WO2009096548A1 - Matériau adsorbant/décomposant un complexe argent - (oxyde de titane) - zéolite et son procédé de fabrication - Google Patents

Matériau adsorbant/décomposant un complexe argent - (oxyde de titane) - zéolite et son procédé de fabrication Download PDF

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WO2009096548A1
WO2009096548A1 PCT/JP2009/051629 JP2009051629W WO2009096548A1 WO 2009096548 A1 WO2009096548 A1 WO 2009096548A1 JP 2009051629 W JP2009051629 W JP 2009051629W WO 2009096548 A1 WO2009096548 A1 WO 2009096548A1
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Prior art keywords
titanium oxide
zeolite
composite
zeolite composite
silver
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Japanese (ja)
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Masaya Ueki
Teruo Henmi
Satoru Fukugaichi
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Ehime University NUC
Shimadzu System Solutions Co Ltd
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Ehime University NUC
Shimadzu System Solutions Co Ltd
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Priority to CN2009801015938A priority Critical patent/CN101909750A/zh
Priority to JP2009551616A priority patent/JP4943516B2/ja
Publication of WO2009096548A1 publication Critical patent/WO2009096548A1/fr
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    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • B01J23/48—Silver or gold
    • B01J23/50—Silver

Definitions

  • the present invention relates to an adsorptive decomposition material having a skeleton structure of a titanium oxide-zeolite composite or a titanium oxide-zeolite mixture in which titanium oxide is dispersed in a zeolite crystal.
  • the present inventors have not used a method in which a zeolite is used as a support and titanium oxide is supported on the zeolite, but titanium oxide is contained in a raw material composition for artificially synthesizing the zeolite.
  • An attempt was made to synthesize zeolite in the existing state (see Patent Document 1). Thereafter, the synthesis method was repeatedly improved to obtain a titanium oxide-zeolite composite in which titanium oxide and zeolite were combined. In addition to the various characteristics of zeolite, this composite has the photocatalytic activity of titanium oxide.
  • titanium oxide-zeolite composite is hydrophilic, it is difficult to exert its adsorptive decomposition function for low polarity organic compounds such as toluene and xylene.
  • a mixture of zeolite and titanium oxide is conceivable as an intermediate structure between a zeolite supported on titanium oxide and a titanium oxide-zeolite composite. Since this mixture is also hydrophilic, it cannot be expected to exhibit an adsorptive decomposition function for organic compounds having low polarity like the titanium oxide-zeolite composite.
  • the zeolite hydrophobic it is conceivable to make the zeolite hydrophobic. For example, it is to synthesize a high-silica zeolite having a high silica ratio in the zeolite (Kayban ratio (Si / Al atomic ratio) of 10 or more). Although synthesis of high silica zeolite is possible, there are problems such as extremely difficult synthesis and extremely low synthesis efficiency such that the yield of the synthesized product is about 1/10.
  • the present invention enables a framework structure containing a titanium oxide-zeolite complex and a zeolite-titanium oxide mixture to adsorb organic compounds having low polarity by other methods rather than a method of making the zeolite contained therein hydrophobic. It is for the purpose.
  • the titanium oxide-zeolite composite was synthesized so that the alkali metal ions were bound in the titanium oxide-zeolite composite, and the metal ions were immersed in various metal ion solutions to convert the metal ions into alkali metal ions.
  • the inventors have obtained the knowledge that, depending on the type of metal ion, it is possible to adsorb and decompose an organic compound having a low polarity. Similar findings were obtained for the zeolite-titanium oxide mixture.
  • the present invention is an adsorptive decomposition material in which silver (Ag) ions are bonded to a skeleton structure composed of titanium oxide and zeolite.
  • the framework structure is a titanium oxide-zeolite composite in which titanium oxide is dispersed in a zeolite crystal.
  • framework structure includes a mixture of zeolite and titanium oxide.
  • the production method of the present invention is a method of producing an adsorptive decomposition material having a titanium oxide-zeolite composite skeleton, which is a preferred form of the adsorptive decomposition material, and includes the following steps (A) and (B) .
  • (A) a step of producing a titanium oxide-zeolite composite having photocatalytic activity by treating a mixture containing titanium oxide and an aluminum component and a silicon component prepared in a composition constituting zeolite with an alkali; and
  • an alkali metal hydroxide is preferable. If an alkali metal hydroxide is used, alkali metal ions are taken into the synthesized titanium oxide-zeolite composite. This is because if it is an alkali metal ion, the ion exchange reaction with the silver ion in the step (B) easily proceeds.
  • zeolite As the zeolite, a porous material or a material having a Keiban ratio (Si / Al atom number ratio) of less than 10 is desirable. This is because zeolite with a low Keiban ratio has high hydrophilicity and easily accepts treatment in a liquid phase.
  • the material for producing the titanium oxide-zeolite composite in the step (A) can be prepared using a pure reagent so as to have a predetermined composition, but the mixture contains inorganic components such as paper sludge or paper sludge incineration ash. It is also possible to obtain a practical cost merit by using waste containing sinter or calcined metakaolin.
  • the present invention includes applying the method of the invention described in Patent Document 1 as step (A).
  • a mixture containing titanium oxide and an aluminum component and a silicon component prepared in a composition constituting the zeolite is obtained by adding a silicon component to (a) papermaking sludge containing titanium oxide and an aluminum component or incinerated ash thereof.
  • FIG. 2 is a scanning electron microscope image of the titanium oxide-zeolite composite in Example 1.
  • FIG. It is a scanning electron microscope image of zeolite.
  • FIG. 2 shows ESCA spectra before and after silver loading of the titanium oxide-zeolite composite in Example 1, with the bottom before loading and the top after loading.
  • FIG. 2 is an X-ray diffraction spectrum before and after silver loading of the titanium oxide-zeolite composite in Example 1, with the top before loading and the bottom after loading.
  • 4 is a scanning electron microscope image of a titanium oxide-zeolite mixture in Example 3.
  • FIG. 2 is a graph showing the results of a toluene adsorption decomposition test using the Ag-titanium oxide-zeolite composite of Example 1.
  • FIG. 4 is a graph showing the relationship between the amount of silver supported in the Ag-titanium oxide-zeolite composite of Example 1 and toluene adsorption performance.
  • FIG. 4 is a graph showing the results of toluene adsorption decomposition tests for the Ag-titanium oxide-zeolite composite of Example 1 and the Ag-titanium oxide-zeolite mixture of Example 3, with the bottom of Example 1 and the top of Example 3 belongs to.
  • 4 is a graph showing the results of a toluene adsorption decomposition test using a Na-titanium oxide-zeolite composite of Comparative Example 1.
  • 6 is a graph showing the results of a toluene adsorption decomposition test using a Ca-substituted-titanium oxide-zeolite composite of Comparative Example 2.
  • 4 is a graph showing the results of a toluene adsorptive decomposition test using a Fe-substituted titanium oxide-zeolite composite of Comparative Example 3.
  • 7 is a graph showing the results of a toluene adsorption decomposition test using a Cu-substituted titanium oxide-zeolite composite of Comparative Example 4.
  • Example 1 As Example 1, a production method in which an Ag-titanium oxide-zeolite composite was synthesized using a pure reagent will be described.
  • Titanium oxide powder was added in a range of 1 to 90% by weight to a solution containing 40 to 400 mg / ml water glass and 30 to 300 mg / ml sodium aluminate to prepare sodium hydroxide 3N, followed by aging.
  • silicic acid source in addition to water glass, a material containing a silicon source that generates silicic acid in an aqueous solution such as a reagent such as colloidal silica or a calcined metakaolin may be used.
  • a reagent such as aluminum hydroxide or an aluminum source that generates aluminum ions in an aqueous solution such as aluminum scrap may be used instead of sodium aluminate.
  • a silicic acid source and an aluminum source are prepared so as to have a zeolite composition in an aqueous solution.
  • the aging is preferably performed under any of the following conditions: standing, shaking, and stirring, and is performed within a temperature range from room temperature to 100 ° C. It is desirable to perform aging for 1 hour or more. Here, it was performed under the condition of standing at room temperature for 24 hours.
  • the solution after aging obtained by the above method was heated at a temperature of 70 ° C. or higher to obtain a zeolite-titanium oxide composite.
  • the Ag-titanium oxide-zeolite composite was produced by ion exchange of sodium ions in the titanium oxide-zeolite composite with silver ions. That is, 1 g of the titanium oxide-zeolite complex obtained in the above step and 30 ml of 0.1 M AgNO 3 aqueous solution are placed in a 50 ml centrifuge tube, shaken for 1 minute, and then centrifuged three times to carry out an ion exchange reaction. I let them. Thereafter, it was washed about 3 times with 30 ml of distilled water and dried at 105 ° C. for 12 hours to obtain an Ag-titanium oxide-zeolite composite.
  • the solution to be impregnated has a pH of 4 or more, and the pH was adjusted to 5 in this example as well as in Examples 2 and 3.
  • FIG. 1 shows a scanning electron microscope image of the titanium oxide-zeolite composite (before silver substitution) obtained during the production method of Example 1.
  • FIG. 2 is a scanning electron micrograph of only zeolite shown for comparison. The crystal surface of the zeolite is smooth and no spherical nanoparticles can be seen. From the crystal shape, it can be seen that the large crystal in FIG. 1 is zeolite and the fine powder crystal is titanium oxide.
  • titanium oxide is uniformly present on the surface of the zeolite crystal. Since the presence of titanium oxide particles is also confirmed in the cracks in the zeolite crystal surface, it can be seen that titanium oxide has also entered the inside of the zeolite crystal.
  • FIG. 3 shows the results of elemental analysis of the titanium oxide-zeolite composite before and after supporting silver in Example 1.
  • FIG. 3 shows the result of analysis by ESCA (Electron Spectroscopy for Chemical Analysis). The lower spectrum is before silver support, and the upper spectrum is after silver support. Two peaks in the vicinity of 350 to 380 eV are peaks derived from silver 3d orbitals. It can be confirmed from this ESCA analysis result that silver is surely present in the Ag-titanium oxide-zeolite composite after the silver is supported.
  • ESCA Electrode Spectroscopy for Chemical Analysis
  • FIG. 4 is an X-ray diffraction spectrum of the titanium oxide-zeolite composite of Example 1, with the upper spectrum before silver support and the lower spectrum after silver support.
  • the silver ions were taken into the composite by replacing sodium ions in the titanium oxide-zeolite composite with silver ions. However, a portion in which silver ions are incorporated into the complex by a reaction other than substitution is also possible. In any case, it is confirmed from the ESCA analysis results that silver is present on the surface of the titanium oxide-zeolite composite, and this silver contributes to the adsorption decomposition reaction.
  • Example 2 As Example 2 of the production method, a method for producing an Ag-titanium oxide-zeolite composite using PS (Paper Sludge) as a zeolite raw material will be described.
  • PS Paper Sludge
  • Paper sludge is an unnecessary part generated as a precipitate or a suspension in a paper manufacturing process in a paper mill, or a precipitate or a suspension generated in drainage from a paper mill.
  • Papermaking sludge incineration ash is the incineration of papermaking sludge.
  • the main components of the incinerated ash of papermaking sludge are silicic acid (SiO 2 ), aluminum oxide (Al 2 O 3 ), magnesium oxide (MgO), and the like. These components are derived from fillers added to paper raw materials such as pulp in the papermaking process. As the filler, talc (talc), calcium carbonate, titanium dioxide, aluminum hydroxide and the like are used in addition to white clay such as kaolin, clay or clay.
  • the ratio of these components in papermaking sludge or papermaking sludge incineration ash is 10 to 40% by weight of silicic acid, 15 to 75% by weight of aluminum oxide, and 7 to 20% by weight of magnesium oxide with respect to the whole inorganic components. is there.
  • the papermaking sludge contains titanium oxide.
  • the content of titanium oxide in the papermaking sludge containing titanium oxide is usually 1 to 35% by weight based on the whole inorganic component.
  • a desired amount of titanium oxide is added to the papermaking sludge or its incinerated ash when the titanium oxide-zeolite composite is synthesized.
  • the titanium oxide to be used may be a titanium oxide having almost no photocatalytic activity as contained in papermaking sludge as a white pigment, or having photocatalytic activity.
  • a paper sludge incinerated ash (PS ash) obtained by incinerating paper sludge was used containing about 20% by weight of anatase type titanium oxide.
  • calcined kaolin, anatase-type titanium oxide and talc were considered to have been used as papermaking sludge and were discharged as papermaking sludge.
  • Amorphous aluminum oxide was sulfuric acid used as a flocculant during wastewater treatment. It is considered that the band (Al 2 (SO 4 ) 3 ) was produced by firing.
  • Minerals expected as a raw material for zeolite are amorphous substances such as calcined metakaolin and amorphous aluminum oxide containing Si and Al.
  • product water glass No. 3 SiO 2 : 28.5% by weight, Na 2 O: 9.30% by weight, H 2 0: 62.2% by weight
  • MiO 2 As water glass, product water glass No. 3 (SiO 2 : 28.5% by weight, Na 2 O: 9.30% by weight, H 2 0: 62.2% by weight) manufactured by Mitsuru Chemical Industry Co., Ltd. is used. did.
  • the titanium oxide-zeolite composite material was allowed to stand at room temperature for 24 hours before the reaction, and then reacted at 95-100 ° C. for 4 hours under normal pressure. During the reaction, a condensing tube was attached to the Erlenmeyer flask to prevent evaporation of water, and stirring was not performed. The reaction product was separated into solid and liquid by a centrifugal separation method, washed about 3 times with about 30 ml of distilled water, and then dried at 105 ° C. for 12 hours to obtain a milky white powder titanium oxide-zeolite complex.
  • the obtained zeolite-titanium oxide composite was impregnated in a solution containing silver ions to be replaced with sodium ions in the same manner as in Example 1 to obtain the target Ag-titanium oxide-zeolite composite.
  • Example 3 As Example 3, an Ag-titanium oxide-zeolite mixture was prepared.
  • titanium oxide powder anatase type, particle size 20 nm
  • zeolite crystal powder Na type faujasite type, particle size 3 ⁇ m
  • the titanium oxide-zeolite mixture thus prepared was impregnated in a solution containing silver ions to be replaced with sodium ions in the same manner as in Example 1 to obtain the target Ag-titanium oxide-zeolite mixture.
  • FIG. 5 shows a scanning electron microscope image of the titanium oxide-zeolite mixture before carrying silver in Example 3. From the image of FIG. 5, it can be seen that the fine particles of titanium oxide are in a solid form and are in non-uniform contact with the outer periphery of the zeolite crystal.
  • the adsorptive decomposition material composed of Ag-titanium oxide-zeolite composite and Ag-titanium oxide-zeolite mixture of these examples, the titanium oxide-zeolite composite not substituted with silver was confirmed.
  • a metal substitution-titanium oxide-zeolite composite substituted with another metal was prepared as a comparative example.
  • Comparative Example 1 The titanium oxide-zeolite composite before metal substitution produced in the production process of the titanium oxide-zeolite composite described as Example 1 is referred to as Comparative Example 1. This sample is referred to as Na-titanium oxide-zeolite composite.
  • Comparative Example 2 is a Ca-titanium oxide-zeolite composite.
  • a Ca-titanium oxide-zeolite composite was prepared in the same manner as in Example 1 except that the AgNO 3 aqueous solution in the production process of the Ag-titanium oxide-zeolite composite in Example 1 was replaced with a 0.5M CaCl 2 aqueous solution. Got the body.
  • Comparative Example 3 is an Fe-titanium oxide-zeolite composite.
  • 1 g of the Ca-substituted titanium oxide-zeolite composite obtained in Comparative Example 2 and 30 ml of 0.01 M Fe 2 (N 0 3 ) 3 aqueous solution were placed in a 50 ml centrifuge tube, and Fe 1 was prepared in the same manner as in Example 1.
  • -A titanium oxide-zeolite composite was obtained.
  • Comparative Example 4 is a Cu-titanium oxide-zeolite composite.
  • a Cu-titanium oxide-zeolite composite was prepared in the same manner as in Example 1 except that the AgNO 3 aqueous solution in the production process of the Ag-titanium oxide-zeolite composite in Example 1 was replaced with a 0.5 M CuCl 2 aqueous solution. Got the body.
  • Toluene adsorption decomposition test Toluene was selected as the nonpolar molecule, and the toluene adsorptive decomposition test was performed on the adsorptive decomposition materials of Examples 1 and 3 and the titanium oxide-zeolite composites of Comparative Examples 1 to 4.
  • 0.10 g of various titanium oxide-zeolite composites or titanium oxide-zeolite mixtures finely ground in an agate mortar are spread on a 25 mm x 77 mm preparation, and distilled water is added to form a suspension.
  • a sample was dried at 105 ° C. for 2 hours and then cooled for 30 minutes in a desiccator. Each sample was allowed to stand in a polyethylene gas bag having a volume of 1000 ml, and then the gas bag was sealed and degassed. After deaeration, 500 ml of room air was introduced into the gas bag.
  • toluene standard gas was injected into the gas bag with a syringe so that the initial concentration of toluene in the gas bag was about 15 to 80 ppm, and the toluene gas concentration in the gas bag was measured over time.
  • Toluene gas concentration was measured by collecting gas from a gas bag and using a gas chromatograph.
  • a wavelength of 365 nm and an intensity of 4. with an ultraviolet lamp installed at a position 5 cm high from the outside of the gas bag from the time when the change in toluene concentration became small. Ultraviolet rays of 0 mW / cm 2 were irradiated.
  • FIG. 6 shows the results of a toluene adsorption decomposition test using the Ag-titanium oxide-zeolite composite of Example 1.
  • FIG. 7 shows the toluene adsorption performance in Example 1 when the amount of silver ions supported is changed. It can be seen that the toluene adsorption performance increases as the silver loading increases by 2%, 8%, and 15% in terms of weight% with respect to the entire composite. From this, it was confirmed that the presence of silver ions enhances the adsorption performance for molecules with low polarity.
  • FIG. 8 compares the toluene adsorption performance of the Ag-titanium oxide-zeolite mixture of Example 3 with that of Example 1.
  • the lower graph is that of Example 1
  • the upper graph is that of Example 3. It can be seen that the toluene adsorption performance until irradiation with ultraviolet rays is superior to the mixture of Example 3 in the composite of Example 1. From this, it is considered that the adsorption performance of toluene is not only the presence of silver ions but also the interaction between silver ions and the crystal skeleton, but the detailed mechanism is unknown.
  • Example 3 although the adsorption capacity of toluene itself is smaller than that of the composite of Example 1, it can be understood that the decomposition ability of toluene after irradiation with ultraviolet rays is similarly provided. Even if the adsorption capacity of toluene itself is small as in Example 3, when toluene adsorbed by ultraviolet irradiation is decomposed and removed from the adsorption site, new toluene molecules are adsorbed on the trace. Since it is decomposed by ultraviolet rays, it is considered that the decomposition performance is sufficiently exhibited.
  • FIG. 9 shows the results of a toluene adsorption decomposition test using the Na-titanium oxide-zeolite composite of Comparative Example 1.
  • FIG. 10 shows the results of a toluene adsorption decomposition test using the Ca-titanium oxide-zeolite composite of Comparative Example 2.
  • FIG. 11 shows the results of a toluene adsorption decomposition test using the Fe-titanium oxide-zeolite composite of Comparative Example 3.
  • FIG. 12 shows the results of a toluene adsorption decomposition test using the Cu-titanium oxide-zeolite composite of Comparative Example 4.
  • titanium oxide-zeolite composite not substituted with metal of Comparative Example 1 and the titanium oxide-zeolite composite substituted with Ca, Fe or Cu of Comparative Examples 2 to 4 were irradiated with no ultraviolet light and irradiated with ultraviolet light.
  • no significant decrease in the toluene concentration was observed, indicating that these titanium oxide-zeolite composites do not have an adsorption decomposition function of toluene.
  • the adsorptive decomposition function was measured for toluene, but toluene is only an example of an organic compound with low polarity, and the adsorptive decomposition material of the present invention can easily exhibit the adsorptive decomposition function for other low polar organic compounds. Can be estimated.
  • the Ag-titanium oxide-zeolite complex and mixture of the present invention are used as a catalyst for adsorbing and decomposing low-polar or non-polar organic compounds such as toluene present in apparatus / factory exhaust gas, air or water of rivers and lakes. can do.

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Abstract

La présente invention concerne un matériau adsorbant/décomposant présentant un squelette complexe de zéolite - (oxyde de titane), qui peut être produit par les étapes (A) et (B) : (A) le traitement d'un mélange contenant un composant d'aluminium et un composant de silicium et présentant une composition chimique à partir de laquelle un oxyde de titane et une zéolite peuvent être formés avec un alcali contenant un ion métallique alcalin pour produire un complexe (oxyde de titane) - zéolite présentant une activité photocatalytique ; et (B) l'immersion du complexe (oxyde de titane) - zéolite produit à l'étape (A) dans une solution contenant un ion argent pour entraîner la substitution de l'ion métallique alcalin dans le complexe (oxyde de titane) - zéolite par l'ion argent par l'intermédiaire d'un échange d'ions.
PCT/JP2009/051629 2008-02-01 2009-01-30 Matériau adsorbant/décomposant un complexe argent - (oxyde de titane) - zéolite et son procédé de fabrication Ceased WO2009096548A1 (fr)

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WO2016034911A1 (fr) * 2014-09-04 2016-03-10 D Onofrio Daniele Composition granulaire et son utilisation
WO2018221702A1 (fr) * 2017-05-31 2018-12-06 古河電気工業株式会社 Structure de photocatalyseur, composition de structure de photocatalyseur, matériau de revêtement de photocatalyseur, procédé de production de structure de photocatalyseur et procédé de décomposition d'aldéhydes
WO2018221693A1 (fr) * 2017-05-31 2018-12-06 国立大学法人北海道大学 Structure fonctionnelle et procédé de production de structure fonctionnelle
US11161101B2 (en) 2017-05-31 2021-11-02 Furukawa Electric Co., Ltd. Catalyst structure and method for producing the catalyst structure
US11547987B2 (en) 2017-05-31 2023-01-10 Furukawa Electric Co., Ltd. Structured catalyst for oxidation for exhaust gas purification, method for producing same, automobile exhaust gas treatment device, catalytic molding, and gas purification method
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US11680211B2 (en) 2017-05-31 2023-06-20 Furukawa Electric Co., Ltd. Structured catalyst for hydrodesulfurization, hydrodesulfurization device including the structured catalyst, and method for producing structured catalyst for hydrodesulfurization
US11684909B2 (en) 2017-05-31 2023-06-27 Furukawa Electric Co., Ltd. Structured catalyst for methanol reforming, methanol reforming device, method for producing structured catalyst for methanol reforming, and method for producing at least one of olefin or aromatic hydrocarbon
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ITFI20130049A1 (it) * 2013-03-07 2014-09-08 Onofrio Daniele D Composizione granulare e suoi utilizzi
WO2016034911A1 (fr) * 2014-09-04 2016-03-10 D Onofrio Daniele Composition granulaire et son utilisation
WO2018221702A1 (fr) * 2017-05-31 2018-12-06 古河電気工業株式会社 Structure de photocatalyseur, composition de structure de photocatalyseur, matériau de revêtement de photocatalyseur, procédé de production de structure de photocatalyseur et procédé de décomposition d'aldéhydes
WO2018221693A1 (fr) * 2017-05-31 2018-12-06 国立大学法人北海道大学 Structure fonctionnelle et procédé de production de structure fonctionnelle
JPWO2018221693A1 (ja) * 2017-05-31 2020-05-28 国立大学法人北海道大学 機能性構造体及び機能性構造体の製造方法
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US11547987B2 (en) 2017-05-31 2023-01-10 Furukawa Electric Co., Ltd. Structured catalyst for oxidation for exhaust gas purification, method for producing same, automobile exhaust gas treatment device, catalytic molding, and gas purification method
US11648542B2 (en) 2017-05-31 2023-05-16 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
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US11654422B2 (en) 2017-05-31 2023-05-23 Furukawa Electric Co., Ltd. Structured catalyst for catalytic cracking or hydrodesulfurization, catalytic cracking apparatus and hydrodesulfurization apparatus including the structured catalyst, and method for producing structured catalyst for catalytic cracking or hydrodesulfurization
US11655157B2 (en) 2017-05-31 2023-05-23 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11666894B2 (en) 2017-05-31 2023-06-06 Furukawa Electric Co., Ltd. Structured catalyst for CO shift or reverse shift and method for producing same, CO shift or reverse shift reactor, method for producing carbon dioxide and hydrogen, and method for producing carbon monoxide and water
US11680211B2 (en) 2017-05-31 2023-06-20 Furukawa Electric Co., Ltd. Structured catalyst for hydrodesulfurization, hydrodesulfurization device including the structured catalyst, and method for producing structured catalyst for hydrodesulfurization
US11684909B2 (en) 2017-05-31 2023-06-27 Furukawa Electric Co., Ltd. Structured catalyst for methanol reforming, methanol reforming device, method for producing structured catalyst for methanol reforming, and method for producing at least one of olefin or aromatic hydrocarbon
JP7352910B2 (ja) 2017-05-31 2023-09-29 国立大学法人北海道大学 機能性構造体及び機能性構造体の製造方法
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US12179182B2 (en) 2017-05-31 2024-12-31 National University Corporation Hokkaido University Method for making functional structural body

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