WO2008001448A1 - Procédé pour produire de l'hydrogène et appareil de production - Google Patents

Procédé pour produire de l'hydrogène et appareil de production Download PDF

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Publication number
WO2008001448A1
WO2008001448A1 PCT/JP2006/313004 JP2006313004W WO2008001448A1 WO 2008001448 A1 WO2008001448 A1 WO 2008001448A1 JP 2006313004 W JP2006313004 W JP 2006313004W WO 2008001448 A1 WO2008001448 A1 WO 2008001448A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
laser
containing compound
liquid
gas
Prior art date
Application number
PCT/JP2006/313004
Other languages
English (en)
Japanese (ja)
Inventor
Kazuyuki Hirao
Kiyotaka Miura
Yasuhiko Shimotsuma
Kunikazu Asaka
Kazuhiro Mae
Tetsuya Shishido
Original Assignee
Kyoto University
Lef Technology, Inc.
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 Kyoto University, Lef Technology, Inc. filed Critical Kyoto University
Priority to JP2008522251A priority Critical patent/JP4333929B2/ja
Priority to PCT/JP2006/313004 priority patent/WO2008001448A1/fr
Publication of WO2008001448A1 publication Critical patent/WO2008001448A1/fr

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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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/121—Coherent waves, e.g. laser beams
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • 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
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0869—Feeding or evacuating the reactor
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0877—Liquid
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0892—Materials to be treated involving catalytically active material
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/185—Details relating to the spatial orientation of the reactor vertical
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/19—Details relating to the geometry of the reactor
    • B01J2219/192—Details relating to the geometry of the reactor polygonal
    • B01J2219/1923—Details relating to the geometry of the reactor polygonal square or square-derived

Definitions

  • the present invention relates to a method and apparatus for producing hydrogen, and more particularly to a method and apparatus for producing hydrogen by non-thermal reaction.
  • Patent documents 1 and 2 describe a method for producing hydrogen, which uses plasma reaction to decompose raw material compounds such as hydrocarbons, ethers, alcohols and water. However, since high voltage is required to generate the plasma, the equipment which becomes highly dangerous becomes large.
  • the plasma reaction is performed in the gas phase. Therefore, it is necessary to gasify the raw material mixture in advance and then use it for the reaction, and the operation is complicated and energy efficiency is low. Furthermore, the gas phase reaction is inferior in reaction selectivity and the yield is high with many by-products.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-338203
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2005-247638
  • an object of the present invention is to provide a method and an apparatus for producing hydrogen which is simple in operation and high in energy efficiency with high safety. It is in.
  • the present invention provides a method and an apparatus for producing hydrogen in which a pulse laser is applied to a liquid of a hydrogen-containing compound, thereby achieving the above object.
  • the raw material compound is used as a liquid in the reaction, and the reaction can be carried out at normal temperature, so the operation is simple and the energy efficiency is high.
  • the reaction selectivity is high and the yield is high because there are few by-products. Furthermore, it does not require a high temperature and high pressure environment or high voltage, and is excellent in safety.
  • the raw material used in the method and apparatus for producing hydrogen of the present invention is a hydrogen-containing compound.
  • the hydrogen-containing compound may, for example, be a hydrocarbon having 1 to 4 carbon atoms, an alcohol having 1 to 4 carbon atoms, an aldehyde having 1 to 9 carbon atoms, an ether having 2 to 8 carbon atoms, an ester having 3 to 5 carbon atoms, etc.
  • Organic compounds, and inorganic compounds such as water, hydrogen sulfide and hydrides. These compounds may be used alone !, but two or more of them may be used in combination.
  • Preferred hydrocarbons include aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons and the like.
  • aliphatic hydrocarbons examples include methane, ethane, propane and dimethylpropane.
  • unsaturated aliphatic hydrocarbons include ethylene, propylene, propyne, butylene and butadiene.
  • the hydrocarbons particularly preferably used in the present invention are methane, ethane and propane.
  • Alcohol includes saturated alcohol, unsaturated alcohol and the like.
  • Saturated alcohols include methanol, ethanol, propanol, butanol, isopropyl alcohol, ethylene glycol and the like
  • unsaturated alcohols include paryl alcohol and the like.
  • Alcohols preferably used in the present invention are methanol, ethanol, propanol and butanol.
  • Alcohols particularly preferably used in the present invention are methanol and ethanol.
  • aldehydes for example, formaldehyde, acetaldehyde, propionaldehyde, acrolein, benzaldehyde, cinnamaldehyde
  • ethers for example, dimethyl ether, ethyl methyl ether, etc.
  • water other than pure water, rainwater, tap water, primary-treated waste water, etc. can be used.
  • sulfur compounds such as hydrogen sulfide, silanes such as SiH
  • phosphines such as PH can also be used.
  • the hydrogen-containing mixture may be in a liquid state upon irradiation. That is, a hydrogen-containing composite which can be cooled, heated, pressurized, reduced pressure, etc. can be used as a raw material.
  • the hydrogen-containing compound is preferably liquid at normal temperature (25 ° C.) and normal pressure (1 atm). It takes equipment and energy to liquefy or maintain a liquid hydrogen-containing compound that is gas or solid at normal temperature, which complicates the reaction operation.
  • a preferable hydrogen-containing composite has a vapor pressure of 400 kPa or less, preferably 1 Pa to LOO kPa at normal temperature, and a boiling point of 20 ° C. or more at 1 atmospheric pressure, preferably 30 to 200 °. It is a C thing.
  • the intense hydrogen-containing mixture is irradiated with a femtosecond laser.
  • the hydrogen-containing compound to be irradiated is a liquid.
  • the hydrogen-containing compound may be cooled or heated to maintain its liquid state. Even if heat is applied at that time, it is considered that the heat does not contribute much to the reaction of the hydrogen-containing compound.
  • the laser irradiation is usually performed at normal temperature by storing the hydrogen-containing compound at least partially in a container capable of transmitting a femtosecond laser. At that time, it is preferable to introduce oxygen gas simultaneously with the laser irradiation. If oxygen is present in the reaction system, carbon monoxide, which is a by-product, is oxidized and reformed to CO. Irradiation may be performed batchwise or continuously.
  • the irradiation spot diameter of the femtosecond laser is not particularly limited, and can be appropriately selected according to the size of the lens, the numerical aperture or the magnification, and is, for example, 50 m or less (preferably 0.1 to 10 m). Range forces of degree) can also be selected.
  • the femtosecond laser the pulse width of the laser is referred to lasers one several to several hundreds of femtoseconds, hydrogen production method and production apparatus of the present invention, the pulse width is 10 1 2 seconds
  • the ultrashort pulse laser is preferably used.
  • the pulse width of 1 X 10_ 15 seconds ⁇ 1 X 10 _ 12 sec, pulsed laser preferably 1 X 10_ 15 seconds ⁇ 1 X 10_ 14 seconds, more preferably 10 X 10_ 15 seconds ⁇ 500 X 10_ 15 seconds Is used.
  • a femtosecond laser can be obtained, for example, by regenerating and amplifying a laser with a titanium sapphire crystal as a medium, a fiber laser of erbium-doped quartz, or a dye laser.
  • the wavelength of the femtosecond laser is also appropriately selected, for example, from 250 to 1000 nm.
  • the repetition rate of the femtosecond laser is, for example, selected from the range of 1 ⁇ to 80 ⁇ , and is usually about 10 Hz to 500 kHz.
  • the fluence of the irradiation energy of the femtosecond laser depends on the focusing condition by the focusing lens, it is 1 to 1 ⁇ 10 6 j / cm 2 , preferably 1 ⁇ 10 3 to 1 ⁇ 10 5 j / cm 2 Adjust to If the fluence of the irradiation energy is less than 1 x 10 3 jZcm 2 , the reaction is insufficient and sufficient hydrogen generation can not be obtained, and if it exceeds 1 x 10 5 j / cm 2 , it is simply collected in air. Even if only light is emitted, an optical breakdown generates a plasma in the vicinity of the focal point, and the irradiation of the hydrogen-containing compound needs to be performed in a vacuum chamber, which complicates the reaction operation.
  • the optical electric field strength of the laser irradiated to the hydrogen-containing complex is preferably 10 12 WZ cm 2 or more. If the optical electric field strength of the laser is less than 10 12 WZ cm 2 , the energy potential of the molecule can not interact with the laser light sufficiently, and it is not possible to induce molecule dissociation due to ionization of the molecule or Coulomb explosion.
  • the laser irradiation unit which is a laser irradiation unit, includes an optical system having a condensing lens, and the laser generated by the laser generation unit is condensed by the optical system to form a hydrogen-containing bond. Irradiate the object.
  • a catalyst since the use of a catalyst improves the yield of hydrogen, the decomposition reaction may be carried out in the presence of a catalyst.
  • preferred catalysts are compounds commonly referred to as "methanol reforming catalysts".
  • the methanol reforming catalyst is, for example, a powder of a metal compound in which a white metal element such as platinum or a beryl metal element such as copper, nickel, chromium, zinc and the acid or the like is supported on a support such as alumina.
  • —ZnO-based, or Cu—ZnO—M (where M is other metal replacing zinc, and aluminum, chromium, gallium, iron, manganese, cerium, palladium, platinum and gold) are also selected. Such as at least one metal). It may also be a photocatalyst represented by TiO.
  • the amount of the catalyst used is also dependent on the wavelength of the femtosecond laser to be irradiated. In the case of a wavelength of 800 nm, it is 0.10 wt%, preferably 0. 05-0. 05 wt% relative to the hydrogen-containing compound. It is%. If the amount of the catalyst used is too small, the effect of improving the yield is insufficient. If it is too large, the transmittance of the laser light decreases inside the hydrogen-containing compound to which the catalyst is added, and sufficient laser light is obtained. Since the light can not be collected inside the hydrogen-containing mixture, no significant improvement effect can be obtained.
  • the glass power that can transmit a laser with a pulse width of 10 to 12 seconds or less is 10 mm in length, 10 mm in width, and 20 mm in height with a branched spectrometric cell (container) 3 (5 cc capacity) Put in methanol of purity 99.8% as a plug closed with silicone rubber plug 6. Insert 2 syringe needles 7 into the container, and while stirring with the magnetic stirrer 5, supply N gas from N gas cylinder 9 through the syringe needle and publish for about 10 minutes to remove methanol.
  • a spectrometric cell (container) 3 5 cc capacity
  • the syringe 10 was attached.
  • the laser 12 emitted from the laser generation unit 11 of the laser irradiation unit 10 was condensed by a condensing lens 13 and irradiated to methanol contained in the spectroscopic cell 3.
  • the laser irradiation unit 10 was adjusted so that the laser focusing unit of the laser 12 emitted from the laser first irradiation unit 10 was positioned near the center of the inside of the spectroscopic cell.
  • the optical electric field intensity of the laser spot condensed by the condensing lens 13 was measured. As a result of the measurement, the optical electric field intensity was 66 XI 0 15 WZ cm 2 .
  • the methanol was stirred by the magnetic stirrer 5.
  • the irradiation conditions of the laser are shown in Table 1.
  • the methanol was decomposed by laser irradiation, and the generated gas was collected by a gas tight syringe.
  • a predetermined amount of one company "MDC-3" was weighed to prepare a methanol suspension having a concentration of 0.01% by weight.
  • the decomposition reaction was performed in the same manner as in Example 1 except that the obtained suspension was used instead of methanol, and the generated gas was collected and analyzed.
  • the amount of evolved gas was about 7 mL.
  • the analysis of the collected gas was carried out by injecting 4 mL of the generated gas volume of about 7 mL into the gas chromatography apparatus. The analysis results are shown in Table 2.
  • FIG. 1 is a schematic view showing the configuration of a hydrogen production apparatus according to an embodiment of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electromagnetism (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un procédé pour produire de l'hydrogène et un appareil de production, qui fonctionne simplement et de manière très sûre et très efficace du point de vue énergétique. L'invention propose un procédé de production d'hydrogène qui comprend l'étape qui consiste à irradier un liquide de composé contenant de l'hydrogène avec un laser pulsé dont les pulsations ont une largeur de 10-12 secondes ou moins. L'invention concerne en outre un appareil de production d'hydrogène qui comprend un récipient pour placer un liquide de composé contenant de l'hydrogène, qui présente une zone de transmission laser constituée d'un matériau qui permet la transmission laser et un moyen d'irradiation par laser qui irradie le liquide de composé contenant de l'hydrogène avec un laser pulsé dont les pulsations ont une largeur de 10-12 secondes ou moins et ont traversé la zone de transmission laser.
PCT/JP2006/313004 2006-06-29 2006-06-29 Procédé pour produire de l'hydrogène et appareil de production WO2008001448A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2008522251A JP4333929B2 (ja) 2006-06-29 2006-06-29 水素の製造方法及び製造装置
PCT/JP2006/313004 WO2008001448A1 (fr) 2006-06-29 2006-06-29 Procédé pour produire de l'hydrogène et appareil de production

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2006/313004 WO2008001448A1 (fr) 2006-06-29 2006-06-29 Procédé pour produire de l'hydrogène et appareil de production

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WO2008001448A1 true WO2008001448A1 (fr) 2008-01-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009184919A (ja) * 2009-04-15 2009-08-20 Kyoto Univ 水素の製造方法及び製造装置

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005060183A (ja) * 2003-08-18 2005-03-10 Sony Corp 燃料改質装置および燃料改質方法
JP2005247638A (ja) * 2004-03-04 2005-09-15 Nissan Motor Co Ltd 水素発生装置、水素発生システム及び水素発生方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005060183A (ja) * 2003-08-18 2005-03-10 Sony Corp 燃料改質装置および燃料改質方法
JP2005247638A (ja) * 2004-03-04 2005-09-15 Nissan Motor Co Ltd 水素発生装置、水素発生システム及び水素発生方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHIN S.L. ET AL.: "Generation of H2, O2 and H2O2 from water by the use of intense femtosecond laser pulses and the possibility of laser sterilization", APPL. OPT., vol. 35, no. 6, 1996, pages 907 - 911, XP000559715 *
MCGRATH T.E. ET AL.: "Laser-Initiated Chemical Reactions in Carbon Suspensions", J. PHYS. CHEM. A, vol. 106, no. 43, 2002, pages 10072 - 10078, XP003019898 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009184919A (ja) * 2009-04-15 2009-08-20 Kyoto Univ 水素の製造方法及び製造装置

Also Published As

Publication number Publication date
JP4333929B2 (ja) 2009-09-16
JPWO2008001448A1 (ja) 2009-11-26

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