WO2012105355A1 - Procédé de production de gaz d'hydrogène - Google Patents

Procédé de production de gaz d'hydrogène Download PDF

Info

Publication number
WO2012105355A1
WO2012105355A1 PCT/JP2012/051351 JP2012051351W WO2012105355A1 WO 2012105355 A1 WO2012105355 A1 WO 2012105355A1 JP 2012051351 W JP2012051351 W JP 2012051351W WO 2012105355 A1 WO2012105355 A1 WO 2012105355A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
oxygen
catalyst
hydrogen gas
containing gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/051351
Other languages
English (en)
Japanese (ja)
Inventor
啓之 畑
貴裕 土屋
広昭 笹野
茂 森本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Seika Chemicals Co Ltd
Original Assignee
Sumitomo Seika Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Seika Chemicals Co Ltd filed Critical Sumitomo Seika Chemicals Co Ltd
Priority to JP2012555801A priority Critical patent/JP6168775B2/ja
Priority to KR1020137022961A priority patent/KR101869580B1/ko
Publication of WO2012105355A1 publication Critical patent/WO2012105355A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalysts
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1223—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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method for producing hydrogen gas. More specifically, the present invention relates to a method for producing hydrogen gas that can efficiently produce hydrogen gas.
  • Methanol is an energy source that can be easily transported and stored, and is expected as a raw material for generating hydrogen gas on-site.
  • a steam reforming method is generally known in which hydrogen gas is produced by bringing methanol into contact with water vapor in the presence of a catalyst in an oxygen-containing gas atmosphere.
  • the autothermal method is known as a method capable of efficiently producing hydrogen gas.
  • heat generated when methanol is partially oxidized and reformed to carbon dioxide and hydrogen gas is converted into an endothermic reaction in which methanol is reformed to carbon dioxide and hydrogen gas by contacting with water vapor.
  • the autothermal method when a copper-zinc catalyst is used as a catalyst, there is a drawback that the activity of the catalyst is lowered.
  • the present invention has been made in view of the prior art, and can stably produce a certain amount of hydrogen gas over a long period of time without requiring a complicated operation of adjusting the flow rate of the oxygen-containing gas.
  • An object of the present invention is to provide a method for producing hydrogen gas that can extend the catalyst life.
  • the present invention produces a reaction gas by contacting methanol and water with an oxygen-containing gas in the presence of a catalyst while supplying the oxygen-containing gas, and produces hydrogen gas by separating the hydrogen gas from the reaction gas.
  • the present invention relates to a method for producing hydrogen gas, wherein a copper oxide / aluminum oxide catalyst is used as the catalyst, and the supply of the oxygen-containing gas is temporarily stopped.
  • a constant amount of hydrogen gas can be produced stably over a long period of time without requiring complicated adjustment of the flow rate of the oxygen-containing gas, and the catalyst life can be reduced. There is an excellent effect that it can be extended.
  • a method for producing hydrogen gas by producing a reaction gas by bringing methanol, water, and an oxygen-containing gas into contact with each other in the presence of a catalyst while supplying the oxygen-containing gas, and separating the hydrogen gas from the reaction gas When the catalyst regeneration operation of regenerating the catalyst by temporarily stopping the supply of the oxygen-containing gas is performed, as described in Patent Document 1, a decrease in the catalyst activity is suppressed to some extent. it can. However, in such a method, when the regeneration operation is repeated, the catalyst activity is greatly reduced compared to the catalyst activity before the regeneration operation.
  • a reaction gas is produced by contacting methanol, water, and an oxygen-containing gas in the presence of a catalyst while supplying the oxygen-containing gas, and the hydrogen gas is separated from the reaction gas. As a result, hydrogen gas is produced.
  • Methanol and water are usually used by vaporizing.
  • the amount of water per mole of methanol is preferably 1.2 moles or more, more preferably from the viewpoint of efficiently generating hydrogen gas and increasing the yield of hydrogen gas by reducing the residual amount of carbon monoxide gas. Is not less than 1.5 mol, and even if the amount of water is too large, the yield of hydrogen gas is not improved so much, preferably from the viewpoint of increasing energy efficiency by reducing the amount of water having a large latent heat of vaporization, 2.5 mol or less, more preferably 2.0 mol or less.
  • methanol and water do not necessarily have to be heated at the same time, and methanol evaporation and water evaporation may be performed separately, or methanol and water are mixed and the resulting aqueous methanol solution is evaporated. You may let them.
  • methanol is usually used as methanol gas, and water is used as water vapor.
  • the temperature of methanol gas and water vapor when contacting with the oxygen-containing gas is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, from the viewpoint of promoting the oxidation reaction of methanol and reducing the residual amount of unreacted methanol. From the viewpoint of improving energy efficiency and improving the yield of hydrogen gas, it is preferably 300 ° C. or lower, more preferably 280 ° C. or lower.
  • a part of the methanol is represented by the formula (2) without involving oxygen gas: CH 3 OH ⁇ CO + 2H 2 (2) As expressed by carbon monoxide gas and hydrogen gas, or the formula (3): CH 3 OH + H 2 O ⁇ CO 2 + 3H 2 (3) As shown, it decomposes into carbon dioxide gas and hydrogen gas. Since these decomposition reactions are endothermic reactions, part of the heat generated by the oxidation reaction is canceled out. As a result, the temperature in the system is somewhat lower than the temperature when only the oxidation reaction occurs. In addition to these reactions, the formula (4): CO + H 2 O ⁇ CO 2 + H 2 (4) It is believed that a shift reaction represented by
  • Oxygen-containing gas has a small heat capacity compared to methanol and water, so it does not need to be heated in particular, but may be heated if necessary.
  • oxygen-containing gas examples include air, oxygen gas and the like, and mixed gas of inert gas such as nitrogen gas and argon gas and oxygen gas.
  • inert gas such as nitrogen gas and argon gas and oxygen gas.
  • present invention is limited to such examples. It is not a thing.
  • the amount of oxygen gas contained in the oxygen-containing gas per mole of methanol is preferably 0.05 mol or more, more preferably 0.1 mol or more, from the viewpoint of reducing the remaining amount of unreacted methanol. From the viewpoint of avoiding an increase in the reaction temperature due to the reaction between the hydrogen gas generated from methanol and the oxygen gas, and avoiding the consumption of the generated hydrogen gas due to the reaction with the oxygen gas. 25 mol or less, more preferably 0.2 mol or less.
  • a catalyst When reacting the raw material gas and the oxygen-containing gas, a catalyst is used from the viewpoint of increasing the production efficiency of hydrogen gas.
  • one major feature is that a copper oxide / aluminum oxide catalyst is used as the catalyst.
  • a copper oxide / aluminum oxide catalyst is used as the catalyst, the hydrogen gas is allowed to flow for a long time without performing complicated operations for adjusting the flow rate of the oxygen-containing gas as in the invention described in Patent Document 1.
  • the catalyst can be produced efficiently and the life of the catalyst can be extended. Further, when a copper oxide / aluminum oxide catalyst is used as a catalyst, there is an advantage that sintering is unlikely to occur even when heated to a high temperature of about 600 ° C.
  • the copper oxide / aluminum oxide catalyst is obtained by attaching copper oxide (CuO) to aluminum oxide (Al 2 O 3 ) particles of a support.
  • the mass ratio of copper oxide (CuO) to aluminum oxide (Al 2 O 3 ) [copper oxide (CuO) / aluminum oxide (Al 2 O 3 )] is sufficient for the catalytic activity of copper oxide (CuO) as an additive
  • it is preferably 0.005 or more, imparting sufficient mechanical strength to the added copper oxide (CuO), and the copper oxide (CuO) is used from above the catalyst during use. From the viewpoint of avoiding detachment as a powder, it is preferably 1 or less.
  • the copper oxide / aluminum oxide catalyst is preferably reduced prior to its use.
  • the copper oxide / aluminum oxide catalyst is reduced, the copper oxide is reduced to copper, so that the catalytic activity can be enhanced.
  • the method of reducing the copper oxide / aluminum oxide catalyst include a method of bringing the copper oxide / aluminum oxide catalyst into contact with a reducing gas, but the present invention is not limited to such a method.
  • the reducing gas include hydrogen gas, and mixed gas of hydrogen gas and inert gas such as nitrogen gas and argon gas. However, the present invention is not limited to such examples. .
  • the particle diameter of the copper oxide / aluminum oxide catalyst is preferably 0.5 mm or more, more preferably 1 mm or more from the viewpoint of improving the air permeability between the catalyst particles.
  • the amount of the copper oxide / aluminum oxide catalyst is preferably about 20 to 300 ml per 1 g / min of methanol that is usually sent to a reaction gas production apparatus that is generally used.
  • the reaction temperature rises with time at a location where an oxidation reaction occurs due to contact with an oxygen-containing gas.
  • the reactions represented by the formulas (2) to (4) proceed on the copper / aluminum oxide (Cu / Al 2 O 3 ), which is a reduced product obtained by reducing the copper oxide / aluminum oxide catalyst in advance.
  • copper / aluminum oxide (Cu / Al 2 O 3 ) is gradually oxidized by the oxygen-containing gas to become copper oxide / aluminum oxide (CuO / Al 2 O 3 ).
  • the reactions represented by the formulas (2) to (4) are difficult to proceed, the methanol oxidation reaction represented by the formula (1) occurs preferentially, so that exotherm appears significantly. It is thought that the catalyst life is shortened because the reaction temperature gradually increases.
  • the present inventors conducted extensive research and found that the supply of the oxygen-containing gas may be temporarily stopped while using a copper oxide / aluminum oxide catalyst as the catalyst.
  • a copper oxide / aluminum oxide catalyst as the catalyst.
  • the oxidation reaction of methanol by the oxygen gas contained in the oxygen-containing gas gradually stops, so the reaction temperature decreases.
  • the amount of oxygen gas in the reaction system is reduced. Therefore, copper / aluminum oxide is less likely to be oxidized by oxygen gas.
  • the copper oxide / aluminum oxide catalyst is reduced by contact with methanol, the copper oxide / aluminum oxide used in the copper oxide / aluminum oxide catalyst is reduced to copper / aluminum oxide having catalytic activity. . Therefore, it is considered that the catalytic activity of the copper oxide / aluminum oxide catalyst is recovered.
  • the reaction temperature is preferably 300 ° C. or higher from the viewpoint of efficiently reforming methanol into hydrogen, and preferably from the viewpoint of suppressing the reaction between generated hydrogen and oxygen contained in the oxygen-containing gas. Is 450 ° C. or lower.
  • the pressure during the reaction is not particularly limited, but usually it is preferably about 0.2 to 1.5 MPa in terms of gauge pressure.
  • the temperature of the copper oxide / aluminum oxide catalyst is lowered by temporarily stopping the supply of the oxygen-containing gas.
  • the copper oxide / aluminum oxide used in the copper oxide / aluminum oxide catalyst is reduced to copper / aluminum oxide.
  • the catalytic activity of the aluminum oxide catalyst is restored. Therefore, the reaction temperature returns to the temperature before stopping the supply of the oxygen-containing gas in a short time, and hydrogen gas can be efficiently produced again.
  • the time from the start of the supply of the oxygen-containing gas to the stop of the supply of the oxygen-containing gas is from the viewpoint of returning the catalyst temperature that decreases during the stop period of the supply of the oxygen-containing gas to near the temperature before the stop, Preferably, it is 10 seconds or more, more preferably 20 seconds or more, so that the amount of hydrogen gas generated from methanol is stabilized, and the catalyst temperature is kept at a certain temperature or more even during the stop period of the oxygen-containing gas. From the viewpoint of maintaining, it is preferably 10 minutes or less, more preferably 5 minutes or less.
  • the time for stopping the supply of the oxygen-containing gas is to reduce the catalyst activity of the copper oxide / aluminum oxide catalyst by reducing the copper oxide / aluminum oxide used in the copper oxide / aluminum oxide catalyst to copper / aluminum oxide. From the viewpoint of efficiently producing hydrogen gas by shortening the time for stopping the supply of the oxygen-containing gas, preferably 3 seconds or more, more preferably 5 seconds or more, preferably 60 seconds or less, more preferably 40 seconds or less.
  • the time for stopping the supply of the oxygen-containing gas with respect to the time required for one cycle from the start of the supply of the oxygen-containing gas to the start of the supply of the next oxygen-containing gas after the supply of the oxygen-containing gas is stopped
  • the ratio of formula (I): [Ratio of oxygen gas stop time] [(Time for stopping supply of oxygen gas) ⁇ (Time required for one cycle)] ⁇ 100
  • the time for supplying the oxygen-containing gas is preferably 7 seconds or more, and the time for stopping the supply of the oxygen-containing gas is preferably 3 seconds or less.
  • the reaction gas obtained by the above operation contains not only hydrogen gas but also impurity gases such as unreacted methanol vapor, carbon dioxide gas, carbon monoxide gas, and water vapor. Therefore, in order to produce hydrogen gas having high purity, hydrogen gas contained in the reaction gas is separated from the reaction gas obtained above.
  • an adsorbent When separating hydrogen gas, for example, an adsorbent can be used.
  • the adsorbent include a carbon-based adsorbent when removing carbon dioxide, methanol, and the like, and a zeolite when removing carbon monoxide, and removing water vapor and the like. In some cases, alumina and the like can be mentioned, but the present invention is not limited to such examples.
  • these adsorbents are preferably mixed and used in order to remove them by adsorbing unreacted methanol vapor, carbon dioxide gas, carbon monoxide gas, water vapor and other impurity gases.
  • the hydrogen gas can be separated according to, for example, a method for separating a target gas described in JP-A No. 2004-66125.
  • the adsorbed and removed impurity gas can be recovered as a residual gas, for example, after the production of hydrogen gas is stopped.
  • the residual gas contains hydrogen gas in addition to impurity gas. It is preferable that the residual gas is not disposed of as waste gas or discarded, but is effectively used by burning it. If methanol and water are heated using combustion heat generated when the residual gas is burned, methanol gas and water vapor can be produced efficiently. In addition, the heat of combustion in the residual gas can supplement the heat in the endothermic reaction in the reactions represented by the reaction formulas (2) to (4), so that hydrogen gas can be generated efficiently.
  • a platinum catalyst is preferable because of its high catalytic activity and excellent heat resistance.
  • the platinum catalyst may be platinum particles, may be one in which platinum is supported on a carrier such as alumina particles, or may be one in which platinum is supported on a carrier having a honeycomb structure.
  • air is not particularly limited as long as the hydrogen gas contained in the residual gas is sufficiently combusted. Since the temperature of the combustion gas generated by burning the residual gas can be controlled by this air amount, the temperature of the combustion gas can be adjusted by controlling the air amount. Further, the temperature of the combustion gas can be adjusted by introducing air into the generated combustion gas.
  • the heating temperature of methanol and water by the combustion heat generated when the residual gas is burned is preferably 250 ° C. or higher from the viewpoint of increasing the amount of hydrogen gas generated by reducing the residual amount of unreacted methanol, From the viewpoint of suppressing the deterioration of the catalyst, the temperature is preferably 600 ° C. or lower.
  • combustion catalysts including a platinum catalyst
  • the combustion catalyst include platinum, noble metals such as palladium, ruthenium, rhodium, and silver, and compounds of these metals, but the present invention is not limited only to such examples.
  • the combustion catalyst can be used by adhering to, for example, a metal honeycomb, a ceramic honeycomb, a ball pellet, or the like.
  • Example 1 In a reactor having a length of 20 cm and an inner diameter of 2.3 cm, a copper oxide / aluminum oxide catalyst [manufactured by Aldrich, mass ratio of copper oxide (CuO) and aluminum oxide (Al 2 O 3 ) [copper oxide (CuO) / After filling with aluminum oxide (Al 2 O 3 )]: 12/88], a nitrogen gas containing hydrogen gas was introduced into the reactor for about 10 hours to activate the copper oxide / aluminum oxide catalyst.
  • a copper oxide / aluminum oxide catalyst manufactured by Aldrich, mass ratio of copper oxide (CuO) and aluminum oxide (Al 2 O 3 ) [copper oxide (CuO) / After filling with aluminum oxide (Al 2 O 3 )]: 12/88
  • a nitrogen gas containing hydrogen gas was introduced into the reactor for about 10 hours to activate the copper oxide / aluminum oxide catalyst.
  • the internal temperature of the reactor was controlled at 300 ° C., methanol and water were introduced into the reactor at a flow rate of 3.8 g / min and 3.0 g / min, respectively, and air was supplied at a standard state (NTP) of 2
  • NTP standard state
  • the operation of introducing at a flow rate of 2 L / min was performed for 90 seconds, and then the operation of stopping the operation of introducing air for 10 seconds was repeated periodically as one cycle.
  • the molar ratio of water / methanol was 1.44 / 1
  • the molar ratio of oxygen / methanol was 0.16 / 1.
  • the ratio of the oxygen gas stop time represented by the formula (I) was 10%.
  • the gauge pressure in the reactor was controlled to 0.8 MPa. Meanwhile, the maximum temperature and hydrogen concentration in the reactor were examined. The hydrogen concentration was examined by analyzing the reaction gas discharged from the reactor by gas chromatography. The results are shown in Table 1.
  • Example 2 In Example 1, except that air was aerated at a flow rate of 2.2 L / min for 10 minutes in a standard state, and then the operation of stopping the ventilation of the air for 60 seconds was periodically repeated as one cycle. The same operation was performed. At that time, the ratio of the oxygen gas stop time represented by the formula (I) was about 9%. The results are shown in Table 2.
  • Example 1 Comparative Example 1 In Example 1, the reaction was performed in the same manner as in Example 1 except that air was supplied at a constant flow rate of 2.0 L / min in the standard state. The results are shown in Table 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

Selon la présente invention, lorsqu'un gaz réactif est produit en mettant du méthanol et de l'eau en contact avec un gaz contenant de l'oxygène en présence d'un catalyseur tout en alimentant du gaz d'oxygène, du gaz d'hydrogène est produit par séparation du gaz d'hydrogène du gaz réactif, l'alimentation du gaz contenant de l'oxygène est temporairement arrêtée grâce à l'utilisation d'un catalyseur d'oxyde de cuivre/oxyde d'aluminium.
PCT/JP2012/051351 2011-01-31 2012-01-23 Procédé de production de gaz d'hydrogène Ceased WO2012105355A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2012555801A JP6168775B2 (ja) 2011-01-31 2012-01-23 水素ガスの製造方法
KR1020137022961A KR101869580B1 (ko) 2011-01-31 2012-01-23 수소 가스의 제조 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-017867 2011-01-31
JP2011017867 2011-01-31

Publications (1)

Publication Number Publication Date
WO2012105355A1 true WO2012105355A1 (fr) 2012-08-09

Family

ID=46602574

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/051351 Ceased WO2012105355A1 (fr) 2011-01-31 2012-01-23 Procédé de production de gaz d'hydrogène

Country Status (4)

Country Link
JP (2) JP6168775B2 (fr)
KR (1) KR101869580B1 (fr)
TW (1) TWI511920B (fr)
WO (1) WO2012105355A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6236001A (ja) * 1985-08-07 1987-02-17 Mitsubishi Heavy Ind Ltd メタノ−ル改質法
JPH04200640A (ja) * 1990-05-25 1992-07-21 Agency Of Ind Science & Technol メタノール改質用触媒の再生法
JP2001226103A (ja) * 2000-02-18 2001-08-21 Nissan Motor Co Ltd 燃料改質装置
JP2005342543A (ja) * 2003-05-20 2005-12-15 Idemitsu Kosan Co Ltd 酸素含有炭化水素の改質触媒、それを用いた水素又は合成ガスの製造方法及び燃料電池システム
WO2009107592A1 (fr) * 2008-02-25 2009-09-03 住友精化株式会社 Procédé et appareil de production d'hydrogène

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001098202A1 (fr) * 2000-06-22 2001-12-27 Consejo Superior De Investigaciones Cientificas Procede d'obtention d'hydrogene par oxydation partielle du methanol
TW200836836A (en) * 2007-03-12 2008-09-16 Univ Nat Central Hydrogen production via partial oxidation of methanol over Au/Al2O3-CuO catalysts

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6236001A (ja) * 1985-08-07 1987-02-17 Mitsubishi Heavy Ind Ltd メタノ−ル改質法
JPH04200640A (ja) * 1990-05-25 1992-07-21 Agency Of Ind Science & Technol メタノール改質用触媒の再生法
JP2001226103A (ja) * 2000-02-18 2001-08-21 Nissan Motor Co Ltd 燃料改質装置
JP2005342543A (ja) * 2003-05-20 2005-12-15 Idemitsu Kosan Co Ltd 酸素含有炭化水素の改質触媒、それを用いた水素又は合成ガスの製造方法及び燃料電池システム
WO2009107592A1 (fr) * 2008-02-25 2009-09-03 住友精化株式会社 Procédé et appareil de production d'hydrogène

Also Published As

Publication number Publication date
JPWO2012105355A1 (ja) 2014-07-03
JP6168775B2 (ja) 2017-07-26
TWI511920B (zh) 2015-12-11
TW201245037A (en) 2012-11-16
KR20140023895A (ko) 2014-02-27
KR101869580B1 (ko) 2018-06-20
JP2016196410A (ja) 2016-11-24

Similar Documents

Publication Publication Date Title
JP5373410B2 (ja) アンモニア合成方法
JP7319965B2 (ja) 自己熱アンモニア分解方法
KR20250048204A (ko) 탄화수소의 직접 분해 장치 및 직접 분해 방법
JP2006315891A (ja) 低級炭化水素の直接分解による機能性ナノ炭素及び水素の製造方法
CN114341083A (zh) 制造甲烷的方法和制造系统
JP2024530251A5 (fr)
Lin et al. Preparation of a highly efficient carbon-supported ruthenium catalyst by carbon monoxide treatment
JP5616754B2 (ja) 水素ガス製造装置
JP6168775B2 (ja) 水素ガスの製造方法
JP5730402B2 (ja) メタノールの製造方法
WO2022045327A1 (fr) Procédé de production de méthanol
JP5387154B2 (ja) グリセリン改質装置および改質方法
JP2008036451A (ja) メタン改質用の触媒担体及び触媒、及びその製造方法
JP5659067B2 (ja) 水素ガスの製造方法
TWI501920B (zh) Production method and apparatus for hydrogen
JP4203326B2 (ja) 合成ガス製造の運転方法
JP5387175B2 (ja) 一酸化炭素の製造方法
JP5868178B2 (ja) メタノールの製造方法
TWI518031B (zh) Hydrogen production methods
TW200848364A (en) Process for removing no and N2O from gas mixtures
JP2009190929A (ja) 二酸化炭素を含有する混合ガスの改質・分離方法
JPWO2015029543A1 (ja) 水素の製造方法
JP2007516924A (ja) メタン‐二酸化炭素混合物の処理方法
JP2023157643A (ja) 二酸化炭素吸蔵還元型触媒
JP2007055849A (ja) 水蒸気改質触媒機能を備えた二酸化炭素吸収材、その製造方法、および水素製造システムにおける燃料ガスの改質方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12742511

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2012555801

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20137022961

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 12742511

Country of ref document: EP

Kind code of ref document: A1