JP2013111562A - Composition and method for manufacturing ammonia using the composition - Google Patents

Composition and method for manufacturing ammonia using the composition Download PDF

Info

Publication number
JP2013111562A
JP2013111562A JP2011262899A JP2011262899A JP2013111562A JP 2013111562 A JP2013111562 A JP 2013111562A JP 2011262899 A JP2011262899 A JP 2011262899A JP 2011262899 A JP2011262899 A JP 2011262899A JP 2013111562 A JP2013111562 A JP 2013111562A
Authority
JP
Japan
Prior art keywords
ruthenium
composition
catalyst
ammonia
lanthanoid
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.)
Granted
Application number
JP2011262899A
Other languages
Japanese (ja)
Other versions
JP6017777B2 (en
Inventor
Katsutoshi Nagaoka
勝俊 永岡
Manami Kono
まなみ 河野
Susumu Kitagawa
進 北川
Hiroshi Kitagawa
宏 北川
Masakazu Higuchi
雅一 樋口
Miho Yamauchi
美穂 山内
Takashi Kajiwara
隆史 梶原
Hideyuki Higashimura
秀之 東村
Daisuke Watabe
大輔 渡部
Shinji Oshima
伸司 大島
Yoshiko Mitsuya
由子 三津家
Kazuo Nagashima
和郎 永島
Original Assignee
Sumitomo Chemical Co Ltd
住友化学株式会社
Jx Nippon Oil & Energy Corp
Jx日鉱日石エネルギー株式会社
Shoei Chem Ind Co
昭栄化学工業株式会社
Oita Univ
国立大学法人 大分大学
Kyoto Univ
国立大学法人京都大学
Hokkaido Univ
国立大学法人北海道大学
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 Chemical Co Ltd, 住友化学株式会社, Jx Nippon Oil & Energy Corp, Jx日鉱日石エネルギー株式会社, Shoei Chem Ind Co, 昭栄化学工業株式会社, Oita Univ, 国立大学法人 大分大学, Kyoto Univ, 国立大学法人京都大学, Hokkaido Univ, 国立大学法人北海道大学 filed Critical Sumitomo Chemical Co Ltd
Priority to JP2011262899A priority Critical patent/JP6017777B2/en
Publication of JP2013111562A publication Critical patent/JP2013111562A/en
Application granted granted Critical
Publication of JP6017777B2 publication Critical patent/JP6017777B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Abstract

A composition capable of producing ammonia in a high yield under low pressure conditions, and a method for producing ammonia using the composition.
(1) Ruthenium, an alloy containing ruthenium or a compound containing ruthenium, (2) a compound containing lanthanoid, and (3) a composition containing a basic promoter and / or a porous metal complex; The lanthanoid-containing compound is preferably a lanthanoid oxide; the basic promoter is an alkali metal oxide, alkali metal hydroxide, alkaline earth metal oxide or alkaline earth metal hydroxide. It is preferable that the porous metal complex has at least one metal selected from the group consisting of zinc, copper, magnesium, aluminum, manganese, iron, cobalt and nickel; using the composition as a catalyst A method for producing ammonia by reacting nitrogen and hydrogen.
[Selection figure] None

Description

  The present invention relates to a composition suitable for synthesizing ammonia from nitrogen and hydrogen, and an ammonia production method using the composition.

  Ammonia has long been produced by the Harbor Bosch process using an iron-based catalyst. However, since the Harbor Bosch method requires the reaction to be performed under a high pressure of about 150 atm, it has problems such as equipment investment, increased power consumption, and complicated manufacturing processes.

  In recent years, a method for producing ammonia under a low pressure condition of about 10 atm using a ruthenium catalyst has been reported for the above problem. By using this catalyst, not only ammonia can be produced under low pressure conditions, but also ammonia synthesis inhibition by carbon monoxide and water can be reduced, and the ammonia yield is improved (Non-Patent Documents 1 to 3). 3).

  In ammonia production using a ruthenium catalyst, the ruthenium catalyst may be supported on a carrier. As a carrier for supporting ruthenium, general alumina is widely used as a catalyst carrier. Recently, it has been disclosed that the amount of ruthenium used can be reduced and the reaction temperature can be lowered by using a rare earth oxide as a support instead of alumina (Patent Document 1).

JP-A-6-79177

Kenichi Akika, "Catalyst", 1996, Vol. 38, No. 4, p287-292 Kenichi Akika, "Catalyst", 1998, Vol. 40, No. 8, pp. 588-595 Kenichi Akika, "Catalyst", 2003, Vol. 45, No. 1, p17-19

  However, in the above ammonia production method, the ammonia yield when producing ammonia under a lower pressure condition is not sufficient.

  This invention is made | formed in view of the said subject, Comprising: It aims at providing the composition which can manufacture ammonia by a high yield under low-pressure conditions, and the ammonia manufacturing method using this composition.

In the present invention, the following compositions [1] to [4] and an ammonia production method [5] are provided.
[1] (1) Ruthenium, an alloy containing ruthenium or a compound containing ruthenium,
(2) a compound containing a lanthanoid, and
(3) A composition containing a basic promoter and / or a porous metal complex.
[2] The composition according to [1], wherein the compound containing the lanthanoid is a lanthanoid oxide.
[3] The composition according to [1] or [2], wherein the basic promoter is an alkali metal oxide, an alkali metal hydroxide, an alkaline earth metal oxide, or an alkaline earth metal hydroxide. .
[4] Any one of [1] to [3], wherein the porous metal complex has at least one metal selected from the group consisting of zinc, copper, magnesium, aluminum, manganese, iron, cobalt, and nickel. The composition according to item.
[5] A method for producing ammonia by reacting nitrogen and hydrogen using the composition according to any one of [1] to [4] as a catalyst.

  According to the present invention, ammonia can be produced in high yield even under low pressure conditions. Further, since ammonia can be produced under low pressure conditions, a pressurizing device such as a compressor is not required, and not only capital investment but also power consumption can be reduced.

It is a schematic diagram which shows the ammonia manufacturing apparatus used in the Example. It is a schematic diagram which shows the ammonia sampling method of an Example.

[Composition]
The composition of the first aspect of the present invention comprises:
(1) ruthenium, an alloy containing ruthenium or a compound containing ruthenium,
(2) a compound containing a lanthanoid, and
(3) A basic promoter and / or a porous metal complex is blended.
The composition can be suitably used as a catalyst in the production of ammonia.
Hereinafter, each component will be described in order. Hereinafter, the blending components are referred to as “component (1)”, “component (2)”, and “component (3)”, respectively.

(1) Ruthenium, an alloy containing ruthenium or a compound containing ruthenium In the composition of the present invention, the component (1) can function as a catalyst in ammonia production.
When component (1) is an alloy containing ruthenium, the metal element other than ruthenium is not particularly limited as long as it can be a eutectic or solid solution with ruthenium, but has ammonia synthesis reactivity. At least one selected from the group consisting of iron, molybdenum and nickel is preferable because the catalytic ability can be improved, and iron is more preferable because it is industrially used for ammonia synthesis.

  The alloy containing ruthenium may contain only one kind of metal element other than ruthenium, or may contain two or more kinds. Moreover, in addition to ruthenium and metal elements other than ruthenium, nonmetallic elements, such as carbon and silicon, may be included.

  When component (1) is a compound containing ruthenium, the ligand contained in the compound other than ruthenium is not particularly limited, and even if it is a neutral ligand, it is an ionic ligand. Also good.

  Specific examples of the compound containing ruthenium include ruthenium chloride, ruthenium acetylacetonate, potassium ruthenium cyanate, sodium ruthenate, potassium ruthenate, ruthenium oxide, dodecacarbonyltriruthenium, and ruthenium nitrate.

  As the component (1), only one of ruthenium, an alloy containing ruthenium, and a compound containing ruthenium may be used, or two or more kinds may be used in combination.

  When component (1) is an alloy containing ruthenium or a compound containing ruthenium, the content of ruthenium in the alloy or the compound is preferably 1% by mass to 99% by mass, and it is easy to ensure the reactivity. To 50 mass% to 95 mass%.

The blending ratio of component (1) in the composition is not particularly limited as long as it is a ratio capable of exhibiting good catalytic ability, but is preferably 0.01 to 15% by mass, More preferably, it is 13 mass%, and it is further more preferable that it is 1-10 mass%.
Moreover, when a component (1) is ruthenium, it is preferable that the mixture ratio of ruthenium is 0.005-15 mass%, It is more preferable that it is 0.05-13 mass%, 0.5-10 mass % Is more preferable.

  Moreover, it is preferable that the mixture ratio of a component (1) with respect to the sum total of a component (1) and the component (2) mentioned later is 0.1-15 mass%, and it is more preferable that it is 1-10 mass%. preferable. By setting it to 0.1% by mass or more, good catalytic activity can be obtained, and by setting it to 15% by mass or less, it is possible to balance catalyst activity and cost.

(2) Compound containing lanthanoid In the composition of the present invention, component (2) can function as a simple substance carrying component (1). The compound containing a lanthanoid is not particularly limited, and may be a compound containing any of 15 lanthanoids.
Among them, a compound containing any one of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, and dysprosium is preferable, and since it is strongly basic, electron supply to ruthenium and ammonia synthesis are good. More preferred are lanthanum, cerium and praseodymium.

Moreover, as a compound containing a lanthanoid, a compound containing a lanthanoid oxide such as a lanthanoid oxide, a lanthanoid sulfide, a lanthanoid hydroxide, a lanthanoid sulfate, and a group 16 element (chalcogen);
A compound containing a lanthanoid such as a lanthanoid chloride and a group 17 element (halogen), etc.
Since the component (1) can be favorably supported, a lanthanoid oxide is preferable. That is, as the component (2), lanthanum oxide, cerium oxide, or praseodymium oxide is preferable.

  As component (2), a commercially available product may be used, or it may be produced. When the component (2) which is a lanthanoid oxide is produced, for example, a commercially available lanthanoid compound (lanthanoid nitrate, lanthanoid nitrate hydrate, etc.) is dispersed in an alkaline solution, and a solid is obtained by precipitation. It can manufacture by baking the obtained solid substance. Since the lanthanoid oxide thus obtained has a stable crystal structure, the component (1) can be favorably supported.

As an alkaline solution, 5-50 mass%, More preferably, 15-35 mass% ammonia water is preferable.
The solid can be obtained by filtering the precipitate.
Firing can be performed at 250 to 900 ° C, more preferably 300 to 750 ° C. Moreover, you may perform temporary baking at low temperature rather than baking before this baking. The calcination temperature is preferably 200 to 400 ° C. (however, lower temperature than calcination).

  The blending ratio of component (2) in the composition is not particularly limited as long as it is a ratio that can favorably support component (1), but it is preferably 40 to 99.98% by mass, and 50 More preferably, it is -99.8 mass%, and it is further more preferable that it is 70-98 mass%.

(3) Basic promoter and / or porous metal complex In the composition of the present invention, component (3) is used to improve the catalyst efficiency of component (1). As a component (3), only a basic promoter may be used, only a porous metal complex may be used, and both may be used in combination.

  In the present invention, the basic co-catalyst means one having an electron donating property and capable of promoting the catalytic ability when used together with the components (1) and (2). The component (3) can promote the reaction by donating an electron to the ruthenium of the component (1).

The basic promoter is not particularly limited,
Compounds containing alkali metals and compounds containing alkaline earth metals are preferred,
More preferred are alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides and alkaline earth metal hydroxides,
Alkali metal oxides and alkali metal hydroxides are more preferred.

  Specific examples of precursors that can be used as raw materials for alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides include alkali metal and alkaline earth metal nitrates, Examples thereof include sulfates and phosphates.

  As the alkali metal and alkaline earth metal, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium are preferable, and since they have excellent electron donating property to the component (1), sodium, potassium, Rubidium and cesium are more preferable, and cesium is still more preferable.

  The porous metal complex is not particularly limited, and those usually used as a functional material such as a carrier can be appropriately selected. By using a porous metal complex as the component (3), the gas taken into the porous metal complex can improve the catalyst efficiency of the component (1).

  Examples of the porous metal complex include Reference 1 (Low et al., “Journal of American Chemical Society”, 2009, 131, p.15834-15842) and Reference 2 (Schroder et al., “Journal of American Chemical Chemistry,” 2008, 130, p.6119-6130) can be used.

Among them, those having at least one metal selected from the group consisting of zinc, copper, magnesium, aluminum, manganese, iron, cobalt and nickel are preferable, and it is estimated that ammonia resistance is easily secured. Those shown in FIG.
HKUST-1
(Represents Cu 3 (Benzenetricboxylate) 2 (H 2 O) 3 ),
Cr-MIL-101
(Represents Cr 3 F (H 2 O) O (Benzene dicarboxylicboxylate) 3 · nH 2 O).
Al-MIL-110
(Al 8 (OH) 12 {(OH) 3 (H 2 O) 3 (Benzenetricboxylate) 3 · nH 2 O is represented)],
Zn-MOF-74
(Represents Zn 2 (Dioxodobenzaldehyde)),
Al-MIL-53
(Al (OH) (represents Benzene dicarboxylate)),
Al-BTB
(Represents Al [benzene-1,3,5-tris (phenylcarboxylate)]).
ZIF-8
(Represents Zn (2-methylimidazolate) 2 · (N, N-dimethylformamide) · (H 2 O) 3 ),
ZIF-90
([Zn (ICA) 2 ] n represents Mg (HCOO) 2 ).
Among these, Al-BTB is more preferable because it has high activity stably at 350 to 400 ° C.
The above-mentioned “ICA” represents “imidazolate-2-carboxaldehyde”.

  The blending ratio of component (3) in the composition is not particularly limited, but is preferably 0.01 to 15% by mass, more preferably 0.1 to 13% by mass. More preferably, it is mass%.

  The composition of the present invention may contain other components other than components (1) to (3). Other components are not particularly limited as long as the effects of the present invention are not impaired.

In the present invention, the method for preparing the composition by blending the components (1) to (3) is not particularly limited, but a composition used as an ammonia production catalyst (hereinafter referred to as “catalyst composition”). As an example in the case of preparing ()) (i) a step of supporting component (1) on component (2), and
(Ii) The preparation method which has a process of further mix | blending component (3) with the product of the said process (i), and manufacturing a catalyst composition is mentioned.
Hereinafter, each process will be described.

(Process (i))
The method of supporting the component (1) on the component (2) is not particularly limited, but the method of supporting the component (2) by adding the component (2) after dispersing the component (1) in a solvent or water ( Impregnation method).

  Although it does not specifically limit as a solvent, Alcohol solvents, such as polar solvents, such as acetone and tetrahydrofuran, methanol, ethanol, etc. are mentioned.

  After the addition of component (2), the mixture can be stirred, the solvent or water can be distilled off, and the resulting product can be dried, if necessary.

  Moreover, when the ruthenium used as the component (1) is a compound containing ruthenium, the anion or ligand contained in the compound is preferably removed in advance before the start of the step (ii). The anion or the ligand can be removed by, for example, heat treatment under vacuum conditions or in the presence of an inert gas such as He. Heating is preferably performed at 50 to 600 ° C, preferably 150 to 550 ° C for 0.5 to 20 hours.

(Step (ii))
-Basic promoter When using a basic promoter as the component (3), for example, by an impregnation method in which the product obtained in step (i) is added to an aqueous basic promoter solution and impregnated with the basic promoter. A catalyst composition can be prepared.

  After the addition of the basic promoter, the mixed solution can be stirred, water can be distilled off, and the resulting product can be dried as necessary.

  The addition amount of the basic promoter is preferably such that the atomic ratio with respect to component (1) is 0.01 to 20% by mass. By setting the lower limit value or more, the catalytic activity can be particularly improved, and by setting the upper limit value or less, it is possible to prevent a decrease in the catalytic activity due to the presence of an excessive basic promoter.

  When a compound containing an alkali metal or a compound containing an alkaline earth metal is used as the basic promoter, it is preferable to remove an anion or a ligand contained in the compound. The removal of the ligand can be performed in the same manner as the removal of the anion or ligand contained in the ruthenium compound.

-Porous metal complex When using a porous metal complex as the component (3), for example, the catalyst composition is prepared by a method of complexing the product obtained in step (i) and the porous metal complex by physical mixing. Can be prepared. As the physical mixing method, a known method such as mixing with a mortar or ball mill can be used.

  The catalyst composition prepared as described above may be further subjected to a hydrogen reduction reaction. Catalytic performance is improved by reducing ruthenium, which is a catalyst, to a metallic state. The hydrogen reduction reaction is preferably performed at 100 to 700 ° C., preferably 300 to 600 ° C., in a hydrogen-containing atmosphere for 0.5 to 20 hours.

The method for preparing the composition is not limited to the above method. For example, after impregnating the component (2) with the basic promoter in the impregnation method, the component (1) is further impregnated in the impregnation method. Also good.
Further, when the catalyst composition is a combination of both a basic promoter and a porous metal complex, after step (i), before the start of step (ii), the porous metal complex and step (i) The product may be physically mixed and then impregnated with a basic promoter, or after impregnating the basic promoter in step (ii), the porous metal complex may be physically mixed.

[Ammonia production method]
The ammonia production method of the second aspect of the present invention uses the composition of the first aspect as a catalyst.
The method for producing ammonia is not particularly limited. For example, ammonia is produced by supplying a raw material gas composed of hydrogen gas and nitrogen gas into a reaction vessel filled with the composition of the first aspect. can do.

  The composition of the first aspect may be used for the production of ammonia after previously pulverizing, molding, sizing and the like.

  The reaction temperature is preferably 200 ° C to 600 ° C, more preferably 250 ° C to 500 ° C, and further preferably 300 ° C to 450 ° C. In the ammonia production method of the present invention, by using the composition of the first aspect, ammonia can be produced in a high yield even when the inside of the reaction vessel is under low pressure conditions. Therefore, the pressure in the reaction vessel is preferably 1 to 20 atm which is a low pressure, more preferably 1 to 10 atm, and further preferably 1 to 5 atm.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

The reactor used in this example will be described below.
As the ammonia production apparatus, the fixed bed flow type apparatus shown in FIG. 1 was used. In a normal pressure experiment, a quartz reactor having an inner diameter of 7 mm was used.
As a pretreatment for ammonia production, the reactor was filled with the composition (catalyst) used for the study, and hydrogen reduction was performed at 500 ° C. for 1 hour. Subsequently, the temperature was lowered to 310 ° C. as the reaction temperature while performing Ar purge, and when the temperature was stabilized, supply of the reaction gas was started and the temperature was raised to 350 ° C. The reaction gas was N 2 / H 2 = 1/3 (SV = 18000 ml / (h · g)). The reaction formula is as shown below.
N 2 + 3H 2 → 2NH 3

(Reaction conditions)
Catalyst amount: 0.2g
Activation treatment conditions: H 2 flow under, 10ml / min, 500 ℃, 1h.
Reaction temperature: 350 ° C
Reaction pressure: 0.1 MPa (1 atm)
Reaction gas: N 2 15 ml / min, H 2 45 ml / min

The reaction temperature was 350 ° C. and sampling was performed for 30 minutes. A schematic diagram of the ammonia sampling method is shown in FIG. The reactor outlet gas (ammonia, hydrogen, nitrogen) was passed through a 0.001 M or 0.01 M sulfuric acid solution as an ammonia trap to collect only ammonia. The reaction formula at this time is as shown below.
2NH 3 + H 2 SO 4 → 2NH 4 + + SO 4 2−

  Ammonium ions and sulfate ions are produced from the ammonia in the outlet gas of the reaction tank and the sulfuric acid solution in the trap. The decrease in electrical conductivity in this reaction was monitored, and the activity of the catalyst for ammonia synthesis was measured.

  Furthermore, as a confirmation of the ammonia yield calculated from the electrical conductivity value, the ammonia concentration was measured by ion chromatography. For ion chromatography, the ammonia trap sulfuric acid solution collected at each temperature of ammonia synthesis was collected and measured.

(Ion chromatography analysis conditions)
Column: ShodexIC YK-421
Column size: inner diameter 4.6mm, length 125mm
Filler: Weakly acidic cation exchanger with silica gel coated with polymer having carboxyl group Eluent: 4 mmol / l phosphoric acid solution

  The nitrogen yield was used as an internal standard for the calculation of ammonia yield. The calculation formula is as follows.

<Preparation Example 1-1>
In 500mL beaker, 0.1 mol equivalent of Pr (NO 3) 3 · 6H 2 O ( manufactured by Kanto Chemical Co., Inc.) were weighed, and stirred and dissolved by adding ion-exchanged water 400 mL. Moreover, 200 mL of 25% ammonia water was put into another 1 L beaker and stirred with a stirrer. Then, using a microtube pump, the nitrate aqueous solution was dropped into the 25% aqueous ammonia in about 4 hours, and then stirring was continued overnight. Thereafter, filtration and washing with ion-exchanged water were repeated. The obtained solid matter was subjected to drying at 70 ° C. in a dryer for 12 hours or more, pre-baking at 300 ° C. in the air in an exhaust firing furnace for 3 hours, and pulverized in a mortar after cooling. Further, this was calcined in the atmosphere at 700 ° C. for 3 hours in a muffle furnace to obtain Pr 6 O 11 .

<Preparation Example 1-2>
In 500mL beaker, 0.1 mol equivalent of Ce (NO 3) 3 · 6H 2 O ( manufactured by Kanto Chemical Co., Inc.) were weighed, and stirred and dissolved by adding ion-exchanged water 400 mL. Further, 200 mL of 25% aqueous ammonia was put into another 1 L beaker and stirred with a stirrer. Then, using a microtube pump, the nitrate aqueous solution was dropped into the 25% aqueous ammonia in about 4 hours, and then stirring was continued overnight. Thereafter, filtration and washing with ion-exchanged water were repeated. The obtained solid matter was subjected to drying at 70 ° C. in a dryer for 12 hours or more, pre-baking at 300 ° C. in the air in an exhaust firing furnace for 3 hours, and pulverized in a mortar after cooling. Further, this was calcined in the muffle furnace at 700 ° C. for 3 hours in the atmosphere to obtain CeO 2 .

<Preparation Example 1-3>
In 500mL beaker, 0.1 mol equivalent of La (NO 3) 3 · 6H 2 O ( manufactured by Kanto Chemical Co., Inc.) were weighed, and stirred and dissolved by adding ion-exchanged water 400 mL. Further, 200 mL of 25% aqueous ammonia was put into another 1 L beaker and stirred with a stirrer. Then, using a microtube pump, the nitrate aqueous solution was dropped into the 25% aqueous ammonia in about 4 hours, and then stirring was continued overnight. Thereafter, filtration and washing with ion-exchanged water were repeated. The obtained solid matter was subjected to drying at 70 ° C. in a dryer for 12 hours or more, pre-baking at 300 ° C. in the air in an exhaust firing furnace for 3 hours, and pulverized in a mortar after cooling. Further, this was calcined in the atmosphere at 700 ° C. for 3 hours in a muffle furnace to obtain La 2 O 3 .

<Preparation Example 2-1>
Ru 3 (CO) 12 (manufactured by Wako Pure Chemical Industries, Ltd.), 565 mg (0.88 mmol) was placed in an eggplant flask, dissolved in 200 ml of tetrahydrofuran, and then the carrier (Pr) obtained in <Preparation Example 1-1> above. 6 O 11 ) 5.0 mg (4.9 mmol) was added, and the mixture was stirred with a magnetic stirrer at room temperature for 12 hours. Thereafter, the solvent was removed by heating using a rotary evaporator. At this time, the temperature of the warm bath was gradually raised to 70 ° C. The obtained solid material was transferred from the eggplant flask to a baking dish and dried for one day with a dryer at 70 ° C., then placed in a Pyrex (registered trademark) glass (Corning) boat and a horizontal tubular furnace under He circulation. The ligand of the ruthenium compound was removed by heat treatment at 350 ° C. for 5 hours. The product obtained by such a procedure was 5 mass% Ru / Pr 6 O 11 carrying 5 mass% of ruthenium.

<Preparation Example 2-2>
<Preparation Example 2-1 above, except that 5.0 g (29 mmol) of the carrier (CeO 2 ) obtained in <Preparation Example 1-2> was used in place of the carrier obtained in <Preparation Example 1-1>. In the same manner as above, 5% by mass Ru / CeO 2 supporting 5% by mass of ruthenium was prepared.

<Preparation Example 2-3>
<Preparation Example 2> except that 5.0 g (15 mmol) of the carrier (La 2 O 3 ) obtained in <Preparation Example 1-3> was used in place of the carrier obtained in <Preparation Example 1-1>. -1> and was similarly prepared 5 wt% Ru / La 2 O 3 was 5 wt% supported ruthenium.

<Preparation Example 2-4>
As the carrier, La 2 O 3 prepared according to <Preparation Example 1-3> was used.
157 mg of Ru 3 Cl 3 n hydrate, 666.6 mg of polyvinylpyrrolidone, and 290 ml of ethylene glycol were stirred at 23 ° C. for 5 minutes in an argon atmosphere. After stirring at 23 ° C. for 30 minutes and at 220 ° C. for 2 hours, the mixture was cooled, filtered, and washed with ethanol, acetone, diethyl ether, and water to obtain Ru nanoparticles.
869 mg of the obtained Ru nanoparticles were dissolved in 40 ml of ethanol, 2.0 g of La 2 O 3 was added, and ultrasonic irradiation was performed for 5 minutes. Methanol was evaporated on a water bath to obtain 2.54 g of Ru nanoparticle supported catalyst.
Elemental analysis was performed with ICP-AES (ICPE-9000, manufactured by Shimadzu Corporation), and it was found that 3.0% by mass of Ru was supported. Hereinafter, the catalyst may be referred to as 3.0 mass% Ru / La 2 O 3 .

<Preparation Example 2-5>
As the carrier, La 2 O 3 prepared according to <Preparation Example 1-3> was used.
RuCl 3 n-hydrate (313 mg), Fe [C 3 H 8 O 2 ] 3 (43 mg), polyvinylpyrrolidone (266 mg), sodium hydroxide (10 mg), and ethylene glycol (300 ml) were placed in an eggplant flask and heated and stirred to 140 ° C. under an argon atmosphere. . After adding 454 mg of sodium borohydride, the temperature was raised to 180 ° C. and stirred for 120 minutes. The mixture was cooled, filtered and washed with ethanol, acetone, diethyl ether and water to obtain 230 mg of RuFe nanoparticles.
1,050 mg of the obtained RuFe nanoparticles were dissolved in 40 ml of methanol, 2.0 g of La 2 O 3 was added, and ultrasonic irradiation was performed for 5 minutes. Methanol was evaporated on a water bath to obtain 2.38 g of a RuFe nanoalloy supported catalyst.
When elemental analysis was performed by ICP-AES, it was found that 4.7% by mass of Ru and 0.3% by mass of Fe were supported. Hereinafter sometimes referred to as 4.7 mass% Ru-0.3 wt% Fe / La 2 O 3 the catalyst.

<Preparation Example 2-6>
As the carrier, La 2 O 3 prepared according to <Preparation Example 1-3> was used.
RuCl 3 n-hydrate 564 mg, Ni (CH 3 CO 2 ) 2 60 mg, polyvinylpyrrolidone 1,333 mg, and ethylene glycol 200 ml were placed in an eggplant flask, heated to 170 ° C. under an argon atmosphere, and stirred for 15 minutes. The mixture was cooled, filtered, and washed with ethanol, acetone, diethyl ether, and water to obtain 800 mg of RuNi nanoparticles. 800 mg of the prepared RuNi nanoparticles were dissolved in 40 ml of methanol, 1.4 g of La 2 O 3 was added, and ultrasonic irradiation was performed for 5 minutes. Methanol was evaporated on a water bath to obtain 1.42 g of a RuNi nanoalloy supported catalyst.
When elemental analysis was performed by ICP-AES, it was found that 4.3 mass% Ru and 0.1 mass% Ni were supported. Hereinafter, the catalyst may be referred to as 4.3 mass% Ru-0.1 mass% Ni / La 2 O 3 .

<Reference Examples 1-2, Comparative Example 1>
Using the catalyst shown in Table 1, the ammonia synthesis activity (unit:%, synthesis yield per gram of Ru) at 350 ° C. was measured by the method described above, and the ammonia yield was calculated. The results are shown in Table 1. The catalyst was sufficiently pulverized and mixed in a mortar, formed into a disk, and then pulverized again to adjust the particle size to 250 to 500 μm.

  From the above results, the catalysts of Reference Examples 1 and 2 in which a small amount of a base metal such as Fe and Ni was alloyed with Ru and supported on the lanthanoid carrier were compared with the catalyst of Comparative Example 1 in which Ru alone was supported on the lanthanoid carrier. As a result, it was found that ammonia synthesis activity was enhanced and ammonia could be produced in high yield even at normal pressure.

<Example 1>
Al-BTB and 5 mass% Ru / Pr 6 O 11 obtained in the above <Preparation Example 2-1> were physically mixed using a mortar at a mass ratio of 1: 9. By such a procedure, Al-BTB + 5 mass% Ru / Pr 6 O 11 was obtained. Using the obtained catalyst, ammonia was produced by the method described above, and the ammonia yield was calculated to be 0.15%. The results are shown in Table 2.
The catalyst was used after being pulverized, mixed, molded, reground and sized in the same manner as in Reference Examples 1 and 2. The same applies to Examples 2 to 10 and Comparative Example 2 below.

<Example 2>
In the following steps, a catalyst obtained by blending the alkali metal oxides were prepared in 5 wt% Ru / Pr 6 O 11 <Preparation Example 2-1>. The atomic ratio of alkali metal to ruthenium in the catalyst was set to 1.0.
150 ml of distilled water was put into a 300 ml beaker, and 193 mg (0.99 mmol) of CsNO 3 (manufactured by Kanto Chemical Co., Ltd.), which is an alkali metal oxide precursor, was added and stirred with a magnetic stirrer to dissolve.
Thereafter, 2.0 mg (Ru: 0.99 mmol) of 5 mass% Ru / Pr 6 O 11 obtained in the above <Preparation Example 2-1> was added and stirred at room temperature for 12 hours. Thereafter, the water was evaporated by heating and stirring on a hot stirrer, and the paste was sufficiently dried with a dryer at 70 ° C. and pulverized and mixed in a mortar.
Then, it is put into a boat made of Pyrex (registered trademark) glass (manufactured by Corning), and heated in a horizontal tubular furnace under 100% H 2 flow at 500 ° C. for 1 hour, so that nitric acid in the alkali metal oxide precursor. The roots were removed to give the product.
The product obtained by such a procedure was Cs / 5 wt% Ru / Pr 6 O 11 supporting Cs and 5 wt% ruthenium. Using the obtained product as a catalyst, ammonia was produced by the method described above, and the ammonia yield was calculated to be 1.01%. The results are shown in Table 2.

<Example 3>
The following procedure was used to prepare a catalyst containing a combination of alkali metal oxide 5 wt% Ru / CeO 2 <Preparation Example 2-2>. The atomic ratio of alkali metal to ruthenium in the catalyst was set to 0.5.
150 ml of distilled water was put into a 300 ml beaker, and 96 mg (0.49 mmol) of CsNO 3 (manufactured by Kanto Chemical Co.), which is an alkali metal oxide precursor, was added and stirred with a magnetic stirrer to dissolve.
Thereafter, 2.0 mg (Ru: 0.99 mmol) of a predetermined amount of 5 mass% Ru / CeO obtained in the above <Preparation Example 2-2> was added and stirred at room temperature for 12 hours. Thereafter, the water was evaporated by heating and stirring on a hot stirrer, and the paste was sufficiently dried with a dryer at 70 ° C. and pulverized and mixed in a mortar.
Then, it is put into a boat made of Pyrex (registered trademark) glass (manufactured by Corning), and heated in a horizontal tubular furnace under 100% H 2 flow at 500 ° C. for 1 hour, so that nitric acid in the alkali metal oxide precursor. The roots were removed to give the product.
The catalyst obtained by such a procedure was Cs / 5 mass% Ru / CeO 2 . Using the obtained catalyst, ammonia was produced by the method described above, and the ammonia yield was calculated to be 0.79%. The results are shown in Table 2.

<Example 4>
A catalyst was prepared by blending the alkali metal oxides in the following steps 5 wt% Ru / La 2 O 3 <Preparation Example 2-3>. The atomic ratio of alkali metal to ruthenium in the catalyst was set to 0.1.
150 ml of distilled water was put into a 300 ml beaker, 19 mg (0.097 mmol) of CsNO 3 (manufactured by Kanto Chemical Co., Ltd.), which is an alkali metal oxide precursor, was added and stirred with a magnetic stirrer to dissolve.
Thereafter, 2.0 mg (Ru: 0.99 mmol) of a predetermined amount of 5 mass% Ru / La 2 O 3 obtained in the above <Preparation Example 2-3> was added and stirred at room temperature for 12 hours.
Thereafter, the water was evaporated by heating and stirring on a hot stirrer, and the paste was sufficiently dried with a dryer at 70 ° C. and pulverized and mixed in a mortar.
Then, it is put into a boat made of Pyrex (registered trademark) glass (manufactured by Corning) and heated in a horizontal tubular furnace under a flow of 100% H 2 at 500 ° C. for 1 hour, so that the alkali metal oxide precursor The nitrate radical was removed to obtain the product.
The catalyst obtained by such a procedure was Cs / 5 mass% Ru / La 2 O 3 . Using the obtained catalyst, ammonia was produced by the method described above, and the ammonia yield was calculated to be 0.72%. The results are shown in Table 2.

<Example 5>
The following steps 3 wt% Ru / La 2 O 3 catalyst containing a combination of alkali metal oxide in <Preparation Example 2-4> is prepared. The atomic ratio of alkali metal to ruthenium in the catalyst is set to 0.1.
Add 150 ml of distilled water to a 300 ml beaker, add CsNO 3 (manufactured by Kanto Chemical Co., Inc.), which is an alkali metal oxide precursor, and stir with a magnetic stirrer to dissolve.
Thereafter, the predetermined amount of 3 mass% Ru / La 2 O 3 obtained in the above <Preparation Example 2-4> is added and stirred at room temperature for 12 hours.
Then, the water is evaporated by heating and stirring on a hot stirrer, and the paste is sufficiently dried with a dryer at 70 ° C. and pulverized and mixed in a mortar.
After that, it was put into a boat made of Pyrex (registered trademark) glass (Corning) and heated in a horizontal tube furnace under 100% H 2 flow at 500 ° C. for 1 hour, so that nitric acid in the alkali metal oxide precursor Remove the roots to obtain the product.
The catalyst obtained by such a procedure is Cs / 3 wt% Ru / La 2 O 3 .

<Example 6>
Preparing a catalyst obtained by blending alkali metal oxide of 4.7 wt% Ru-0.3 wt% Fe / La 2 O 3 <Preparation Example 2-5> by the following procedure. The atomic ratio of alkali metal to ruthenium in the catalyst is set to 0.1.
Add 150 ml of distilled water to a 300 ml beaker, add CsNO 3 (manufactured by Kanto Chemical Co., Inc.), which is an alkali metal oxide precursor, and stir with a magnetic stirrer to dissolve.
Thereafter, the predetermined amount of 4.7% by mass Ru-0.3% by mass Fe / La 2 O 3 obtained in the above <Preparation Example 2-5> is added and stirred at room temperature for 12 hours.
Then, the water is evaporated by heating and stirring on a hot stirrer, and the paste is sufficiently dried with a dryer at 70 ° C. and pulverized and mixed in a mortar.
After that, it was put into a boat made of Pyrex (registered trademark) glass (Corning) and heated in a horizontal tube furnace under 100% H 2 flow at 500 ° C. for 1 hour, so that nitric acid in the alkali metal oxide precursor Remove the roots to obtain the product.
Catalyst obtained by such a procedure is Cs / 4.7 wt% Ru-0.3 wt% Fe / La 2 O 3.

<Example 7>
Preparing a catalyst obtained by blending alkali metal oxide of 4.3 wt% Ru-0.1 wt% Ni / La 2 O 3 <Preparation Example 2-6> by the following procedure. The atomic ratio of alkali metal to ruthenium in the catalyst is set to 0.1.
In a 300 ml beaker, 150 ml of distilled water is added, an alkali metal oxide precursor (CsNO 3 (manufactured by Kanto Chemical Co., Inc.)) is added and stirred and dissolved with a magnetic stirrer. It was added to the resultant 4.3 wt% Ru-0.1 wt% Ni / La 2 O 3 in a predetermined amount and stirred at room temperature for 12 hours then hot stirrer -. water is evaporated by heating and stirring on, the paste The resulting product is thoroughly dried in a dryer at 70 ° C. and pulverized and mixed in a mortar, then placed in a Pyrex (registered trademark) glass (Corning) boat and 100% H 2 in a horizontal tube furnace. The nitrate radical in the alkali metal oxide precursor is removed by heat treatment at 500 ° C. for 1 hour under flow to obtain a product.
The catalyst obtained in this procedure is a Cs / 4.3 wt% Ru-0.1 wt% Ni / La 2 O 3.

<Example 8>
Al-BTB and 3 mass% Ru / La 2 O 3 obtained in the above <Preparation Example 2-4> are physically mixed using a mortar at a mass ratio of 1: 9.
Obtain Al-BTB + 3 wt% Ru / La 2 O 3 in such a procedure.

<Example 9>
Physical mixing of Al-BTB and 4.7% by mass Ru-0.3% by mass Fe / La 2 O 3 obtained in the above <Preparation Example 2-5> using a mortar at a mass ratio of 1: 9 To do.
Obtain Al-BTB + 4.7 wt% Ru-0.3 wt% Fe / La 2 O 3 in such a procedure.

<Example 10>
And al-BTB, and 4.3 wt% Ru-0.1 wt% Ni / La 2 O 3 obtained in the above <Preparation Example 2-6>, a weight ratio of 1: 9 using a mortar in a physical mixture To do.
Obtain Al-BTB + 4.3 wt% Ru-0.1 wt% Ni / La 2 O 3 in such a procedure.

<Comparative example 2>
Ammonia was produced by the method described above using the catalyst obtained in Comparative Example 1, and the ammonia yield was calculated to be 0.06%. The results are shown in Table 2.

  From the above results, when using the catalyst of Examples 2 to 4 blended with the basic promoter and the catalyst of Example 1 blended with the porous metal complex, the basic promoter and the porous metal complex were blended. It was found that ammonia can be produced in a high yield even at normal pressure as compared with the catalyst of Comparative Example 2 that is not present.

Claims (5)

  1. (1) ruthenium, an alloy containing ruthenium or a compound containing ruthenium,
    (2) a compound containing a lanthanoid, and
    (3) A composition containing a basic promoter and / or a porous metal complex.
  2.   The composition according to claim 1, wherein the compound containing the lanthanoid is a lanthanoid oxide.
  3.   The composition according to claim 1 or 2, wherein the basic promoter is an alkali metal oxide, an alkali metal hydroxide, an alkaline earth metal oxide, or an alkaline earth metal hydroxide.
  4.   The composition according to any one of claims 1 to 3, wherein the porous metal complex has at least one metal selected from the group consisting of zinc, copper, magnesium, aluminum, manganese, iron, cobalt, and nickel. object.
  5.   A method for producing ammonia by reacting nitrogen and hydrogen using the composition according to any one of claims 1 to 4 as a catalyst.
JP2011262899A 2011-11-30 2011-11-30 Method for producing catalyst composition for ammonia production and method for producing ammonia Active JP6017777B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2011262899A JP6017777B2 (en) 2011-11-30 2011-11-30 Method for producing catalyst composition for ammonia production and method for producing ammonia

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2011262899A JP6017777B2 (en) 2011-11-30 2011-11-30 Method for producing catalyst composition for ammonia production and method for producing ammonia

Publications (2)

Publication Number Publication Date
JP2013111562A true JP2013111562A (en) 2013-06-10
JP6017777B2 JP6017777B2 (en) 2016-11-02

Family

ID=48707687

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2011262899A Active JP6017777B2 (en) 2011-11-30 2011-11-30 Method for producing catalyst composition for ammonia production and method for producing ammonia

Country Status (1)

Country Link
JP (1) JP6017777B2 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015066468A (en) * 2013-09-26 2015-04-13 住友化学株式会社 Ammonia synthesis catalyst and ammonia producing method
WO2016133213A1 (en) * 2015-02-20 2016-08-25 国立大学法人大分大学 Ammonia synthesis catalyst and method for producing same
JP2017018907A (en) * 2015-07-13 2017-01-26 国立大学法人 大分大学 Composition for ammonia synthesis catalyst and method for producing the same, and method for synthesizing ammonia
WO2017014313A1 (en) * 2015-07-23 2017-01-26 昭栄化学工業株式会社 Metal oxide nanocrystal production method, multi-element oxide nanocrystal production method and metal oxide nanocrystal
JP2017148810A (en) * 2017-05-26 2017-08-31 住友化学株式会社 Ammonia synthesis catalyst and ammonia producing method
CN107530686A (en) * 2015-02-20 2018-01-02 国立研究开发法人科学技术振兴机构 ammonia synthesis catalyst and preparation method thereof
WO2019059190A1 (en) 2017-09-25 2019-03-28 国立研究開発法人科学技術振興機構 Composite oxide, metal-supporting material and ammonia synthesis catalyst

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017001037A (en) * 2016-09-29 2017-01-05 住友化学株式会社 Catalyst composition for manufacturing ammonia, manufacturing method of catalyst composition for manufacturing ammonia and ammonia manufacturing method

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03106445A (en) * 1989-09-21 1991-05-07 Shinnenshiyou Syst Kenkyusho:Kk Catalyst for preparing ammonia
JPH0679177A (en) * 1992-09-02 1994-03-22 Mitsui Toatsu Chem Inc Catalyst and process for synthesizing ammonia
JPH08141399A (en) * 1994-11-24 1996-06-04 Mitsui Toatsu Chem Inc Ammonia synthesizing catalyst and preparation thereof
JP2001246251A (en) * 2000-03-09 2001-09-11 Nkk Corp Method for preparing catalyst used in synthesis of ammonia and method for synthesizing ammonia
JP2002052341A (en) * 2000-07-06 2002-02-19 Haldor Topsoe As Catalytic ammonia production method and production and recovery method for ammonia synthesis catalyst
JP2004261728A (en) * 2003-03-03 2004-09-24 Jfe Engineering Kk Ammonia synthesizing catalyst and method for manufacturing the same
JP2006231229A (en) * 2005-02-25 2006-09-07 Honda Motor Co Ltd Ammonia synthesis catalyst and its production method
WO2010010050A1 (en) * 2008-07-21 2010-01-28 Basf Se Method for technical extraction of propene
JP2011056488A (en) * 2009-09-09 2011-03-24 Katsutoshi Nagaoka Ammonia reforming catalyst and method of manufacturing hydrogen using the same
JP2011126775A (en) * 2009-12-15 2011-06-30 Samsung Electronics Co Ltd Hybrid porous material and method for producing the same

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03106445A (en) * 1989-09-21 1991-05-07 Shinnenshiyou Syst Kenkyusho:Kk Catalyst for preparing ammonia
JPH0679177A (en) * 1992-09-02 1994-03-22 Mitsui Toatsu Chem Inc Catalyst and process for synthesizing ammonia
JPH08141399A (en) * 1994-11-24 1996-06-04 Mitsui Toatsu Chem Inc Ammonia synthesizing catalyst and preparation thereof
JP2001246251A (en) * 2000-03-09 2001-09-11 Nkk Corp Method for preparing catalyst used in synthesis of ammonia and method for synthesizing ammonia
JP2002052341A (en) * 2000-07-06 2002-02-19 Haldor Topsoe As Catalytic ammonia production method and production and recovery method for ammonia synthesis catalyst
JP2004261728A (en) * 2003-03-03 2004-09-24 Jfe Engineering Kk Ammonia synthesizing catalyst and method for manufacturing the same
JP2006231229A (en) * 2005-02-25 2006-09-07 Honda Motor Co Ltd Ammonia synthesis catalyst and its production method
WO2010010050A1 (en) * 2008-07-21 2010-01-28 Basf Se Method for technical extraction of propene
JP2011056488A (en) * 2009-09-09 2011-03-24 Katsutoshi Nagaoka Ammonia reforming catalyst and method of manufacturing hydrogen using the same
JP2011126775A (en) * 2009-12-15 2011-06-30 Samsung Electronics Co Ltd Hybrid porous material and method for producing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JPN6016012577; Chao HUO, et al.: 'Efficient La-Ba-MgO Supported Ru Catalysts for Ammonia Synthesis' Catalysis Letters Volume 141, Issue 9, 20110702, Pages 1275-1281 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015066468A (en) * 2013-09-26 2015-04-13 住友化学株式会社 Ammonia synthesis catalyst and ammonia producing method
WO2016133213A1 (en) * 2015-02-20 2016-08-25 国立大学法人大分大学 Ammonia synthesis catalyst and method for producing same
CN107530686A (en) * 2015-02-20 2018-01-02 国立研究开发法人科学技术振兴机构 ammonia synthesis catalyst and preparation method thereof
EP3260198A4 (en) * 2015-02-20 2018-12-05 Japan Science and Technology Agency Ammonia synthesis catalyst and method for producing same
JP2017018907A (en) * 2015-07-13 2017-01-26 国立大学法人 大分大学 Composition for ammonia synthesis catalyst and method for producing the same, and method for synthesizing ammonia
WO2017014313A1 (en) * 2015-07-23 2017-01-26 昭栄化学工業株式会社 Metal oxide nanocrystal production method, multi-element oxide nanocrystal production method and metal oxide nanocrystal
US10640882B2 (en) 2015-07-23 2020-05-05 Shoei Chemical Inc. Method for producing nanocrystals and nanocrystal production device
JP2017148810A (en) * 2017-05-26 2017-08-31 住友化学株式会社 Ammonia synthesis catalyst and ammonia producing method
WO2019059190A1 (en) 2017-09-25 2019-03-28 国立研究開発法人科学技術振興機構 Composite oxide, metal-supporting material and ammonia synthesis catalyst

Also Published As

Publication number Publication date
JP6017777B2 (en) 2016-11-02

Similar Documents

Publication Publication Date Title
Gu et al. Synergistic catalysis of metal–organic framework-immobilized Au–Pd nanoparticles in dehydrogenation of formic acid for chemical hydrogen storage
Cai et al. Comparative study of 3D ordered macroporous Ce 0.75 Zr 0.2 M 0.05 O 2− δ (M= Fe, Cu, Mn, Co) for selective catalytic reduction of NO with NH 3
Eid et al. One-step synthesis of porous bimetallic PtCu nanocrystals with high electrocatalytic activity for methanol oxidation reaction
Poreddy et al. Copper oxide as efficient catalyst for oxidative dehydrogenation of alcohols with air
DE102013225764B4 (en) Catalyst particles with a layered core-shell-shell structure and process for their preparation
Li et al. Covalent triazine framework supported non-noble metal nanoparticles with superior activity for catalytic hydrolysis of ammonia borane: from mechanistic study to catalyst design
US8273504B2 (en) Method for manufacture of noble metal alloy catalysts and catalysts prepared therewith
Zhang et al. Influence of ZnO facets on Pd/ZnO catalysts for methanol steam reforming
Concepción et al. Chemoselective hydrogenation catalysts: Pt on mesostructured CeO2 nanoparticles embedded within ultrathin layers of SiO2 binder
JP4351913B2 (en) Ceria-based mixed metal oxide structure, its preparation and use
Ma et al. Promoting effect of rhenium on catalytic performance of Ru catalysts in hydrogenolysis of glycerol to propanediol
JP6152381B2 (en) Method for producing conductive mayenite type compound powder
US7566440B2 (en) Metal oxide catalysts
US4629709A (en) Non-noble metal catalytic microaggregates, a method for their preparation and their application in the catalysis of the photoreduction of water
Rakap et al. Hydrogen generation from the hydrolysis of ammonia borane using cobalt-nickel-phosphorus (Co–Ni–P) catalyst supported on Pd-activated TiO2 by electroless deposition
CA2823165C (en) Zeolite having copper and alkali earth metal supported thereon
Kydd et al. Flame‐Synthesized Ceria‐Supported Copper Dimers for Preferential Oxidation of CO
US7001586B2 (en) CO-free hydrogen from decomposition of methane
Thavornprasert et al. Highly productive iron molybdate mixed oxides and their relevant catalytic properties for direct synthesis of 1, 1-dimethoxymethane from methanol
CN102151568B (en) Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof
US20060024539A1 (en) Catalytic method to remove CO and utilize its energy content in CO-containing streams
JP3882044B2 (en) Method for preparing Fischer-Tropsch synthesis catalyst
CN101850243B (en) Carrier of silver catalyst for producing ethylene oxide, preparation method thereof, silver catalyst prepared by using same and application thereof in producing ethylene oxide
WO2008099961A9 (en) Catalyst for alcohol production
Eid et al. One-step synthesis of trimetallic Pt–Pd–Ru nanodendrites as highly active electrocatalysts

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20141003

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20150514

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20150616

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20150817

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20151117

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20160115

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20160405

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20160830

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20160929

R150 Certificate of patent or registration of utility model

Ref document number: 6017777

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

S533 Written request for registration of change of name

Free format text: JAPANESE INTERMEDIATE CODE: R313533

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250