be that the oxygen carrier has sufficient oxygen mobility (oxygen storage/release capacity), and from the viewpoint of effectively utilizing the low temperature waste heat, the lower the reaction temperature is, the lower the reaction temperature is. Is more preferable.
  • Examples of the lower limit of the reaction temperature include room temperature or higher, 100°° or higher, 150°° or higher, 200°° or higher, 250°° or higher, and the like.
  • the upper limit of the reaction time is not particularly limited, but in order to achieve further shortening, the reaction time is preferably 50 minutes or less, more preferably 33 minutes or less, and even 25 minutes. It is more preferably not more than 20 minutes, even more preferably not more than 20 minutes, particularly preferably not more than 10 minutes.
  • the lower limit of the reaction time is not particularly limited, but the reaction time is preferably 4 minutes or more, and more preferably 5 minutes or more in order to surely proceed the reaction in the first reactor 10. More preferable.
  • the material of the first reactor 10 is not particularly limited, and is not limited to a material having high temperature resistance such as chrome-molybdenum steel and stainless steel, and may be ordinary steel.
  • the reaction from a hydrocarbon material to hydrogen requires a high temperature condition of 700 ° C or higher, and the material of the reactor is also a temperature resistant material such as chrome-molybdenum steel or stainless steel. It needs to be expensive.
  • low temperature waste heat can be used, and ordinary steel having relatively small temperature resistance can also be used.
  • a material having high temperature resistance imposes a large load on the environment when manufacturing the material.
  • the greenhouse gas emissions in the life cycle of manufacturing chrome molybdenum steel and stainless steel are 2.42 and 4.3 5 ! ⁇ 9 _ ⁇ , respectively. ⁇ 2 equivalents / 1 ⁇ 9 _ steel (see Non-Patent Document 2).
  • the greenhouse gas emissions in the life cycle of manufacturing ordinary steel are limited to 2.1 1 kg _ C ⁇ 2 equivalents/kg _ steel (see Non-Patent Document 2).
  • the second reactor 20 has a second inlet 21 and a second outlet 22. Water is supplied from the second inlet 21. Then, as the water moves from the second inlet 21 toward the second outlet 22, the water reacts with the reduced oxygen carrier M () inside the second reactor 20 and is oxidized. It produces oxygen carrier M (0) and hydrogen. Then, hydrogen is discharged from the second outlet 22. On the other hand, the oxidized oxygen carrier M ( ⁇ ) circulates toward the first inlet 11 of the first reactor 10.
  • M () represents a reduced oxygen carrier
  • M (o) represents an oxidized oxygen carrier
  • the hydrogen is discharged from the outlet of the second reactor 20, the system as a whole, cut with recovery and high purity hydrogen and a mixed gas of C_ ⁇ (C0 2) and H 2.
  • a medium coexists, or that an oxygen carrier carry a metal promoter.
  • metal promoter a 1 to 1 2 can be released to the metal, to prevent oxidation from 1 to 1 2 to 1 to 1 2 ⁇ , it can be increased 1-1 2 recovery amount.
  • the oxygen component contained in water oxidizes the oxygen carrier, which produces hydrogen.
  • the reaction in the second reactor 20 is an exothermic reaction, and the reaction suitably proceeds even at low temperature. Therefore, the reaction temperature in the second reactor 20 is not particularly limited.
  • the reaction in the second reactor 20 is an exothermic reaction
  • the oxidized oxygen carrier IV! ( ⁇ ) which is one of the reaction products in the second reactor 20 is It is possible to recover the waste heat generated by the exothermic reaction.
  • Oxygen carrier IV! (0) circulates from second reactor 20 to first reactor 10 and absorbs waste heat in first reactor 10!
  • the heat required for the endothermic reaction of the hydrocarbon-based material is supplied by bringing the hydrocarbon-based material into contact with the hydrocarbon-based material. That is, the system 1 described in the present embodiment can not only function the oxygen carrier as the oxygen transport source, but also function as the heat transport source. It is possible to suppress the amount of heat supplied to the container 10.
  • the methanol synthesis system (not shown), which is one component of the methanol synthesis apparatus according to the present embodiment, synthesizes methanol using at least a part of hydrogen and synthesis gas obtained from the hydrogen and synthesis gas production system 1 as raw materials.
  • System The configuration of this system is not particularly limited.
  • Hexanoic acid decoration synthesized by supercritical method as oxidised oxygen carrier ⁇ 60 2 nanocube manufactured by Aitec Co., Ltd., 0831 ⁇ 1 ⁇ .1 306 -3 8-3, average primary particle size : 10 nm ⁇ 3 nm
  • this nanocube is controlled by using an organic modifier (hexanoic acid in this example) so that the (100) plane becomes the main exposed surface. .. Therefore, the nano-cube was burned at 300° for 2 hours to remove the organic modifier from the nano-cube.
  • Rei_6_rei 2 Rei_6_rei of 2 nanocubes was Rei_6_rei 2 Rei_6_rei of 2 nanocubes. It should be noted that the color of Rei_6_rei 2 nano cube was a yellow.
  • Rei_ ⁇ _ ⁇ 2 is reacted with nanocube and methane was conducted the first reaction producing a carbon dioxide Rei_ ⁇ 2 ⁇ 3 nanocubes and hydrogen.
  • the internal volume of the reactor was 5011_. Before the reaction, the 0. 19 0 62 0 2 nanocube was placed in a batch reactor under an atmosphere of 8 "in a glove box. After that, methane (purity: 99. 99995%, manufactured by Tanuma Oxygen Company) was introduced into the reactor at a pressure of 0.61 ⁇ /1 3. The reactor was placed in an electric furnace heated to the temperature shown in Table 1. After reacting for 10 to 60 minutes, the reactor was placed in a water bath. Upon cooling, a gas bag was used to collect the gas product through a valve fitted to the reactor.
  • the gas product recovered in the gas bag was analyzed by a gas chromatograph equipped with a thermal conductivity detector (device name: 001-001 0000-201 4, packing material: 31 ⁇ 1 1 1 ⁇ 10 8 [3 ⁇ 4mi ⁇ 37 50/80) was used for analysis.
  • the same batch reactor used in the first reaction was equipped with 0 6 2 0 3 nanocubes. Further loaded 63 Shino pure water (manufactured by Daiwa Pharmaceutical Co.), for easily recovering a gaseous product was entering guide to ⁇ . 31 ⁇ / 1 batch reactor 1 ⁇ 1 2 gas at third pressure .. The reaction was carried out at the temperatures listed in Table 1. After the reaction (5-60 minutes), the reactor was quenched and the gas product was collected and analyzed by the same method as in the first reaction.
  • Figs. 3A to 3D show iso_C ⁇ 2 emission amount maps in Reference Example 1-1 and Examples 1-1 to 1-3.
  • the numbers on the line in Figure 3 shows the percentage of C0 2 emissions when compared to conventional processes.
  • the conventional process for comparison in this test example is the methane reforming process shown in FIG.
  • the C_ ⁇ 2 emissions in conventional processes is 0. 432 kg -C_ ⁇ 2 equivalents / kg -CH 3 ⁇ H, this number was the following Non-Patent Document 3 as a reference.
  • Non-Patent Document 3 A. Primas, Methanol, at plant, GLO, eco invent database version 2.0, eco invent report 8 (2007) 432-442.
  • Figure 4 shows the relationship between the reaction temperature and the conversion and hundred 2 emissions in the first reaction.
  • Fig. 4 shows the relationship in the conventional process, and
  • Fig. 4 shows the relationship in the process according to this test example.
  • reaction temperature exceeds 900 ° ⁇
  • the reforming reaction of methane in the methane reforming process is almost saturated, and when the reaction temperature is higher than 900 ° ⁇ , it leads to heat loss. , the heat must be supplemented by the combustion of the fuel, leading to hundred 2 emissions.
  • oxygen carrier particles IV! ( ⁇ ) are reduced by methane to form partially reduced oxygen carrier particles IV! (). Then, the partially reduced oxygen carrier particles IV! () are transported to the reactor in the second reaction. Then, in the reactor in the second reaction, as shown in equation (2), the reducible oxygen carrier particles IV! () Is oxidized by water vapor, oxygen carrier particles IV! (0) and? - 1 2 It is formed. Then, oxygen carrier particles IV! ( ⁇ ) are transported again to the reactor in the first reaction.
  • an oxygen carrier particles IV! ( ⁇ ) is ⁇ 6_Rei 2, its physical properties, density 7.
  • oxygen carrier particles IV! ( ⁇ ) are present inside the reactor in the first reaction. That is, the reaction time from the oxygen carrier particles IV! ( ⁇ ) to the reduced oxygen carrier particles IV! ( ⁇ ) is from the oxygen carrier particles IV! ( ⁇ ). ⁇ 02020/175444 28 ⁇ (: 170? 2020 /007378
  • the rate constant of oxygen release by the oxygen carrier particles IV! ( ⁇ ) determines the amount of methane that can be treated in the first reaction.
  • the reactivity index of oxygen carrier particles IV! (0) that is equal to (the amount of oxygen available for methane reforming in oxygen carrier particles IV! ( ⁇ ))
  • X oxygen release rate constant: ⁇ 10 1 ⁇ 9 -1 111 ⁇ use.
  • Figure 5 1 5001 at a diameter of 1 0 and a height 30 scale reactor: - ⁇ 1-1 4 / day methane reforming oxygen carrier particles for feasible IV (0 ) And the oxygen release rate constant of 03 (3).
  • the oxygen release rate constant of oxygen carrier particles IV! If it is 1 ⁇ - 1 (the residence time inside the first reactor 10 of the oxygen carrier particle IV! (0) is 10 minutes), the oxygen carrier particle IV! ( ⁇ ) required ⁇ 3 ⁇ is ⁇ 4 1 ⁇ 1 ⁇ I- ⁇ (Dot point 8 in Fig. 5).
  • 03_Rei oxygen carrier particles IV! (0) is not required necessarily 0.1 6 higher than the molar 9- 1.
  • the oxygen release rate constant is on the horizontal axis (X axis), and 03 (3) of oxygen carrier particles IV! (0) is on the vertical axis (so axis).
  • the oxygen carrier particle M ( ⁇ ) is It is suitable for using the chemical loop type hydrogen production system in this test example.
  • Non-Patent Document 4 G. Guan, C. Fushimi, M. Ikeda, Y. Nakamura, A. Tsutsu mi, T. Suda, M. Ishizuka, H. Hatano, S. Matsuda, Y. Suzuki, F low beha viors in a high solid f lux circulating fluidized bed composed of ari ser, a downer and a bubbling fluidized bed, in: S. D Kim, J. Kang, J. K. Lee, YC Seo (Eds ⁇ ), Proceedings of the 13th International Conference on Fluidization-New Paradigm in Fluidization (Gyeong-ju, Korea)
  • FIG. 6 shows the first reactor 10 and the second reactor when oxygen carrier particles M ( ⁇ ) having an oxygen carrier capacity of 0.23 mo I - ⁇ /kg -C e ⁇ 2 were used. The flow of each compound and energy at 20 is shown.
  • FIG. 6(A) shows each compound and energy flow in the first reactor 10 and
  • FIG. 6(B) shows each compound and energy flow in the second reactor 20.
  • Ce_ ⁇ 2 valence state is modeled using a mixture of Ce_ ⁇ 2 and Ce 2 ⁇ 3, the amount of these materials corresponds to the valence state of cerium.
  • a heat balance can be established by supplying heat to the first reactor 10 and cooling the second reactor 20.
  • the sensible heat generated by the oxygen transfer of oxygen carrier particles M (0) can be used for the heat balance of the system. Therefore, it is possible to suppress the amount of external heat supplied from outside the system to the inside of the system by improving the ⁇ SC of the oxygen carrier particles M ( ⁇ ).
  • Fig. 7 shows the equivalent ratio in the reforming reaction from methane to methanol.
  • Comparative Example 1-1 is the equivalent ratio in the conventional process, that is, the methane reforming process shown in Fig. 8.
  • Comparative Example 1 _ 1 is the current process, in which methane as a fuel is added to the raw material methane 1, and as products on the right side, methanol is produced at 0. 793 and C 0 2 # 0. 268. Does not produce hydrogen.
  • the following reaction takes place.
  • methane fuel is also used to generate combustion heat.
  • Example 1-2 the methane reforming device in Fig. 8 is replaced with a chemical loop device. At that time, the reaction temperature was 400 ° ⁇ , and Comparative Example 1 —
  • methanol can only be produced. Therefore, according to this embodiment, as compared with the conventional methanol production system, without using methane as a fuel for a low temperature, significantly reducing hundred 2 emissions, and can produce methanol at a high efficiency.
  • Example 1-2 the amount of carbon dioxide produced can be suppressed as compared with Comparative Example 1-1, which can also contribute to environmental protection.
  • the oxygen storage and release capacity ( ⁇ 30) was measured for each of 350° ⁇ , 400° ⁇ , 450° ⁇ and 500° ⁇ . The results are shown in Figure 10. It should be noted that 030 means the number of moles of oxygen contained in a unit mass of oxygen carrier.
  • the oxygen carrier 030 is measured by the following method. ⁇ 02020/175444 32 ⁇ (: 170? 2020 /007378
  • Reaction temperature that is, detection temperature (1 to 16 gas flows in the measurement system at 200° ⁇ , 250° ⁇ , 300° ⁇ , 350° ⁇ , 400° ⁇ , 450° ⁇ and 500° ⁇ ( This is the pretreatment.)
  • Hexanoic acid modified by supercritical method as oxygen carrier ⁇ 60 2 nanocube manufactured by Aitec Co., Ltd., ⁇ 8 31 ⁇ 1 ⁇ .1 306 -38-3, average particle size: 10 nm ⁇ 3 nm
  • this nanocube was controlled using an organic modifier (hexanoic acid in this example) so that the (100) plane becomes the main exposed surface. ing. Then, the nanocube was burned at 300° for 2 hours to remove the organic modifier from the nanocube.
  • the organic modifier is removed (1 00) surface that Rei_ ⁇ _ ⁇ 2 nano cube was ⁇ 6 ⁇ 2 exposure.
  • the oxygen carrier 0 0 3 was measured by the same method as in Example 2-1-1. The results are shown in Figure 10.
  • Chromium-doped cerium oxide ( ⁇ "one Rei_6_rei 2) was synthesized by a flow-through supercritical hydrothermal synthesis method reported. 0 The apparatus 30 shown in Fig. 9 was used for the synthesis of 60 2 .
  • the device 30 includes a raw material supply unit 31, a supercritical water supply unit 32, a mixing unit 33 for mixing the raw material and the supercritical water, and cooling the mixed liquid of the raw material and the supercritical water, And a cooling unit 34 which is contained in the container.
  • the raw material supply section 31 has a raw material storage container 31 for storing the raw material, and a pump 3 1 pump for pumping the raw material stored in the raw material storage container 3 18 toward the mixing section 3 3. .. Pipes are connected between the raw material storage container 31 8 and the pump 3 1 9 and between the pump 3 1 1 and the mixing section 3 3, respectively.
  • the supercritical water supply unit 32 includes a water container 32 for containing water and a water container.
  • Have 0 and. Connect the water container 3 28 and the pump 3 2 9 with pipes, the pump 3 2 2 and the heating unit 3 2 (3, and the heating unit 3 2 (3 and the mixing unit 3 3 respectively. Has been done.
  • temperature and pressure can be controlled.
  • supercritical water preheated in the supercritical water supply unit 32 is supplied to the mixing unit 33 from another pipe different from the pipe provided in the raw material storage container 31.
  • the temperature of the raw material was raised to the supercritical state.
  • the raw material contains decanoic acid, which is an organic molecule
  • both organic molecules and inorganic aqueous solution form a homogeneous phase in the supercritical state, and particle synthesis occurs there.
  • rapid cooling was carried out by an external water cooling unit 348 provided in the cooling section 34, and the pressure was thereafter controlled by a back pressure valve (not shown).
  • the reaction temperature in the mixing section 33 is 400° and the reaction pressure is The reaction time was less than 2 seconds.
  • the container 34 containing the post-reaction liquid was cooled in a water bath at room temperature.
  • 51 Hexane was used to extract the nanoparticle (hexane phase) from the decanoic acid modified product.
  • 100 1 of ethanol as a poor solvent reagent was added to precipitate a precipitate from the hexane phase.
  • centrifugation was carried out to obtain cubic crystals ⁇ “doped ⁇ ⁇ 2 nanoparticles.
  • O 3 (3) of the oxygen carrier was measured by the same method as in Example 2 _ 1 _ 1 except that the oxygen carrier was the above-mentioned cubic ⁇ “doped 602 2 nanoparticles. Shown in.
  • Example 2 - 1 - 4 Iron oxide-zirconia based composite oxide (6 ⁇ father one " ⁇ 2)
  • Oxygen carrier 03 ⁇ was measured by the same method as in Example 2-1 1 except that the oxygen carrier was the iron oxide-zirconia-based composite oxide particles. The results are shown in Figure 10.
  • Fig. 10 is a diagram showing the results of evaluation of the oxygen storage/release capacity ( ⁇ ) in the low temperature range of Test Example 2_1. Compared with 0 2 , exposed surface controlled cerium oxide (Example 2-1 -2) was higher, and ⁇ "doped cerium oxide (Example 2-1-3) was higher, and iron zirconia (Example 2-).
  • 60 ⁇ 1 ” 2 is particularly excellent in 030, followed by chromium-doped cerium oxide ( ⁇ “_ 060 2 ), 060 2 nano It was confirmed that the cubes were superior in order.
  • Oxygen mobility is related to the strain of the crystal lattice, Is doped, which causes lattice distortion and facilitates the formation of oxygen vacancies. This more chromium-doped, large oxygen mobility than 06_Rei 2 undoped is presumed reason obtained. ⁇ 0 2020/175 444 36 ⁇ (: 170? 2020 /007378
  • Figure 11 shows that the average primary particle size from the top is 11 9 n, 8 n 01, 7 1 ⁇ 111, 6 1 ⁇ 111, 5 Column of cerium element when
  • Figure 12 shows the image of the cerium element IV! in Test Example 2-2.
  • Figure 12 shows the interatomic strain. The part that looks bright has a large distortion ⁇ 0 2020/175 444 37 ⁇ (: 170? 2020 /007378
  • the image on the left is the image of cerium element IV with an average primary particle size of 11 11 and the image on the right shows an average primary particle size of 6
  • the dots on the left and right images of the Tetsumi IV! represent cerium atoms, and the region surrounded by four cerium atoms is the region where oxygen can be incorporated into the molecule.
  • (Min) in Fig. 12 is a visualization of the distortion between the cerium atoms by analyzing the image of Dinami 1 ⁇ /1 shown in (8) of Fig. 6.
  • the color is gray (when the value is close to 0), the interatomic strain is small. The lighter the color is (the closer it is to white), the more the interatomic voids expand, indicating that oxygen is more easily incorporated into the voids. On the other hand, the darker the color (closer to black), the smaller the interatomic voids, indicating that it is difficult to incorporate oxygen into the voids.
  • Fig. 13 shows the proportion of the lattice expansion of the cerium element from the left to the right in the image of Dingmi IV! shown in (8) of Fig. 12.
  • (8) in Fig. 13 shows the state for the cerium element with an average primary particle size of 11 1 and (M) in Fig. 13 has an average primary particle size of 6 n. Is the state for the element cerium. From Fig. 13 also, it is confirmed that the smaller the average primary particle size of the oxygen carrier, the larger the lattice expansion between the atoms, and the easier the formation of oxygen vacancies due to lattice strain.
  • Fig. 14 is a diagram showing the relationship between the rate at which lattice expansion is observed in cerium nanoparticles and the energy required to form oxygen vacancies between cerium atoms. According to Fig. 14, particles with a higher lattice expansion ratio ⁇ 02020/175444 38 ⁇ (: 170? 2020 /007378
  • Oxygen carrier is cerium oxide ( ⁇ 3 6 ⁇ 2 ) [ ⁇ ⁇ 2 produced]
  • Example 2 - 1 - cerium oxide used in 1 ( ⁇ 6 ⁇ 2) oxidation state was charged into a single reactor. Then, by introducing Rei_1 ⁇ 1 4, at 300 ° ⁇ oxidizes Rei_1 ⁇ 1 4, was measured the time course of the amount of carbon dioxide. At that time, the reaction pressure was 0.61 ⁇ /1 3. The results are shown in Figure 15 (8).
  • Example 2 — 1 — 1 The cerium oxide used in Example 2 — 1 — 1 was brought to a reduced state and charged into one reactor. Then, water vapor was introduced to oxidize the reduced cerium oxide at 300 ° C, and the change with time in the amount of hydrogen produced was measured. At that time, the reaction pressure was 8 IV! 8. The results are shown in Figure 15 (Minami).
  • Iron oxide-zirconia based composite oxide (6 ⁇ father - " ⁇ 2) used in Example 2_ 1 _ 4.
  • Example 2 — 1 — 4 The iron oxide-zirconia-based composite oxide used in Example 2 — 1 — 4 was put into a reduced state and charged into one reactor. Then, water vapor was introduced to oxidize the complex oxide in the reduced state at 400 ° C, and the time-dependent change in the amount of hydrogen produced was measured. At that time, the reaction pressure was 81 ⁇ /1 3. The results are shown in Fig. 16 (Minami).
  • the reaction rate constant in the carbon dioxide production reaction from Rei_1 ⁇ 1 4, ⁇ . 060 is [ ⁇ nl], in the production reaction of hydrogen from the gas Mizu ⁇ The reaction rate constant was ⁇ .044 [ ⁇ ! Inl].
  • the oxygen carrier is iron oxide-zirconia based composite oxide
  • the hydrogen production reaction from steam The reaction rate constant at was 0.13 [0 1 1 ⁇ -1 ].
  • This also supports that the iron oxide-zirconia-based composite oxide is particularly excellent as an oxygen carrier in this reaction system.
  • Fig. 17 shows the result of simulating the industrially suitable apparatus scale of the chemical loop manufacturing system 1 shown in Fig. 1.
  • the horizontal axis in Fig. 17 is the operating temperature of the chemical loop manufacturing system 1 (Fig. 1), and the vertical axis is the chemical loop manufacturing system 1 (Fig. 1) required to manufacture the expected amount of methanol. )
  • the capacity of the chemical loop manufacturing system 1 (FIG. 1), about 5 0 0 0 3 Is.
  • the capacity of the chemical loop manufacturing system 1 (Fig. 1) is about 100 3 and the oxygen carrier is sufficient.
  • iron oxide-zirconia based composite oxide (6_Rei X _ " ⁇ 2) Chemical loop manufacturing system 1 (FIG. 1) is sufficient in about 1 0 0 3.
  • the device can be downsized as compared with the conventional synthesis system by appropriately selecting the type of oxygen carrier.

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Abstract

Le problème décrit par la présente invention est de fournir un système permettant d'obtenir le reformage en masse d'un matériau hydrocarboné en hydrogène en un laps de temps court en utilisant la chaleur perdue à basse température présentant une température inférieure à 700 °C. La solution selon l'invention porte sur un appareil de synthèse de méthanol qui est pourvu : d'un système (1) pour produire de l'hydrogène et un gaz de synthèse et d'un système de synthèse de méthanol (non représenté) pour synthétiser du méthanol à l'aide d'au moins une partie de l'hydrogène et d'au moins une partie du gaz de synthèse en tant que matières premières. Le système (1) de formation est équipé : d'un premier réacteur (10) pour faire réagir un transporteur d'oxygène oxydé M(O) avec un matériau de type hydrocarbure pour produire un transporteur d'oxygène réduit M( ), de l'hydrogène et un oxyde de carbone ; et d'un second réacteur (20) pour faire réagir le transporteur d'oxygène réduit M( ) avec de l'eau pour produire un transporteur d'oxygène oxydé M(O) et de l'hydrogène. Le système (1) peut être du type mode en boucle chimique dans lequel le transporteur d'oxygène M(O) peut circuler et circuler entre le premier réacteur (10) et le second réacteur (20), ou peut être du type à mode de fonctionnement cyclique dans lequel des gaz à fournir peuvent être commutés entre eux.
PCT/JP2020/007378 2019-02-27 2020-02-25 Système de synthèse de méthanol et procédé destiné à ladite synthèse WO2020175444A1 (fr)

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